WO2013080799A1 - Pellicule et dispositif électroluminescent organique - Google Patents

Pellicule et dispositif électroluminescent organique Download PDF

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WO2013080799A1
WO2013080799A1 PCT/JP2012/079526 JP2012079526W WO2013080799A1 WO 2013080799 A1 WO2013080799 A1 WO 2013080799A1 JP 2012079526 W JP2012079526 W JP 2012079526W WO 2013080799 A1 WO2013080799 A1 WO 2013080799A1
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layer
light
refractive index
conductive
organic
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PCT/JP2012/079526
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English (en)
Japanese (ja)
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飛世　学
雄一郎 板井
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富士フイルム株式会社
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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
    • H05B33/12—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
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8051—Anodes
    • H10K59/80515—Anodes characterised by their shape
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/875—Arrangements for extracting light from the devices
    • H10K59/877—Arrangements for extracting light from the devices comprising scattering means
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/805—Electrodes
    • H10K59/8051—Anodes
    • H10K59/80516—Anodes combined with auxiliary electrodes, e.g. ITO layer combined with metal lines

Definitions

  • the present invention relates to a laminate having a light diffusion layer and a light-transmitting conductive layer in this order on a transparent substrate, and an organic electroluminescent device.
  • An organic electroluminescent device is a self-luminous light emitting device having a pair of electrodes consisting of an anode and a cathode on a substrate, and an organic layer including a light emitting layer between the pair of electrodes. Application to applications is expected. In order to take out the light generated in the light emitting layer, the organic electroluminescent device requires that at least one of the anode and the cathode is a light-transmitting electrode, and the light-transmitting electrode is indium tin oxide ( ITO) is commonly used. Furthermore, in order to improve light extraction efficiency, it is known to provide a light diffusion layer having a function of scattering light between a substrate and a light-transmitting electrode (see Patent Document 1).
  • the surface of the light diffusion layer formed on the substrate has an uneven shape. Since it is difficult to form ITO on the uneven surface by sputtering or the like, it is also difficult to form a flat surface suitable for forming an organic layer such as a light emitting layer on the ITO, It is necessary to form ITO after providing a planarizing layer on the light diffusion layer. In addition, since the flattening layer is also affected by the unevenness of the light diffusion layer, it is considered necessary to relax the unevenness by making it relatively thick. Thus, when ITO is used as the transparent electrode, there is a problem that the degree of freedom in element design is small. In addition, since the ITO film forming process is costly, a transparent electrode that replaces ITO is required.
  • Patent Documents 2 and 3 it is known to form a transparent electrode by a coating method using a conductive polymer.
  • flexibility is improved by using a conductive polymer, or conductive nanoparticles (conductive polymer) having a refractive index substantially equal to that of the conductive polymer in a matrix made of the conductive polymer.
  • the light transmittance is increased by adding a difference in refractive index of 0.01 or less).
  • Patent Document 3 in the light emitting device, the smoothness of the transparent electrode is improved by using a conductive polymer, and the light emitting layer to be laminated is thinned, or a conductive filler is contained in the conductive polymer layer. It is described that the hole injection property is improved by segregating the conductive filler downward.
  • Japanese Unexamined Patent Publication No. 2005-190931 Japanese Unexamined Patent Publication No. 2005-327910 Japanese Unexamined Patent Publication No. 2011-175974
  • the refractive index of the transparent electrode obtained by the technique of Patent Document 2 is lower than that of ITO.
  • an electrode on the light extraction side of an organic electroluminescent device has a refractive index that is the same as or higher than that of the organic layer in order to efficiently extract light generated in the organic layer (including the light emitting layer). Need to be. Therefore, when the transparent electrode obtained by Patent Document 2 is used as an electrode on the light extraction side of an organic electroluminescence device, when the refractive index of the transparent electrode is lower than the refractive index of the organic layer, the organic layer-transparent electrode There is a problem that total reflection occurs between them, and the light extraction efficiency decreases. Similarly, Patent Document 3 has a problem that the light extraction efficiency is lowered.
  • a transparent electrode that can be easily formed on an uneven surface such as a light diffusion layer, has a simple film formation process, and is advantageous in terms of cost, and a light diffusion layer and the transparent electrode on a transparent substrate.
  • laminates having:
  • organic electroluminescent device that has the laminate and is excellent in terms of light extraction efficiency.
  • An object of the present invention is to solve the above-described problems and achieve the following objects. That is, an object of the present invention is to provide a laminate having a transparent electrode that can be easily formed on an uneven surface, has a simple film forming process, and is advantageous in cost. It is another object of the present invention to provide an organic electroluminescent device that has the laminate and is excellent in terms of light extraction efficiency.
  • the present inventors have intensively studied to solve the above problems, and by using a conductive layer made of a conductive matrix as a transparent electrode, even if a planarizing layer is not provided on an uneven surface such as a light diffusion layer, Alternatively, a transparent electrode can be formed even if the flattening layer is thin, and a flat surface suitable for forming an organic layer such as a light emitting layer thereon can be obtained. Doping particles having a refractive index larger than that of the conductive matrix makes the refractive index of the conductive layer the same as that of an organic layer such as a light-emitting layer, and allows total reflection of light from the organic layer to the conductive layer. It was found that the light extraction efficiency can be improved. That is, the means for solving the above problems are as follows.
  • a laminate comprising: [2] The laminate according to [1] above, wherein a particle having a refractive index larger than that of the conductive matrix has a refractive index of 2.0 or more and 3.0 or less. [3] The laminate according to [1] or [2], wherein an average particle size of particles having a refractive index larger than that of the conductive matrix is 1 nm or more and 100 nm or less.
  • the laminated body which can be formed easily also on an uneven
  • the organic electroluminescent apparatus which has the said laminated body and is excellent in the viewpoint of light extraction efficiency can be provided.
  • a resistance lower than that of the conductive layer is provided between the light diffusion layer and the conductive layer, thereby reducing the resistance of the transparent electrode including the conductive layer and the wiring. Therefore, even if the light emitting surface of the organic electroluminescent device is enlarged, a voltage drop hardly occurs and light emission unevenness can be reduced.
  • FIG. 1 is a schematic view showing an example of a laminate of the present invention.
  • FIG. 2 is a schematic view showing an example of the laminate of the present invention.
  • FIG. 3 is a schematic view showing an example of the laminate of the present invention.
  • FIG. 4 is a schematic view showing an example of the laminate of the present invention.
  • FIG. 5 is a schematic view showing an example of the organic electroluminescent device of the present invention.
  • FIG. 6 is a schematic view showing an example of the organic electroluminescent device of the present invention.
  • FIG. 7 is a schematic view showing an example of the organic electroluminescent device of the present invention.
  • FIG. 8 is a schematic view showing an example of the organic electroluminescent device of the present invention.
  • FIG. 9 is a schematic view showing an organic electroluminescent device of Comparative Example 1.
  • FIG. 10 is a schematic view showing an organic electroluminescent device of Comparative Example 2.
  • FIG. 11 is a schematic view showing an organic electroluminescent device of Comparative Example 3.
  • FIG. 12 is a schematic view showing an organic electroluminescent device of Comparative Example 4.
  • FIG. 13 is a schematic view showing an organic electroluminescent device of Comparative Example 5.
  • FIG. 14 is a schematic view showing an organic electroluminescent device of Comparative Example 0.
  • FIG. 15 is a schematic diagram showing light reflection and diffusion when the conductive layer contains high refractive index particles.
  • FIG. 16 is a schematic diagram showing light reflection when the conductive layer does not contain high refractive index particles.
  • FIG. 17 is a schematic view showing a method for measuring unevenness of light emission on the light emitting surface of the organic electroluminescent device.
  • the laminate of the present invention is a laminate having at least a transparent substrate, a light diffusion layer, and a light-transmitting conductive layer in this order, and the conductive layer is composed of a conductive matrix and the conductive matrix. And particles having a large refractive index.
  • the schematic diagram showing an example of the laminated body of this invention was shown in FIG.
  • the laminate 10 of the present invention includes a transparent substrate 1, a light diffusion layer 2, and a conductive layer 3 having optical transparency in this order.
  • the light-transmitting conductive layer 3 contains a conductive matrix and particles having a refractive index larger than that of the conductive matrix.
  • the conductive layer contained in the laminate of the present invention is a conductive layer containing a conductive matrix and particles having a higher refractive index than the conductive matrix and having light transmittance.
  • the thickness of the conductive layer is preferably 100 nm or more and 5 ⁇ m or less, more preferably 200 nm or more and 3 ⁇ m or less, and further preferably 300 nm or more and 2 ⁇ m or less from the viewpoint of the balance between light transmittance and resistance. .
  • a conductive polymer As the conductive matrix, a conductive polymer is preferable. As the conductive polymer, a ⁇ -conjugated conductive polymer and a ⁇ -conjugated conductive polymer are preferable, and a ⁇ -conjugated conductive polymer is more preferable. Examples of the ⁇ -conjugated conductive polymer include poly (methylphenylsilane), poly (methylpropylsilane), poly (phenyl-p-biphenylsilane), poly (dihexylsilane), and the like.
  • the ⁇ -conjugated conductive polymer is not particularly limited as long as it is an organic polymer having a main chain composed of a ⁇ -conjugated system.
  • the ⁇ -conjugated conductive polymer is preferably a ⁇ -conjugated heterocyclic compound or a derivative of a ⁇ -conjugated heterocyclic compound because of compound stability and high conductivity.
  • Examples of ⁇ -conjugated conductive polymers include aliphatic conjugated polyacetylene, polyacene, polyazulene, aromatic conjugated polyphenylene, heterocyclic conjugated polypyrrole, polythiophene, polyisothianaphthene, heteroatom-containing polyaniline.
  • Polythienylene vinylene mixed conjugated poly (phenylene vinylene), double chain conjugated system having a plurality of conjugated chains in the molecule, derivatives of these conductive polymers, and conjugated high
  • conductive composites which are polymers in which molecular chains are grafted or block-copolymerized onto saturated polymers.
  • polypyrrole, polythiophene and polyaniline or derivatives thereof are preferable, and polythiophene, polyaniline, or derivatives thereof (that is, polythiophene, polyaniline, polythiophene derivatives, and polyaniline derivatives) are more preferable.
  • a ⁇ -conjugated conductive polymer can obtain sufficient conductivity and compatibility with a binder resin even if it is not substituted.
  • an alkyl group, a carboxy group, a sulfo group can be obtained. It is preferable to introduce a functional group such as a group, an alkoxy group or a hydroxy group into the ⁇ -conjugated conductive polymer.
