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WO2018190010A1 - Élément électroluminescent organique - Google Patents

Élément électroluminescent organique Download PDF

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Publication number
WO2018190010A1
WO2018190010A1 PCT/JP2018/007047 JP2018007047W WO2018190010A1 WO 2018190010 A1 WO2018190010 A1 WO 2018190010A1 JP 2018007047 W JP2018007047 W JP 2018007047W WO 2018190010 A1 WO2018190010 A1 WO 2018190010A1
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WIPO (PCT)
Prior art keywords
layer
group
organic
meth
inorganic protective
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PCT/JP2018/007047
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English (en)
Japanese (ja)
Inventor
孝敏 末松
隼 古川
和喜 田地
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コニカミノルタ株式会社
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Priority to JP2019512368A priority Critical patent/JPWO2018190010A1/ja
Publication of WO2018190010A1 publication Critical patent/WO2018190010A1/fr

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    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/02—Details
    • H05B33/04—Sealing arrangements, e.g. against humidity
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/22—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of auxiliary dielectric or reflective layers
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/26—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode
    • H05B33/28—Light sources with substantially two-dimensional radiating surfaces characterised by the composition or arrangement of the conductive material used as an electrode of translucent electrodes
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/84—Passivation; Containers; Encapsulations
    • H10K50/842—Containers
    • H10K50/8426—Peripheral sealing arrangements, e.g. adhesives, sealants

Definitions

  • the present invention relates to an organic electroluminescence element.
  • organic EL devices such as organic electroluminescence elements (hereinafter also referred to as “organic EL elements”) and organic solar cells are required to have high efficiency, large area, and flexibility.
  • organic EL elements organic electroluminescence elements
  • organic solar cells are required to have high efficiency, large area, and flexibility.
  • a method using a transparent electrode using a thin metal wire is known for increasing the area.
  • a technique for incorporating a conductive fiber such as a metal nanowire into a transparent electrode has been disclosed (see, for example, Patent Document 1).
  • the present invention has been made in view of the above-described problems and situations, and a problem to be solved is to provide an organic electroluminescence element that has excellent rectification characteristics and suppresses the generation of dark spots.
  • the present inventor has suppressed the generation of dark spots in the organic EL device by laminating an inorganic protective layer on the second electrode when sealing using an adhesive is used in the organic EL device. Further, the inventors have found that the rectification characteristics are improved and have reached the present invention. This is presumably because damage to the organic functional layer was reduced. The reason why the generation of dark spots is suppressed is considered to be because the inorganic protective layer can suppress the influence of diffusion of moisture and the like caused by the adhesive. Moreover, it discovered that generation
  • the rectification characteristic specifically means a rectification ratio.
  • An organic electroluminescence device in which a first electrode, an organic functional layer, a second electrode, an inorganic protective layer, an adhesive layer, and a sealing member including at least a thin metal wire and a transparent conductive layer are sequentially laminated on a transparent flexible substrate.
  • Cross-sectional schematic diagram showing a schematic configuration as an example of the organic EL element of the present invention Cross-sectional schematic diagram showing a schematic configuration as another example of the organic EL device of the present invention
  • ⁇ representing a numerical range is used in the sense that numerical values described before and after the numerical value range are included as a lower limit value and an upper limit value.
  • the organic EL device of the present invention includes a first electrode, an organic functional layer, a second electrode, an inorganic protective layer, and at least a thin metal wire and a transparent conductive layer on a transparent flexible substrate (hereinafter also referred to as a substrate).
  • An adhesive layer and a sealing member (sealing layer) are sequentially laminated.
  • FIG. 1 shows a schematic configuration of the organic EL element of the present invention.
  • the organic EL element 1 includes a transparent flexible substrate 2, a first electrode 3 as a transparent electrode, an organic functional layer 4, a second electrode 5 as a counter electrode, an inorganic protective layer 6, and an adhesive.
  • the layer 7 and the sealing member 8 are sequentially laminated.
  • transparent transparent
  • translucent means that the light transmittance at a wavelength of 550 nm is 50% or more.
  • the first electrode 3 is configured by laminating a thin metal wire 3a and a transparent conductive layer 3b formed in this order from the transparent flexible substrate 2 side. 2, the transparent conductive layer 3b from the transparent flexible base material 2 side and the fine metal wires 3a formed in a pattern may be laminated in this order, and further, the fine metal wires 3a are covered. In this way, an insulating layer (not shown) may be provided.
  • the first electrode 3 is preferably configured by laminating at least the fine metal wires 3a and the transparent conductive layer 3b formed in a pattern from the transparent flexible substrate 2 side.
  • the organic functional layer 4 includes at least a light emitting layer, and may have various organic layers such as a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and the like.
  • the hole injection layer and the hole transport layer may be provided as a hole transport injection layer.
  • the electron transport layer and the electron injection layer may be provided as an electron transport injection layer.
  • the electron injection layer may be made of an inorganic material.
  • the organic functional layer 4 may have a hole blocking layer, an electron blocking layer, or the like as necessary.
  • the second electrode 5 may have a laminated structure as necessary.
  • the inorganic protective layer 6 may have a laminated structure as necessary.
  • the inorganic protective layer 6 may be composed of a first inorganic protective layer 6a, a second inorganic protective layer 6b, and a third inorganic protective layer 6c.
  • the inorganic protective layer 6 may be composed of two layers or may be composed of four or more layers.
  • the organic EL element 1 only a portion where the organic functional layer 4 is sandwiched between the first electrode 3 and the second electrode 5 is a light emitting region in the organic EL element 1. And the organic EL element 1 is the structure which takes out the light (henceforth emitted light) generated at least from the transparent flexible base material 2 side.
  • extraction electrodes are provided at the ends of the first electrode 3 and the second electrode 5.
  • the first electrode 3 and the second electrode 5 are electrically connected to an external power source (not shown) via the extraction electrode.
  • the organic EL element 1 of the present invention may have various other functional layers as necessary.
  • a gas barrier layer 9 may be provided on the transparent flexible substrate 2.
  • a base layer 10 may be provided between the transparent flexible base material 2 and the first electrode 3.
  • a gas barrier layer 9 and an underlayer 10 may be provided in this order between the transparent flexible base material 2 and the first electrode 3.
  • a particle-containing layer may be provided on the surface of the transparent flexible substrate 2 opposite to the first electrode 3. The particle-containing layer is preferably disposed in the outermost layer.
  • the fine metal wires used in the present invention are formed with a metal content ratio that is mainly composed of metal and that can provide conductivity.
  • the ratio of the metal in the fine metal wire is preferably 50% by mass or more.
  • the fine metal wire contains a metal material and is formed in a pattern so as to have an opening.
  • An opening is a part which does not have a metal fine wire, and is a translucent part of a 1st electrode.
  • the pattern shape of the fine metal wires There are no particular restrictions on the pattern shape of the fine metal wires.
  • Examples of the pattern shape of the fine metal wire include a stripe shape (parallel line shape), a lattice shape, a honeycomb shape, and a random network shape. From the viewpoint of transparency, a stripe shape is particularly preferable.
  • the ratio occupied by the openings is preferably 80% or more from the viewpoint of transparency.
  • the line width of the fine metal wire is preferably in the range of 5 to 100 ⁇ m. Desired conductivity can be obtained when the line width of the fine metal wire is 5 ⁇ m or more, and the light emission efficiency of the organic EL element can be further improved by setting it to 100 ⁇ m or less.
  • the distance between the fine metal wires is preferably within a range of 0.01 to 1 mm.
  • the height (thickness) of the fine metal wire is preferably in the range of 0.05 to 3.0 ⁇ m, and more preferably in the range of 0.1 to 0.6 ⁇ m.
  • the desired conductivity is obtained when the height of the fine metal wire is 0.05 ⁇ m or more, and the thickness of the fine metal wire is the layer thickness distribution of the functional layer when used for an organic EL element when the height is 3.0 ⁇ m or less. Can be reduced.
  • the arithmetic average roughness Ra of the fine metal wire is preferably 1 to 20 nm.
  • the arithmetic average roughness Ra is based on JIS B 0601: 2001.
  • the arithmetic average roughness is 1 nm or more due to the influence of the material and forming method of the thin metal wire.
  • the arithmetic average roughness Ra of the fine metal wire is more preferably 10 nm or less from the viewpoint of generation of dark spots and rectification characteristics.
  • the arithmetic average roughness Ra can be measured using, for example, an atomic force microscope (manufactured by Digital Instruments), and is a value obtained by measuring a central portion of a metal thin wire 5 ⁇ m square.
  • the center part of a metal fine wire is the site
  • the center of the metal thin wire 5 ⁇ m square is a rectangular portion of 5 ⁇ m in length ⁇ 5 ⁇ m in width with the intersecting point as the center.
  • the arithmetic average roughness Ra can be controlled by appropriately selecting the forming material, forming conditions, and forming method of the fine metal wires.
  • Metal nanoparticle-containing composition As will be described later, after preparing and applying a metal nanoparticle-containing composition in which a metal or a metal-forming material is blended, a thin metal wire is subjected to a drying treatment or a firing treatment. Processes are performed as appropriate.
  • a metal used for a metal nanoparticle metals, such as gold
  • the metal nanoparticle-containing composition is preferably a metal colloid or metal nanoparticle dispersion liquid in which the surface of metal nanoparticles is coated with a surface protective agent and stably dispersed in a solvent.
  • the average particle diameter of the metal nanoparticles in the metal nanoparticle-containing composition is preferably 1000 nm or less from the atomic scale.
  • the metal nanoparticles preferably have an average particle size in the range of 3 to 300 nm, and more preferably in the range of 5 to 100 nm.
  • silver nanoparticles having an average particle diameter of 5 to 100 nm are preferable.
  • the average particle diameter of the metal nanoparticles and the metal colloid can be determined by measuring the particle diameter of the metal nanoparticles in the dispersion using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • the average particle diameter can be calculated by measuring the particle diameters of 300 independent metal nanoparticles that are not overlapped among the particles observed in the TEM image.
  • an organic ⁇ -junction ligand is preferable as a protective agent for coating the surface of the metal nanoparticles.
  • Conductivity is imparted to the metal colloid by ⁇ -junction of the organic ⁇ -conjugated ligand to the metal nanoparticles.
  • the organic (pi) junction ligand the 1 type, or 2 or more types of compound chosen from the group which consists of a phthalocyanine derivative, a naphthalocyanine derivative, and a porphyrin derivative is preferable.
  • the organic ⁇ -junction ligand in order to improve coordination to metal nanoparticles and dispersibility in a dispersion medium, an amino group, an alkylamino group, a mercapto group, a hydroxyl group, At least one selected from a carboxyl group, a phosphine group, a phosphonic acid group, a sulfonic acid group, a halogen group, a selenol group, a sulfide group, a selenoether group, an amide group, an imide group, a cyano group, a nitro group, and salts thereof It is preferable to have a substituent.
  • organic ⁇ -conjugated ligand described in International Publication No. 2011/114713 can be used as the organic ⁇ -junction ligand.
  • OTAN 2,3,11,12,20,21,29,30-octakis [(2-N, N-dimethylaminoethyl) thio] naphthalocyanine
  • OCAN 2,3,11,12,20,21,29,30-naphthalocyanine octacarboxylic acid
  • a liquid phase reduction method may be mentioned.
  • the production of the organic ⁇ -junction ligand of this embodiment and the preparation of the metal nanoparticle dispersion containing the organic ⁇ -junction ligand are performed according to the method described in Paragraphs 0039 to 0060 of International Publication No. 2011/114713. It can be done according to this.
  • the average particle diameter of the metal colloid is usually in the range of 3 to 500 nm, preferably in the range of 5 to 50 nm. When the average particle diameter of the metal colloid is within the above range, fusion between particles is likely to occur, and the conductivity of the obtained metal fine wire can be improved.
  • the protective agent for coating the surface of the metal nanoparticles it is preferable to use a protective agent that removes the ligand at a low temperature of 200 ° C. or lower. As a result, the protective agent is detached due to low temperature or low energy, the metal nanoparticles are fused, and conductivity can be imparted.
  • a protective agent that removes the ligand at a low temperature of 200 ° C. or lower.
  • the protective agent is detached due to low temperature or low energy, the metal nanoparticles are fused, and conductivity can be imparted.
