WO2018135656A1 - Composition pour former une couche électroluminescente et élément électroluminescent organique contenant ladite composition pour former une couche électroluminescente - Google Patents

Composition pour former une couche électroluminescente et élément électroluminescent organique contenant ladite composition pour former une couche électroluminescente Download PDF

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WO2018135656A1
WO2018135656A1 PCT/JP2018/001764 JP2018001764W WO2018135656A1 WO 2018135656 A1 WO2018135656 A1 WO 2018135656A1 JP 2018001764 W JP2018001764 W JP 2018001764W WO 2018135656 A1 WO2018135656 A1 WO 2018135656A1
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compound
light emitting
emitting layer
composition
forming
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PCT/JP2018/001764
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English (en)
Japanese (ja)
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逸美 西尾
石橋　孝一
良子 梶山
大輔 弘
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三菱ケミカル株式会社
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Priority to CN201880007700.XA priority Critical patent/CN110235265B/zh
Priority to KR1020197019714A priority patent/KR102544020B1/ko
Priority to JP2018562476A priority patent/JP6950710B2/ja
Publication of WO2018135656A1 publication Critical patent/WO2018135656A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/10—Organic polymers or oligomers
    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
    • 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
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole

Definitions

  • the present invention relates to a composition for forming a light emitting layer and an organic electroluminescent device containing the composition for forming a light emitting layer.
  • organic electroluminescent elements can emit light in various colors with a simple element configuration, in recent years, they have been actively developed as a technique for manufacturing light emitting devices such as displays and lighting.
  • the organic electroluminescence device obtains light emission by injecting holes and electrons from an anode and a cathode, allowing each charge to reach the light emitting layer, and recombining the charge in this light emitting layer. From this principle, it is possible to improve luminous efficiency by forming a light emitting layer using a composition for forming a light emitting layer containing not only a light emitting material but also a charge transport material, and retaining charges in the light emitting layer. It has been studied (see Patent Document 1).
  • retaining the charge in the light emitting layer deteriorates the current-voltage characteristics of the organic electroluminescent element.
  • it is generally performed by a method of retaining a charge by creating a charge trap level in the film. According to these methods, it is possible to increase the light emission efficiency by retaining the charge in the light emitting layer, but at the same time, the current-voltage characteristics are deteriorated, that is, the driving voltage of the organic electroluminescent element is increased. Since the power consumption increases as the driving voltage increases, for example, a technique for reducing the driving voltage by setting the total number of charge transport materials contained in the composition for forming a light emitting layer to three or more has been proposed. (See Patent Document 2). However, when the number of types of charge transport materials is increased, there are still insufficient studies on methods for improving the driving life, which is an important characteristic of organic electroluminescent devices, and methods for maintaining storage stability at high temperatures. it is conceivable that.
  • An object of the present invention is to provide an organic electroluminescence device having a long driving life and excellent storage stability, and an object thereof is to provide a composition for forming a light emitting layer suitable for the organic electroluminescence device.
  • a driving life is obtained by using a compound having a glass transition temperature higher than a predetermined temperature and a compound lower than the predetermined temperature for the composition for forming a light emitting layer. It has been found that an organic electroluminescent element is obtained that is long and has a drive life that does not easily decrease even after high-temperature storage.
  • the present invention has been achieved based on such findings, and the gist thereof is as follows.
  • a composition for forming a light-emitting layer of an organic electroluminescent device comprising a light-emitting material, a non-light-emitting material, and an organic solvent, the non-light-emitting material comprising a high Tg compound and glass having a glass transition temperature of 130 ° C. or higher
  • a low Tg compound having a transition temperature of 100 ° C. or lower the content of the low Tg compound in all the non-light emitting materials is 8 to 70% by mass, and at least one of the non-light emitting materials is a pyrimidine skeleton or
  • a composition for forming a light emitting layer which is a material having a triazine skeleton.
  • the molecular weight of all the non-light emitting materials whose content is 1.0% by mass or more with respect to the total amount of all the non-light emitting materials contained in the composition for forming a light emitting layer is 5000 or less.
  • R 1 to R 15 each independently represents a monovalent compound in which a hydrogen atom or a phenyl group or aromatic hydrocarbon monocyclic compound having 6 to 30 carbon atoms is bonded.
  • R 1 to R 15 each independently represents a monovalent compound in which a hydrogen atom or a phenyl group or aromatic hydrocarbon monocyclic compound having 6 to 30 carbon atoms is bonded.
  • An organic electroluminescence device having a light-emitting layer wet-formed using the composition for forming a light-emitting layer according to any one of [1] to [8].
  • an organic electroluminescent element having a long driving life and high luminous efficiency can be obtained after storage at high temperature.
  • FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of an organic electroluminescent element of the present invention.
  • FIG. 2 is a schematic cross-sectional view showing another example of the embodiment of the organic electroluminescent element of the present invention.
  • composition for forming a light emitting layer is used for forming a light-emitting layer of an organic electroluminescence device, and includes a light-emitting material, a non-light-emitting material, and an organic solvent.
  • Tg includes a high Tg compound having a temperature of 130 ° C. or higher and a low Tg compound having a Tg of 100 ° C. or lower.
  • Luminescent material As the light-emitting material, any known material that is usually used as a light-emitting material of an organic electroluminescent element can be applied, and there is no particular limitation. Light is emitted at a desired light emission wavelength, and the light emission efficiency is good. A substance may be used.
  • the light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, but is preferably a phosphorescent light emitting material from the viewpoint of internal quantum efficiency and low heat generation.
  • a long-period type periodic table (hereinafter, unless otherwise specified, the term “periodic table” refers to a long-period type periodic table) selected from Group 7 to 11 Wellner type complexes or organometallic complexes containing the above metal as the central metal.
  • Preferred examples of the metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold.
  • the metal selected from Groups 7 to 11 of the periodic table iridium and platinum are more preferable.
  • an aryl group such as an arylpyridine ligand, a heteroarylpyridine ligand, an arylpyrazole ligand, a heteroarylpyrazole ligand, or a heteroaryl group such as pyridine, pyrazole, or phenanthroline And the like, and a phenylpyridine ligand and a phenylpyrazole ligand are particularly preferable.
  • phosphorescent materials include tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, tris (2- Phenylpyridine) osmium, tris (2-phenylpyridine) rhenium, octaethylplatinum porphyrin, octaphenylplatinum porphyrin, octaethyl palladium porphyrin, octaphenyl palladium porphyrin, and the like.
  • the organometallic complex of the phosphorescent material is preferably a compound represented by the following formula (I).
  • ML (q ⁇ j) L ′ j (I) M represents a metal, q represents a valence of the metal, L and L ′ represent a bidentate ligand, and j represents a number of 0, 1 or 2.
  • M represents any metal. Specific examples of preferable M include the metals described above as the metal selected from Groups 7 to 11 of the periodic table.
  • bidentate ligand L represents a ligand having the following partial structure.
  • ring A1 represents an aromatic ring group which may have a substituent.
  • the aromatic ring group in the present invention may be an aromatic hydrocarbon group or an aromatic heterocyclic group.
  • ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent.
  • examples of the bidentate ligand L ′ include the ligands shown below.
  • the organometallic complex of the phosphorescent material in the present invention from the viewpoint of easily interacting with the non-light emitting material coexisting in the light emitting layer, the above formula having a bidentate ligand having a relatively three-dimensional and bulky molecule ( The compounds represented by I) are preferred. Further, for example, a fluorescent material and a phosphorescent material may be used in combination such that a fluorescent material is used for blue and a phosphorescent material is used for green and red.
  • the symmetry and rigidity of the molecules of the light emitting material are reduced.
  • the molecular weight of the luminescent material in the present invention is preferably 5000 or less, more preferably 4000 or less, and particularly preferably 3000 or less. Further, the molecular weight of the light emitting material in the present invention is usually 400 or more, preferably 600 or more, more preferably 800 or more, and particularly preferably 1000 or more. With this molecular weight range, it is considered that the light-emitting materials can be uniformly mixed with the non-light-emitting material without aggregating the light-emitting materials, and a light-emitting layer with high light emission efficiency can be obtained.