  • Polypyrrole polypyrrole, poly (N-methylpyrrole), poly (3-methylpyrrole), poly (3-ethylpyrrole), poly (3-n-propylpyrrole), poly (3-butylpyrrole), poly (3 -Octylpyrrole), poly (3-decylpyrrole), poly (3-dodecylpyrrole), poly (3,4-dimethylpyrrole), poly (3,4-dibutylpyrrole), poly (3-carboxypyrrole), poly (3-methyl-4-carboxypyrrole), poly (3-methyl-4-carboxyethylpyrrole), poly (3-methyl-4-carboxybutylpyrrole), poly (3-hydroxypyrrole), poly (3-methoxy Pyrrole), poly (3-ethoxypyrrole), poly (3-butoxypyrrole), poly (3-methyl-4-hexyloxy) Roll),
  • Polythiophenes poly (thiophene), poly (3-methylthiophene), poly (3-ethylthiophene), poly (3-propylthiophene), poly (3-butylthiophene), poly (3-hexylthiophene), poly ( 3-heptylthiophene), poly (3-octylthiophene), poly (3-decylthiophene), poly (3-dodecylthiophene), poly (3-octadecylthiophene), poly (3-bromothiophene), poly (3- Chlorothiophene), poly (3-iodothiophene), poly (3-cyanothiophene), poly (3-phenylthiophene), poly (3,4-dimethylthiophene), poly (3,4-dibutylthiophene), poly ( 3-hydroxythiophene), poly (3-methoxythiophene), poly (3-ethoxythione) Phen), poly (3-but
  • Polyanilines Polyaniline, poly (2-methylaniline), poly (3-isobutylaniline), poly (2-aniline sulfonic acid), poly (3-aniline sulfonic acid) and the like.
  • the ⁇ -conjugated conductive polymer is preferably used together with a polymer dopant having an anion group (also referred to as “polyanion dopant”). That is, in this case, an organic conductive polymer composition containing an organic conductive polymer compound ( ⁇ -conjugated conductive polymer) and a polymer dopant having an anion group is obtained.
  • a ⁇ -conjugated conductive polymer in combination with a polymer dopant having an anion group high conductivity, improved stability over time of the conductivity, and water resistance in a laminate state are improved.
  • the polyanion dopant includes, for example, at least one of a substituted or unsubstituted polyalkylene, a substituted or unsubstituted polyalkenylene, a substituted or unsubstituted polyimide, a substituted or unsubstituted polyamide, and a substituted or unsubstituted polyester.
  • a substituted or unsubstituted polyalkylene a substituted or unsubstituted polyalkenylene
  • a substituted or unsubstituted polyimide a substituted or unsubstituted polyamide
  • a substituted or unsubstituted polyester examples thereof include a polymer having any structure and including a structural unit having an anionic group.
  • the anionic group of the polyanion dopant -O-SO 3 - X + , -SO 3 - X +, -COO - X + (. X + is the hydrogen ion in each of the formulas, represents an alkali metal ion), and the like.
  • —SO 3 ⁇ X + and —COO ⁇ X + are preferable from the viewpoint of doping ability into the organic conductive polymer compound.
  • polyisoprene sulfonic acid a copolymer containing polyisoprene sulfonic acid, polysulfoethyl methacrylate, a copolymer containing polysulfoethyl methacrylate, poly (4- Sulfobutyl methacrylate), copolymers containing poly (4-sulfobutyl methacrylate), polymethallyloxybenzene sulfonic acid, copolymers containing polymethallyloxybenzene sulfonic acid, polystyrene sulfonic acid, copolymers containing polystyrene sulfonic acid Polymers are preferred.
  • the degree of polymerization of the polyanion dopant is preferably in the range of 10 to 100,000 monomer units, and more preferably in the range of 50 to 10,000 from the viewpoint of solvent solubility and conductivity.
  • the content of the polyanion dopant is preferably in the range of 0.1 to 10 mol and more preferably in the range of 1 to 7 mol with respect to 1 mol of the organic conductive polymer compound.
  • the number of moles is defined by the number of structural units derived from a monomer containing an anion group that forms a polyanion dopant and the number of structural units derived from a monomer such as pyrrole, thiophene, or aniline that forms an organic conductive polymer compound.
  • the dispersibility and solubility in the solvent are increased, and it is easy to obtain a uniform dispersion.
  • the content of the polyanion dopant is 10 mol or less with respect to 1 mol of the organic conductive polymer compound, a large amount of the organic conductive polymer compound can be contained, and sufficient conductivity can be easily obtained.
  • the conductive polymer is preferably soluble in water or an organic solvent from the viewpoint of applicability. More specifically, the conductive polymer is preferably soluble at least 1.0% by mass in water or an organic solvent having a water content of 5% by mass or less and a dielectric constant of 2 to 30%.
  • “soluble” refers to a state in which a solvent is dissolved in a single molecule state or a state in which a plurality of single molecules are associated, or is dispersed in a particle shape having a particle diameter of 300 nm or less.
  • an organic conductive polymer has high hydrophilicity and is dissolved in water or a solvent containing water as a main component.
  • the organic conductive polymer examples thereof include a method of adding a compound that increases the affinity with an organic solvent, a dispersant in the organic solvent, and the like to the composition containing molecules.
  • organic solvent for example, alcohols, aromatic hydrocarbons, ethers, ketones, esters and the like are suitable.
  • particles having a refractive index larger than that of the conductive matrix are preferable, and metal oxide fine particles, for example, fine particles of oxides of aluminum, titanium, zirconium, and antimony are preferable. From the viewpoint of refractive index, fine particles of titanium oxide are particularly preferable.
  • the titanium oxide fine particles are preferably those obtained by subjecting the photocatalytic effect to an inert treatment.
  • the titanium oxide fine particles subjected to the photocatalytic deactivation treatment are not particularly limited as long as they do not have photocatalytic activity, and can be appropriately selected according to the purpose.
  • the surface of the titanium oxide fine particles is made of alumina, silica, and zirconia. Examples include titanium oxide fine particles coated with at least one kind, and (2) titanium oxide fine particles formed by coating a resin on the coated surface of the titanium oxide fine particles coated in (1). Examples of the resin include polymethyl methacrylate (PMMA).
  • the confirmation that the photocatalytically inactive titanium oxide fine particles have no photocatalytic activity can be performed by, for example, the methylene blue method.
  • the titanium oxide fine particles in the photocatalyst-inactivated titanium oxide fine particles are not particularly limited and can be appropriately selected according to the purpose.
  • the crystal structure is mainly composed of rutile, a mixed crystal of rutile / anatase, and anatase. It is preferable that the rutile structure is a main component.
  • the titanium oxide fine particles may be compounded by adding a metal oxide other than titanium oxide.
  • the metal oxide that can be combined with the titanium oxide fine particles is preferably at least one metal oxide selected from Sn, Zr, Si, Zn, and Al.
  • the amount of the metal oxide added to titanium is preferably 1 mol% to 40 mol%, more preferably 2 mol% to 35 mol%, still more preferably 3 mol% to 30 mol%.
  • the average particle size (primary average particle size) of the particles having a refractive index larger than that of the conductive matrix is preferably 1 nm or more and 100 nm or less, more preferably 1 nm or more and 30 nm or less, particularly preferably 1 nm or more and 25 nm or less, and 1 nm. More preferably, it is 20 nm or less. If the primary average particle size is 100 nm or less, it is preferable because the dispersion is less likely to become cloudy and sedimentation is not likely to occur, and if it is 1 nm or more, the crystal structure is not clearly amorphous and changes such as gelation over time. Is preferable because it is difficult to occur.
  • the primary average particle diameter can be measured, for example, by calculation from a half-value width of a diffraction pattern measured by an X-ray diffractometer or statistical calculation from a diameter of an electron microscope (TEM) image.
  • the shape of the particles having a refractive index larger than that of the conductive matrix is not particularly limited and can be appropriately selected according to the purpose.
  • the shape of rice grains, spheres, cubes, spindles, or irregular shapes preferable.
  • the titanium oxide fine particles may be used alone or in combination of two or more.
  • the particles having a refractive index larger than that of the conductive matrix are preferably 2.0 or more and 3.0 or less, and preferably 2.2 or more and 3.0 or less in order to increase the refractive index of the conductive layer. Is more preferably 2.2 or more and 2.8 or less, and particularly preferably 2.2 or more and 2.6 or less. If the refractive index is 2.0 or more, the refractive index of the conductive layer can be effectively increased, and if the refractive index is 3.0 or less, there is no inconvenience such as particle coloring. preferable.
  • the refractive index of particles having a refractive index greater than that of the conductive matrix can be measured as follows.
  • a resin material having a known refractive index is doped with particles having a refractive index larger than that of the conductive matrix, and a coating film is formed on the Si substrate or the quartz substrate with the resin material in which the particles are dispersed.
  • the refractive index of the coating film is measured with an ellipsometer, and the refractive index of the particles can be determined from the resin material constituting the coating film and the volume fraction of the particles.
  • Particles having a refractive index greater than that of the conductive matrix are required to increase the refractive index of the conductive matrix to be as high as the refractive index of the organic layer (especially the light emitting layer). It is preferably contained in an amount of 10% to 50% by volume, more preferably 15% to 50% by volume, and more preferably 20% to 50% by volume based on the total volume of the conductive layer. More preferably, it is contained below.
  • the content is 10% by volume or more, the refractive index of the conductive layer can be effectively increased, and the light extraction effect is improved.
  • the content is 50% by volume or less, Rayleigh scattering is increased. Therefore, it is preferable because the light extraction effect is improved.
  • the refractive index of the conductive layer is preferably not less than the refractive index of an organic layer such as a light emitting layer of an organic electroluminescence device, specifically, not less than 1.7 and not more than 2.2. It is preferable that it is 1.7 or more and 2.1 or less, more preferably 1.7 or more and 2.0 or less.
  • the conductive layer is preferably formed by applying a composition containing a conductive matrix and particles having a higher refractive index than the conductive matrix. Since the upper surface of the light diffusion layer usually has irregularities, the conductive layer formed by coating in this way is suitable for further forming an organic layer thereon due to the leveling effect. A flat surface can be obtained.
  • the resistance of the conductive layer is preferably 1 ⁇ / ⁇ ( ⁇ / sq.) Or more and 1000 ⁇ / ⁇ or less, more preferably 1 ⁇ / ⁇ or more and 500 ⁇ / ⁇ or less, and more preferably 1 ⁇ / ⁇ or more and 300 ⁇ / ⁇ or less. More preferably.
  • the light transmittance of the conductive layer is preferably 70% to 99%, more preferably 75% to 99%, and still more preferably 80% to 99%.
  • the light diffusion layer included in the laminate of the present invention has a function of diffusing light incident on the layer.
  • the light diffusion layer preferably contains at least one kind of particles, and more preferably contains at least a binder and light diffusion particles.
  • the binder contained in the light diffusion layer preferably contains a polymer.
  • the polymer is not particularly limited and may be appropriately selected depending on the purpose.
  • a thermoplastic resin (2) a combination of a reactive curable resin and a curing agent, or (3) a binder.
  • examples thereof include a polymer obtained from a combination of a precursor (a curable polyfunctional monomer or polyfunctional oligomer described below) and a polymerization initiator.
  • thermoplastic resin there is no restriction
  • a polystyrene resin a polyester resin, a cellulose resin, a polyether resin, vinyl chloride
  • examples thereof include resins, vinyl acetate resins, vinyl chloride-vinyl acid copolymer resins, polyacrylic resins, polymethacrylic resins, polyolefin resins, urethane resins, silicone resins, and imide resins. These may be used individually by 1 type and may use 2 or more types together.