  • Specific examples include metal nanoparticle dispersions described in JP2013-142173A, JP2012-162767A, JP2014-139343A, Patent No. 5606439, and the like.
  • the metal forming material examples include metal salts, metal complexes, organometallic compounds (compounds having a metal-carbon bond), and the like.
  • the metal salt and metal complex may be either a metal compound having an organic group or a metal compound having no organic group.
  • an organic silver complex produced by reacting a silver compound represented by “Ag n X” with an ammonium carbamate compound is preferably used.
  • n is an integer of 1 to 4
  • X is oxygen, sulfur, halogen, cyano, cyanate, carbonate, nitrate, nitrate, sulfate, phosphate, thiocyanate, chlorate, perchlorate, tetrafluoroborate, A substituent selected from the group consisting of acetylacetonate and carboxylate.
  • the silver compound examples include silver oxide, thiocyanate silver, silver cyanide, silver cyanate, silver carbonate, silver nitrate, silver nitrite, silver sulfate, silver phosphate, silver perchlorate, silver tetrafluoroborate, acetylacetate. Examples thereof include silver nitrate, silver acetate, silver lactate, and silver oxalate. As the silver compound, use of silver oxide or silver carbonate is preferable in terms of reactivity and post-treatment.
  • ammonium carbamate compounds include ammonium carbamate, ethyl ammonium ethyl carbamate, isopropyl ammonium isopropyl carbamate, n-butyl ammonium n-butyl carbamate, isobutyl ammonium isobutyl carbamate, t-butyl ammonium t-butyl carbamate, 2-ethylhexyl ammonium 2 -Ethylhexyl carbamate, octadecyl ammonium octadecyl carbamate, 2-methoxyethyl ammonium 2-methoxyethyl carbamate, 2-cyanoethyl ammonium 2-cyanoethyl carbamate, dibutyl ammonium dibutyl carbamate, dioctadecyl ammonium dioctadecyl carbamate, methyl decyl ammonium methyl dec
  • the organic silver complex can be produced by the method described in JP-A-2011-148795. For example, it can be synthesized by directly reacting one or more of the above silver compounds and one or more of the above ammonium carbamate compounds at normal pressure or under pressure in a nitrogen atmosphere without using a solvent.
  • alcohols such as methanol, ethanol, isopropanol and butanol
  • glycols such as ethylene glycol and glycerin
  • acetates such as ethyl acetate, butyl acetate and carbitol acetate
  • ethers such as diethyl ether, tetrahydrofuran and dioxane
  • Ketones such as methyl ethyl ketone and acetone
  • hydrocarbons such as hexane and heptane
  • aromatics such as benzene and toluene
  • halogen substituted solvents such as chloroform, methylene chloride and carbon tetrachloride Can be reacted.
  • the structure of the organic silver complex can be represented by “Ag [A] m ”.
  • A is the ammonium carbamate compound, and m is 0.7 to 2.5.
  • organic silver complex is well soluble in various solvents including solvents for producing organic silver complexes, such as alcohols such as methanol, esters such as ethyl acetate, and ethers such as tetrahydrofuran. For this reason, the organic silver complex can be easily applied to a coating or printing process as a metal nanoparticle-containing composition.
  • solvents for producing organic silver complexes such as alcohols such as methanol, esters such as ethyl acetate, and ethers such as tetrahydrofuran.
  • examples of the metal silver forming material include silver carboxylate having a group represented by the formula “—COOAg”.
  • the silver carboxylate is not particularly limited as long as it has a group represented by the formula “—COOAg”.
  • the number of groups represented by the formula “—COOAg” may be one, or two or more.
  • the position of the group represented by the formula “—COOAg” in the silver carboxylate is not particularly limited.
  • the silver carboxylate is preferably at least one selected from the group consisting of silver ⁇ -ketocarboxylate and silver carboxylate (4) described in JP-A-2015-66695.
  • As the metal silver forming material not only silver ⁇ -ketocarboxylate and silver carboxylate (4), but also silver carboxylate having a group represented by the formula “—COOAg”, which includes them, is used. it can.
  • the metal nanoparticle-containing composition contains the above-mentioned silver carboxylate as a metal forming material, an amine compound and quaternary ammonium salt having 25 or less carbon atoms, ammonia, and an amine compound or ammonia together with silver carboxylate are acid. It is preferable that at least one nitrogen-containing compound selected from the group consisting of ammonium salts formed by reaction with is blended.
  • the amine compound has 1 to 25 carbon atoms, and may be any of primary amine, secondary amine, and tertiary amine.
  • the quaternary ammonium salt has 4 to 25 carbon atoms.
  • the amine compound and the quaternary ammonium salt may be either chain or cyclic. Further, the number of nitrogen atoms constituting the amine moiety or ammonium salt moiety (for example, the nitrogen atom constituting the amino group “—NH 2 ” of the primary amine) may be one, or may be two or more.
  • the metal fine line pattern is formed using a metal nanoparticle-containing composition.
  • a conventionally well-known method can be utilized.
  • a method using a photolithography method, a coating method, a printing method, or the like can be used.
  • the metal nanoparticle-containing composition contains the metal nanoparticles described above and a solvent, and may contain additives such as a dispersant, a viscosity modifier, and a binder.
  • additives such as a dispersant, a viscosity modifier, and a binder.
  • Solvents used in the metal nanoparticle-containing composition include water, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tetradecanol, hexadecanol, hexanediol, Heptanediol, octanediol, nonanediol, decanediol, farnesol, dedecadienol, linalool, geraniol, nerol, heptadienol, tetradecenol, hexadecenol, phytol, oleyl alcohol, dedecenol, decenol, undecylenyl alcohol, nonenol, citronellol , Octenol, hep
  • a method generally used for electrode pattern formation is applicable.
  • the gravure printing method include those described in JP 2009-295980 A, JP 2009-259826 A, JP 2009-96189 A, JP 2009-90662 A, and the like.
  • the printing method methods described in JP-A-2004-268319, JP-A-2003-168560, etc., and for screen printing methods, JP-A 2010-34161, JP-A 2010-10245, JP-A-2009.
  • JP-A-302345 and the like is disclosed in JP 2011-180562 A, JP 2000-127410 A, JP 8-238774 A and the like in the inkjet printing method, and in the 2014 2014 in the super inkjet printing method.
  • the method described in JP-A-146665 It is.
  • a film of the metal nanoparticle-containing composition is formed on the entire surface of the transparent flexible substrate by printing or coating. After performing a drying process and a baking process, which will be described later, the film is processed into a desired pattern by etching using a known photolithography method.
  • the drying process can be performed using a known drying method. Drying methods include, for example, air cooling drying, convection heat transfer drying using hot air, radiant heat drying using infrared rays, conductive heat transfer drying using a hot plate, vacuum drying, internal using microwaves Exothermic drying, IPA vapor drying, Marangoni drying, Rotagoni drying, freeze drying, and the like can be used.
  • the drying by heating is preferably performed in a temperature range of 50 to 200 ° C. at a temperature at which the transparent flexible base material is not deformed. It is more preferable to heat the transparent flexible substrate under the condition that the surface temperature is 50 to 150 ° C. When a PET substrate is used as the transparent flexible base material, it is particularly preferable to heat in a temperature range of 100 ° C. or lower.
  • the firing time depends on the temperature and the size of the metal nanoparticles used, but is preferably in the range of 10 seconds to 30 minutes, and in the range of 10 seconds to 15 minutes from the viewpoint of productivity. More preferably, it is in the range of 10 seconds to 5 minutes.
  • the drying process it is preferable to perform a drying process by infrared irradiation.
  • a specific wavelength region By selectively using a specific wavelength region, it is possible to selectively irradiate a specific wavelength effective for cutting the absorption region of the transparent flexible substrate or the solvent of the metal nanoparticle-containing composition.
  • an infrared heater in which the filament temperature of the light source is in the range of 1600 to 3000 ° C.
  • the pattern of the dried metal nanoparticle-containing composition is baked.
  • the type of metal composition contained in the metal nanoparticle-containing composition for example, silver colloid having the above-mentioned organic ⁇ -junction ligand
  • the conductivity may be sufficiently exhibited by the drying treatment. It does not have to be done.
  • the patterning of the metal nanoparticle-containing composition is preferably performed by light irradiation (flash baking) using a flash lamp in order to improve the conductivity of the first electrode.
  • flash baking a discharge tube of a flash lamp used in flash firing
  • a discharge tube of xenon, helium, neon, argon or the like can be used, but a xenon lamp is preferably used.
  • the preferable spectral band of the flash lamp is preferably in the range of 240 to 2000 nm. Within this range, there is little damage such as thermal deformation of the transparent flexible substrate due to flash firing.
  • the light irradiation conditions of the flash lamp are arbitrary, but the total light irradiation energy is preferably in the range of 0.1 to 50 J / cm 2 , and preferably in the range of 0.5 to 10 J / cm 2. More preferred.
  • the light irradiation time is preferably in the range of 10 ⁇ sec to 100 msec, and more preferably in the range of 100 ⁇ sec to 10 msec. Further, the number of times of light irradiation may be one time or a plurality of times, and it is preferably performed within the range of 1 to 50 times.
  • the flash lamp irradiation on the transparent flexible substrate is preferably performed from the side where the pattern of the metal nanoparticle-containing composition of the transparent flexible substrate is formed.
  • a transparent flexible base material is transparent, you may irradiate from the transparent flexible base material side, and may irradiate from both surfaces of a transparent flexible base material.
  • the surface temperature of the transparent flexible substrate during flash firing is the heat resistance temperature of the transparent flexible substrate, the boiling point (vapor pressure) of the dispersion medium of the solvent contained in the metal nanoparticle-containing composition, the type of atmospheric gas,
  • the pressure may be determined in consideration of the thermal behavior such as dispersibility and oxidizability of the metal nanoparticle-containing composition, and it is preferably performed at room temperature (25 ° C.) or higher and 200 ° C. or lower.
  • the flash lamp light irradiation device only needs to satisfy the above irradiation energy and irradiation time.
  • flash baking may be performed in air
  • the fine metal wires may be formed by using a known vacuum film formation in the same manner as in the case of forming a conventional metal layer.
  • a conventional method for forming a metal layer it can be formed by various deposition methods, sputtering methods, ion plating methods, and the like.
  • a method for forming a metal fine line pattern a known pattern may be processed by etching using a known photolithography method, or a mask pattern may be used during film formation.
  • the first electrode used in the present invention includes at least a fine metal wire and a transparent conductive layer. It is preferable that the transparent conductive layer is provided on the fine metal wire so as to cover the entire surface of the fine metal wire.
  • a metal oxide layer or an organic conductive layer is preferably used as the transparent conductive layer.
  • the transparent conductive layer is preferably a metal oxide (metal oxide layer) from the viewpoint of further improving luminous efficiency. Note that “being a metal oxide” includes, for example, a case where a metal oxide is contained as a main component and other impurities are contained.
  • the film thickness of the transparent conductive layer is preferably 50 to 300 nm. Even if the thickness of a transparent conductive layer is in the said range, the 1st electrode used for this invention can fully exhibit electroconductivity. Moreover, if the film thickness of a transparent conductive layer is 50 nm or more, a rectification characteristic will become more favorable. Moreover, when the film thickness of the transparent conductive layer is 300 nm or less, the generation of dark spots is further suppressed and the rectification characteristics are improved.
  • the metal oxide layer and the organic conductive layer are preferably formed using a highly conductive metal oxide having a volume resistivity in the range of 1 ⁇ 10 ⁇ 5 to 1 ⁇ 10 ⁇ 2 ⁇ ⁇ cm.
  • the volume resistivity can be obtained by measuring the sheet resistance and the film thickness measured in accordance with the resistivity test method of the conductive plastic of JIS K 7194-1994 by the four-probe method.
  • the film thickness can be measured using a contact-type surface shape measuring device (for example, DECTAK) or an optical interference surface shape measuring device (for example, WYKO).
  • the metal oxide layer and the organic conductive layer have a sheet resistance of 10,000 ⁇ / sq. From the viewpoint of ensuring the conductivity. Or less, preferably 2000 ⁇ / sq. The following is more preferable.
  • Metal oxide layer The metal oxide that can be used for the metal oxide layer is not particularly limited as long as the material is excellent in transparency and conductivity.