  • the molecular weight of the luminescent material is high in Tg, melting point, decomposition temperature, etc., excellent in heat resistance of the luminescent material and the formed luminescent layer, and film quality deterioration due to gas generation, recrystallization, molecular migration, etc. In view of the fact that the increase in the impurity concentration accompanying the thermal decomposition of the material or the like hardly occurs, it is preferable.
  • the molecular weight of the light-emitting material is preferably small in that the organic compound can be easily purified and easily dissolved in a solvent.
  • the non-light emitting material in the present invention refers to all nonvolatile materials other than the light emitting material.
  • the non-volatile material is a material other than the organic solvent in the composition for forming a light emitting layer, and means a material included in the light emitting layer when the light emitting layer is formed.
  • the non-light emitting material includes at least a high Tg compound and a low Tg compound, which will be described later, but may include materials other than these.
  • At least one of the non-light emitting materials is a material having a pyrimidine skeleton or a triazine skeleton, and at least one of the high Tg compound and the low Tg compound described later.
  • One of the materials is preferably a material having a pyrimidine skeleton or a triazine skeleton.
  • any of the non-light-emitting materials is a material having a triazine skeleton, and it is particularly preferable that at least one of a high Tg compound or a low Tg compound described later is a material having a triazine skeleton.
  • the low Tg compound is a material having a triazine skeleton.
  • the molecular weight of all the non-light-emitting materials having a content ratio of 1.0% by mass or more with respect to the total amount of all the non-light-emitting materials contained in the composition for forming a light-emitting layer It is preferably 5000 or less, more preferably 4000 or less, particularly preferably 3000 or less, most preferably 2000 or less, usually 300 or more, preferably 350 or more, and more preferably 400 or more.
  • the high Tg compound of the present invention is a compound having a Tg of 130 ° C. or higher.
  • a compound having a Tg of 130 ° C. or higher may be appropriately selected from the compounds usually used for forming the light emitting layer of the organic electroluminescent device.
  • the high Tg compound is usually contained in the light emitting layer. It is preferable that the charge transport material be
  • the compound having a Tg of 130 ° C. or higher is preferably a compound that bonds a condensed ring structure of three or more rings to a central skeleton excellent in charge transportability.
  • a compound having two or more condensed ring structures having three or more rings and / or a compound having at least one condensed ring having five or more rings is preferable.
  • the rigidity of the molecule is increased, and the effect of suppressing the degree of molecular motion in response to heat is easily obtained.
  • central skeleton with excellent charge transportability examples include aromatic structures, aromatic amine structures, triarylamine structures, dibenzofuran structures, naphthalene structures, phenanthrene structures, phthalocyanine structures, porphyrin structures, thiophene structures, and benzylphenyl structures.
  • the high Tg compound in the present invention is preferably a material having a structure excellent in electron transporting property in that the light emitting material itself can suppress deterioration of the light emitting material due to transport of electrons and extend the driving life.
  • a compound having a structure excellent in hole transportability is also preferable, and among the central skeleton excellent in charge transportability, a carbazole structure, dibenzofuran structure, triarylamine structure, naphthalene structure, phenanthrene structure or pyrene structure is a hole.
  • a structure excellent in transportability is preferable, and a carbazole structure, a dibenzofuran structure, or a triarylamine structure is more preferable.
  • the high Tg compound in the present invention is a material having a structure excellent in hole transportability in that the light emitting material itself can suppress the deterioration of the light emitting material due to transporting holes and can extend the driving life.
  • the high Tg compound of the present invention preferably has a condensed ring structure of 3 or more rings, and / or at least one compound having 2 or more condensed ring structures of 3 or more rings and / or 5 or more condensed rings. More preferably, it is a compound which has.
  • condensed ring structure having three or more rings examples include anthracene structure, phenanthrene structure, pyrene structure, chrysene structure, naphthacene structure, triphenylene structure, fluorene structure, benzofluorene structure, indenofluorene structure, indolofluorene structure, Examples thereof include a carbazole structure, an indenocarbazole structure, an indolocarbazole structure, a dibenzofuran structure, and a dibenzothiophene structure.
  • a carbazole structure or an indolocarbazole structure is more preferable from the viewpoint of durability against electric charges.
  • the molecular weight of the high Tg compound in the present invention is usually 5000 or less, preferably 4000 or less, more preferably 3000 or less, and most preferably 2000 or less. Further, the molecular weight of the high Tg compound in the present invention is usually 300 or more, preferably 350 or more, and more preferably 400 or more.
  • the molecular weight of the high Tg compound is preferably large from the viewpoint that film quality deterioration due to gas generation, recrystallization, molecular migration or the like hardly occurs. On the other hand, the molecular weight of the high Tg compound is preferably small in view of easy purification of the organic compound and easy dissolution in a solvent.
  • the Tg of the high Tg compound in the present invention is arbitrary as long as the effect of the present invention is not significantly impaired as long as it is 130 ° C. or higher.
  • the Tg of the high Tg compound in the present invention is preferably 135 ° C. or higher, more preferably 140 ° C. or higher, since the film during high temperature storage is stable.
  • the Tg of the high Tg compound in the present invention is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 180 ° C. or lower, and still more preferably 160 ° C. or lower because of its high solubility in organic solvents.
  • the temperature inside the vehicle may exceed 80 ° C. when the vehicle is parked under the hot summer sun. Reliability is required. Therefore, a general high-temperature storage test of an organic electroluminescent element is usually performed at 100 ° C. or higher, and at most about 120 ° C.
  • changes in film properties and morphology near Tg actually occur gradually before and after Tg. From the above, the Tg of the high Tg compound in the present invention is 130 ° C. or higher, which is a sufficiently higher temperature than the storage test.
  • the composition for forming a light emitting layer of the present invention may contain at least one high Tg compound, but may contain a plurality of high Tg compounds.
  • the low Tg compound of the present invention is a compound having a Tg of 100 ° C. or lower.
  • the low Tg compound is preferably a compound in which monocyclic compounds are bonded via a direct bond and / or a linking group.
  • the compound may have a substituent, and the substituent is not particularly limited, but an alkyl group or an aralkyl group is preferable from the viewpoint of excellent solubility and ink storage stability.
  • the linking group is not particularly limited as long as it is an atom or a substituent that is usually used as a material for an organic electroluminescent device.
  • linking group means that the monocyclic compound is bonded to all bonds.
  • These linking groups may link monocyclic compounds to each other, or may link compounds in which monocyclic compounds are bonded via a direct bond. Further, the monocyclic compounds to be linked at this time, or the compounds in which the monocyclic compounds are bonded via a direct bond may have the same structure or different structures.
  • a nitrogen atom is a linking group and a compound in which monocyclic compounds are bonded via a direct bond is an aryl group, it means a triarylamine, and the three substituents of the triarylamine are the same. Or different.
  • the linking group is more preferably a nitrogen atom or an alkylene group from the viewpoint that the twist of the adjacent ring is larger, the planarity of the molecule is low, and crystallization due to molecular packing is difficult to cause. Further, from the viewpoint of durability against electric charges, a compound consisting of only a direct bond is more preferable.
  • a compound satisfying the above conditions may be appropriately selected from the compounds usually used for forming the light emitting layer of the organic electroluminescence device.
  • a monocyclic compound may be used as the low Tg material.
  • Aromatic hydrocarbon monocyclic compounds are bonded to each other through a direct bond and / or a linking group, and a compound having an aromatic structure, an aromatic amine structure or a benzylphenyl structure is more excellent in charge transporting properties. It is further preferable.
  • a compound in which monocyclic compounds are bonded via a direct bond and / or a linking group is preferable in that the planarity as a molecule is low and crystallization due to molecular packing is unlikely to occur.
  • a compound in which aromatic hydrocarbon monocyclic compounds are bonded via a direct bond and / or a linking group is advantageous in that the influence of hydrogen bond is small and the rotation of the bond is easy to be placed and the planarity of the molecule can be further lowered. More preferred.