  • polyacrylic resins and polymethacrylic resins are preferable, polyacrylic resins derived from acrylic or methacrylic having a fluorene structure, and polymethacrylic resins are more preferable, and polyacrylic resins having a fluorene structure are particularly preferable.
  • thermosetting resin and / or an ionizing radiation curable resin.
  • thermosetting resin for example, a phenol resin, urea resin, diallyl phthalate resin, melamine resin, guanamine resin, unsaturated polyester resin, polyurethane resin, epoxy Examples thereof include resins, amino alkyd resins, melamine-urea cocondensation resins, silicon resins, polysiloxane resins, and the like.
  • the ionizing radiation curable resin is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a radical polymerizable unsaturated group ⁇ (meth) acryloyloxy group, vinyloxy group, styryl group, vinyl group, etc.
  • a resin having a functional group such as a cationically polymerizable group (epoxy group, thioepoxy group, vinyloxy group, oxetanyl group, etc.), for example, a relatively low molecular weight polyester resin, polyether resin, (meth) acrylic resin, Examples thereof include epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, and polythiol polyene resins. These may be used individually by 1 type and may use 2 or more types together.
  • a crosslinking agent epoxy compound, polyisocyanate compound, polyol compound, polyamine compound, melamine compound, etc.
  • polymerization initiator azobis compound, organic peroxide compound, organic halogen compound
  • curing agents such as onium salt compounds and UV photoinitiators such as ketone compounds
  • polymerization accelerators organic metal compounds, acid compounds, basic compounds, etc.
  • Specific examples include compounds described by Fuzo Yamashita and Tosuke Kaneko “Crosslinking Agent Handbook” (Taiseisha, published in 1981).
  • the functional group of the photocurable polyfunctional monomer or polyfunctional oligomer that is the precursor of the binder may be a radical polymerizable functional group or a cationic polymerizable functional group.
  • radical polymerizable functional group examples include ethylenically unsaturated groups such as (meth) acryloyl group, vinyloxy group, styryl group, and allyl group.
  • ethylenically unsaturated groups such as (meth) acryloyl group, vinyloxy group, styryl group, and allyl group.
  • a (meth) acryloyl group is particularly preferable, and a polyfunctional monomer containing two or more radically polymerizable groups in the molecule is particularly preferable.
  • the radical polymerizable polyfunctional monomer is preferably selected from compounds having at least two terminal ethylenically unsaturated bonds.
  • a compound having 2 to 6 terminal ethylenically unsaturated bonds in the molecule is preferable.
  • Such a compound group is widely known in the polymer material field, and these can be used without particular limitation in the present invention. These can have chemical forms such as monomers, prepolymers (ie, dimers, trimers and oligomers) or mixtures thereof, and copolymers thereof.
  • radical polymerizable monomer examples include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, amides, and the like.
  • unsaturated carboxylic acids for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.
  • esters thereof esters thereof, amides, and the like.
  • an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, and an amide of an unsaturated carboxylic acid and an aliphatic polyamine compound are particularly preferable.
  • a dehydration condensation reaction product with an acid or the like is also preferably used.
  • a reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
  • a compound group in which an unsaturated phosphonic acid, styrene, or the like is substituted for the unsaturated carboxylic acid may be used.
  • Examples of the aliphatic polyhydric alcohol compound include alkanediol, alkanetriol, cyclohexanediol, cyclohexanetriol, inositol, cyclohexanedimethanol, pentaerythritol, sorbitol, dipentaerythritol, tripentaerythritol, glycerin, diglycerin and the like.
  • Examples of polymerizable ester compounds (monoesters or polyesters) of these aliphatic polyhydric alcohol compounds and unsaturated carboxylic acids include those described in paragraphs [0026] to [0027] of JP-A No. 2001-139663. Compounds.
  • polymerizable esters include, for example, vinyl alcohol, allyl methacrylate, allyl acrylate, aliphatic alcohols described in JP-B-46-27926, JP-B-51-47334, JP-A-57-196231, and the like. Those having an aromatic skeleton described in JP-A-2-226149 and those having an amino group described in JP-A-1-165613 are also preferably used.
  • polymerizable amides formed from aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis (meth) acrylamide, 1,6-hexamethylene bis (meth) acrylamide, and diethylenetriamine tris (meth) acrylamide. And xylylene bis (meth) acrylamide, and those having a cyclohexylene structure described in JP-B-54-21726.
  • vinyl urethane compounds containing two or more polymerizable vinyl groups in one molecule Japanese Patent Publication No. 48-41708, etc.
  • urethane acrylates Japanese Patent Publication No. 2-16765, etc.
  • ethylene oxide skeleton Urethane compounds having a characteristic Japanese Patent Publication No. 62-39418, etc.
  • polyester acrylates Japanese Patent Publication No. 52-30490, etc.
  • Photocurable monomers and oligomers can also be used. Two or more kinds of these radical polymerizable polyfunctional monomers may be used in combination.
  • cation polymerizable compound or “cation polymerizable organic compound” that can be used for forming the binder of the light diffusion layer.
  • any compound that undergoes a polymerization reaction and / or a crosslinking reaction when irradiated with an active energy ray in the presence of an active energy ray-sensitive cationic polymerization initiator can be used.
  • examples thereof include a compound, a cyclic thioether compound, a cyclic ether compound, a spiro orthoester compound, a vinyl hydrocarbon compound, and a vinyl ether compound.
  • One or more of the cationically polymerizable organic compounds may be used.
  • the number of cation polymerizable groups in one molecule is preferably 2 to 10, more preferably 2 to 5.
  • the weight average molecular weight of the compound is preferably 3,000 or less, more preferably 200 to 2,000, and still more preferably 400 to 1,500. If the weight average molecular weight is equal to or higher than the lower limit value, there will be no inconvenience such as a problem of volatilization in the film formation process. If the weight average molecular weight is equal to or lower than the upper limit value, the compatibility with the light diffusion layer forming material is eliminated. Is preferable because it does not cause problems such as deterioration.
  • Examples of the epoxy compound include aliphatic epoxy compounds and aromatic epoxy compounds.
  • aliphatic epoxy compounds examples include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate, and the like. be able to.
  • epoxy compounds for example, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxy stearate, octyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene And so on.
  • the alicyclic epoxy compound include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, or unsaturated alicyclic rings (for example, cyclohexene, cyclopentene, dicyclooctene, tricyclodecene, etc. ) Cyclohexene oxide or cyclopentene oxide-containing compound obtained by epoxidizing the containing compound with a suitable oxidizing agent such as hydrogen peroxide or peracid.
  • a suitable oxidizing agent such as hydrogen peroxide or peracid.
  • aromatic epoxy compound examples include mono- or polyglycidyl ethers of monovalent or polyvalent phenols having at least one aromatic nucleus, or alkylene oxide adducts thereof.
  • aromatic epoxy compounds examples include compounds described in paragraphs [0084] to [0086] of JP-A No. 11-242101 and paragraphs [0044] to [0046] of JP-A No. 10-158385. And the compounds described.
  • epoxy compounds aromatic epoxides and alicyclic epoxides are preferable, and alicyclic epoxides are more preferable in view of fast curability.
  • One of the epoxy compounds may be used alone, or two or more may be used in appropriate combination.
  • Examples of the cyclic thioether compound include compounds having a thioepoxy ring instead of the epoxy ring of the epoxy compound.
  • the compound containing an oxetanyl group as the cyclic ether compound include compounds described in paragraphs [0024] to [0025] of JP-A No. 2000-239309. These compounds are preferably used in combination with an epoxy group-containing compound.
  • Examples of the spiro orthoester compound include compounds described in JP 2000-506908 A.
  • vinyl hydrocarbon compounds examples include styrene compounds, vinyl group-substituted alicyclic hydrocarbon compounds (vinyl cyclohexane, vinyl bicycloheptene, etc.), compounds described in the above radical polymerizable monomers, propenyl compounds ⁇ “J. Polymer Science: Part”. A: Polymer Chemistry ”, 32, 2895 (1994), etc. ⁇ , alkoxy allene compound ⁇ “ J. Polymer Science: Part A: Polymer Chemistry ”, 33, 2493 (1995), etc.], vinyl compound ⁇ “J.
  • the polyfunctional compound is preferably a compound containing in the molecule at least one selected from the radical polymerizable group and the cationic polymerizable group. Examples thereof include compounds described in paragraph numbers [0031] to [0052] in JP-A-8-277320, compounds described in paragraph number [0015] in JP-A 2000-191737, and the like. The compounds used in the present invention are not limited to these.
  • the radical polymerizable compound and the cation polymerizable compound described above are preferably contained in a mass ratio of radical polymerizable compound: cation polymerizable compound in a ratio of 90:10 to 20:80, and 80:20 More preferably, it is contained in a ratio of ⁇ 30: 70.
  • the binder preferably contains a polymerization initiator.
  • the polymerization initiator include a thermal polymerization initiator and a photopolymerization initiator.
  • the polymerization initiator is preferably a compound that generates radicals or acids upon irradiation with light and / or heat.
  • the photopolymerization initiator preferably has a maximum absorption wavelength of 400 nm or less. Thus, the handling can be performed under a white light by setting the absorption wavelength to the ultraviolet region. A compound having a maximum absorption wavelength in the near infrared region can also be used.
  • the compound that generates radicals refers to a compound that generates radicals by irradiation with light and / or heat, and initiates and accelerates polymerization of a compound having a polymerizable unsaturated group.
  • a known polymerization initiator or a compound having a bond with a small bond dissociation energy can be appropriately selected and used.
  • produces a radical can be used individually or in combination of 2 or more types.
  • Examples of the compound that generates radicals include conventionally known organic peroxide compounds, thermal radical polymerization initiators such as azo polymerization initiators, organic peroxide compounds (Japanese Patent Laid-Open No. 2001-139663, etc.), amine compounds ( JP-B-44-20189), metallocene compounds (described in JP-A-5-83588, JP-A-1-304453, etc.), hexaarylbiimidazole compounds (US Pat. No.
  • radical photopolymerization of disulfone compounds JP-A-5-239015, JP-A-61-166544, etc.
  • organic halogenated compounds carbonyl compounds, organic boric acid compounds, phosphine oxide compounds, phosphonate compounds, etc.
  • the radical generator is more preferably a phosphine oxide compound or a phosphonate compound, particularly preferably an acyl phosphine oxide, an acyl phosphonate, or the like.
  • bis (2,4,6-trimethylbenzoyl)- It is phenylphosphine oxide.
  • organic halogenated compound examples include Wakabayashi et al., “Bull. Chem. Soc Japan”, 42, 2924 (1969), US Pat. 27830, M.M. P. Hutt, “J. Heterocyclic Chemistry”, Vol. 1 (No. 3), (1970) ”and the like, and in particular, an oxazole compound substituted with a trihalomethyl group: an s-triazine compound. More preferred are s-triazine derivatives in which at least one mono-, di- or trihalogen-substituted methyl group is bonded to the s-triazine ring.