  • Examples of the metal oxide that can be used for the metal oxide layer include ITO (tin doped indium oxide), IZO (indium oxide / zinc oxide), IGO (gallium doped indium oxide), IWZO (indium oxide / tin oxide), ZnO ( Zinc oxide), GZO (gallium-doped zinc oxide), IGZO (indium gallium zinc oxide) and the like.
  • IZO, IGO, and IWZO are preferable as the metal oxide that can be used for the metal oxide layer.
  • the transparent conductive layer is particularly preferably an amorphous metal oxide. That is, the transparent conductive layer is preferably an amorphous metal oxide layer.
  • the transparent conductive layer is preferably an amorphous metal oxide layer.
  • the amorphous metal oxide include amorphous IZO, amorphous ITO, and amorphous IGZO.
  • a plurality of metal oxide layers may be provided.
  • the metal oxide layer can be formed by various sputtering methods, ion plating methods, and the like in the same manner as in the case of forming a conventional metal oxide layer. it can.
  • Examples of the sputtering method include DC sputtering, RF sputtering, DC magnetron sputtering, RF magnetron sputtering, ECR plasma sputtering, and ion beam sputtering. Further, in the sputtering method, by examining various conditions as described below, even if the composition is the same as in IZO, it is possible to adjust conductivity and gas barrier properties.
  • the metal oxide layer is formed by a direct current magnetron sputtering method with a distance between target substrates in the range of 50 to 100 mm during sputtering and a sputtering gas pressure in the range of 0.5 to 1.5 Pa. Can do.
  • the distance between the target substrates when the distance between the target substrates is shorter than 50 mm, the kinetic energy of the sputtered particles to be deposited increases, so that the damage received by the transparent flexible base material increases. In addition, the film thickness becomes non-uniform and the film thickness distribution becomes worse. When the distance between the target substrates is longer than 100 mm, the film thickness distribution is improved, but the kinetic energy of the sputtered particles deposited becomes too low, densification due to diffusion hardly occurs, and the density of the metal oxide layer is not preferable.
  • the sputtering gas pressure if the sputtering gas pressure is lower than 0.5 Pa, the kinetic energy of the sputtered particles to be deposited increases, so that the damage received by the transparent flexible substrate increases.
  • the sputtering gas pressure is higher than 1.5 Pa, not only the film formation rate is slowed, but also the kinetic energy of the sputtered particles deposited becomes too low, densification due to diffusion does not occur, and the density of the metal oxide layer is low. Therefore, it is not preferable.
  • the organic conductive layer is mainly composed of a conductive polymer and a binder.
  • a conductive polymer and the binder compounds described in Japanese Patent No. 5750908 and Japanese Patent No. 5882855 can be used.
  • the preparation (method) of the organic conductive composition for forming the organic conductive layer, the formation (method) of the organic conductive layer, and the like should be performed in accordance with the methods described in Japanese Patent No. 5750908 and Japanese Patent No. 5882855. Can do.
  • the transparent flexible base material used in the present invention is not particularly limited as long as it has high light transmittance, and it is a transparent resin base material from the viewpoint of productivity, performance such as lightness and flexibility. preferable.
  • resin which can be used as a transparent resin base material For example, polyethylene-terephthalate (PET), polyethylene naphthalate (PEN), polyester-type resins, such as a modified polyester, polyethylene (PE) resin, polypropylene (PP) resin, polystyrene Resins, polyolefin resins such as cyclic olefin resins, vinyl resins such as polyvinyl chloride and polyvinylidene chloride, polyether ether ketone (PEEK) resins, polysulfone (PSF) resins, polyether sulfone (PES) resins, polycarbonate (PC) resin, polyamide resin, polyimide resin, acrylic resin, triacetyl cellulose (TAC) resin, etc. are mentioned. These resins may be used alone or in combination. Further, the transparent resin substrate may be an unstretched film or a stretched film.
  • PET polyethylene-terephthalate
  • PEN polyethylene naphthalate
  • polyester-type resins
  • the transparent flexible substrate has a total light transmittance in a visible light wavelength region of 50% or more measured by a method in accordance with JIS K 7361-1: 1997 (Plastic—Test method for total light transmittance of transparent material). Is more preferable and 80% or more is more preferable.
  • the transparent flexible substrate may be subjected to a surface activation treatment in order to improve adhesion with an underlayer or a gas barrier layer described later.
  • a clear hard coat layer may be provided.
  • the surface activation treatment include corona discharge treatment, flame treatment, ultraviolet treatment, high frequency treatment, glow discharge treatment, active plasma treatment, and laser treatment.
  • the material for the clear hard coat layer include polyester, polyamide, polyurethane, vinyl copolymer, butadiene copolymer, acrylic copolymer, vinylidene copolymer, epoxy copolymer, and the like.
  • An ultraviolet curable resin can be preferably used.
  • the organic functional layer used in the present invention is a layer located between the anode and the cathode, and is composed of an organic layer, a metal layer, or the like, but is not limited thereto.
  • the organic functional layer includes at least a light emitting layer, and may have various organic layers such as a hole injection layer, a hole transport layer, an electron transport layer, and an electron injection layer.
  • the hole injection layer and the hole transport layer may be provided as a hole transport injection layer.
  • the electron transport layer and the electron injection layer may be provided as an electron transport injection layer.
  • the electron injection layer may be made of an inorganic material.
  • the organic functional layer may have a hole blocking layer, an electron blocking layer, or the like as necessary.
  • the configuration of (vii) is preferable but not particularly limited.
  • the thickness of the organic functional layer is preferably in the range of 100 to 500 nm. If the thickness of the organic functional layer is 500 nm or less, an increase in driving voltage can be suppressed, and if it is 100 nm or more, rectification characteristics can be maintained.
  • the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer, and the electron injection layer are not particularly limited.
  • JP-A-2014-120334 The compounds described in JP2013-89608A can be used.
  • the organic EL device has an organic functional layer sandwiched between a pair of electrodes including a first electrode as a transparent electrode and a second electrode as a counter electrode.
  • One of the first electrode and the second electrode serves as the anode of the organic EL element, and the other serves as the cathode.
  • the transparent conductive layer 3b of the first electrode 3 is made of a transparent conductive material
  • the second electrode 5 is made of a highly reflective material.
  • the 2nd electrode 5 is also comprised with a transparent conductive material.
  • the second electrode when the second electrode is used as an anode, a material having a work function (4 eV or more) of a metal, an alloy, an electrically conductive compound and a mixture thereof is preferably used.
  • the electrode substance that can constitute the anode include metals such as Au and Ag, and conductive transparent materials such as CuI, ITO, SnO 2 , and ZnO.
  • an amorphous material such as IDIXO (In 2 O 3 —ZnO) capable of forming a transparent conductive film may be used.
  • the second electrode when the second electrode is used as a cathode, a metal having a small work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof are used as electrode materials.
  • an electron injecting metal used as the cathode is an electrode film that functions as a cathode (cathode) that supplies electrons to the light emitting layer.
  • the cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering.
  • the electrode material include aluminum, 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.
  • 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, A magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al 2 O 3 ) mixture, a lithium / aluminum mixture, aluminum, or the like is preferable.
  • the sheet resistance as a cathode is several hundred ⁇ / sq.
  • the following are preferable, and the thickness is usually selected within the range of 10 nm to 5 ⁇ m, preferably within the range of 50 to 200 nm.
  • a transparent or semi-transparent cathode can be produced by producing a conductive transparent material on the metal after the metal is produced with a thickness of 1 to 20 nm as a cathode.
  • An element in which both the anode and the cathode are transmissive can be manufactured.
  • the extraction electrode is for electrically connecting the conductive layer of the transparent electrode and the external power source, and the material is not particularly limited, and a known material can be suitably used.
  • a three-layer structure A metal film such as a MAM electrode (Mo / Al ⁇ Nd alloy / Mo) made of can be used.
  • the inorganic protective layer used in the present invention is provided on the upper surface of the second electrode.
  • the inorganic protective layer may be provided on a part of the second electrode, but is preferably provided on the entire surface.
  • the material that can be used for the inorganic protective layer is not particularly limited, and examples thereof include silicon compounds such as silicon oxide, silicon nitride, silicon oxynitride, silicon carbide, and silicon nitride carbide.
  • the inorganic protective layer is preferably composed mainly of silicon nitride from the viewpoint of barrier properties, and specifically, is preferably silicon nitride. That is, the inorganic protective layer is preferably a silicon nitride layer.
  • silicon nitride includes, for example, the case of containing silicon nitride as a main component and other impurities.
  • the inorganic protective layer may be formed as a composite film or a laminated film in which films containing silicon compounds having the same composition or different compositions as main components are combined. Thus, when forming an inorganic protective layer as a composite film or a laminated film, the function as an inorganic protective layer should just be expressed as a whole.
  • the inorganic protective layer preferably has a water vapor permeability (25 ⁇ 0.5 ° C., relative humidity 90 ⁇ 2% RH) of less than 0.1 g / (m 2 ⁇ 24 h), and 0.01 g / (m 2 ⁇ 24h) or less, more preferably 0.001 g / (m 2 ⁇ 24h) or less.
  • the water vapor permeability of the inorganic protective layer is a value measured by a method based on JIS K 7129-1992.
  • the film thickness of the inorganic protective layer is preferably 500 to 1500 nm. If the thickness of the inorganic protective layer is 500 nm or more, generation of dark spots due to the thickness of the inorganic protective layer is further suppressed. Moreover, if the film thickness of an inorganic protective layer is 1500 nm or less, generation
  • the film thickness of an inorganic protective layer can be measured using a contact-type surface shape measuring device (for example, DECTAK).
  • the film density of the inorganic protective layer is preferably 4.0 to 10.0 ⁇ 10 22 atoms / cm 3 .
  • the inorganic protective layer is preferably formed from two or more layers having different film densities.
  • the inorganic protective layer 6 is preferably formed of three layers having different film densities.
  • the inorganic protective layer 6 includes a first inorganic protective layer 6a on the second electrode 5 side, a second inorganic protective layer 6b that is an intermediate layer, and a third inorganic protective layer 6c on the adhesive layer 7 side. It is configured.
  • the three layers having different film densities mean that at least one layer may have a film density different from that of the other two layers, and the other two layers may have the same film density. Each of the three layers may have a different film density. Since the inorganic protective layer is formed of three layers having different film densities, the generation of dark spots is further suppressed.
  • the film densities of the first inorganic protective layer, the second inorganic protective layer, and the third inorganic protective layer are preferably 4.0 to 10.0 ⁇ 10 22 atoms / cm 3 , respectively.
  • middle layer is the lowest among the inorganic protective layers which consist of said 3 layers. According to such a configuration, the rectification characteristic becomes better.
  • an inorganic protective layer is three or more layers, it is preferable that an intermediate
  • the difference in film density between the second inorganic protective layer and the first inorganic protective layer and the difference in film density between the second inorganic protective layer and the third inorganic protective layer Is preferably 0.3 to 3.0 ⁇ 10 22 atoms / cm 3 .
  • the film density can be measured by measuring the formed single film using Rutherford backscattering analysis method and measuring the film thickness by TEM of the formed cross section.
  • the film density can be controlled by the film formation conditions during film formation.
  • the inorganic protective layer has a thickness of the second inorganic protective layer as the intermediate layer that is 20 to 20 times the total thickness of the inorganic protective layer when the second inorganic protective layer as the intermediate layer has the lowest film density. It is preferable that it is 50%. If the thickness of the second inorganic protective layer is 20 to 50% of the total thickness of the inorganic protective layer, the influence of diffusion of moisture and the like due to the adhesive is suppressed, and the generation of dark spots is further suppressed. At the same time, the rectification characteristics become better. In the case of four or more layers, it is preferable that the intermediate layer having the lowest film density (other than the lowermost layer and the uppermost layer) is 20 to 50% of the total thickness of the inorganic protective layer.
  • the inorganic protective layer can be formed by a dry process.
  • the dry process include film deposition methods such as vacuum deposition (resistance heating, EB method, etc.), magnetron sputtering, ion plating, and CVD.
  • film deposition methods such as vacuum deposition (resistance heating, EB method, etc.), magnetron sputtering, ion plating, and CVD.
  • it can carry out by the method similar to the process of forming this inorganic protective layer.
  • a plasma CVD method using an organic silicon compound will be described.
  • a silicon compound is formed by a reaction product of an organic silicon compound.