  • the low Tg compound contained in the composition for forming a light emitting layer of the present invention comprises only a compound in which aromatic hydrocarbon monocyclic compounds are directly bonded to each other in terms of excellent durability against electric charges.
  • a compound represented by the following formula (A) is preferable as a low Tg compound in which aromatic hydrocarbon monocyclic compounds are directly bonded to each other.
  • R 1 to R 15 each independently represents a monovalent compound in which a hydrogen atom or a phenyl group or an aromatic hydrocarbon monocyclic compound having 6 to 30 carbon atoms is bonded.
  • the low Tg compound having the structure of the formula (A) has a high durability against electric charges, and is a structure that can easily achieve both molecular motion and stability due to heat and the like.
  • the structure of Formula (A) is a compound in which only a single ring of an aromatic hydrocarbon is bonded, it is preferable to easily fill a gap between high Tg compounds.
  • the structure of the formula (A) is preferable when the high Tg compound has a condensed ring structure having 3 or more rings or a condensed ring structure having 5 or more rings, because the gap between the high Tg compounds generated by the condensed ring is easily filled. Further, the structure of the formula (A) has a high affinity with the formula (A) which is an aromatic hydrocarbon compound when the condensed ring contains an aromatic hydrocarbon ring or an aromatic heterocycle, and a high Tg compound. The state in which the gaps between them are filled is considered to be more stable, which is preferable.
  • a preferable low Tg compound in the present invention is a compound in which monocyclic compounds are bonded through a direct bond and / or a linking group.
  • pyridine-based compounds, pyrimidine-based compounds, triazine-based compounds and the like which are materials having excellent electron transport properties and relatively stable structures, are preferable.
  • the light emitting material itself can suppress deterioration of the light emitting material due to transport of electrons, thereby extending the driving life.
  • the low Tg compound in the present invention is a material having an excellent electron transporting property and a relatively stable structure in that the light emitting material itself can suppress deterioration of the light emitting material due to transport of electrons and can extend the driving life.
  • the low Tg compound in the present invention is a material having a structure excellent in hole transportability in that the light emitting material itself can suppress the deterioration of the light emitting material due to transporting holes and can extend the driving life. It is preferable.
  • a dicycloalkylarylamine structure, a cycloalkyldiarylamine structure, and a triarylamine structure are preferable.
  • a triarylamine structure is more preferable from the viewpoint of durability.
  • the molecular weight of the low Tg compound in the present invention is usually 5000 or less, preferably 4000 or less, more preferably 3000 or less, and most preferably 2000 or less. Further, the molecular weight of the low Tg compound in the present invention is usually 300 or more, preferably 350 or more, more preferably 400 or more.
  • the molecular weight of the low Tg compound is preferably large in that it is difficult for the film quality to deteriorate due to gas generation, recrystallization, molecular migration, or the like.
  • the molecular weight of the low Tg compound is preferably small in that the organic compound can be easily purified and easily dissolved in a solvent.
  • the Tg of the low Tg compound in the present invention is arbitrary as long as the effect of the present invention is not significantly impaired as long as it is 100 ° C. or lower.
  • the Tg of the low Tg compound in the present invention is preferably 95 ° C. or lower, more preferably 90 ° C. or lower.
  • the Tg of the low Tg compound in the present invention is usually 60 ° C. or higher, preferably 70 ° C. or higher, more preferably 80 ° C. or higher, and still more preferably 85 ° C. or higher.
  • the Tg of the low Tg compound in the present invention is preferably low from the viewpoint of solubility in a solvent and device stability due to suppression of crystallization in the film.
  • the Tg of the low Tg compound is preferably high from the viewpoint of ensuring non-volatility, thermal stability in element fabrication process and element storage.
  • the composition for forming a light emitting layer of the present invention may contain at least one kind of low Tg compound, but may contain a plurality of low Tg compounds.
  • the composition for forming a light emitting layer of the present invention is preferably formed as a light emitting layer by using a wet film forming method such as an ink jet method.
  • the organic solvent used in the present invention is not particularly limited as long as the light emitting layer material such as the light emitting material and the non-light emitting material can be dissolved or dispersed well.
  • the solubility of the organic solvent is usually 0.01% by mass or more, preferably 0.05% by mass or more, and more preferably 0.1% by mass of the luminescent material and the non-luminescent material, respectively, at 25 ° C. and 1 atm. It is preferable to dissolve by mass% or more.
  • an organic solvent is not limited to these.
  • organic solvent examples include alkanes such as n-decane, cyclohexane, ethylcyclohexane, decalin, and bicyclohexane; aromatic hydrocarbons such as toluene, xylene, methicylene, cyclohexylbenzene, tetramethylcyclohexanone, and tetralin; Halogenated aromatic hydrocarbons such as chlorobenzene and trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3 -Aromatic ethers such as dimethylanisole, 2,4-dimethylanisole, diphenyl ether; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, ethy
  • the organic solvent preferably, it is at least one selected from the group consisting of alkanes and / or aromatic hydrocarbons, more preferably toluene, xylene and cyclohexylbenzene.
  • alkanes and / or aromatic hydrocarbons more preferably toluene, xylene and cyclohexylbenzene.
  • it is non-polar and hardly affected by moisture, and the material is easily dissolved, so that the ink can be stored stably.
  • One of these organic solvents may be used alone, or two or more thereof may be used in any combination and ratio.
  • the organic solvent evaporates from the liquid film immediately after the film formation at an appropriate rate.
  • the boiling point of the organic solvent is usually 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher.
  • the boiling point of the organic solvent is usually 270 ° C. or lower, preferably 250 ° C. or lower, more preferably 230 °
  • the composition for forming a light emitting layer of the present invention may contain other components as appropriate as long as it contains at least the high Tg compound and the low Tg compound as described above.
  • the content of the low Tg compound with respect to all the non-light emitting materials contained in the composition for forming a light emitting layer (hereinafter simply referred to as the content of the low Tg compound) is 8 to 70% by mass, More preferably, it is 10 to 70% by mass.
  • the content rate of a low Tg compound is 8 mass% or more, 10 mass% or more is preferable and 15 mass% or more is more preferable.
  • the content rate of a low Tg compound is 80 mass% or less, 70 mass% or less is preferable, 50 mass% or less is more preferable, 40 mass% or less is further more preferable, and 35 mass% or less is especially preferable.
  • the content of the low Tg compound is preferably high from the viewpoints of solubility in a solvent, ink storage stability after dissolution, and the light emitting surface is uniform and stable because crystallization of the light emitting layer is difficult to occur.
  • the content of the low Tg compound is preferably low in that the film morphology hardly changes when the device is stored at high temperature.
  • the content of the high Tg compound with respect to all the non-light emitting materials contained in the composition for forming the light emitting layer (hereinafter simply referred to as the content of the high Tg compound) is preferably 10% by mass or more, and more preferably 15% by mass or more. Moreover, 90 mass% or less is preferable, and 70 mass% or less is still more preferable. Contrary to the low Tg compound, the content of the high Tg compound is low in that it is soluble in a solvent, storage stability after dissolution, and the light emitting surface is uniform and stable because crystallization of the light emitting layer is difficult to occur. It is preferable that it is high in that the film morphology hardly changes when the device is stored at high temperature.
  • the content of the light emitting material in all the nonvolatile materials contained in the composition for forming a light emitting layer is preferably 5% by mass or more, more preferably 10% by mass or more, and preferably 40% by mass or less, and 30% by mass. The following is more preferable.
  • the heat resistance of the film is improved, and by including a low Tg compound, a uniform film can be formed during film formation.
  • High Tg compounds are easy to crystallize at the time of film formation and are rigid compounds. Therefore, high Tg compounds are difficult to come into close contact with each other at the molecular level, thereby reducing the charge transport property of the film.
  • a low Tg compound when a low Tg compound is present, it is presumed that the low Tg compound fills the gaps between the rigid high Tg compounds, suppresses crystallization of the high Tg compound, and forms a uniform film.