  • Examples of the carbonyl compound include, for example, “Latest UV Curing Technology”, pages 60 to 62 [published by Technical Information Association, 1991], paragraph numbers [0015] to [0016] of JP-A-8-134404, Examples thereof include compounds described in paragraph numbers [0029] to [0031] of Kaihei 11-217518.
  • benzoin compounds such as acetophenone, hydroxyacetophenone, benzophenone, thioxan, benzoin ethyl ether, benzoin isobutyl ether, benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, benzyldimethyl
  • benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, benzyldimethyl
  • benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate, ethyl p-diethylaminobenzoate, benzyldimethyl
  • benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate, ethyl p-die
  • organic borate compound examples include, for example, Japanese Patent Nos. 2764769 and 2002-116539, and Kunz, Martin, “Rad. Tech'98. Proceeding April 19-22, 1998, Chicago”. And the organic borates described in the above.
  • examples of other organic boron compounds include JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7-306527, and JP-A-7-292014.
  • Specific examples include organoboron transition metal coordination complexes.
  • radical generating compounds may be added alone or in combination of two or more.
  • the addition amount is preferably 0.1% by mass to 30% by mass, more preferably 0.5% by mass to 25% by mass, and still more preferably 1% by mass to 20% by mass with respect to the total amount of the radical polymerizable monomer.
  • the light diffusing layer forming material has high polymerization without problems with respect to time stability.
  • photoacid generator that can be used as a photopolymerization initiator
  • examples of the photoacid generator include known compounds such as photoinitiators for photocationic polymerization, photodecolorants for dyes, photochromic agents, or known photoacid generators used in microresists, and the like. And the like.
  • examples of the photoacid generator include organic halogenated compounds, disulfone compounds, onium compounds, and the like. Among these, organic halogenated compounds and disulfone compounds are particularly preferable. Specific examples of the organic halogen compound and the disulfone compound are the same as those described for the compound generating the radical.
  • onium compounds examples include diazonium salts, ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, selenonium salts, and the like.
  • diazonium salts ammonium salts, iminium salts, phosphonium salts, iodonium salts, sulfonium salts, arsonium salts, selenonium salts, and the like.
  • an onium salt is particularly preferably used, and among them, a diazonium salt, an iodonium salt, a sulfonium salt, and an iminium salt are preferable from the viewpoint of photosensitivity at the start of photopolymerization, material stability of the compound, and the like.
  • the onium salt include, for example, an amylated sulfonium salt described in paragraph No. [0035] of JP-A-9-268205 and paragraph Nos. [0010] to [0011] of JP-A No. 2000-71366.
  • Diaryl iodonium salt or triarylsulfonium salt described in JP-A-2001-288205, sulfonium salt of thiobenzoic acid S-phenyl ester described in JP-A-2001-288205, paragraph number in JP-A-2001-133696 Examples include the onium salts described in [0030] to [0033].
  • photoacid generator examples include organic acids / organic halides described in JP-A-2002-29162, paragraphs [0059] to [0062], and photoacids having an o-nitrobenzyl type protecting group.
  • examples thereof include compounds such as a generator and a compound that generates photosulfonic acid to generate sulfonic acid (such as iminosulfonate).
  • the addition amount of the acid generator is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and more preferably 1% by mass to 10% by mass with respect to the total mass of the total cationically polymerizable monomer. % Is more preferable.
  • the addition amount is preferably in the above range from the stability of the light diffusion layer forming material, the polymerization reactivity, and the like.
  • the light diffusion layer forming material is 0.5% to 10% by mass of radical polymerization initiator or 1% to 10% by mass of cationic polymerization initiator with respect to the total mass of the radical polymerizable compound or the cationic polymerizable compound. %, Preferably 1% to 5% by weight of radical polymerization initiator, or more preferably 2% to 6% by weight of cationic polymerization initiator.
  • the solvent is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alcohols, ketones, esters, amides, ethers, ether esters, aliphatic hydrocarbons, halogenated carbons. Hydrogen etc. are mentioned.
  • alcohol for example, methanol, ethanol, propanol, butanol, benzyl alcohol, ethylene glycol, propylene glycol, ethylene glycol monoacetate, etc.
  • ketone for example, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, methylcyclohexanone, etc.
  • ester for example, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl formate, propyl formate, butyl formate, ethyl lactate, etc.
  • aliphatic hydrocarbons eg, hexane, cyclohexane
  • halogenated hydrocarbons eg, methyl chloroform
  • aromatic Group hydrocarbons eg benzene, toluene, xylene, ethylbenzene, etc.
  • amides eg dimethyl
  • dioxane tetrahydrofuran, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, etc.
  • ether alcohols such as 1-methoxy-2-propanol, ethyl cellosolve, methyl carbinol and the like
  • aromatic hydrocarbons and ketones are preferable, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are more preferable, and toluene and xylene are particularly preferable.
  • the refractive index of the binder in the light diffusion layer is preferably 1.7 or more and 2.2 or less, more preferably 1.7 or more and 2.1 or less, and more preferably 1.7 or more and 2.0 or less from the viewpoint of light extraction efficiency. Further preferred.
  • the refractive index of the binder in the light diffusion layer is preferably equal to or higher than the refractive index of the light emitting layer in the organic electroluminescent layer.
  • the light diffusing particles are not particularly limited as long as they can diffuse light, and can be appropriately selected according to the purpose.
  • the light diffusing particles may be organic particles, inorganic particles, or two or more kinds. You may contain particle
  • the organic particles include polymethyl methacrylate particles, crosslinked polymethyl methacrylate particles, acrylic-styrene copolymer particles, melamine particles, polycarbonate particles, polystyrene particles, crosslinked polystyrene particles, polyvinyl chloride particles, benzoguanamine-melamine formaldehyde particles, Etc.
  • inorganic particles for example ZrO 2, TiO 2, Al 2 O 3, In 2 O 3, ZnO, SnO 2, Sb 2 O 3, and the like.
  • TiO 2 , ZrO 2 , ZnO, and SnO 2 are particularly preferable.
  • the light diffusing particles are preferable in view of solvent resistance and dispersibility in the binder, and crosslinked polymethyl methacrylate particles are particularly preferable. It can be confirmed that the light diffusing particles are crosslinked resin particles by dispersing in a solvent, for example, toluene, and seeing the difficulty of dissolving the resin particles.
  • the refractive index of the light diffusing particles is not particularly limited and can be appropriately selected depending on the purpose, but is preferably 1.0 or more and 3.0 or less, more preferably 1.2 or more and 2.0 or less. More preferably, it is 3 or more and 1.7 or less. When the refractive index is 1.0 or more and 3.0 or less, light diffusion (scattering) does not become too strong, and thus light extraction efficiency is likely to be improved.
  • the refractive index of the light diffusing particles is determined by measuring the refractive index of the refracting liquid using, for example, an automatic refractometer (KPR-2000, manufactured by Shimadzu Corporation) and then using a precision spectrometer (GMR-1DA, Shimadzu Corporation). (Manufactured by Seisakusho Co., Ltd.) and can be measured by the Shribsky method.
  • the average particle diameter of the light diffusing particles is preferably from 0.5 ⁇ m to 10 ⁇ m, more preferably from 0.5 ⁇ m to 6 ⁇ m, and still more preferably from 1 ⁇ m to 3 ⁇ m.
  • the average particle diameter of the light diffusing particles is 10 ⁇ m or less, the light hardly scatters forward, and the ability to convert the angle of light by the light diffusing particles is unlikely to decrease.
  • the average particle diameter of the light diffusing particles is 0.5 ⁇ m or more, the wavelength dependence of the scattering efficiency of the light diffusing particles is not smaller than the wavelength of visible light and Mie scattering hardly changes to the Rayleigh scattering region.
  • the average particle diameter of the light diffusing particles can be measured, for example, by an apparatus using a dynamic light scattering method such as Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd., or by image processing of an electron micrograph.
  • the content of the light diffusion particles in the light diffusion layer is preferably 30% by volume or more and 66% by volume or less, more preferably 40% by volume or more and 60% by volume or less, and particularly preferably 45% by volume or more and 55% by volume or less.
  • the content is 30% by volume or more, there is a high probability that light incident on the light diffusion layer is scattered by the light diffusion particles, and the ability to convert the light angle of the light diffusion layer is large.
  • the light extraction efficiency is improved without increasing the thickness.
  • the cost since it is not necessary to increase the thickness of the light diffusing layer, the cost is reduced, the variation in the thickness of the light diffusing layer is reduced, and the scattering effect in the light emitting surface is less likely to vary.
  • the content is 66% by volume or less, the surface of the light diffusing layer is not excessively rough, and cavities are not easily formed inside, so that the physical strength of the light diffusing layer is hardly lowered.
  • the light diffusion layer preferably contains the resin particles and titanium oxide fine particles that have been subjected to photocatalytic inactivation treatment.
  • Specific examples and preferable ranges of the photocatalyst-inactivated titanium oxide fine particles are the same as those described in the conductive layer.
  • the content of the titanium oxide fine particles subjected to the photocatalytic inactivation treatment is preferably 10% by volume to 50% by volume, more preferably 10% by volume to 40% by volume, and more preferably 20% by volume to 40% by volume with respect to the binder. % Or less is more preferable.
  • the content is 10% by volume or more, the effect of increasing the refractive index of the binder is excellent and the light extraction effect is improved.
  • Rayleigh scattering does not become strong and the light extraction effect is suppressed. It is hard to be done.
  • (absolute value) between the refractive index A of the binder and the refractive index B of the light diffusing particles is preferably 0.2 or more and 1.0 or less. 0.2 or more and 0.5 or less are more preferable, and 0.2 or more and 0.4 or less are still more preferable.
  • is 0.2 or more, the light diffusion (scattering) does not become too weak and the light extraction efficiency is easily improved, and when it is 1.0 or less, the light diffusion (scattering). ) Does not become too strong, and the light extraction efficiency is likely to improve.
  • the average thickness of the light diffusion layer is preferably 1 ⁇ m to 10 ⁇ m, more preferably 2 ⁇ m to 8 ⁇ m, and particularly preferably 3 ⁇ m to 6 ⁇ m.
  • the average thickness of the light diffusion layer can be determined, for example, by cutting a part of the light diffusion layer and measuring it with a scanning electron microscope (S-3400N, manufactured by Hitachi High-Tech Co., Ltd.).
  • the above-mentioned various materials are placed above the transparent substrate, for example, dip coating method, air knife coating method, curtain coating method, roller coating method, wire bar coating method, gravure coating method, micro gravure coating method, extrusion.
  • It can be prepared by applying by a known thin film forming method such as a coating method and drying, irradiating with light and / or heat.
  • curing by light irradiation is advantageous from the viewpoint of rapid curing.
  • the heating temperature is preferably 60 ° C. to 105 ° C., more preferably 70 ° C. to 100 ° C., and still more preferably 70 ° C. to 90 ° C.