  • the organic silicon compound used in the plasma CVD method include hexamethyldisiloxane, 1,1,3,3-tetramethyldisiloxane, vinyltrimethylsilane, methyltrimethylsilane, hexamethyldisilane, methylsilane, dimethylsilane, and trimethylsilane.
  • the source gas is a mole of oxygen as a reaction gas with respect to the molar amount (flow rate) of hexamethyldisiloxane.
  • the amount (flow rate) is preferably 12 times or less (more preferably 10 times or less) which is the stoichiometric ratio.
  • the lower limit of the molar amount of oxygen in the film forming gas is preferably 0.1 times or more, more preferably 0.5 times or more of the molar amount of hexamethyldisiloxane.
  • Si 3 N 4 is the stoichiometric representative value, but there is a certain ratio of width in an actual film, and these are included and handled as SiN.
  • the above-mentioned atomic ratio can be determined by a conventionally known method, and can be measured by, for example, an analyzer using X-ray photoelectron spectroscopy (XPS).
  • the film density of the inorganic protective layer can be controlled by the film forming conditions when the film is formed by the CVD method. That is, the film formation by the CVD method proceeds by a surface reaction on the film formation surface and a gas phase reaction in the film formation atmosphere. At this time, for example, by increasing the flow rate of the source gas to increase the gas phase reaction, the film formation speed increases and the film density decreases. On the other hand, by reducing the flow rate of the source gas to increase the surface reaction, the film formation rate is lowered and the film density is increased.
  • the silicon nitride film as the inorganic protective layer is configured as a film in which the film density is controlled by adjusting the total flow rate of ammonia gas and silane gas.
  • the high-density inorganic protective layer is a film formed by the CVD method with a relatively low film formation speed mainly for surface reaction.
  • the low-density inorganic protective layer is a film formed by a CVD method in which the film formation rate mainly for the gas phase reaction is higher than that of the high-density inorganic protective layer.
  • the gas phase reaction and surface reaction in the CVD film formation are controlled by, for example, the base material temperature and the gas pressure in the film formation atmosphere in addition to the above-described flow rate of the source gas. At this time, for example, by lowering the substrate temperature or increasing the gas pressure in the film formation atmosphere, the gas phase reaction increases, the film formation speed increases, and the film density decreases.
  • the film densities of the first inorganic protective layer, the second inorganic protective layer, and the third inorganic protective layer may be controlled by the method described above.
  • the film density may be controlled by the method described above.
  • the adhesive layer used in the present invention is provided on the upper surface of the inorganic protective layer.
  • the adhesive layer may be provided on a part of the inorganic protective layer, but is preferably provided on the entire surface.
  • the adhesive layer is used as an agent for closely attaching the sealing member to the organic EL element.
  • the adhesive layer has a role of fixing the sealing member to the substrate side.
  • Specific examples of the adhesive layer include photo-curing and thermosetting adhesives having reactive vinyl groups of acrylic acid oligomers and methacrylic acid oligomers, and moisture-curing adhesives such as 2-cyanoacrylates. An agent can be mentioned.
  • examples of the adhesive layer include an epoxy-based heat and chemical curing type (two-component mixing).
  • hot-melt type polyamide, polyester, and polyolefin can be mentioned.
  • a cationic curing type ultraviolet curing epoxy resin adhesive can be mentioned.
  • the organic EL element is sealed with a sealing member for the purpose of preventing deterioration of an organic functional layer formed using an organic material or the like.
  • the sealing member is a plate-like (film-like) member that covers the upper surface of the organic EL element, and is fixed to the base material side by an adhesive layer.
  • the sealing member may be a sealing film.
  • Such a sealing member is provided in a state in which the electrode terminal portion of the organic EL element is exposed and at least the organic functional layer is covered.
  • the structure which provides an electrode in a sealing member and makes the electrode terminal part of an organic EL element and the electrode of a sealing member electrically connect may be sufficient.
  • the plate-like (film-like) sealing member examples include a glass substrate, a polymer substrate, a metal substrate, and the like, and these substrates may be used in the form of a thinner film.
  • the glass substrate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz.
  • the polymer substrate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
  • the metal substrate examples include those made of one or more metals or alloys selected from the group consisting of stainless steel, iron, copper, aluminum, magnesium, nickel, zinc, chromium, titanium, molybdenum, silicon, germanium, and tantalum.
  • the element since the element can be thinned, it is preferable to use a polymer substrate or a metal substrate as a thin film as the sealing member.
  • the substrate material may be processed into a concave plate shape and used as a sealing member. In this case, the substrate member described above is subjected to processing such as sandblasting and chemical etching to form a concave shape.
  • the polymer substrate in the form of a film has an oxygen permeability measured by a method according to JIS K 7126-1987 of 1 ⁇ 10 ⁇ 3 mL / (m 2 ⁇ 24 h ⁇ atm) or less, and conforms to JIS K 7129-1992.
  • the water vapor permeability (25 ⁇ 0.5 ° C., (90 ⁇ 2)% RH) measured by a compliant method is preferably 1 ⁇ 10 ⁇ 3 g / (m 2 ⁇ 24 h) or less.
  • the adhesive layer may be applied using a commercially available dispenser or printing such as screen printing.
  • the organic material which comprises an organic EL element may deteriorate with heat processing.
  • the adhesive layer is preferably one that can be adhesively cured from room temperature (25 ° C.) to 80 ° C. Further, a desiccant may be dispersed in the adhesive layer.
  • the foundation layer used in the present invention is a layer that serves as a foundation for forming a fine metal wire pattern or a transparent conductive layer, and improves the adhesion between the substrate and the first electrode.
  • the underlayer contains at least one selected from a compound having a thiol group, a poly (meth) acrylate having an aminoethyl group, and a poly (meth) acrylamide having an aminoethyl group. The above may be used in combination.
  • the base layer may contain inorganic particles in addition to the above compound, and is preferably formed to contain oxide particles.
  • the underlayer contains oxide particles, adhesion with the metal fine line pattern and the metal oxide layer is improved.
  • the base layer can be provided with a function other than improving the adhesion with the metal fine line pattern or the metal oxide layer.
  • a function other than adhesion it is preferable to have a light extraction function.
  • the underlayer may contain fluorine in order to make the fine metal wires thinner.
  • the thickness of the underlayer is preferably in the range of 10 to 1000 nm, more preferably in the range of 10 to 100 nm.
  • the thickness of the underlayer is 10 nm or more, the underlayer itself becomes a continuous film, the surface becomes smooth, and the influence on the organic EL element is small.
  • the thickness of the underlayer is 1000 nm or less, the transparency of the transparent electrode caused by the underlayer and the adsorbed gas derived from the underlayer can be reduced, and the deterioration of the resistance of the metal fine wire pattern can be suppressed. Can do.
  • the thickness of the underlayer is 1000 nm or less, damage to the underlayer when the transparent electrode is bent can be suppressed.
  • the film thickness of a base layer can be measured using a contact-type surface shape measuring device (for example, DECTAK).
  • the transparency of the underlayer can be arbitrarily selected depending on the application, but the higher the transparency, the better the application to the transparent electrode, which is preferable from the viewpoint of expanding the application.
  • the total light transmittance of the underlayer is at least 40% or more, preferably 50% or more.
  • the total light transmittance can be measured according to a known method using a spectrophotometer or the like.
  • the compound having a thiol group (also referred to as a mercapto group) (hereinafter also referred to as a thiol group-containing compound) is not particularly limited as long as the effects of the present invention are not impaired.
  • the thiol group-containing compound used in the present invention is preferably a polyfunctional thiol group-containing compound having two or more thiol groups. Thereby, the adhesiveness with the metal fine wire containing a metal material more can be aimed at.
  • the thiol group-containing compound is preferably a condensate of a compound having a structure represented by the following general formula (I) with a monovalent or polyvalent alcohol or amine.
  • R 1 and R 2 each independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, at least one of which is an alkyl group having 1 to 10 carbon atoms.
  • m is an integer of 0 to 2
  • n is 0 or 1.
  • the alkyl group having 1 to 10 carbon atoms in R 1 and R 2 may be linear or branched, and specifically includes a methyl group, an ethyl group, an n-propyl group, an iso- Examples thereof include a propyl group, an n-butyl group, an iso-butyl group, a tert-butyl group, an n-hexyl group, and an n-octyl group, and a methyl group or an ethyl group is preferable.
  • R 1 and R 2 may have a known substituent as long as the effects of the present invention are not impaired.
  • n is an integer of 0 to 2, preferably 0 or 1.
  • n is 0 or 1, but preferably 0.
  • Examples of the compound having the structure represented by the general formula (I) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 2-mercaptoisobutyric acid, and 3-mercaptoisobutyric acid.
  • Monohydric alcohols include methanol, ethanol, 1-propanol, isopropyl alcohol, 1-butanol, 2-butanol, t-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl- 1-butanol, 3-methyl-1-butanol, 3-methyl-2-butanol, 1-hexanol, 2-hexanol, 3-hexanol, 2-methyl-1-pentanol, 2-methyl-2-pentanol, 2-methyl-3-pentanol, 3-methyl-1-pentanol, 3-methyl-2-pentanol, 3-methyl-3-pentanol, 4-methyl-1-pentanol, 4-methyl-2 -Pentanol, 1-heptanol, 2-heptanol, 2-methyl-2-heptanol, 2-methyl-3-hept Nord, and the like.
  • polyhydric alcohol examples include glycols (wherein the alkylene group preferably has 2 to 10 carbon atoms, and the carbon chain thereof may be branched), such as ethylene glycol, diethylene glycol, 1,2-propylene. Glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, glycerin, trimethylolethane, trimethylolpropane, trimethylolbutane And dipentaerythritol.
  • glycols wherein the alkylene group preferably has 2 to 10 carbon atoms, and the carbon chain thereof may be branched
  • ethylene glycol diethylene glycol
  • 1,2-propylene examples include 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanedio
  • ethylene glycol 1,2-propylene glycol, 1,2-butanediol, 1,4-butanediol, trimethylolethane, trimethylolpropane, and dipentaerythritol are preferable.
  • the amine is not particularly limited and may be any of primary to tertiary amines.
  • silsesquioxane derivative having a thiol group (hereinafter also simply referred to as a silsesquioxane derivative) can be used.
  • a silsesquioxane derivative is a compound which has a cage type siloxane structure represented with the following general formula (A).
  • X A is representative of the following X 1 or X 2, at least one of X A is X 2.
  • R 1 to R 5 each independently represents an alkyl group having 1 to 8 carbon atoms or an aromatic hydrocarbon ring group.
  • A represents a divalent hydrocarbon group having 1 to 8 carbon atoms.
  • the alkyl group having 1 to 8 carbon atoms of R 1 to R 5 in X 1 and X 2 may be linear or branched, and specifically includes a methyl group, an ethyl group, Examples thereof include an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert-butyl group, and an n-pentyl group.
  • Examples of the aromatic hydrocarbon ring group of R 1 to R 5 in X 1 and X 2 include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.
  • X 1 and X 2 may have a known substituent as long as the effects of the present invention are not impaired.
  • Examples of the divalent hydrocarbon group having 1 to 8 carbon atoms of A in X 2 include linear or branched alkylene groups having 1 to 8 carbon atoms. Among these, a straight-chain alkylene group having 2 or 3 carbon atoms such as —CH 2 CH 2 — and —CH 2 CH 2 CH 2 — is preferable from the viewpoint of easy synthesis of the silsesquioxane derivative.
  • A may have a known substituent as long as the effects of the present invention are not impaired.
  • Composelan (registered trademark) SQ100 series manufactured by Arakawa Chemical Co., Ltd. can be used.
  • JP-A-2015-59108, JP-A-2012-180464 and the like can be referred to.
  • poly (meth) acrylate having aminoethyl group and poly (meth) acrylamide having aminoethyl group are not particularly limited as long as the effects of the present invention are not inhibited, but the partial structure represented by the following general formula (II) It is preferable to have.
  • R 3 represents a hydrogen atom or a methyl group.
  • Q represents —C ( ⁇ O) O— or —C ( ⁇ O) NRa—.
  • Ra represents a hydrogen atom or an alkyl group.
  • A represents a substituted or unsubstituted alkylene group, or — (CH 2 CHRbNH) x —CH 2 CHRb—, Rb represents a hydrogen atom or an alkyl group, x represents the average number of repeating units, and is a positive integer It is.