  • a composition containing a low Tg compound and a high Tg compound is formed into a wet film, it is dried in a state where the low Tg compound and the high Tg compound are uniformly mixed. That is, it is considered that a film in which the gap between the high Tg compounds rigid with the low Tg compound is filled can be easily formed, and a uniform film excellent in transportability can be easily formed.
  • the conventional vacuum heating vapor deposition method since the material is deposited in clusters, it is considered that the low Tg compound is difficult to fill the gap between the high Tg compounds.
  • a low Tg compound exists between the high Tg compounds, so that it is considered that the film has high heat resistance in which crystallization of the high Tg compound is suppressed.
  • heat resistance is usually insufficient, and thus it is believed that the organic electroluminescent device is accelerated by storage at a high temperature, or is accelerated by energization driving.
  • the present invention has found an unexpected effect that the heat resistance of the organic electroluminescence device is improved by the interaction of the low Tg compound and the high Tg compound by mixing the low Tg compound and the high Tg compound. It was. This is presumably because the thermal motion of the low Tg compound due to heat during high-temperature storage and heat generation during energization driving is suppressed by the high Tg compound present in the vicinity of the low Tg compound.
  • the solubility in an organic solvent can be improved and the storage stability of the composition can be ensured, and crystallization in the film of the organic electroluminescent device can be suppressed, and driving at room temperature is possible.
  • the lifetime can be extended.
  • a high Tg compound it is possible to suppress changes in film properties and morphology under high temperature storage near 100 ° C., which is a concern due to low Tg compounds, and stable and long driving life even after high temperature storage Can be obtained.
  • the reason why the Tg of the high Tg compound is 130 ° C. or higher is as described above. Further, when the Tg of the low Tg compound is 100 ° C. or lower, the interaction with the high Tg compound is suppressed, and the effect of suppressing the crystallization of the low Tg compound tends to be easily exhibited. When there is a difference of 30 ° C. or more as in the present invention, it is considered that the effects derived from each other's Tg are sufficiently developed.
  • the difference in Tg between the high Tg compound and the low Tg compound is not particularly limited, but is preferably 30 ° C or higher, more preferably 40 ° C or higher, and further preferably 50 ° C or higher.
  • 70 degrees C or less is preferable and 65 degrees C or less is more preferable.
  • the Tg difference is increased to some extent, and the high Tg compound is less susceptible to the molecular motion of the low Tg compound, so that the film morphology is less likely to change even at high temperatures.
  • the content of the low Tg compound is 8 to 70% by mass as described above. By being 8 mass% or more, there is an influence on the intermolecular interaction of the high Tg compound, and it is easy to suppress crystallization in the film and the organic solvent. Moreover, by being 70% by mass or less, the change in crystallinity during high-temperature storage caused by the low Tg compound can be absorbed by other materials less than 30% by mass, and the change in the morphology of the entire film is suppressed. It tends to be possible.
  • any of the high Tg compound and the low Tg compound has a high electron transporting property and a pyrimidine skeleton or a triazine skeleton excellent in structural stability, so that the probability that electrons are localized on the light emitting material is lowered and stable. Luminescence can be obtained. Therefore, the effect of extending the life can be sufficiently obtained. Furthermore, when the low Tg compound is a compound in which monocyclic compounds are bonded directly and / or via a linking group, the planarity as a molecule is lower and crystallization due to molecular packing is less likely to occur. Therefore, the effect of suppressing the crystallization can be further obtained.
  • the molecular weight of each non-light emitting material having a content of 1.0% by mass or more based on the total amount of all non-light emitting materials contained in the composition for forming a light emitting layer of the present invention is preferably 5000 or less.
  • the molecular weight is within this range, it is preferable that a film is formed in a state where most non-light emitting materials are uniformly mixed.
  • the high molecular weight compound is small in the film, the three-dimensional molecular entanglement is suppressed, and the high Tg compound and the low Tg compound are easily mixed uniformly. As a result, the generation of a minute region in which low Tg compounds are gathered is suppressed, and stability during high-temperature storage is easily obtained.
  • the molecular weight is not more than the upper limit of the molecular weight, the solubility of the compound in the solvent is improved, the entanglement of the molecular chain in the solvent is suppressed, and the impurities (that is, the deterioration-causing substance) can be easily removed.
  • the weighted average glass transition temperature of all non-light emitting materials contained in the composition for forming a light emitting layer is preferably 100 ° C. or higher, more preferably 115 ° C. or higher.
  • the weighted average glass transition temperature is preferably 150 ° C. or lower, more preferably 145 ° C. or lower.
  • the weighted average glass transition temperature is 100 ° C. or higher, the film morphology is less likely to change under the influence of heat during high-temperature storage and heat generated in the organic electroluminescence device when energized, that is, the driving life is more become longer.
  • the weighted average glass transition temperature is 150 ° C. or lower, the gaps between the molecules are easily filled, and the driving life is improved in terms of charge transportability in the film.
  • non-light emitting materials examples include additives such as a charge transport material and an antioxidant.
  • the composition for forming a light emitting layer of the present invention may contain a charge transport material that does not belong to either the high Tg compound or the low Tg compound. For convenience, this is referred to as a third charge transport material.
  • a third charge transport material As the third charge transport material, a material having a skeleton excellent in charge transportability is preferable.
  • skeleton having excellent charge transportability examples include aromatic structures, aromatic amine structures, triarylamine structures, dibenzofuran structures, naphthalene structures, phenanthrene structures, phthalocyanine structures, porphyrin structures, thiophene structures, benzylphenyl structures, Fluorene structure, quinacridone structure, triphenylene structure, carbazole structure, pyrene structure, anthracene structure, phenanthroline structure, quinoline structure, pyridine structure, pyrimidine structure, triazine structure, oxadiazole structure, imidazole structure and the like can be mentioned.
  • the third charge transporting material in the present invention is a material having a structure excellent in electron transporting property in that the light emitting material itself can suppress deterioration of the light emitting material due to transport of electrons and can extend the driving life. Is preferred.
  • a compound having a structure excellent in hole transportability is also preferable, and among the central skeleton excellent in charge transportability, a carbazole structure, dibenzofuran structure, triarylamine structure, naphthalene structure, phenanthrene structure or pyrene structure is a hole.
  • a structure excellent in transportability is preferable, and a carbazole structure, a dibenzofuran structure, or a triarylamine structure is more preferable.
  • the third charge transporting material in the present invention is a material having a structure excellent in hole transporting property in that the light emitting material itself can suppress the deterioration of the light emitting material due to transporting holes and can extend the driving life. Preferably there is.
  • the molecular weight of the third charge transport material in the present invention is arbitrary as long as the effects of the present invention are not significantly impaired.
  • the molecular weight of the third charge transport material in the present invention is usually 5000 or less, preferably 4000 or less, more preferably 3000 or less, and most preferably 2000 or less.
  • the molecular weight of the third charge transport material in the present invention is usually 300 or more, preferably 350 or more, more preferably 400 or more.
  • the molecular weight of the third charge transport material is large in that the film quality is hardly deteriorated due to gas generation, recrystallization, molecular migration, or the like.
  • the molecular weight of the third charge transport material is preferably small in that the organic compound can be easily purified and easily dissolved in a solvent.
  • the composition for forming a light emitting layer of the present invention preferably contains a third charge transport material that does not belong to either the high Tg compound or the low Tg compound. Two or more third charge transport materials may be used.
  • the light emitting layer according to the present invention is formed by a wet film forming method using the above-described composition for forming a light emitting layer of the present invention.
  • the wet film forming method refers to a film forming method, that is, a method in which a wet film forming method is employed as a coating method, and this coating film is dried to form a film.
  • coating methods include spin coating, dip coating, die coating, bar coating, blade coating, roll coating, spray coating, capillary coating, ink jet, nozzle printing, screen printing, and gravure. Examples thereof include a printing method and a flexographic printing method.
  • spin coating, spray coating, ink jet, nozzle printing, and the like are preferable.