  • the light source for light irradiation may be any wavelength near the wavelength (absorption wavelength) at which the photopolymerization initiator reacts.
  • each light source can be an ultrahigh pressure, high pressure, medium pressure, low pressure mercury lamp, A chemical lamp, a carbon arc lamp, a metal halide lamp, a xenon lamp, sunlight, etc. are mentioned.
  • Various available laser light sources having wavelengths of 350 nm to 420 nm may be irradiated in a multi-beam form.
  • examples of the light source include a halogen lamp, a xenon lamp, and a high-pressure sodium lamp.
  • Various available laser light sources having a wavelength of 750 nm to 1,400 nm may be irradiated in a multi-beam form. .
  • the atmosphere has a reduced oxygen concentration.
  • the oxygen concentration range is preferably 0 to 1,000 ppm, more preferably 0 to 800 ppm, and still more preferably 0 to 600 ppm.
  • Irradiation intensity of ultraviolet irradiation is preferably from 0.1mW / cm 2 ⁇ 100mW / cm 2, irradiation amount on the coating film surface, 100mJ / cm 2 ⁇ 10,000mJ / cm 2 are preferred, 100 mJ / cm 2 to 5,000 mJ / cm 2 is more preferable, and 100 mJ / cm 2 to 1,000 mJ / cm 2 is particularly preferable.
  • the light irradiation amount is less than 100 mJ / cm 2 , the light diffusion layer is not sufficiently cured, and may be dissolved when a planarizing layer is applied on the light diffusion layer, or may be collapsed during substrate cleaning. .
  • the temperature in the light irradiation step is preferably 15 ° C. to 70 ° C., more preferably 20 ° C. to 60 ° C., and particularly preferably 25 ° C. to 50 ° C.
  • the temperature is less than 15 ° C, it may take time to cure the light diffusion layer by photopolymerization.
  • the temperature exceeds 70 ° C the photopolymerization initiator itself is affected and cannot be photopolymerized (cured). Sometimes.
  • the conductive layer can be formed on the uneven surface by coating.
  • the conductive layer can be adjacent, the surface of the light diffusion layer on the conductive layer side may be flattened, or a planarization layer may be provided between the light diffusion layer and the conductive layer.
  • the method for flattening the light emitting surface of the light diffusion layer include a method of laminating a layer obtained by removing light diffusion particles from the light diffusion layer on the light diffusion layer.
  • FIG. 4 is a schematic view showing the laminate 10 of the present invention in the case where the planarizing layer 8 is provided.
  • the planarizing layer preferably has a composition that does not include the light diffusing particles in the light diffusing layer, and can be formed in the same manner as the light diffusing layer.
  • the average thickness of the flattening layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 1 ⁇ m to 10 ⁇ m, more preferably 2 ⁇ m to 8 ⁇ m, and particularly preferably 3 ⁇ m to 7 ⁇ m.
  • the average thickness of the flattening layer is 1 ⁇ m or more, the surface of the protruding light diffusion layer can be flattened, and when it is 10 ⁇ m or less, the light extraction ability is reduced due to light absorption of the flattening layer. Hard to do.
  • the total average thickness of the light diffusion layer and the planarizing layer is preferably 2 ⁇ m to 15 ⁇ m, more preferably 3 ⁇ m to 14 ⁇ m, and particularly preferably 5 ⁇ m to 12 ⁇ m. If the total average thickness is 2 ⁇ m or more, sufficient diffusion and planarization can be achieved, and if the total average thickness is 15 ⁇ m or less, light extraction efficiency may be reduced due to absorption in the planarization layer and excessive diffusion in the light diffusion layer. Absent.
  • the refractive index of the planarizing layer is preferably 1.7 or more and 2.2 or less, more preferably 1.7 or more and 2.1 or less, and even more preferably 1.7 or more and 2.0 or less from the viewpoint of light extraction efficiency.
  • the planarization layer preferably has a refractive index equal to or higher than that of the light diffusion layer.
  • the shape, structure, size, material, etc. of the transparent substrate in the laminate of the present invention are not particularly limited and can be appropriately selected according to the purpose.
  • Examples of the shape include a flat plate shape.
  • the structure may be a single layer structure or a laminated structure, and the size may be appropriately selected according to the size of the light extraction member.
  • inorganic materials such as a yttria stabilized zirconia (YSZ) and glass (an alkali free glass, soda-lime glass, etc.)
  • polyethylene examples thereof include polyester resins such as terephthalate (PET) and polyethylene naphthalate (PEN), polycarbonate, polyimide resin (PI), polyethylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and styrene-acrylonitrile copolymer. These may be used individually by 1 type and may use 2 or more types together.
  • a polyester resin is preferable, and polyethylene terephthalate (PET) and polyethylene naphthalate (PEN) are particularly preferable from the viewpoint of applicability with a roll.
  • the surface of the substrate is preferably subjected to a surface activation treatment in order to improve adhesion with the light diffusion layer provided thereon.
  • Examples of the surface activation treatment include glow discharge treatment and corona discharge treatment.
  • the substrate may be appropriately synthesized or a commercially available product may be used. There is no restriction
  • the refractive index of the substrate is preferably from 1.3 to 1.8, more preferably from 1.4 to 1.7, and still more preferably from 1.4 to 1.6.
  • the refractive index of the substrate is 1.3 or more, the difference in refractive index between the substrate and the light diffusion layer does not become too large, and when light from the light diffusion layer enters, Fresnel reflection does not become too strong, and light The extraction efficiency is easy to improve.
  • the refractive index of the substrate is 1.8 or less, the difference in refractive index between the substrate and air (light emission side) does not become too large, Fresnel reflection does not become too strong, and the light extraction efficiency is easily improved.
  • a wiring (also referred to as “auxiliary wiring”) having a resistance lower than that of the conductive layer is provided between the light diffusion layer and the conductive layer.
  • auxiliary wiring By having a wiring with a resistance lower than that of the conductive layer, the overall resistance as a transparent electrode combining the conductive layer and the wiring can be lowered, and when the light emitting surface of the organic electroluminescent device becomes a large area In addition, the voltage drop can be suppressed, and uneven light emission can be prevented.
  • the structure which has auxiliary wiring between a light-diffusion layer and an electroconductive layer, and the electroconductive layer has covered auxiliary wiring is more preferable.
  • the conductive layer can be provided so as to cover the wiring by forming the conductive layer by a coating method, in the organic electroluminescence device, the wiring can be configured not to contact the organic layer, and light emission Light emission is possible on all sides of the layer.
  • the presence of the auxiliary wiring is not easily seen by the light diffusion layer, and the design is excellent.
  • the auxiliary wiring preferably contains a metal, more preferably contains silver, aluminum, gold, or copper, and more preferably contains silver or aluminum.
  • the auxiliary wiring can be formed by vacuum deposition of the metal and etching using photolithography or a mask. Moreover, it can also form by printing, application
  • the thickness of the auxiliary wiring is preferably 10 nm or more and 3 ⁇ m or less, and preferably 30 nm or more and 1 ⁇ m or less from the viewpoint of reducing the resistance of the conductive layer and preventing the formation of irregularities on the surface by the auxiliary wiring. More preferably, it is 50 nm or more and 500 nm or less.
  • the width of the auxiliary wiring is preferably 1 ⁇ m or more and 1 mm or less, more preferably 5 ⁇ m or more and 500 ⁇ m or less, and further preferably 10 ⁇ m or more and 200 ⁇ m or less, from the viewpoints of reducing the resistance of the conductive layer and shielding light. preferable.
  • FIG. 2 is a schematic diagram showing an example of the laminate of the present invention in the case of having auxiliary wiring.
  • the laminate 10 of the present invention has a transparent substrate 1, a light diffusion layer 2, an auxiliary wiring 7, and a light-transmitting conductive layer 3 in this order, and the conductive layer 3 covers the auxiliary wiring 7. ing.
  • the cross-sectional shape of the auxiliary wiring may be such that the upper surface (conductive layer side) and the lower surface (light diffusion layer side) are both flat and parallel, but the upper surface (conductive layer side) is It is preferable that the surface is not flat but round (see FIG. 3), uneven, or the upper surface (conductive layer side) and the lower surface (light diffusion layer side) are not parallel.
  • the upper surface of the auxiliary wiring is not flat but round (see FIG. 3), has irregularities, or the upper surface (conductive layer side) and the lower surface (light diffusion layer side) are not parallel.
  • the scattering phenomenon due to the high refractive index particles of the conductive layer is such that the shape of the cross section of the auxiliary wiring is flat and parallel on the upper surface (conductive layer side) and the lower surface (light diffusion layer side).
  • the refractive index is (the refractive index of the organic layer ⁇ the refractive index of the conductive layer ⁇ the refractive index of the planarizing layer, or the light diffusion layer).
  • the light is transmitted through the planarizing layer or the light diffusing layer without total reflection, but part of the light returns to the conductive layer due to total reflection to the organic layer having a low refractive index. It can be considered that the light extraction efficiency is improved.
  • the conductive layer does not have the high refractive index particles in the present invention
  • the auxiliary wiring is provided, the light reflected on the auxiliary wiring is reflected to the organic layer side. Efficiency decreases due to light shielding by auxiliary wiring.
  • the refractive index of the conductive layer is smaller than that of the organic layer, and the reflected light is easy to return to the organic layer without being totally reflected, thereby further reducing the light extraction efficiency ( Attenuated by light absorption in the organic layer).
  • the laminate of the present invention has a transparent substrate, a light diffusing layer, a wiring, and a conductive layer in this order, and can improve light extraction efficiency and reduce light emission unevenness when the light emitting surface has a large area. Since it can reduce, it can use suitably for an organic electroluminescent apparatus etc.
  • the organic electroluminescent device of the present invention comprises a transparent substrate, a light diffusion layer, a light-transmitting conductive layer (transparent electrode), an organic electroluminescent layer, and a reflective electrode in this order,
  • the portion including the transparent substrate, the light diffusion layer, and the light-transmitting conductive layer is composed of the laminate of the present invention.
  • the organic electroluminescent device of the present invention preferably has a barrier layer between the transparent electrode and the light diffusion layer.
  • a method for producing an organic electroluminescent device of the present invention comprises a step of applying a light diffusing layer forming material of the present invention on a substrate and forming a light diffusing layer, A flattening layer forming step of applying a flattening layer forming material obtained by removing light diffusing particles from the light diffusing layer forming material of the present invention on the light diffusing layer, and forming a flattening layer.
  • the light diffusion layer forming step is performed within 24 hours after adding the polymerization initiator to the light diffusion layer forming material
  • the planarization layer forming step is performed within 24 hours after the addition of the polymerization initiator to the planarization layer formation material.
  • the viscosity is gradually changed, which is preferable in that the film thickness abnormality after coating and insufficient curing can be prevented.
  • the organic electroluminescent layer has at least a light emitting layer.
  • the functional layer other than the light emitting layer include a hole transport layer, an electron transport layer, a hole block layer, an electron block layer, a hole injection layer, and an electron injection layer.