  • alkyl group in Ra for example, a linear or branched alkyl group having 1 to 5 carbon atoms is preferable, and a methyl group is more preferable.
  • alkyl groups may be substituted with a substituent.
  • substituents include alkyl groups, cycloalkyl groups, aryl groups, heterocycloalkyl groups, heteroaryl groups, hydroxy groups, halogen atoms, alkoxy groups, alkylthio groups, arylthio groups, cycloalkoxy groups, aryloxy groups, Acyl group, alkylcarbonamide group, arylcarbonamide group, alkylsulfonamide group, arylsulfonamide group, ureido group, aralkyl group, nitro group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, alkylcarbamoyl group, Arylcarbamoyl group, alkylsulfamoyl group, arylsulfamoyl group, acyloxy group, alkenyl group, alkynyl group, alkylsulf
  • the alkyl group as the substituent may be branched and preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 8 carbon atoms.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a hexyl group, and an octyl group.
  • the cycloalkyl group preferably has 3 to 20 carbon atoms, more preferably 3 to 12 carbon atoms, and still more preferably 3 to 8 carbon atoms.
  • Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.
  • the aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. Examples of the aryl group include a phenyl group and a naphthyl group.
  • the heterocycloalkyl group preferably has 2 to 10 carbon atoms, and more preferably 3 to 5 carbon atoms. Examples of the heterocycloalkyl group include a piperidino group, a dioxanyl group, and a 2-morpholinyl group.
  • the heteroaryl group preferably has 3 to 20 carbon atoms, more preferably 3 to 10 carbon atoms.
  • the heteroaryl group include a thienyl group and a pyridyl group.
  • halogen atom a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned.
  • the alkoxy group may be branched and preferably has 1 to 20 carbon atoms, more preferably 1 to 12, more preferably 1 to 6, and more preferably 1 to 4. Is most preferred.
  • alkoxy group examples include a methoxy group, an ethoxy group, a 2-methoxyethoxy group, a 2-methoxy-2-ethoxyethoxy group, a butyloxy group, a hexyloxy group, and an octyloxy group, and an ethoxy group is preferable.
  • the alkylthio group may be branched and preferably has 1 to 20 carbon atoms, more preferably 1 to 12, more preferably 1 to 6, and more preferably 1 to 4. Is most preferred.
  • Examples of the alkylthio group include a methylthio group and an ethylthio group.
  • the arylthio group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the arylthio group include a phenylthio group and a naphthylthio group.
  • the cycloalkoxy group preferably has 3 to 12 carbon atoms, more preferably 3 to 8 carbon atoms.
  • Examples of the cycloalkoxy group include a cyclopropoxy group, a cyclobutoxy group, a cyclopentyloxy group, a cyclohexyloxy group, and the like.
  • the aryloxy group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms.
  • Examples of the aryloxy group include a phenoxy group and a naphthoxy group.
  • the acyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. Examples of the acyl group include a formyl group, an acetyl group, and a benzoyl group.
  • the alkylcarbonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the alkylcarbonamide group include an acetamide group.
  • the aryl carbonamido group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms. Examples of the arylcarbonamide group include a benzamide group.
  • the alkylsulfonamide group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • Examples of the sulfonamide group include a methanesulfonamide group.
  • the arylsulfonamide group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms.
  • Examples of the arylsulfonamido group include a benzenesulfonamido group and a p-toluenesulfonamido group.
  • the aralkyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms.
  • Examples of the aralkyl group include a benzyl group, a phenethyl group, and a naphthylmethyl group.
  • the alkoxycarbonyl group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. Examples of the alkoxycarbonyl group include a methoxycarbonyl group.
  • the aryloxycarbonyl group preferably has 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms. Examples of the aryloxycarbonyl group include a phenoxycarbonyl group.
  • the aralkyloxycarbonyl group preferably has 8 to 20 carbon atoms, and more preferably 8 to 12 carbon atoms.
  • Examples of the aralkyloxycarbonyl group include a benzyloxycarbonyl group.
  • the acyloxy group preferably has 1 to 20 carbon atoms, more preferably 2 to 12 carbon atoms.
  • Examples of the acyloxy group include an acetoxy group and a benzoyloxy group.
  • the alkenyl group has preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms.
  • Examples of the alkenyl group include a vinyl group, an allyl group, and an isopropenyl group.
  • the alkynyl group preferably has 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms. An ethynyl group etc. are mentioned as an alkynyl group.
  • the alkylsulfonyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms.
  • Examples of the alkylsulfonyl group include a methylsulfonyl group and an ethylsulfonyl group.
  • the arylsulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the arylsulfonyl group include a phenylsulfonyl group and a naphthylsulfonyl group.
  • the alkyloxysulfonyl group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • alkyloxysulfonyl group examples include a methoxysulfonyl group and an ethoxysulfonyl group.
  • the aryloxysulfonyl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the aryloxysulfonyl group include a phenoxysulfonyl group and a naphthoxysulfonyl group.
  • the alkylsulfonyloxy group preferably has 1 to 20 carbon atoms, and more preferably 1 to 12 carbon atoms.
  • alkylsulfonyloxy group examples include a methylsulfonyloxy group and an ethylsulfonyloxy group.
  • the arylsulfonyloxy group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms.
  • Examples of the arylsulfonyloxy group include a phenylsulfonyloxy group and a naphthylsulfonyloxy group.
  • the substituents may be the same or different, and these substituents may be further substituted.
  • the alkylene group in A preferably has 1 to 5 carbon atoms, more preferably an ethylene group or a propylene group. These alkylene groups may be substituted with the substituent mentioned above.
  • the alkyl group in Rb is preferably a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a methyl group. These alkyl groups may be substituted with the aforementioned substituents.
  • the average number of repeating units x is not particularly limited as long as it is a positive integer, but it is preferably in the range of 1 to 20.
  • the weight average molecular weight (Mw) of poly (meth) acrylate and poly (meth) acrylamide is preferably in the range of 10,000 to 500,000, more preferably in the range of 30,000 to 200,000. If the weight average molecular weight (Mw) is 10,000 or more, the underlying layer containing poly (meth) acrylate and poly (meth) acrylamide is hard, so the film thickness changes with time and forced deterioration conditions, and interface deterioration with other layers. Without causing any electrical or optical problems.
  • the solubility in the coating solution for forming the underlayer and the compatibility with other compounds are good, and further, there is a problem of peeling from other layers having different hardness in a low temperature or high temperature environment. It does not occur.
  • poly (meth) acrylate having aminoethyl group examples include a polymer or copolymer of (meth) acrylate having an aminoethyl group.
  • examples of (meth) acrylates include monofunctional or bifunctional (meth) acrylates having one or two (meth) acryloyl groups, and polyfunctional (meth) acrylates having three or more (meth) acryloyl groups. .
  • Examples of monofunctional (meth) acrylates include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and sec-butyl.
  • bifunctional (meth) acrylate examples include allyl (meth) acrylate, ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-propanediol di (meth) acrylate, and 1,4-butane.
  • Alkanediol di (meth) acrylates such as diol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, and alkane polyol di (meta) such as glycerin di (meth) acrylate ) Acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polypropylene glycol Polyalkylene glycol di (meth) acrylate such as urdi (meth) acrylate, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxydiethoxyphenyl) ) Di (meth) acrylates and fatty acids of C 2-4 alkylene oxide adduct
  • bifunctional (meth) acrylate for example, epoxy di (meth) acrylate (bisphenol A type epoxy di (meth) acrylate, novolac type epoxy di (meth) acrylate, etc.), polyester di (meth) acrylate (for example, aliphatic polyester) Type di (meth) acrylate, aromatic polyester type di (meth) acrylate, etc.), (poly) urethane di (meth) acrylate (polyester type urethane di (meth) acrylate, polyether type urethane di (meth) acrylate etc.), silicon (meta ) Oligomers such as acrylates or resins are also included.
  • epoxy di (meth) acrylate bisphenol A type epoxy di (meth) acrylate, novolac type epoxy di (meth) acrylate, etc.
  • polyester di (meth) acrylate for example, aliphatic polyester) Type di (meth) acrylate, aromatic polyester type di (meth) acrylate, etc
  • polyfunctional (meth) acrylate esterified product of polyhydric alcohol and (meth) acrylic acid
  • polyhydric alcohol for example, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate
  • examples include pentaerythritol tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate.
  • the polyhydric alcohol may be an adduct of alkylene oxide (for example, C2-4 alkylene oxide such as ethylene oxide or propylene oxide).
  • polyfunctional (meth) acrylates tri- to 6-functional (meth) acrylates such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate are preferable.
  • Pentaerythritol Tri- to tetra-functional (meth) acrylates such as tri (meth) acrylate are more preferable.
  • the polyfunctional (meth) acrylate is preferably a polyfunctional (meth) acrylate that is not modified with an amine (an unmodified polyfunctional (meth) acrylate that is not added with amines by Michael addition or the like).
  • Examples Compounds PE-1 to PE-9 are shown below as specific examples of poly (meth) acrylates having aminoethyl groups applicable to the underlayer according to the present invention.
  • x and y in the following exemplary compounds represent the polymerization ratio of the copolymer.
  • the exemplified compounds PE-1 to PE-9 can be synthesized by a known method. More specifically, (i) a method in which (meth) acrylate is aminoethylated and then polymerized or copolymerized, and (ii) a method in which (meth) acrylate is polymerized and then aminoethylated. As an example, a method for synthesizing Exemplified Compound PE-7 is shown below.
  • poly (meth) acrylamide having an aminoethyl group examples include a polymer or copolymer of (meth) acrylamide having an aminoethyl group.
  • (meth) acrylamide examples include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-butyl (meth) acrylamide, and N-benzyl (meth).
  • Acrylamide N-hydroxyethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-tolyl (meth) acrylamide, N- (hydroxyphenyl) (meth) acrylamide, N- (sulfamoylphenyl) (meth) acrylamide N- (phenylsulfonyl) (meth) acrylamide, N- (tolylsulfonyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N-methyl-N-phenyl (meth) acrylamide, N-hydroxyethyl- N-methyl (Meth) acrylamide.
  • Examples Compounds PA-1 to PA-12 are shown below as specific examples of poly (meth) acrylamide having an aminoethyl group applicable to the underlayer used in the present invention.
  • x and y in the following exemplary compounds represent the polymerization ratio of the copolymer.
  • the exemplified compounds PA-1 to PA-12 can be synthesized by known methods.
  • the aminoethylation of (meth) acrylamide or the aminoethylation of poly (meth) acrylamide (homopolymer) can be performed in the same manner as the aminoethylation of (meth) acrylate or poly (meth) acrylate described above.
  • the resin constituting the base layer is not particularly limited as long as the base layer can be formed.
  • a known natural polymer material having a monomer repeating structure or a synthetic polymer material can be used.
  • organic polymer materials, inorganic polymer materials, organic-inorganic hybrid polymer materials, and mixtures thereof can be used. These resins can be used in combination of two or more.
  • the above resin can be synthesized by a known method.
  • Natural polymer materials can be synthesized from microorganisms such as extracted from natural raw materials or cellulose.
  • the synthetic polymer can be obtained by radical polymerization, cationic polymerization, anionic polymerization, coordination polymerization, ring-opening polymerization, polycondensation, addition polymerization, addition condensation, and living polymerization thereof.
  • These resins may be either homopolymers or copolymers, and can have any regularity of random, syndiotactic and isotactic when a monomer having an asymmetric carbon is used. Moreover, in the case of a copolymer, forms, such as random copolymerization, alternating copolymerization, block copolymerization, and graft copolymerization, can be taken.
  • the form of the resin may be liquid or solid.
  • the resin is preferably dissolved in the solvent or uniformly dispersed in the solvent.
  • the resin may be a water-soluble resin or a water-dispersible resin.
  • the resin may be an ionizing radiation curable resin that is cured by ultraviolet rays or an electron beam, a thermosetting resin that is cured by heat, or may be a resin prepared by a sol-gel method. Furthermore, the resin may be crosslinked.
  • the natural polymer material is preferably a natural organic polymer material, and examples thereof include natural fibers such as cotton, hemp, cellulose, silk, and wool, proteins such as gelatin, and natural rubber.