  • the light emitting layer When the light emitting layer is formed by a wet film forming method, it is usually prepared by dissolving the above-described light emitting material, high Tg compound, low Tg compound, and other materials used as necessary in an appropriate organic solvent. A film is formed using the composition for forming a light emitting layer, and the organic solvent is removed by heating, decompression, or the like. As a method for removing the organic solvent, heating or reduced pressure can be used. As the heating means used in the heating method, a clean oven, a hot plate, or the like is preferable because heat is uniformly applied to the entire film.
  • the heating temperature in the heating step is arbitrary as long as the effects of the present invention are not significantly impaired. However, a higher temperature is preferable in terms of shortening the drying time, and a lower temperature is preferable in terms of less damage to the material.
  • the upper limit is usually 250 ° C. or lower, preferably 200 ° C. or lower, more preferably 150 ° C. or lower.
  • the lower limit is usually 30 ° C. or higher, preferably 50 ° C. or higher, more preferably 80 ° C. or higher.
  • the temperature is not more than the upper limit, decomposition or crystallization of a commonly used charge transport material or phosphorescent material can be suppressed.
  • the removal time of a solvent can be shortened because it is more than the said minimum.
  • the heating time in the heating step is appropriately determined depending on the boiling point and vapor pressure of the solvent in the composition for forming the light emitting layer, the heat resistance of the material, and the heating conditions.
  • Tg glass transition temperature
  • ⁇ Glass transition temperature measurement conditions Differential scanning calorimeter (DSC): Shimadzu DTA-50 Sample amount: about 4mg Sample container: Aluminum pan Atmosphere: Air Temperature range: Room temperature (25 ° C) to 300 ° C Temperature increase rate: 10 ° C / min The weighted average glass transition temperature is the sum of all non-luminescent materials multiplied by the weight ratio of each non-luminescent material to the Tg of each non-luminescent material determined by the above method.
  • DSC Differential scanning calorimeter
  • FIG. 1 is a schematic cross-sectional view showing a structural example of an organic electroluminescent device 10 according to the present invention.
  • 1 is a substrate
  • 2 is an anode
  • 3 is a hole injection layer
  • 4 is a hole transport layer
  • Reference numeral 5 denotes a light emitting layer
  • 6 denotes a hole blocking layer
  • 7 denotes an electron transport layer
  • 8 denotes an electron injection layer
  • 9 denotes a cathode.
  • the substrate 1 serves as a support for the organic electroluminescent element, and a quartz or glass plate, a metal plate or a metal foil, a plastic film or a sheet is usually used. Of these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable.
  • the substrate 1 is preferably made of a material having a high gas barrier property because the organic electroluminescence element is hardly deteriorated by the outside air. For this reason, when using a material having a low gas barrier property, such as a synthetic resin substrate, it is preferable to provide a dense silicon oxide film or the like on at least one surface of the substrate 1 to improve the gas barrier property.
  • the anode 2 has a function of injecting holes into the layer on the light emitting layer side.
  • the anode 2 is usually made of a metal such as aluminum, gold, silver, nickel, palladium, or platinum; a metal oxide such as an oxide of indium and / or tin; a metal halide such as copper iodide; a carbon black and a poly (3 -Methylthiophene), conductive polymers such as polypyrrole and polyaniline, and the like.
  • the anode 2 is often formed by a dry method such as a sputtering method or a vacuum deposition method.
  • an appropriate binder resin solution It can also be formed by being dispersed in and coated on a substrate.
  • a conductive polymer a thin film can be directly formed on the substrate by electrolytic polymerization, or the anode 2 can be formed by applying a conductive polymer on the substrate (Appl. Phys. Lett., 60, 2711, 1992).
  • the anode 2 usually has a single layer structure, but may have a laminated structure as appropriate. When the anode 2 has a laminated structure, different conductive materials may be laminated on the first anode.
  • the thickness of the anode 2 may be determined according to required transparency and material. In particular, when high transparency is required, a thickness at which visible light transmittance is 60% or more is preferable, and a thickness at which 80% or more is more preferable.
  • the thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably 500 nm or less. On the other hand, when transparency is not required, the thickness of the anode 2 may be arbitrarily set according to the required strength.
  • the anode 2 may have the same thickness as the substrate 1.
  • impurities on the anode are removed and the ionization potential thereof is adjusted by performing treatment such as ultraviolet ray + ozone, oxygen plasma, argon plasma before film formation. It is preferable to improve the hole injection property.
  • the layer responsible for transporting holes from the anode side to the light emitting layer side is usually called a hole injection transport layer or a hole transport layer.
  • the layer closer to the anode side may be referred to as the hole injection layer 3.
  • the hole injection layer 3 is preferably used from the viewpoint of enhancing the function of transporting holes from the anode to the light emitting layer side.
  • the hole injection layer 3 is usually formed on the anode.
  • the thickness of the hole injection layer 3 is usually 1 nm or more, preferably 5 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
  • the formation method of the hole injection layer 3 may be a vacuum deposition method or a wet film formation method. In terms of excellent film forming properties, it is preferable to form the film by a wet film forming method.
  • the hole injection layer 3 preferably contains a hole transporting compound, and more preferably contains a hole transporting compound and an electron accepting compound. Further, the hole injection layer preferably contains a cation radical compound, and particularly preferably contains a cation radical compound and a hole transporting compound.
  • the composition for forming a hole injection layer usually contains a hole transporting compound that becomes the hole injection layer 3. In the case of a wet film forming method, a solvent is usually further contained. It is preferable that the composition for forming a hole injection layer has high hole transportability and can efficiently transport injected holes. For this reason, it is preferable that the hole mobility is high and impurities that become traps are less likely to be generated during production or use. Moreover, it is preferable that it is excellent in stability, has a small ionization potential, and has high transparency to visible light. In particular, when the hole injection layer 3 is in contact with the light emitting layer 5, it is preferable that the light emission from the light emitting layer 5 does not quench or that the light emitting layer 5 is exciplexed and the light emission efficiency is not lowered.
  • the hole transporting compound is preferably a compound having an ionization potential of 4.5 eV to 6.0 eV from the viewpoint of a charge injection barrier from the anode 2 to the hole injection layer 3.
  • hole transporting compounds include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, compounds in which tertiary amines are linked by a fluorene group, hydrazones Compound, silazane compound compound, quinacridone compound and the like.
  • an aromatic amine compound is preferable and an aromatic tertiary amine compound is particularly preferable from the viewpoint of amorphousness and visible light transmittance.
  • the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine.
  • the type of the aromatic tertiary amine compound is not particularly limited, but is a polymer compound having a weight average molecular weight of 1,000 to 1,000,000 (polymerization compound in which repeating units are linked) from the viewpoint of easily obtaining uniform light emission due to the surface smoothing effect. Is preferably used.
  • Preferable examples of the aromatic tertiary amine polymer compound include a polymer compound having a repeating unit represented by the following formula (II).
  • Ar 1 and Ar 2 each independently represent an aromatic group that may have a substituent or a heteroaromatic group that may have a substituent.
  • Ar 3 To Ar 5 each independently represents an optionally substituted aromatic group or an optionally substituted heteroaromatic group, wherein Y is selected from the following group of linking groups. Represents a selected linking group, and among Ar 1 to Ar 5 , two groups bonded to the same N atom may be bonded to each other to form a ring.
  • the linking group is shown below.
  • Ar 6 to Ar 16 each independently represents an aromatic group which may have a substituent or a heteroaromatic group which may have a substituent.
  • R 105 and R 106 each independently represents a hydrogen atom or an arbitrary substituent.
  • the aromatic group and heteroaromatic group of Ar 1 to Ar 16 include a benzene ring, a naphthalene ring, a phenanthrene ring, a thiophene ring, or pyridine from the viewpoint of the solubility, heat resistance, and hole injection / transport properties of the polymer compound.
  • a group derived from a ring is preferable, and a group derived from a benzene ring or a naphthalene ring is more preferable.
  • Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by the formula (II) include those described in International Publication No. 2005/089024.
  • the hole injection layer 3 preferably contains an electron accepting compound because the conductivity of the hole injection layer 3 can be improved by oxidation of the hole transporting compound.