  • the organic electroluminescent layer preferably has a hole transport layer between the anode and the light emitting layer, and preferably has an electron transport layer between the cathode and the light emitting layer.
  • a hole injection layer may be provided between the hole transport layer and the anode, or an electron injection layer may be provided between the electron transport layer and the cathode.
  • a hole transporting intermediate layer (electron blocking layer) may be provided between the light emitting layer and the hole transporting layer, and an electron transporting intermediate layer (hole blocking layer) is provided between the light emitting layer and the electron transporting layer. Layer) may be provided.
  • Each functional layer may be divided into a plurality of secondary layers.
  • These functional layers including the light emitting layer can be suitably formed by any of dry film forming methods such as vapor deposition and sputtering, wet coating methods, transfer methods, printing methods, and ink jet methods.
  • dry film forming methods such as vapor deposition and sputtering, wet coating methods, transfer methods, printing methods, and ink jet methods.
  • the light-emitting layer receives holes from an anode, a hole injection layer, or a hole transport layer when an electric field is applied, receives electrons from a cathode, an electron injection layer, or an electron transport layer, and recombines holes and electrons. It is a layer having a function of providing a field to emit light.
  • the light emitting layer includes a light emitting material.
  • the light emitting layer may be composed of only a light emitting material, or may be a mixed layer of a host material and a light emitting material (in the latter case, the light emitting material may be referred to as “light emitting dopant” or “dopant”).
  • the light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, and two or more kinds may be mixed.
  • the host material is preferably a charge transport material.
  • the host material may be one type or two or more types.
  • the light emitting layer may contain a material that does not have charge transporting properties and does not emit light.
  • the thickness of the light emitting layer is not particularly limited and can be appropriately selected depending on the purpose. However, it is preferably 2 nm to 500 nm, and more preferably 3 nm to 200 nm from the viewpoint of external quantum efficiency. More preferably, it is 5 nm to 100 nm.
  • the said light emitting layer may be 1 layer, or may be two or more layers, and each layer may light-emit with a different luminescent color.
  • Luminescent material As the light emitting material, any of a phosphorescent light emitting material, a fluorescent light emitting material and the like can be suitably used.
  • the light emitting material has an ionization potential difference ( ⁇ Ip) and an electron affinity difference ( ⁇ Ea) of 1.2 eV> ⁇ Ip> 0.2 eV and / or 1.2 eV> ⁇ Ea> with the host compound.
  • a dopant satisfying the relationship of 0.2 eV is preferable from the viewpoint of driving durability.
  • the light emitting material in the light emitting layer is generally contained in the light emitting layer in an amount of 0.1% by mass to 50% by mass with respect to the total compound mass forming the light emitting layer. From the viewpoint, the content is preferably 1% by mass to 50% by mass, and more preferably 2% by mass to 50% by mass.
  • examples of the phosphorescent material include complexes containing a transition metal atom or a lanthanoid atom.
  • the transition metal atom is not particularly limited and may be appropriately selected depending on the purpose. Examples thereof include ruthenium, rhodium, palladium, tungsten, rhenium, osmium, iridium, gold, silver, copper, and platinum. Rhenium, iridium, and platinum are more preferable, and iridium and platinum are more preferable.
  • Examples of the ligand of the complex include G.I. Wilkinson et al., Comprehensive Coordination Chemistry, Pergamon Press 1987, H.C. Listed by Yersin, "Photochemistry and Photophysics of Coordination Compounds", published by Springer-Verlag, 1987, Akio Yamamoto, “Organic Metal Chemistry-Fundamentals and Applications,” published by Yukabosha, 1982, etc. .
  • the complex may have one transition metal atom in the compound or may be a so-called binuclear complex having two or more. Different metal atoms may be contained at the same time.
  • phosphorescent materials for example, US6303238B1, US6097147, WO00 / 57676, WO00 / 70655, WO01 / 08230, WO01 / 39234A2, WO01 / 41512A1, WO02 / 02714A2, WO02 / 15645A1, WO02 / 44189A1, WO05 / 19373A2, WO2004 / 108857A1, WO2005 / 042444A2, WO2005 / 042550A1, JP2001-247859, JP2002-302671, JP2002-117978, JP2003-133074, JP2002-1235076, JP2003-123982, JP2002-170684, EP121257, JP2002-226495, JP2002 234894, JP-A-2001-247659, JP-A-2001-298470, JP-A-2002-173675, JP-A-2002-203678, JP-A-2002-203679,
  • Ir complex, Pt complex, Cu complex, Re complex, W complex, Rh complex, Ru complex, Pd complex, Os complex, Eu complex, Tb complex, Gd complex, Dy complex, and Ce complex are preferable, and Ir complex , Pt complex, or Re complex is more preferable, and Ir complex, Pt complex, or Re complex including at least one coordination mode of metal-carbon bond, metal-nitrogen bond, metal-oxygen bond, metal-sulfur bond is further included.
  • an Ir complex, a Pt complex, or an Re complex containing a tridentate or higher polydentate ligand is particularly preferable.
  • phosphorescent material examples include the following compounds, but are not limited thereto.
  • the fluorescent light emitting material is not particularly limited and may be appropriately selected depending on the intended purpose.
  • a hole-transporting host material having excellent hole-transporting property may be described as a hole-transporting host
  • an electron-transporting host compound having excellent electron-transporting property (described as an electron-transporting host) May be used).
  • Hole-transporting host material examples include the following materials. Pyrrole, indole, carbazole, azaindole, azacarbazole, triazole, oxazole, oxadiazole, pyrazole, imidazole, thiophene, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styrylanthracene, fluorenone Hydrazone, stilbene, silazane, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidin compound, porphyrin compound, polysilane compound, poly (N-vinylcarbazole), aniline copolymer, thiophene oligomer, Examples thereof include conductive polymer oligomers such as polythiophene, organic silanes, carbon films, or derivatives thereof.
  • indole derivatives carbazole derivatives, aromatic tertiary amine compounds, thiophene derivatives, and those having a carbazole group in the molecule are preferred, and compounds having a t-butyl substituted carbazole group are more preferred.
  • Electrode pyridine, pyrimidine, triazine, imidazole, pyrazole, triazole, oxazole, oxadiazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyran dioxide, carbodiimide, fluoreni Heterocyclic tetracarboxylic anhydrides such as redenemethane, distyrylpyrazine, fluorine-substituted aromatic compounds, naphthaleneperylene, phthalocyanines, or derivatives thereof (may form condensed rings with other rings), 8-quinolinol derivatives And various metal complexes represented by metal complexes having metal phthalocyanine, benzoxazole or benzothiazole as a ligand.
  • a metal complex compound is preferable from the viewpoint of durability, and a metal complex having a ligand having at least one nitrogen atom, oxygen atom, or sulfur atom coordinated to a metal is more preferable.
  • the metal complex electron transporting host include Japanese Patent Application Laid-Open No. 2002-235076, Japanese Patent Application Laid-Open No. 2004-214179, Japanese Patent Application Laid-Open No. 2004-221106, Japanese Patent Application Laid-Open No. 2004-221665, Japanese Patent Application Laid-Open No. 2004-221068. And compounds described in JP-A-2004-327313.
  • hole transporting host material and the electron transporting host material include the following compounds, but are not limited thereto.
  • Hole injection layer, hole transport layer-- The hole injection layer or the hole transport layer is a layer having a function of receiving holes from the anode or the layer on the anode side and transporting them to the cathode side.
  • the hole injecting material and hole transporting material used for these layers may be a low molecular compound or a high molecular compound.
  • pyrrole derivatives carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, styryl Anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aromatic tertiary amine compounds, styrylamine compounds, aromatic dimethylidin compounds, phthalocyanine compounds, porphyrin compounds, thiophene derivatives, organosilane derivatives, carbon, Etc. are preferred.
  • the hole injection layer or the hole transport layer may contain an electron accepting dopant.
  • an inorganic compound or an organic compound can be used as long as it has an electron accepting property and oxidizes an organic compound.
  • the inorganic compound include metal halides such as ferric chloride, aluminum chloride, gallium chloride, indium chloride, and antimony pentachloride, and metal oxides such as vanadium pentoxide and molybdenum trioxide.
  • a compound having a nitro group, halogen, cyano group, trifluoromethyl group or the like as a substituent, a quinone compound, an acid anhydride compound, fullerene, or the like can be preferably used.
  • These electron-accepting dopants may be used alone or in combination of two or more.
  • the amount of the electron-accepting dopant varies depending on the type of material, but is preferably 0.01% by mass to 50% by mass, more preferably 0.05% by mass to 40% by mass with respect to the hole transport layer material. 1 mass% to 30 mass% is particularly preferable.
  • the hole injection layer or the hole transport layer may have a single layer structure composed of one or more of the materials described above, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Also good.
  • Electron injection layer, electron transport layer-- The electron injection layer or the electron transport layer is a layer having a function of receiving electrons from the cathode or a layer on the cathode side and transporting them to the anode side.
  • the electron injection material and the electron transport material used for these layers may be a low molecular compound or a high molecular compound.
  • the electron injection layer or the electron transport layer may contain an electron donating dopant.
  • the electron-donating dopant introduced into the electron-injecting layer or the electron-transporting layer is not limited as long as it has an electron-donating property and has a property of reducing an organic compound.
  • Alkali metals such as Li and alkaline earths such as Mg Metals, transition metals including rare earth metals, reducing organic compounds, and the like are preferably used.
  • the metal a metal having a work function of 4.2 eV or less can be preferably used. Specifically, Li, Na, K, Be, Mg, Ca, Sr, Ba, Y, Cs, La, Sm, Gd , And Yb.
  • Examples of the reducing organic compound include nitrogen-containing compounds, sulfur-containing compounds, and phosphorus-containing compounds. These electron donating dopants may be used alone or in combination of two or more.
  • the amount of the electron-donating dopant varies depending on the type of material, but is preferably 0.1% by mass to 99% by mass, more preferably 1.0% by mass to 80% by mass with respect to the electron transport layer material. 0% by mass to 70% by mass is particularly preferable.
  • the electron injection layer or the electron transport layer may have a single layer structure composed of one or more of the above-described materials, or a multilayer structure composed of a plurality of layers having the same composition or different compositions. Good.
  • the hole blocking layer is a layer having a function of preventing holes transported from the anode side to the light emitting layer from passing through to the cathode side, and is usually provided as an organic compound layer adjacent to the light emitting layer on the cathode side.
  • the electron blocking layer is a layer having a function of preventing electrons transported from the cathode side to the light emitting layer from passing to the anode side, and is usually provided as an organic compound layer adjacent to the light emitting layer on the anode side.
  • Examples of the compound constituting the hole blocking layer include aluminum complexes such as BAlq, triazole derivatives, phenanthroline derivatives such as BCP, and the like.
  • the thickness of the hole blocking layer and the electron blocking layer is preferably 1 nm to 500 nm, more preferably 5 nm to 200 nm, and still more preferably 10 nm to 100 nm.
  • the hole blocking layer and the electron blocking layer may have a single-layer structure made of one or more of the materials described above, or a multilayer structure made up of a plurality of layers having the same composition or different compositions. Also good.