  • Synthetic polymer materials include polyolefin resin, polyacrylic resin, polyvinyl resin, polyether resin, polyester resin, polyamide resin, polyurethane resin, polyphenylene resin, polyimide resin, polyacetal resin, polysulfone resin, fluororesin, epoxy resin, silicone resin Phenol resin, melamine resin, polyurethane resin, polyurea resin, polycarbonate resin, polyketone resin and the like.
  • polystyrene resin examples include polyethylene, polypropylene, polyisobutylene, poly (1-butene), poly-4-methylpentene, polyvinylcyclohexane, polystyrene, poly (p-methylstyrene), poly ( ⁇ -methylstyrene), polyisoprene. , Polybutadiene, polycyclopentene, polynorbornene and the like.
  • polyacrylic resin include polymethacrylate, polyacrylate, polyacrylamide, polymethacrylamide, polyacrylonitrile and the like.
  • polyvinyl resin examples include polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, polymethyl vinyl ether, polyethyl vinyl ether, polyisobutyl vinyl ether, and the like.
  • polyether resin examples include polyalkylene glycols such as polyethylene oxide and polypropylene oxide.
  • polyester resin examples include polyalkylene phthalates such as polyethylene terephthalate and polybutylene terephthalate, and polyalkylene naphthalates such as polyethylene naphthalate.
  • polyamide resin examples include polyamide 6, polyamide 6,6, polyamide 12, and polyamide 11.
  • fluororesin examples include polyvinylidene fluoride, polyvinyl fluoride, polytetrafluoroethylene, ethylene tetrafluoroethylene copolymer, polychlorotrifluoroethylene, and the like.
  • the above-mentioned water-soluble resin means a resin that dissolves 0.001 g or more in 100 g of water at 25 ° C.
  • the degree of dissolution can be measured with a haze meter, a turbidimeter, or the like.
  • the color of the water-soluble resin is not particularly limited, but is preferably transparent.
  • the number average molecular weight of the water-soluble resin is preferably in the range of 3000 to 2000000, more preferably in the range of 4000 to 500000, and still more preferably in the range of 5000 to 100,000.
  • the number average molecular weight and molecular weight distribution of the water-soluble resin can be measured by generally known gel permeation chromatography (GPC).
  • the solvent to be used is not particularly limited as long as the binder dissolves, but tetrahydrofuran (THF), dimethylformamide (DMF), and dichloromethane (CH 2 Cl 2 ) are preferable, more preferably THF and DMF, and still more preferably DMF. It is.
  • the measurement temperature is not particularly limited, but is preferably 40 ° C.
  • water-soluble resins include natural polymer materials and synthetic polymer materials such as acrylic resins, polyester resins, polyamide resins, polyurethane resins, and fluorine resins.
  • casein starch, agar , Carrageenan, sesulose, hydroxyethylcellulose, carboxymethylcellulose, hydroxyethylcellulose, dextran, dextrin, pullulan, polyvinyl alcohol, gelatin, polyethylene oxide, polyvinylpyrrolidone, polyacrylic acid, polymethacrylic acid, poly (2-hydroxyethyl acrylate), poly ( 2-hydroxyethyl methacrylate), polyacrylamide, polymethacrylamide, polystyrene sulfonic acid, water-soluble polyvinyl butyral, and the like.
  • the above-mentioned water-dispersible resin means a resin that can be uniformly dispersed in an aqueous solvent and in which colloidal particles made of resin are dispersed without being aggregated in the aqueous solvent.
  • the size (average particle diameter) of colloidal particles is generally in the range of 1 to 1000 nm. The average particle diameter of the colloidal particles can be measured with a light scattering photometer.
  • the aqueous solvent is not only pure water such as distilled water and deionized water, but also an aqueous solution containing an acid, alkali, salt, etc., a water-containing organic solvent, and a hydrophilic organic solvent. And alcohol-based solvents such as methanol and ethanol, mixed solvents of water and alcohol, and the like.
  • the water dispersible resin is preferably transparent.
  • the water-dispersible resin is not particularly limited as long as it is a medium for forming a film. Examples of the water-dispersible resin include an aqueous acrylic resin, an aqueous urethane resin, an aqueous polyester resin, an aqueous polyamide resin, and an aqueous polyolefin resin.
  • aqueous acrylic resin examples include vinyl acetate, acrylic acid, a polymer of acrylic acid-styrene, or a copolymer with other monomers.
  • the acid moiety responsible for the function of imparting dispersibility to an aqueous solvent is a copolymer of an anionic, nitrogen atom-containing monomer that forms a counter salt with ions such as lithium, sodium, potassium, and ammonium, and nitrogen.
  • ions such as lithium, sodium, potassium, and ammonium, and nitrogen.
  • nonionic systems in which a site such as a hydroxyl group or ethylene oxide is introduced, in which an atom forms a hydrochloride or the like, it is preferably anionic.
  • water-based urethane resin examples include water-dispersed urethane resin and ionomer-type water-based urethane resin (anionic).
  • water-dispersed urethane resins include polyether-based urethane resins and polyester-based urethane resins, and polyester-based urethane resins are preferred.
  • non-yellowing isocyanate having no aromatic ring.
  • Examples of the ionomer-type water-based urethane resin include polyester-based urethane resins, polyether-based urethane resins, and polycarbonate-based urethane resins, and polyester-based urethane resins and polyether-based urethane resins are preferable.
  • the aqueous polyester resin is synthesized from a polybasic acid component and a polyol component.
  • the polybasic acid component include terephthalic acid, isophthalic acid, phthalic acid, naphthalene dicarboxylic acid, adipic acid, succinic acid, sebacic acid, dodecanedioic acid and the like, and these may be used alone. Two or more kinds may be used in combination, and the polybasic acid component that can be particularly preferably used is industrially produced in large quantities and is inexpensive, so terephthalic acid and isophthalic acid Is particularly preferred.
  • polyol component examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, diethylene glycol, dipropylene glycol, cyclohexane dimethanol, bisphenol, and the like. May be used in combination, or two or more may be used in combination.
  • ethylene is mass-produced industrially, is inexpensive, and is balanced in various performances such as improvement in solvent resistance and weather resistance of the resin film.
  • Glycol, propylene glycol or neopentyl glycol is particularly preferred.
  • examples of the inorganic polymer material include polysiloxane, polyphosphazene, polysilane, polygermane, polystannane, borazine polymer, polymetalloxane, polysilazane, titanium oligomer, and silane coupling agent.
  • Specific examples of the polysiloxane include silicone, silsesquioxane, and silicone resin.
  • organic / inorganic hybrid polymer materials polycarbosilane, polysilylene arylene, polysilole, polyphosphine, polyphosphine oxide, poly (ferrocenylsilane), silsesquioxane derivatives based on silsesquioxane Examples thereof include a resin in which silica is combined with a resin.
  • silsesquioxane derivatives having silsesquioxane as a basic skeleton include photo-curing type SQ series (Toagosei Co., Ltd.), Composelan SQ (Arakawa Chemical Co., Ltd.), Sila-DEC (Chisso Corporation). Etc.
  • Specific examples of the resin in which silica is combined with the resin include the Composelan series (Arakawa Chemical Co., Ltd.).
  • a curable resin such as an ionizing radiation curable resin or a thermosetting resin
  • the ionizing radiation curable resin is a resin that can be cured by an ordinary curing method of an ionizing radiation curable resin composition, that is, by irradiation with an electron beam or ultraviolet rays.
  • keV emitted from various electron beam accelerators such as a Cockrowalton type, a bandegraph type, a resonant transformation type, an insulating core transformer type, a linear type, a dynamitron type, and a high frequency type.
  • An electron beam having an energy within a range of preferably 30 to 300 keV is used.
  • ultraviolet curing ultraviolet rays emitted from rays of ultra-high pressure mercury lamp, high pressure mercury lamp, low pressure mercury lamp, carbon arc, xenon arc, metal halide lamp, etc. can be used.
  • Specific examples of the ultraviolet irradiation device include a rare gas excimer lamp that emits vacuum ultraviolet rays within a range of 100 to 230 nm. Since the excimer lamp has high light generation efficiency, it can be lit with low power. In addition, since light having a long wavelength that causes a temperature rise is not emitted and energy is emitted at a single wavelength in the ultraviolet region, the temperature rise of the irradiation object due to the irradiation light itself is suppressed.
  • thermosetting resin is a resin that is cured by heating, and it is more preferable that a crosslinking agent is contained in the resin.
  • a heating method of the thermosetting resin a conventionally known heating method can be used, and heater heating, oven heating, infrared heating, laser heating, or the like can be used.
  • a surface energy adjusting agent may be added to the resin used for the underlayer. By adding the surface energy adjusting agent, the adhesion between the fine metal wire pattern and the underlayer, the line width of the fine metal wire pattern, and the like can be adjusted.
  • oxide particles The oxide particles that can be added to the underlayer are not particularly limited as long as they can be applied to a transparent electrode. By adding oxide particles to the resin, physical properties such as film strength, stretchability, and refractive index of the underlayer can be adjusted as appropriate, and the adhesion to the fine metal wire pattern is also improved.
  • the oxide particles include oxides of metals such as magnesium, aluminum, silicon, titanium, zinc, yttrium, zirconium, molybdenum, tin, barium, and tantalum.
  • the oxide particles are preferably titanium oxide, aluminum oxide, silicon oxide, or zirconium oxide.
  • the average particle diameter of the oxide particles is preferably in the range of 5 to 300 nm, and particularly preferably in the range of 5 to 100 nm because it can be suitably used for a transparent electrode.
  • oxide particles having an average particle diameter in the above range are used, sufficient irregularities can be formed on the surface of the underlayer, and the adhesion to the metal fine wire pattern is improved.
  • the average particle size is 100 nm or less, the surface becomes smooth and the influence on the organic EL element is small.
  • the average particle diameter of the oxide particles can be easily measured using a commercially available measuring apparatus using a light scattering method. Specifically, a value measured at 25 ° C. and 1 mL of a sample dilution amount by a laser Doppler method using a Zetasizer 1000 (manufactured by Malvern) can be used.
  • the oxide particles are preferably contained within the range of 10 to 70 vol%, more preferably within the range of 20 to 60 vol%, in the underlayer.
  • the underlayer is formed by preparing a dispersion for forming an underlayer by dispersing resin, oxide particles, a thiol group-containing compound, etc. in a solvent, and applying this underlayer-forming dispersion on a substrate. .
  • the dispersion solvent used for the dispersion liquid for base layer formation It is preferable to select the solvent in which precipitation of resin and aggregation of a thiol group containing compound etc. do not occur.
  • the underlayer contains oxide particles, from the viewpoint of dispersibility, a resin, a thiol group-containing compound, and the mixture of oxide particles are dispersed by a method such as ultrasonic treatment or bead mill treatment. Filtration with a filter or the like is preferable because it can prevent metal oxide aggregates from being generated on the substrate after coating and drying.
  • any appropriate method can be selected as a method for forming the underlayer.
  • a coating method in addition to various printing methods such as a gravure printing method, a flexographic printing method, an offset printing method, a screen printing method, and an ink jet printing method.
  • Various coating methods such as a roll coating method, a bar coating method, a dip coating method, a spin coating method, a casting method, a die coating method, a blade coating method, a curtain coating method, a spray coating method, and a doctor coating method can be used.
  • a gravure printing method, a flexographic printing method, an offset printing, a screen printing method, or an inkjet printing method it is preferable to use a gravure printing method, a flexographic printing method, an offset printing, a screen printing method, or an inkjet printing method.
  • the underlayer is formed by depositing the coating method on a substrate and then drying it by a known heat drying method such as warm air drying or infrared drying, or by natural drying.
  • the temperature for performing heat drying can be appropriately selected according to the substrate to be used, but it is preferably performed at a temperature of 200 ° C. or lower.
  • curing by light energy such as ultraviolet rays or excimer light or heat curing with little damage to the substrate may be performed, and in particular, curing by excimer light may be performed. This is a preferred embodiment.
  • the filament temperature of the light source is 1600 ⁇ It is preferable to use an infrared heater in the range of 3000 ° C. Since the hydroxy group has absorption at a specific wavelength emitted from the infrared heater, the solvent can be dried. On the other hand, since polyethylene terephthalate (PET) or polyethylene naphthalate (PEN) as a base material has little absorption of a specific wavelength emitted from an infrared heater, thermal damage to the base material is small.