  • an electron accepting compound a compound having an oxidizing power and the ability to accept one electron from the above-described hole-transporting compound is preferable, and specifically, a compound having an electron affinity of 4 eV or more is preferable. More preferably, the compound is 5 eV or more.
  • electron-accepting compounds include triarylboron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids.
  • examples thereof include one or more compounds selected from the group. Specifically, onium salts substituted with organic groups such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and triphenylsulfonium tetrafluoroborate (WO 2005/089024 pamphlet); High-valent inorganic compounds such as iron (III) (Japanese Patent Laid-Open No.
  • ⁇ Cation radical compound an ionic compound composed of a cation radical which is a chemical species obtained by removing one electron from a hole transporting compound and a counter anion is preferable.
  • the cation radical is derived from a hole transporting polymer compound
  • the cation radical has a structure in which one electron is removed from the repeating unit of the polymer compound.
  • the cation radical is preferably a chemical species obtained by removing one electron from the compound described above as the hole transporting compound.
  • a chemical species obtained by removing one electron from a compound preferable as a hole transporting compound is preferable in terms of amorphousness, visible light transmittance, heat resistance, solubility, and the like.
  • the cation radical compound can be generated by mixing the hole transporting compound and the electron accepting compound. That is, by mixing the hole transporting compound and the electron accepting compound, electron transfer occurs from the hole transporting compound to the electron accepting compound, and the cation radical and the counter anion of the hole transporting compound A cation ion compound consisting of
  • Oxidative polymerization here refers to oxidation of a monomer chemically or electrochemically with peroxodisulfate in an acidic solution.
  • the monomer is polymerized by oxidation, and a cation radical that is removed from the polymer repeating unit by using an anion derived from an acidic solution as a counter anion is removed.
  • a material for forming the hole injection layer 3 is usually mixed with a soluble solvent (hole injection layer solvent) to form a film forming composition (positive Hole injecting layer forming composition) is prepared, and this hole injecting layer forming composition is applied onto a layer corresponding to the lower layer of the hole injecting layer 3 (usually the anode 2) to form a film and dried. To form.
  • a film forming composition positive Hole injecting layer forming composition
  • the concentration of the hole transporting compound in the composition for forming a hole injection layer is arbitrary as long as the effects of the present invention are not significantly impaired, but in terms of film thickness uniformity, the lower one is preferable. From the viewpoint that defects are unlikely to occur in the hole injection layer 3, a higher value is preferable. Specifically, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and on the other hand, 70% by mass. The content is preferably less than 60% by mass, more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
  • ether solvents examples include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and anisole.
  • PGMEA propylene glycol-1-monomethyl ether acetate
  • Aromatic ethers such as phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole.
  • ester solvent examples include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.
  • aromatic hydrocarbon solvent examples include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, methylnaphthalene and the like.
  • amide solvent examples include N, N-dimethylformamide and N, N-dimethylacetamide.
  • Formation of the hole injection layer 3 by a wet film formation method is usually performed after preparing a composition for forming a hole injection layer, and then forming the composition on a layer (usually the anode 2) corresponding to the lower layer of the hole injection layer 3
  • the film is formed by coating and drying.
  • the hole injection layer 3 is dried by heating or drying under reduced pressure after film formation.
  • the hole injection layer 3 is formed by vacuum vapor deposition
  • one or more of the constituent materials of the hole injection layer 3 are usually vacuumed.
  • a crucible installed in the container if two or more kinds of materials are used, usually put each in separate crucibles
  • evacuate the vacuum container to about 10 -4 Pa with a vacuum pump, then heat the crucible (When using two or more types of materials, each crucible is usually heated) and evaporated while controlling the amount of evaporation of the material in the crucible (when using two or more types of materials, each is usually independent.
  • the hole injection layer 3 is formed on the anode on the substrate placed facing the crucible.
  • the hole injection layer 3 can also be formed by putting a mixture thereof in a crucible, heating and evaporating the mixture.
  • the degree of vacuum at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 ⁇ 10 ⁇ 6 Torr (0.13 ⁇ 10 ⁇ 4 Pa) or more and 9.0 ⁇ 10 ⁇ 6 Torr ( 12.0 ⁇ 10 ⁇ 4 Pa) or less.
  • the deposition rate is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 to 5.0 liters / second or more.
  • the film forming temperature at the time of vapor deposition is not limited as long as the effects of the present invention are not significantly impaired, but it is preferably performed at 10 ° C. or higher and 50 ° C. or lower.
  • the hole transport layer 4 is a layer having a function of transporting holes from the anode side to the light emitting layer side.
  • the hole transport layer 4 is not an essential layer in the organic electroluminescence device of the present invention, but it is preferable to use this layer in terms of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5.
  • the hole transport layer 4 is usually formed between the anode 2 and the light emitting layer 5. Further, when there is the hole injection layer 3 described above, it is formed between the hole injection layer 3 and the light emitting layer 5.
  • the film thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and is usually 300 nm or less, preferably 100 nm or less.
  • the formation method of the hole transport layer 4 may be a vacuum deposition method or a wet film formation method. In terms of excellent film forming properties, it is preferable to form the film by a wet film forming method.
  • the hole transport layer 4 usually contains a hole transport compound that becomes the hole transport layer 4.
  • the hole transporting compound contained in the hole transporting layer 4 in particular, two or more tertiary compounds represented by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl are used.
  • Aromatic diamines containing two or more condensed aromatic rings, including amines, substituted with nitrogen atoms Japanese Patent Laid-Open No. 5-234811
  • An aromatic amine compound having a starburst structure J. Lumin., 72-74, 985, 1997), an aromatic amine compound comprising a tetramer of triphenylamine (Chem. Commun., 2175) 1996), 2,2 ′, 7,7′-tetrakis- (diphenylamino) -9,9′-spirobifluorene and other spiro compounds (Synth.
  • carbazole derivatives such as 4,4′-N, N′-dicarbazolebiphenyl.
  • polyvinyl carbazole polyvinyl triphenylamine (Japanese Patent Laid-Open No. 7-53953), polyarylene ether sulfone (Polym. Adv. Tech., 7, 33, 1996) containing tetraphenylbenzidine, etc. It can be preferably used.
  • the hole injection layer 3 is usually replaced with the hole injection layer forming composition in the same manner as in the case of forming the hole injection layer 3 by a wet film formation method. It forms using the composition for positive hole transport layer formation.
  • the composition for forming a hole transport layer usually further contains a solvent.
  • the solvent used in the composition for forming a hole transport layer the same solvent as the solvent used in the composition for forming a hole injection layer can be used.
  • the concentration of the hole transporting compound in the composition for forming a hole transport layer can be in the same range as the concentration of the hole transporting compound in the composition for forming a hole injection layer.
  • Formation of the hole transport layer 4 by a wet film formation method can be performed in the same manner as the film formation method of the hole injection layer 3 described above.
  • the positive hole injection layer 3 is usually formed in place of the composition for forming the hole injection layer in the same manner as in the case of forming the hole injection layer 3 by the vacuum deposition method. It can be formed using a composition for forming a hole transport layer. Film formation conditions such as the degree of vacuum at the time of vapor deposition, the vapor deposition rate, and the temperature can be formed under the same conditions as those for the vacuum vapor deposition of the hole injection layer 3.
  • the light emitting layer 5 is a layer having a function of emitting light when excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 when an electric field is applied between a pair of electrodes. .
  • the light emitting layer 5 is a layer formed between the anode 2 and the cathode 9, and the light emitting layer 5 is provided between the hole injection layer 3 and the cathode 9 when the hole injection layer 3 is on the anode 2.
  • the hole transport layer 4 is formed on the anode 2, it is formed between the hole transport layer 4 and the cathode 9.
  • the thickness of the light-emitting layer 5 is arbitrary as long as the effects of the present invention are not significantly impaired. However, it is preferable that the thickness of the light-emitting layer 5 is small in that it is difficult to cause defects in the film. Is preferred. Specifically, the thickness is usually 3 nm or more, preferably 5 nm or more, and usually 200 nm or less, preferably 100 nm or less. In the organic electroluminescent element, two or more light emitting layers may be provided. The details of the light emitting layer 5 are as described above. When forming light emitting layers other than the light emitting layer based on this invention by a vacuum evaporation method, it forms as follows.