  • the organic electroluminescent device includes a transparent electrode and a reflective electrode, that is, an anode and a cathode. From the nature of the organic electroluminescent device, at least one of the anode and the cathode is preferably transparent. Usually, the anode only needs to have a function as an electrode for supplying holes to the organic compound layer, and the cathode only needs to have a function as an electrode for injecting electrons into the organic compound layer.
  • the shape, structure, size, and the like are not particularly limited, and can be appropriately selected from known electrode materials according to the use and purpose of the light-emitting device. As a material which comprises an electrode, a metal, an alloy, a metal oxide, an electroconductive compound, or a mixture thereof etc. are mentioned suitably, for example.
  • the organic electroluminescent device of the present invention has a light-transmitting conductive layer in the laminate of the present invention as a transparent electrode.
  • the light-transmitting conductive layer preferably functions as an anode.
  • Examples of the material constituting the cathode include alkali metals (eg, Li, Na, K, Cs, etc.), alkaline earth metals (eg, Mg, Ca, etc.), gold, silver, lead, aluminum, sodium-potassium. Alloy, lithium-aluminum alloy, magnesium-silver alloy, indium, and rare earth metals such as ytterbium. These may be used alone, but two or more can be suitably used in combination from the viewpoint of achieving both stability and electron injection. Among these, alkali metals and alkaline earth metals are preferable from the viewpoint of electron injection properties, and materials mainly composed of aluminum are preferable from the viewpoint of excellent storage stability.
  • alkali metals eg, Li, Na, K, Cs, etc.
  • alkaline earth metals eg, Mg, Ca, etc.
  • gold silver, lead, aluminum, sodium-potassium. Alloy, lithium-aluminum alloy, magnesium-silver alloy, indium, and
  • a material mainly composed of silver having a high reflectance is preferable from the viewpoint of luminous efficiency.
  • the material mainly composed of aluminum is aluminum alone, an alloy of aluminum and 0.01% by mass to 10% by mass of alkali metal or alkaline earth metal, or a mixture thereof (for example, lithium-aluminum alloy, magnesium-aluminum alloy). Etc.).
  • the material mainly composed of silver refers to a mixture of silver alone, silver and 0.01% by mass to 10% by mass of an alkaline earth metal or other metals (for example, an alloy of silver, magnesium and calcium).
  • the method for forming the electrode is not particularly limited, and can be performed according to a known method.
  • a material constituting the electrode from a wet method such as a printing method, a coating method, a physical method such as a vacuum deposition method, a sputtering method, or an ion plating method, or a chemical method such as CVD or plasma CVD method.
  • the film can be formed on the substrate according to an appropriately selected method.
  • ITO is selected as the anode material
  • it can be formed according to a direct current or high frequency sputtering method, a vacuum deposition method, an ion plating method, or the like.
  • a metal or the like is selected as the cathode material, one or more of them can be formed simultaneously or sequentially according to a sputtering method or the like.
  • patterning when forming the electrode, it may be performed by chemical etching such as photolithography, or may be performed by physical etching using a laser or the like. It may be performed by sputtering or the like, or may be performed by a lift-off method or a printing method.
  • the organic layer consisting of an organic material alone, or the inorganic layer consisting of an inorganic material may be single, but the organic layer consisting of an organic material And a multilayer structure in which an inorganic layer made of an inorganic material is laminated.
  • the inorganic materials for example SiNx, SiON, SiO 2, Al 2 O 3, etc. TiO 2 and the like.
  • the organic material include a silicone polymer, an epoxy polymer, an acrylic polymer, and a urethane polymer.
  • the refractive index of the barrier layer (in the case of a multilayer structure, the average refractive index) is preferably 1.7 or more, and more preferably 1.8 to 2.2.
  • the refractive index of the barrier layer is less than 1.7, the total reflection of light from the organic electroluminescent layer increases at the interface between the transparent electrode and the barrier layer, and the light extraction efficiency may decrease.
  • the light transmittance is preferably 80% or more, more preferably 85% or more, and still more preferably 90% or more.
  • the average thickness of the barrier layer is not particularly limited and may be appropriately selected depending on the intended purpose, but is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m, and still more preferably 0.2 ⁇ m to 3 ⁇ m. .
  • the sealing function for preventing the permeation of oxygen and moisture in the atmosphere may be insufficient, and when it exceeds 10 ⁇ m, the light transmittance decreases.
  • transparency is impaired, and when an inorganic material is used in a single layer, barrier properties such as cracking due to a stress difference and separation from an adjacent layer may be impaired.
  • the sealing can has a size, shape, structure, etc. that can enclose a laminate composed of the transparent electrode, the reflective electrode, the organic electroluminescent layer, the planarizing layer, and the light diffusion layer. If there is no restriction
  • a water absorbent or an inert liquid is sealed in a space between the sealing can and the transparent electrode, the reflective electrode, the organic electroluminescent layer, the planarizing layer, and the light diffusing layer. May be.
  • the moisture absorbent is not particularly limited and may be appropriately selected depending on the purpose.
  • barium oxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate, calcium sulfate, magnesium sulfate, phosphorus pentoxide examples thereof include calcium chloride, magnesium chloride, copper chloride, cesium fluoride, niobium fluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite, and magnesium oxide.
  • the inert liquid is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include paraffins, liquid paraffins; fluorinated solvents such as perfluoroalkane, perfluoroamine, and perfluoroether; chlorine System solvents, silicone oils and the like.
  • the organic electroluminescent device can be configured as a device capable of displaying in full color.
  • the three primary colors blue (B)
  • a three-color light emission method in which a layer structure that emits light corresponding to green (G) and red (R) is arranged on a substrate, a white light that divides white light emission by a layer structure for white light emission into three primary colors through a color filter layer
  • a color conversion method in which blue light emission by a layer structure for blue light emission is converted into red (R) and green (G) through a fluorescent dye layer are known.
  • a planar light source having a desired emission color can be obtained by using a combination of a plurality of layer structures having different emission colors obtained by the above method.
  • a white light-emitting light source that combines blue and yellow light-emitting devices a white light-emitting light source that combines blue (B), green (G), and red (R) organic electroluminescent devices.
  • the organic electroluminescent device is, for example, a lighting device, a computer, an on-vehicle display, an outdoor display, a home device, a business device, a home appliance, a traffic display, a clock display, a calendar display, a luminescence. It can be suitably used in various fields including cent screens, audio equipment and the like.
  • the average thickness of the light diffusing layer, the planarizing layer, and the conductive layer can be determined by cutting out a part of each layer and measuring with a scanning electron microscope (S-3400N, manufactured by Hitachi High-Tech Co., Ltd.).
  • the refractive index of the binder constituting the light diffusing layer and the planarizing layer is such that the binder is formed on a Si substrate or a quartz substrate to a thickness of about the wavelength of light, and the binder on the formed substrate is an ellipsometer. Can be used to measure the refractive index.
  • the refractive index of the conductive matrix of the conductive layer can be similarly determined.
  • Titanium oxide dispersion coated with alumina and zirconia on the surface "dispersion of titanium oxide nanoparticles with an average diameter of 15 nm, refractive index 2.45)
  • "Material name: Titanium oxide dispersed toluene, trade name: Highly transparent titanium oxide slurry HTD With respect to “ ⁇ 760T” the presence or absence of photocatalytic activity was measured as follows. As a result, it was found that the photocatalytic activity was suppressed and it was equivalent to zirconium oxide particles having no photocatalytic effect.
  • the photocatalytic activity is measured using a known “methylene blue method” as a general method.
  • the "methylene blue method” is a photocatalyst by placing a methylene blue aqueous solution in a quartz tube, doping each particle into it, measuring the transmittance before light irradiation, irradiating with light, and confirming the change in the transmittance of the methylene blue aqueous solution. Activity was measured quantitatively.
  • planarization layer forming material 1- Titanium oxide dispersion coated with alumina and zirconia on the surface (dispersion of titanium oxide fine particles with an average diameter of 15 nm, refractive index 2.45) "Material name: Titanium oxide dispersed toluene, trade name: Highly transparent titanium oxide slurry HTD-760T , Manufactured by Teika Co., Ltd.), resin material “Material name: Fluorene derivative (acrylate), trade name: Ogsol EA-0200, Osaka Gas Chemical Co., Ltd.” (hereinafter also referred to as “binder”), toluene with a roller and a stirrer.
  • Biner toluene with a roller and a stirrer.
  • the mixture was dissolved by stirring, and the nanoparticles were sufficiently dispersed in the binder by ultrasonic waves (sonifier).
  • the volume ratio of the titanium oxide particles and the resin material was 25:75.
  • a titanium oxide dispersed binder coating solution 1 was obtained.
  • a polymerization initiator (IRGACURE819, manufactured by BASF) was added to obtain a planarization layer forming material 1.
  • the titanium oxide-dispersed binder coating solution 1 has a refractive index of 1.8 after curing and a refractive index of light diffusing particles of 1.49. Therefore, the refractive index difference is sufficiently large, and even a thin film can diffuse sufficiently for light extraction. Obtainable.
  • the resin particles since toluene is used as a solvent, the resin particles must have sufficient solvent resistance, but in this respect, the combination of this material is resistant to the solvent and is very excellent in dispersion deterioration (aggregation, etc.) due to aging. ing.
  • the glass substrate was subjected to silane coupling treatment to improve the adhesion between the light diffusion layer and the glass.
  • the light diffusion layer forming material 1 was applied to a glass substrate that had been cleaned and surface-treated using a wire bar, and then cured by UV irradiation (365 nm) for 10 minutes to form a light diffusion layer (film thickness 5 ⁇ m, refraction) Rate 1.76).
  • planarization layer forming material 1 was applied onto the light diffusion layer using a wire bar, and cured by UV irradiation to form a planarization layer (film thickness 6 ⁇ m, refractive index 1.76).
  • auxiliary wiring After the planarization layer was formed, it was washed and dried, and an aluminum film having a thickness of 100 nm was formed as an auxiliary wiring with a vacuum vapor deposition machine, and formed into an auxiliary wiring shape by a photolithography process.
  • the cross-sectional shape of the auxiliary wiring obtained by the photolithography process was a square.
  • the width of the auxiliary wiring was 100 ⁇ m.
  • the conductive layer coating solution 1 was applied by spin coating so as to have a thickness of 0.3 ⁇ m, and baked at 120 ° C. for 60 minutes (refractive index: 1.76).
  • organic layer organic EL layer
  • cathode a cathode
  • ⁇ -NPD Bis [N- (1-naphthyl) -N-phenyl] benzidine
  • mCP 1,3-Bis (carbazol-9-yl) benzene) (60 mass%) and a light emitting material A (40 mass%) were co-evaporated to 30 nm to form a light emitting layer.
  • the organic electroluminescent device 20 has an organic layer 4 and an electrode 5 on the conductive layer 3 of the laminate 10 and is sealed with a sealing can 6.
  • the size of the light emitting surface of the organic electroluminescent device was 100 ⁇ 100 mm.