  • PET polyethylene terephthalate
  • PEN polyethylene naphthalate
  • Examples of the polar solvent having a hydroxy group include water (pure water such as distilled water and deionized water is preferable), alcohol solvents such as methanol and ethanol, glycols, glycol ethers, and a mixed solvent of water and alcohol. Is mentioned.
  • Specific examples of the glycol ether organic solvent include ethyl carbitol, butyl carbitol and the like.
  • Specific examples of the alcohol-based organic solvent include 1-propanol, 2-propanol, n-butanol, 2-butanol, diacetone alcohol, butoxyethanol and the like in addition to the above-described methanol and ethanol.
  • the organic EL element of this invention it is preferable that it is the structure which provides a gas barrier layer on the transparent flexible base material used for this invention.
  • the transparent flexible base material on which the gas barrier layer is formed has a water vapor permeability of 1 ⁇ 10 ⁇ 3 at a temperature of 25 ⁇ 0.5 ° C. and a humidity of 90 ⁇ 2% RH measured by a method according to JIS K 7129-1992.
  • the oxygen permeability was measured by the method based on JIS K 7126-1987 is, 1 ⁇ 10 -3 ml / m 2 ⁇ 24h ⁇ atm (1atm is 1.01325 ⁇ 10 5 Pa.)
  • the water vapor permeability at a temperature of 25 ⁇ 0.5 ° C. and a humidity of 90 ⁇ 2% RH is 1 ⁇ 10 ⁇ 3 g / m 2 ⁇ 24 h or less. Preferably there is.
  • any material may be used as long as it has a function of suppressing intrusion of an element such as moisture or oxygen that causes deterioration of the element. .
  • the method for forming the gas barrier layer is not particularly limited.
  • a plasma CVD method, a laser CVD method, a thermal CVD method, a coating method, or the like can be used, but an atmospheric pressure plasma polymerization method as described in JP-A-2004-68143 is also preferable.
  • the polysilazane-containing liquid is applied and dried by a wet coating method, and the formed coating film is irradiated with vacuum ultraviolet light (VUV light) having a wavelength of 200 nm or less, and the formed coating film is subjected to a modification treatment, and gas A method of forming a barrier layer is also preferable.
  • VUV light vacuum ultraviolet light
  • the thickness of the gas barrier layer is preferably in the range of 1 to 500 nm, more preferably in the range of 10 to 300 nm. If the thickness of the gas barrier layer is 1 nm or more, the desired gas barrier performance can be exhibited, and if it is 500 nm or less, film quality deterioration such as generation of cracks in a dense silicon oxynitride film can be prevented. Can do.
  • the particle-containing layer is provided on the surface (back surface) opposite to the surface (front surface) on which the first electrode is formed in the transparent flexible base material.
  • the particle-containing layer is composed of particles and a binder resin.
  • the particle-containing layer preferably contains particles in the range of 1 to 900 parts by mass with respect to 100 parts by mass of the binder resin.
  • the particles constituting the particle-containing layer are preferably inorganic fine particles, inorganic oxide particles, conductive polymer particles, conductive carbon fine particles and the like.
  • oxide particles such as ZnO, TiO 2 , SnO 2 , Al 2 O 3 , In 2 O 3 , MgO, BaO, MoO 2 , V 2 O 5 , and inorganic oxide particles such as SiO 2 are preferable.
  • SnO 2 and SiO 2 are preferable.
  • Binder resin examples of the binder resin constituting the particle-containing layer include cellulose derivatives such as cellulose diacetate, cellulose triacetate, cellulose acetate butyrate, cellulose acetate phthalate, and cellulose nitrate, polyvinyl acetate, polystyrene, polycarbonate, polybutylene terephthalate, and copolybutylene.
  • Polyesters such as tele / isophthalate, polyvinyl alcohol, polyvinyl formal, polyvinyl acetal, polyvinyl butyral, polyvinyl alcohol derivatives such as polyvinyl benzal, norbornene-based polymers containing norbornene compounds, polymethyl methacrylate, polyethyl methacrylate, polypropylyl methacrylate , Polybutyl methacrylate, polymethyl acrylate, etc. It can be used a copolymer of acrylic resin or an acrylic resin and other resins, but it is not particularly limited to these exemplified a resin material. Among these, cellulose derivatives and acrylic resins are preferable, and acrylic resins are most preferably used.
  • the above thermoplastic resin having a weight average molecular weight (Mw) of 400,000 or more and a glass transition temperature in the range of 80 to 110 ° C. is preferable in terms of optical properties and the quality of the particle-containing layer to be formed. .
  • the glass transition temperature can be determined by the method described in JIS K 7121: 2012.
  • the binder resin used here is 60% by mass or more, more preferably 80% by mass or more of the total resin mass constituting the particle-containing layer, and an actinic radiation curable resin or a thermosetting resin is applied as necessary. You can also.
  • the formation of the particle-containing layer is preferably performed before the formation of the first electrode, the base layer, and the gas barrier layer.
  • the above-described particles and binder resin are dissolved in an appropriate organic solvent to prepare a coating solution for forming a particle-containing layer in a solution state. And coated and dried to form a particle-containing layer.
  • organic solvent used for the preparation of the particle-containing layer forming coating solution hydrocarbons, alcohols, ketones, esters, glycol ethers, and the like can be appropriately mixed and used. It is not limited to these.
  • Examples of the hydrocarbons include benzene, toluene, xylene, hexane, and cyclohexane.
  • Examples of the alcohols include methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butanol, 2-butanol, tert. -Butanol, pentanol, 2-methyl-2-butanol, cyclohexanol and the like.
  • Examples of the ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and the like.
  • Examples of the esters include formic acid.
  • glycol ethers (1 to 4 carbon atoms) include methyl cellosolve and ethyl cellosol.
  • Propylene glycol monomethyl ether (abbreviation: PGME), propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol monoisopropyl ether, propylene glycol monobutyl ether, propylene glycol mono (1 to 4 carbon atoms) alkyl ether ester
  • Examples of the propylene glycol mono (1 to 4 carbon atoms) alkyl ether esters include propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate.
  • other solvents include N-methyl. Examples include pyrrolidone and the like. Although not particularly limited to these, a solvent in which these are appropriately mixed is also preferably used.
  • a method of applying the particle-containing layer forming coating solution onto the transparent flexible substrate doctor coating, extrusion coating, slide coating, roll coating, gravure coating, wire bar coating, reverse coating, curtain coating, extrusion coating, or the United States Examples include an extrusion coating method using a hopper described in Japanese Patent No. 2681294.
  • a particle-containing layer having a dry film thickness in the range of 0.1 to 20 ⁇ m, preferably in the range of 0.2 to 5 ⁇ m can be formed on the transparent flexible substrate. .
  • a protective member such as a protective film or a protective plate may be provided to mechanically protect the organic EL element.
  • the protective member is disposed at a position where the organic EL element and the sealing member are sandwiched between the first electrode.
  • the sealing member is a sealing film, mechanical protection for the organic EL element is not sufficient, and thus it is preferable to provide such a protective member.
  • a glass plate, a polymer plate, a thinner polymer film, a metal plate, a thinner metal film, or a polymer material film or a metal material film is applied.
  • a polymer film because it is lightweight and thin.
  • a 1st electrode is produced with the above-mentioned manufacturing method.
  • a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer are formed in this order on the first electrode to form an organic functional layer.
  • a film forming method of each of these layers there are a spin coat method, a cast method, an ink jet method, a vapor deposition method, a printing method, etc., but from the point that a uniform film is easily obtained and pinholes are difficult to generate, etc. Vacuum deposition or spin coating is particularly preferred.
  • vapor deposition conditions vary depending on the type of compound used, but generally a boat heating temperature of 50 to 450 ° C. and a degree of vacuum of 1 ⁇ 10 ⁇ 6 to 1 ⁇ 10 ⁇ 2 Each condition is preferably selected as appropriate within the ranges of Pa, vapor deposition rate of 0.01 to 50 nm / second, substrate temperature of ⁇ 50 to 300 ° C., and layer thickness of 0.1 to 5 ⁇ m.
  • a second electrode is formed on the organic functional layer by an appropriate film forming method such as vapor deposition or sputtering. At this time, the second electrode is patterned in a shape in which a terminal portion is drawn from the upper side of the organic functional layer to the periphery of the substrate while maintaining an insulating state with respect to the first electrode by the organic functional layer.
  • an inorganic protective layer is formed by the manufacturing method described above. Thereafter, an adhesive layer and a sealing member are provided on at least the organic functional layer with the terminal portions of the extraction electrode and the second electrode exposed.
  • a desired organic EL element can be obtained.
  • the substrate is taken out from the vacuum atmosphere and subjected to different film forming methods. It doesn't matter. At that time, it is necessary to consider that the work is performed in a dry inert gas atmosphere.
  • Organic EL elements 101 to 136 were produced as follows.
  • the organic EL elements 101 to 105 are comparative examples, and the organic EL elements 106 to 136 are examples.
  • ⁇ Preparation of organic EL element 101> Preparation of base material As a transparent flexible base material, a polyethylene terephthalate (PET / CHC) film (G1SBF, thickness 125 ⁇ m, refractive index 1.59) with a clear hard coat layer manufactured by Kimoto Co., Ltd. was prepared.
  • PET / CHC polyethylene terephthalate
  • a transparent flexible base material was set in a discharge plasma chemical vapor deposition apparatus (Plasma CVD apparatus Precision 5000 manufactured by Applied Materials) and continuously conveyed by roll-to-roll.
  • a magnetic field was applied between the film forming rollers, and power was supplied to each film forming roller to generate plasma between the film forming rollers to form a discharge region.
  • a mixed gas of hexamethyldisiloxane (HMDSO), which is a raw material gas, and oxygen gas (which also functions as a discharge gas), which is a reactive gas is supplied as a film forming gas from the gas supply pipe to the formed discharge region.
  • a gas barrier layer having a thickness of 120 nm was formed under the following conditions.
  • Feed rate of source gas (hexamethyldisiloxane, HMDSO): 50 sccm (Standard Cubic Centimeter per Minute) Reaction gas (O 2 ) supply amount: 500 sccm Degree of vacuum in the vacuum chamber: 3Pa Applied power from the power source for plasma generation: 0.8 kW Frequency of power source for plasma generation: 70 kHz Film transport speed: 0.8 m / min
  • first electrode Formation of metal thin wire
  • a silver film having a thickness of 0.5 ⁇ m is formed on the gas barrier layer by vapor deposition.
  • a lattice pattern having a width of 50 ⁇ m and a pitch of 1 mm was formed by using a photolithography method.
  • a thin metal wire pattern having an arithmetic average roughness Ra of 1.3 nm was formed.
  • arithmetic mean roughness Ra is the value which measured the center part 5 micrometer square of the metal fine wire using the atomic force microscope (made by Digital Instruments).
  • amorphous IZO film an L-430S-FHS sputtering apparatus manufactured by Anelva was used, Ar: 20 sccm, O 2 : 3 sccm, sputtering pressure: 0.25 Pa, room temperature (25 ° C.), target side power: 1000 W, target-substrate It was produced by RF sputtering at a distance of 86 mm.
  • each of the crucibles for vapor deposition in the vacuum vapor deposition apparatus was filled with the following materials constituting each layer of the organic functional layer in an optimum amount for device fabrication.
  • a crucible made of a resistance heating material made of molybdenum or tungsten was used as the evaporation crucible.
  • the deposition crucible containing the following compound A-1 was energized and heated, and deposited on the first electrode (metal oxide layer side) at a deposition rate of 0.1 nm / second.
  • the hole injection layer having a thickness of 10 nm was formed.
  • the deposition crucible containing the following compound M-2 was energized and heated, and deposited on the hole injection layer at a deposition rate of 0.1 nm / second to form a 30 nm thick hole transport layer.
  • the following compound BD-1 and the following compound H-1 are co-deposited at a deposition rate of 0.1 nm / second so that the compound BD-1 has a concentration of 5 mass%, and emits blue light with a thickness of 15 nm.
  • a fluorescent light emitting layer was formed.
  • the following compound GD-1, the following compound RD-1, and the following compound H-2 were deposited at a deposition rate of 0.8% so that the concentration of the compound GD-1 was 17% by mass and the concentration of RD-1 was 0.8% by mass.