  • the constituent materials of the light emitting layer are usually placed in separate crucibles installed in the vacuum container, Is evacuated to about 10 ⁇ 4 Pa with a vacuum pump, and each crucible is heated to evaporate while independently controlling the evaporation amount of the material in each crucible, and on the substrate or the like placed facing each crucible.
  • the light-emitting layer can also be formed by placing a mixture of constituent materials in one crucible and heating and evaporating the mixture.
  • the degree of vacuum at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 ⁇ 10 ⁇ 6 Torr (0.13 ⁇ 10 ⁇ 4 Pa) or more and 9.0 ⁇ 10 ⁇ 6 Torr ( 12.0 ⁇ 10 ⁇ 4 Pa) or less.
  • the deposition rate is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 to 5.0 liters / second or more.
  • the film forming temperature at the time of vapor deposition is not limited as long as the effects of the present invention are not significantly impaired, but it is preferably performed at 10 ° C. or higher and 50 ° C. or lower.
  • a hole blocking layer 6 may be provided between the light emitting layer 5 and an electron injection layer 8 described later.
  • the hole blocking layer 6 is a layer stacked on the light emitting layer 5 so as to be in contact with the cathode side interface of the light emitting layer 5.
  • the hole blocking layer 6 has a role of blocking holes moving from the anode 2 from reaching the cathode 9 and a role of efficiently transporting electrons injected from the cathode 9 toward the light emitting layer 5.
  • Have The physical properties required for the material constituting the hole blocking layer 6 include high electron mobility, low hole mobility, a large energy gap (difference between HOMO and LUMO), and excited triplet level (T1). Is high.
  • Examples of the material of the hole blocking layer 6 satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanolato) aluminum.
  • Mixed ligand complexes such as bis (2-methyl-8-quinolato) aluminum- ⁇ -oxo-bis- (2-methyl-8-quinolinolato) aluminum binuclear metal complexes, distyrylbiphenyl derivatives, etc.
  • Styryl compounds Japanese Patent Laid-Open No.
  • the thickness of the hole blocking layer 6 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less. is there.
  • the electron transport layer 7 is provided between the light emitting layer 5 and the electron injection layer 8 for the purpose of further improving the current efficiency of the device.
  • the electron transport layer 7 is formed of a compound capable of efficiently injecting electrons from the cathode 9 or the electron injection layer 8 between the electrodes to which an electric field is applied, and efficiently transporting electrons in the direction of the light emitting layer 5.
  • the electron transporting compound used for the electron transporting layer 7 a compound that has high electron injection efficiency from the cathode 9 or the electron injection layer 8 and can efficiently transport the injected electrons is usually preferable.
  • Specific examples of the electron transporting compound include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No.
  • the thickness of the electron transport layer 7 is usually 1 nm or more, preferably 5 nm or more, and is usually 300 nm or less, preferably 100 nm or less.
  • the electron transport layer 7 is formed by laminating on the hole blocking layer 6 by a wet film formation method or a vacuum deposition method in the same manner as described above. Usually, a vacuum deposition method is used.
  • An electron injection layer 8 may be provided between the cathode 9 and the electron transport layer 7 or the light emitting layer 5.
  • the electron injection layer 8 plays a role of efficiently injecting electrons injected from the cathode 9 into the electron transport layer 7 or the light emitting layer 5.
  • the material for forming the electron injection layer 8 is preferably a metal having a low work function. Examples include alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium.
  • the film thickness is usually preferably from 0.1 nm to 5 nm.
  • an organic electron transport material represented by a metal complex such as a nitrogen-containing heterocyclic compound such as bathophenanthroline or an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium, rubidium ( (Described in JP-A-10-270171, JP-A-2002-1000047, JP-A-2002-1000048, etc.) also improves electron injection / transport and makes it possible to achieve both excellent film quality. preferable.
  • the film thickness is usually in the range of 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.
  • the electron injection layer 8 is formed by laminating on the light emitting layer 5 or the hole blocking layer thereon by a wet film formation method or a vacuum deposition method. The details of the wet film forming method are the same as those of the light emitting layer 5 described above.
  • the cathode 9 plays a role of injecting electrons into a layer on the light emitting layer side (such as the electron injection layer 8 or the light emitting layer 5).
  • the material used for the anode 2 can be used.
  • a metal having a low work function Metals such as indium, calcium, aluminum and silver, or alloys thereof. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.
  • the cathode 9 made of a metal having a low work function by laminating a metal layer having a high work function and stable to the atmosphere on the cathode 9.
  • the metal to be laminated include metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum.
  • the thickness of the cathode is usually the same as that of the anode 2.
  • the organic electroluminescent element of the present invention may further have other layers as long as the effects of the present invention are not significantly impaired.
  • any other layer described above may be provided between the anode 2 and the cathode 9.
  • ⁇ Other element configuration> The structure opposite to that described above, that is, a cathode, an electron injection layer, a light emitting layer, a hole injection layer, and an anode can be stacked in this order on the substrate.
  • Example 1 An organic electroluminescent element having the configuration shown in FIG. 1 was produced.
  • the anode 2 was formed by patterning.
  • the substrate 1 (ITO substrate) on which the anode 2 was formed was cleaned in the order of ultrasonic cleaning with pure water and then with pure water, dried by nitrogen blowing, and finally subjected to ultraviolet ozone cleaning.
  • the hole injection layer 3 was formed by a wet film formation method as follows.
  • a hole-transporting compound 2.0% by mass of a polymer compound having a repeating structure represented by the following formula (P1) (weight average molecular weight 52000) and 4-isopropyl-4′-methyldiphenyl as an electron-accepting compound
  • P1 weight average molecular weight 52000
  • 4-isopropyl-4′-methyldiphenyl as an electron-accepting compound
  • a composition for forming a hole injection layer in which 0.4% by mass of iodonium tetrakis (pentafluorophenyl) borate and ethyl benzoate were dissolved was prepared, and this composition for forming a hole injection layer was formed on the ITO substrate.
  • a hole injection layer 3 having a film thickness of 32 nm was formed by film formation by spin coating and further heat drying. The film forming conditions were as follows.
  • ⁇ Film formation conditions Spin coating conditions: Spinner rotation speed 500 rpm / 2 seconds ⁇ 2100 rpm / 30 seconds Heating drying conditions: Leave in a clean oven at 230 ° C. for 1 hour
  • a hole transport layer 4 was formed on the formed hole injection layer 3 by a wet film forming method as follows.
  • a polymer compound (HT-1) having a repeating structure shown below was dissolved in cyclohexylbenzene as a solvent to prepare a composition for forming a hole transport layer.
  • the concentration of the polymer compound (HT-1) in the composition for forming a hole transport layer was 2.0% by mass.
  • the composition for forming a hole transport layer is formed on the hole injection layer 3 by a spin coat method, and further heated and dried to cause the polymer compound (HT-1) to undergo a crosslinking reaction to be cured, A hole transport layer 4 having a thickness of 21 nm was formed.
  • the film forming conditions were as follows. ⁇ Film formation conditions> Spin coating conditions: Spinner rotation speed 500 rpm / 2 seconds ⁇ 2900 rpm / 120 seconds Heat drying conditions: Leave on a hot plate at 230 ° C. for 1 hour
  • the light emitting layer 5 was formed on the formed hole transport layer 4 as follows.
  • the following compounds (HH-1), (HH-2), (H-1), (LH-1) and (D-1) were mixed at a mass ratio of 35: 20: 35: 10: 15.
  • a composition for forming a light emitting layer in which xylene was dissolved in xylene so that the mixture was 3.45% by mass was prepared, and the composition for forming a light emitting layer was spin-coated on the hole transport layer 4 in a nitrogen atmosphere.
  • the light emitting layer 5 having a film thickness of 59 nm was formed by forming a film by the method and further drying by heating.