  • Example 2 An organic electroluminescent device of Example 2 was fabricated in the same manner as in Example 1 except that the film thickness of the conductive layer was changed to 1 ⁇ m and the film thickness of the auxiliary wiring was changed to 200 nm.
  • a schematic diagram showing the configuration of the organic electroluminescent device of Example 2 is the same as FIG.
  • Example 3 An organic electroluminescent device of Example 3 was produced in the same manner as in Example 2 except that the auxiliary wiring was produced not by a photolithography process but by a manufacturing method using the following mask. A schematic diagram showing the configuration of the organic electroluminescent device of Example 3 is shown in FIG.
  • Example 4 An organic electroluminescent device of Example 4 was produced in the same manner as in Example 3 except that the titanium oxide particles used for the light diffusion layer, the planarization layer, and the conductive layer were replaced with zirconia particles. Specifically, a light diffusion layer, a planarization layer, and a conductive layer were produced as follows. A schematic diagram showing the configuration of the organic electroluminescent device of Example 4 is shown in FIG.
  • planarization layer forming material 2- Stir zirconia (ZrO x ) particles (average diameter 20 nm, refractive index 2.0), resin material “material name: fluorene derivative (acrylate), trade name: Ogsol EA-0200” and toluene with a roller and a stirrer. After dissolving, the nanoparticles were sufficiently dispersed in the binder by ultrasonic waves (sonifier). The volume ratio of the zirconia (ZrO x ) particles and the resin material was 30:70. In this way, a zirconia dispersed binder coating solution 1 was obtained. Finally, a polymerization initiator (IRGACURE819, manufactured by BASF) was added to obtain a planarization layer forming material 2.
  • IRGACURE819 manufactured by BASF
  • the zirconia-dispersed binder coating solution 1 was doped with light diffusing particles (cross-linked acrylic particles having an average diameter of 1.5 ⁇ m, refractive index 1.49) “Material name: EX-150” and toluene with stirring.
  • the volume ratio of the solid content of the zirconia-dispersed binder coating liquid 1 and the light diffusing particles was 50:50.
  • the light diffusing particles were sufficiently dispersed on the substrate with ultrasonic waves (sonifier), and further stirred well with a stirrer or the like.
  • a polymerization initiator (IRGACURE 819, manufactured by BASF) was added to the diffusion layer coating material to obtain a light diffusion layer forming material 2.
  • the refractive index of the zirconia-dispersed binder coating liquid 1 after curing is 1.75 and the refractive index of the light diffusing particles is 1.49, the refractive index difference is sufficiently large, and even a thin film can obtain sufficient diffusion for light extraction. be able to.
  • the light diffusion layer forming material 2 was applied to the cleaned and surface-treated glass substrate using a wire bar, and then cured by UV irradiation (365 nm) for 10 minutes to form a light diffusion layer (film thickness 5 ⁇ m, refraction) Rate 1.75).
  • planarization layer forming material 2 was applied onto the light diffusion layer using a wire bar, and cured by UV irradiation to obtain a light diffusion layer / planarization layer stack (film thickness 6 ⁇ m, refractive index 1.75). ).
  • Poly (3,4-ethylenedioxythiophene) -poly (styrenesulfonic acid) (PEDOT-PSS) serving as a conductive matrix is doped with zirconia (ZrO x ) particles (average diameter 20 nm, refractive index 2.0), It was well dispersed using an omni mixer to obtain a conductive layer coating solution 2.
  • the conductive layer coating solution 2 was applied by spin coating so as to have a thickness of 1 ⁇ m, and baked at 120 ° C. for 60 minutes (refractive index: 1.76).
  • Example 5 The organic electric field of Example 5 was the same as Example 3 except that the light diffusion layer, planarization layer, auxiliary wiring, conductive layer, organic EL layer, and cathode were formed so as to fit in the sealing can. A light emitting device was manufactured. A schematic diagram showing the configuration of the organic electroluminescent device of Example 5 is shown in FIG.
  • Example 6 In the light diffusion layer forming material 1, the solid volume of the titanium oxide dispersed binder coating solution 1 and the volume ratio of the light diffusion particles are changed to 70:30, the film thickness of the light diffusion layer is 7 ⁇ m, and no planarization layer is provided.
  • the organic electric field of Example 6 was the same as Example 3 except that auxiliary wiring, a conductive layer, an organic EL layer, and a cathode were provided on the light diffusion layer, and the film thickness of the conductive layer was changed to 5 ⁇ m.
  • a light emitting device was manufactured.
  • a schematic diagram showing the configuration of the organic electroluminescent device of Example 6 is shown in FIG.
  • Example 7 An organic electroluminescent device of Example 7 was produced in the same manner as Example 3 except that the cathode material was replaced with silver. A schematic diagram showing the configuration of the organic electroluminescent device of Example 7 is shown in FIG.
  • Example 1 In the same manner as in Example 1, a glass substrate / light diffusion layer / flattening layer was prepared, washed, and dried, and then 100 nm of ITO (Indium Tin Oxide) was formed on the flattening layer using a sputtering apparatus. An organic EL layer and a cathode were provided on ITO in the same manner as in Example 1 and sealed to produce an organic electroluminescent device of Comparative Example 1.
  • the schematic diagram showing the structure of the organic electroluminescent apparatus of the comparative example 1 was described in FIG. 9 (the electrode 9 is ITO).
  • Comparative Example 2 An organic electroluminescent device of Comparative Example 2 was produced in the same manner as in Example 2 except that the light diffusion layer and the planarizing layer were not provided.
  • the surface-treated glass substrate is washed and dried, and auxiliary wiring is provided by a photolithography process, and thereafter a conductive layer, an organic EL layer, and a cathode are provided in the same manner as in Example 2.
  • a schematic diagram showing the configuration of the organic electroluminescent device of Comparative Example 2 is shown in FIG.
  • Comparative Example 3 Similar to Comparative Example 1, a laminate having a configuration of glass substrate / light diffusion layer / flattening layer / ITO was produced. An auxiliary wiring was provided on the ITO by a photolithography process in the same manner as in Example 2, and an organic EL layer and a cathode were provided on the auxiliary wiring in the same manner as in Example 2 to produce an organic electroluminescent device of Comparative Example 3. A schematic diagram showing the configuration of the organic electroluminescent device of Comparative Example 3 is shown in FIG.
  • Comparative Example 4 An organic electroluminescent device of Comparative Example 4 was produced in the same manner as in Example 2 except that the titanium oxide particles were not added in the conductive layer coating solution 1.
  • a schematic diagram showing the configuration of the organic electroluminescent device of Comparative Example 4 is shown in FIG. 12 (3r represents a conductive layer containing no high refractive index particles).
  • Comparative Example 5 Similar to Comparative Example 1, a laminate having a configuration of glass substrate / light diffusion layer / flattening layer / ITO was produced. An auxiliary wiring was provided on the ITO by a photolithography process in the same manner as in Example 2, and the auxiliary wiring was protected with a resist film. An organic electroluminescent device of Comparative Example 5 was produced by providing an organic EL layer and a cathode in the same manner as in Example 2 except that the thickness of the hole injection layer was set to 500 nm on the auxiliary wiring. A schematic diagram showing the structure of the organic electroluminescent device of Comparative Example 5 is shown in FIG.
  • Comparative Example 0 An organic electroluminescent device of Comparative Example 0 was produced in the same manner as Comparative Example 5 except that the light diffusion layer and the planarizing layer were not provided. A schematic diagram showing the configuration of the organic electroluminescent device of Comparative Example 0 is shown in FIG. As will be described later, the light extraction efficiency of other organic electroluminescent devices was evaluated using Comparative Example 0 as a reference.
  • the produced organic electroluminescence device was evaluated for light extraction efficiency and light emission (luminance) unevenness as follows.
  • Examples 1 to 7 all had high light extraction efficiency and suppressed light emission unevenness.
  • Example 6 it was found that the organic electroluminescence device of the present invention had high light extraction efficiency and suppressed light emission unevenness even without a planarizing layer.
  • Example 3 it was found that the light extraction efficiency was further improved by the roundness of the cross section of the auxiliary wiring.
  • the organic electroluminescent device using the ITO of Comparative Example 1 as a transparent electrode and not provided with an auxiliary wiring had lower light extraction efficiency than that of the example, and light emission unevenness was large. Since Comparative Example 2 did not have a light diffusion layer, the light extraction efficiency was low.
  • Comparative Example 3 a voltage was applied to the element to try to emit light, but it did not light up due to leakage from the auxiliary wiring.
  • Comparative Example 4 since the conductive layer did not contain high refractive index particles, the light from the light emitting layer was totally reflected, and the light extraction efficiency was low.
  • Comparative Example 5 the auxiliary wiring is protected with a resist film and the organic layer is thickened to prevent leakage. However, light from the light emitting layer is easily absorbed and blocked by these factors, and the light extraction efficiency is improved. This is considered to be lower than the example.
  • the laminate of the present invention can be easily formed on an uneven surface, the film forming process is simple, and it can be produced at low cost. Moreover, the organic electroluminescent device of the present invention can obtain excellent light extraction efficiency.
  • the light diffusing layer forming material, the light extraction member, and the organic electroluminescence device of the present invention are, for example, various types of lighting, a computer, an on-vehicle display, an outdoor display, a household device, a commercial device, a household appliance, and a traffic relationship. It can be suitably used in various fields including a display device, a clock display device, a calendar display device, a luminescent screen, and an acoustic device.

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  • Electroluminescent Light Sources (AREA)

Abstract

L'invention concerne la production d'une pellicule possédant une électrode transparente, qui peut être formée facilement sur une surface ondulée et qui est avantageuse du point de vue du coût puisqu'on l'on peut lui appliquer un procédé de formation de film simple et facile à mettre en œuvre ; et la production d'un dispositif électroluminescent organique qui comprend la pellicule et qui est excellent du point de vue de l'efficacité de l'extraction de la lumière. L'invention concerne une pellicule qui comprend successivement au moins un substrat transparent, une couche de diffusion de lumière et une couche conductrice photo-émettrice, dans cet ordre. La couche conductrice contient une matrice conductrice et des particules qui ont un indice de réfraction supérieur à celui de la matrice conductrice.
PCT/JP2012/079526 2011-11-29 2012-11-14 Pellicule et dispositif électroluminescent organique WO2013080799A1 (fr)

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JP2011-260899 2011-11-29
JP2011260899A JP5898933B2 (ja) 2011-11-29 2011-11-29 積層体、及び有機電界発光装置

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JP2017107707A (ja) * 2015-12-09 2017-06-15 コニカミノルタ株式会社 透明電極、及び、有機電子デバイス
KR102152159B1 (ko) * 2016-06-14 2020-09-04 코니카 미놀타 가부시키가이샤 투명 도전 부재 및 유기 일렉트로 루미네센스 소자
KR102601451B1 (ko) * 2016-09-30 2023-11-13 엘지디스플레이 주식회사 전극 및 이를 포함하는 유기발광소자, 액정표시장치 및 유기발광표시장치
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