  • Co-evaporation was performed at 1 nm / second to form a phosphorescent light emitting layer having a thickness of 15 nm and exhibiting a yellow color.
  • the following compound E-1 was deposited at a deposition rate of 0.1 nm / second to form an electron transport layer having a thickness of 30 nm.
  • an organic functional layer was formed.
  • a polyethylene terephthalate film having a thickness of 50 ⁇ m in which an aluminum (Al) foil having a thickness of 100 ⁇ m was laminated was prepared as a sealing member.
  • the solution of the prepared adhesive composition was applied to the aluminum side (gas barrier layer side) of the sealing member so that the thickness of the adhesive layer formed after drying was 20 ⁇ m, and at 120 ° C. It was dried for 2 minutes to form an adhesive layer.
  • a release sheet a release treatment surface of a polyethylene terephthalate film having a thickness of 38 ⁇ m was attached to the formed adhesive layer surface to produce a sealing member.
  • the sealing member produced by the above method was left for 24 hours or more in a nitrogen atmosphere. After leaving, the release sheet was removed, and lamination was performed so as to cover the second electrode of the organic EL element 101 with a vacuum laminator heated to 80 ° C. Furthermore, it heated at 120 degreeC for 30 minutes, and sealed the organic EL element 101 with the sealing member.
  • a silver nanoparticle dispersion (FlowMetal SR6000, manufactured by Bando Chemical Co., Ltd.) as a metal nanoparticle-containing composition is 50 ⁇ m wide, 1 mm pitch, and the dried film thickness after firing is 0.00.
  • a pattern was formed by coating in a grid pattern at 5 ⁇ m.
  • an ink jet printing method an ink jet head having an ink droplet ejection amount of 4 pl was used, and a coating speed and an ejection frequency were adjusted to print a pattern.
  • a desktop robot Shotmaster-300 manufactured by Musashi Engineering
  • an ink jet head manufactured by Konica Minolta
  • an ink jet evaluation apparatus EB150 manufactured by Konica Minolta
  • quartz glass plates that absorb infrared rays having a wavelength of 3.5 ⁇ m or more are attached to an infrared irradiation device (ultimate heater / carbon, manufactured by Meidyo Kogyo Co., Ltd.), and wavelength control infrared rays in which cooling air flows between the glass plates.
  • an infrared irradiation device (ultimate heater / carbon, manufactured by Meidyo Kogyo Co., Ltd.), and wavelength control infrared rays in which cooling air flows between the glass plates.
  • the drying process of the pattern of the formed metal nanoparticle containing composition was performed using the heater.
  • metal thin line patterns having an arithmetic average roughness Ra of 13.5 nm, 19.5 nm, and 30.2 nm were formed (organic EL elements 103 to 105).
  • the organic EL element 106 was produced in the same manner as in the production of the organic EL element 101 except that an inorganic protective layer was formed on the second electrode as follows before sealing. did.
  • the organic EL elements 107 to 110 were formed in the same manner as in the production of the organic EL elements 102 to 105, except that an inorganic protective layer was formed on the second electrode as follows before sealing. EL elements 107 to 110 were produced.
  • inorganic protective layer A silicon nitride film was formed as an inorganic protective layer on the second electrode so as to have a thickness shown in Table 1.
  • the film thickness of an inorganic protective layer is the value measured with the contact-type surface shape measuring device (DECTAK).
  • the film density of the inorganic protective layer was 7.0 ⁇ 10 22 atoms / cm 3 , which is a high density.
  • the film density was measured by measuring the formed single film using Rutherford backscattering analysis method and measuring the film thickness by TEM of the formed cross section.
  • the substrate was set in a discharge plasma chemical vapor deposition apparatus (a plasma CVD apparatus Precision5000 manufactured by Applied Materials).
  • a mixed gas of hexamethyldisiloxane (HMDSO) as a raw material gas and oxygen gas (which also functions as a discharge gas) as a reaction gas is supplied at 50 sccm (Standard Cubic Centimeter per Minute) and 500 sccm, respectively.
  • the gas was supplied in an amount from a gas supply pipe, and was formed by plasma CVD under the conditions of a vacuum degree in the chamber of 3 Pa, an applied voltage of 0.8 kW, and a frequency of 70 kHz.
  • Organic EL elements 111 to 114 were manufactured in the same manner except that the thickness of the inorganic protective layer was changed to the value shown in Table 1 in the preparation of the organic EL element 107.
  • the organic EL element 115 the thickness of the inorganic protective layer is two, and the film density and the film thickness are the same as those shown in Table 1 for each of the organic EL elements 115 and 116. 116 was produced.
  • the film density of the inorganic protective layer is 5.1 ⁇ 10 22 atoms / cm 3 for the low density and 7.0 ⁇ 10 22 atoms / cm 3 for the high density, and the film density of the inorganic protective layer is the gas flow rate. And by adjusting the pressure during film formation. The same applies hereinafter.
  • organic EL elements 117 to 123 were produced in the same manner except that the inorganic protective layer was three layers and the film density and film thickness were the values shown in Table 1, respectively.
  • the inorganic protective layer is three layers, the second layer is an intermediate layer.
  • organic EL elements 124 and 125 were produced in the same manner except that the organic EL element 124 was changed to a silicon oxide film and the organic EL element 125 was changed to a silicon oxynitride film as the inorganic protective layer.
  • the silicon oxide film was formed by using tetrahydroxysilane and dinitrogen oxide as source gases.
  • the silicon oxynitride film was formed by using dichlorosilane and ammonia as source gases.
  • the organic EL element 126 is changed to amorphous ITO, and the organic EL element 127 is changed to PEDOT (poly (3,4-ethylenedioxythiophene)).
  • PEDOT poly (3,4-ethylenedioxythiophene
  • Amorphous ITO was formed on a thin metal wire so as to have a thickness shown in Table 1, using the method of International Publication No. 2012/090735.
  • PEDOT was formed by the following method.
  • PEDOT-PSS CLEVIOS PH510 solid content concentration 1.89%, manufactured by HC Starck
  • PEDOT-PSS CLEVIOS PH510 solid content concentration 1.89%, manufactured by HC Starck
  • HC Starck HC Starck
  • Organic EL elements 128 to 131 were manufactured in the same manner except that the thickness of the transparent conductive layer was changed to the values shown in Table 1 in the preparation of the organic EL element 121.
  • the organic EL element 121 was formed in the same manner except that the base layer (thiol-based) was formed on the transparent flexible base material (gas barrier layer) as follows. An EL element 132 was produced.
  • the film thickness of a base layer is the value measured with the contact-type surface shape measuring device (DECTAK).
  • the organic EL element 133 was an aminoethyl group acrylic base layer
  • the organic EL element 134 was an aminoethyl group methacrylic base layer.
  • the organic EL element 133 instead of the Karenz MTBD1 added to the underlayer, the organic EL element 133 uses Polyment NK-350, and the organic EL element 134 uses the exemplified compound PA-4 (weight average molecular weight (Mw) 56000). Except for the above, organic EL elements 133 and 134 were produced in the same manner.
  • the organic EL elements 135 and 136 were produced in the same manner except that the inorganic protective layer was four layers and the film density and film thickness were the values shown in Table 1, respectively.
  • the second and third layers are intermediate layers, but the intermediate layer “[film thickness of intermediate layer / total film thickness of inorganic protective layer] ⁇ 100” in Table 1
  • the film thickness is the film thickness of the intermediate layer (second layer) having the lowest film density.
  • ⁇ Dark spot before storage (DS)> Each manufactured organic EL element is lit under a constant current density condition of 2.5 mA / cm 2 , and the area of a point where no light is emitted (dark spot (DS)) in the region to emit light is measured. It was evaluated by. Of the following evaluations, 3 or more were considered acceptable.
  • DS area in a region to emit light is less than 0.5% 5: DS area in a region to emit light is 0.5% or more and less than 1% 4: DS area in a region to emit light is 1 % To less than 5% 3: DS area in the region to emit light is 5% to less than 10% 2: DS area in the region to emit light is 10% to less than 15% 1: DS in the region to emit light The area of 15% or more
  • ⁇ Dark spot after storage (DS)> Each produced organic EL element is put into a thermostat of 85 ° C. (dry), taken out after 500 hours, then lit under a constant current density condition of 2.5 mA / cm 2 , and does not emit light in the region to emit light
  • the area of (dark spot (DS)) was measured and evaluated according to the following criteria. Of the following evaluations, 3 or more were considered acceptable.
  • DS area in a region to emit light is less than 1% 5: DS area in a region to emit light is 1% or more and less than 2.5% 4: DS area in a region to emit light is 2.5 % To less than 5% 3: DS area in the region to emit light is 5% to less than 10% 2: DS area in the region to emit light is 10% to less than 30% 1: DS in the region to emit light The area of 30% or more
  • Rectification ratio Current value when + 4V is applied / Current value when ⁇ 4V is applied 6: Rectification ratio is 1.0 ⁇ 10 5 or more 5: Rectification ratio is 1.0 ⁇ 10 4 or more and less than 1.0 ⁇ 10 5 4: Rectification ratio is 1.0 ⁇ 10 3 or more and less than 1.0 ⁇ 10 4 3: Rectification ratio is 1.0 ⁇ 10 2 or more and less than 1.0 ⁇ 10 3 2: Rectification ratio is 1.0 ⁇ 10 or more and 1.0 Less than ⁇ 10 2 1: Rectification ratio is less than 1.0 ⁇ 10
  • the generation of dark spots is suppressed as compared with the organic EL elements 111 to 116.
  • the organic EL element 119 having the lowest film density in the intermediate layer was superior in rectification ratio as compared with the organic EL elements 117 and 118.
  • the organic EL elements 120 to 122 in which the film thickness of the intermediate layer is 20 to 50% with respect to the film thickness of the entire inorganic protective layer are superior in rectification ratio and darker than the organic EL elements 119 and 123. The generation of spots was suppressed.
  • the organic EL element 121 in which the inorganic protective layer is silicon nitride generation of dark spots was suppressed as compared with the organic EL elements 124 and 125.
  • the transparent conductive layer is an amorphous metal oxide
  • generation of dark spots is suppressed as compared with the organic EL element 127.
  • the organic EL elements 129 and 130 having a preferable thickness of the transparent conductive layer were excellent in rectification ratio and suppressed generation of dark spots as compared with the organic EL elements 128 and 131.
  • the organic EL elements 132 to 134 provided with the base layer were superior in adhesion between the base material and the fine metal wires compared to the organic EL element 121.

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  • Electroluminescent Light Sources (AREA)

Abstract

La présente invention aborde le problème de la fourniture d'un élément électroluminescent organique qui ne forme plus de point sombre, tout en présentant d'excellentes caractéristiques de redressement. Cet élément électroluminescent organique (1) est obtenu par stratification séquentielle, sur un substrat souple transparent (2), d'une première électrode (3) qui comprend au moins un fil mince métallique (3a) et une couche conductrice transparente (3b), une couche fonctionnelle organique (4), une seconde électrode (5), une couche de protection inorganique (6), une couche adhésive (7) et un élément d'étanchéité (8).
PCT/JP2018/007047 2017-04-11 2018-02-26 Élément électroluminescent organique WO2018190010A1 (fr)

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Cited By (4)

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JP2020119664A (ja) * 2019-01-21 2020-08-06 トヨタ自動車株式会社 塗工装置
JP2020198172A (ja) * 2019-05-31 2020-12-10 パイオニア株式会社 発光装置
WO2022255093A1 (fr) * 2021-05-31 2022-12-08 キヤノン株式会社 Dispositif électroluminescent et dispositif d'affichage, dispositif d'imagerie, appareil électronique, dispositif d'éclairage et corps mobile ayant un dispositif électroluminescent
WO2024150811A1 (fr) * 2023-01-13 2024-07-18 東洋紡株式会社 Dispositif et procédé de fabrication de dispositif

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JP2020198172A (ja) * 2019-05-31 2020-12-10 パイオニア株式会社 発光装置
WO2022255093A1 (fr) * 2021-05-31 2022-12-08 キヤノン株式会社 Dispositif électroluminescent et dispositif d'affichage, dispositif d'imagerie, appareil électronique, dispositif d'éclairage et corps mobile ayant un dispositif électroluminescent
WO2024150811A1 (fr) * 2023-01-13 2024-07-18 東洋紡株式会社 Dispositif et procédé de fabrication de dispositif

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