  • the film forming conditions were as follows.
  • ⁇ Film formation conditions Spin coating conditions: Spinner rotation speed 500 rpm / 2 seconds ⁇ 1700 rpm / 120 seconds Heating drying conditions: Standing on a hot plate at 120 ° C. for 20 minutes
  • the compounds (HH-1), (HH-2), (H-1) and (LH-1) have Tg of 159 ° C., 142 ° C., 113 ° C. and 90 ° C., respectively, and non-light emitting materials Therefore, (HH-1) and (HH-2) correspond to the high Tg compound of the present invention, and (LH-1) corresponds to the low Tg compound of the present invention.
  • the low Tg compound (LH-1) has a pyrimidine skeleton, and monocyclic compounds are bonded to each other through a direct bond and / or a linking group.
  • the molecular weight of each compound is 968.4, 866.3, 636.3, 841 for (HH-1), (HH-2), (H-1), (LH-1) and (D-1), respectively. 4 and 1363.9, both of which had a molecular weight of 5000 or less.
  • the content rate of the low Tg compound with respect to the total amount of all the nonluminous materials contained in the composition for light emitting layer formation was 10 mass%, and the weighted average glass transition temperature of all the nonluminous materials was 133 degreeC.
  • a compound (HB-1) shown below was formed as a hole blocking layer 6 on the formed light emitting layer 5 by a vacuum deposition method so as to have a film thickness of 10 nm.
  • a compound (ET-1) shown below as an electron transport layer 7 was formed on the formed hole blocking layer 6 by a vacuum deposition method so as to have a film thickness of 20 nm.
  • the element that has been vapor-deposited up to the electron transport layer 7 is once taken out from the vacuum vapor deposition apparatus into the atmosphere, and used as a cathode vapor deposition mask with a 2 mm width in a shape orthogonal to the ITO stripe as the anode.
  • a stripe shadow mask is brought into close contact with the element, placed in another vacuum vapor deposition apparatus, and lithium fluoride (LiF) is formed to a thickness of 0.5 nm as the electron injection layer 8 by the same vacuum vapor deposition method as the electron transport layer 7.
  • LiF lithium fluoride
  • aluminum was laminated as the cathode 9 so as to have a film thickness of 80.0 nm.
  • sealing treatment was performed by the method described below.
  • a photocurable resin was applied to the outer periphery of a 23 mm ⁇ 23 mm size glass plate with a width of about 1 mm, and a moisture getter sheet was installed in the center.
  • finished cathode formation was bonded together so that the vapor-deposited surface might oppose a desiccant sheet.
  • coated was irradiated with ultraviolet light, and resin was hardened. Thereby, the organic electroluminescent element which has a light emission area part of 2 mm x 2 mm size was obtained.
  • Example 2 In Example 1, the compounds (HH-2), (LH-1), (LH-2), (H-1) and (D-) are used as the non-light emitting material and the light emitting material contained in the light emitting layer forming composition.
  • An organic electroluminescent element was produced in the same manner as in Example 1 except that 1) was changed to a mixture of 15: 15: 15: 55: 15 at a mass ratio.
  • Compound (LH-2) was a compound having the structure shown below, Tg was 87 ° C., and molecular weight was 762.3. Moreover, the content rate of the low Tg compound with respect to the total amount of all the nonluminous materials contained in the composition for light emitting layer formation was 30 mass%, and the weighted average glass transition temperature of all the nonluminous materials was 110 degreeC.
  • Example 3 In Example 1, compounds (HH-1), (H-2), (H-3), (LH-1) and (D-) are used as the non-light-emitting materials and the light-emitting materials contained in the composition for forming a light-emitting layer.
  • An organic electroluminescent element was produced in the same manner as in Example 1 except that 1) was changed to a mixture of 35: 15: 35: 15: 15 at a mass ratio.
  • Compounds (H-2) and (H-3) are compounds having the following structures, Tg was 129 ° C. and 109 ° C., respectively, and molecular weights were 791.3 and 1157.5, respectively. .
  • the content rate of the low Tg compound with respect to the total amount of all the non-light-emitting materials contained in the composition for forming a light-emitting layer was 15% by mass, and the weighted average glass transition temperature of all the non-light-emitting materials was 127 ° C.
  • Example 4 In Example 1, as a non-light-emitting material and a light-emitting material contained in the composition for forming a light-emitting layer, the compounds (HH-1), (LH-1) and (D-1) were mixed at a mass ratio of 70:30:15. An organic electroluminescent element was produced in the same manner as in Example 1 except that the mixture was changed to that mixed in the above.
  • the content rate of the low Tg compound with respect to the total amount of all non-light-emitting materials contained in the composition for forming a light-emitting layer was 30% by mass, and the weighted average glass transition temperature of all the non-light-emitting materials was 138 ° C.
  • Example 5 In Example 1, (HH-1), (H-2), (LH-1), and (D-1) were used as the non-light-emitting material and the light-emitting material included in the composition for forming a light-emitting layer.
  • An organic electroluminescent element was produced in the same manner as in Example 1 except that the mixture was changed to a mixture with a mass ratio of 15:15.
  • the content rate of the low Tg compound with respect to the total amount of all the non-light-emitting materials contained in the composition for forming a light-emitting layer was 15% by mass, and the weighted average glass transition temperature of all the non-light-emitting materials was 144 ° C. there were.
  • Example 6 In Example 1, (HH-1), (H-3), (LH-1), and (D-1) were used as the non-light-emitting material and the light-emitting material included in the light-emitting layer forming composition: An organic electroluminescent element was produced in the same manner as in Example 1 except that the mixture was changed to a mixture at a mass ratio of 35:30:15. The content of the low Tg compound with respect to the total amount of all the non-light-emitting materials contained in the composition for forming a light-emitting layer was 30% by mass, and the weighted average glass transition temperature of all the non-light-emitting materials was 121 ° C. there were.
  • Example 1 (LH-1), (LH-2), (H-3) and (D-1) were used as non-light emitting materials and light emitting materials contained in the composition for forming a light emitting layer at 30:35.
  • An organic electroluminescence device was produced in the same manner as in Example 1 except that the mixture was changed to a mixture at a mass ratio of 35:15.
  • the weighted average glass transition temperature of all non-luminescent materials was 96 ° C.
  • Example 2 (Comparative Example 2) In Example 1, (HH-1), (HH-2), and (D-1) as a non-light emitting material and a light emitting material contained in the composition for forming a light emitting layer were mixed at a mass ratio of 70:30:15. An organic electroluminescent element was produced in the same manner as in Example 1 except that the mixture was changed to that mixed in the above. The weighted average glass transition temperature of all non-luminescent materials was 154 ° C. And production
  • Example 7 An organic electroluminescent element having the configuration shown in FIG. 2 was produced.
  • the content rate of the low Tg compound with respect to the total amount of all non-light-emitting materials contained in the composition for forming a light-emitting layer was 30% by mass, and the weighted average glass transition temperature of all the non-light-emitting materials was 112 ° C.
  • Example 8 In Example 7, compounds (HH-1), (LH-3), and (D-1) as a non-light-emitting material and a light-emitting material contained in the light-emitting layer forming composition were mixed at a mass ratio of 70:30:15.
  • An organic electroluminescent element was produced in the same manner as in Example 7 except that the mixture was changed to a mixed one.
  • Compound (LH-3) was a compound having the structure shown below, Tg was 95 ° C., and molecular weight was 586.2. Moreover, the content rate of the low Tg compound with respect to the total amount of all the nonluminous materials contained in the composition for light emitting layer formation was 30 mass%, and the weighted average glass transition temperature of all the nonluminous materials was 140 degreeC.
  • Example 9 In Example 7, the compounds (HH-1), (LH-1), (LH-3), and (D-1) were used as the non-light emitting material and the light emitting material contained in the light emitting layer forming composition.
  • An organic electroluminescent element was produced in the same manner as in Example 7 except that the mixture was changed to a mixture of 15:15 by mass.
  • the content of the low Tg compound with respect to the total amount of all the non-light-emitting materials contained in the composition for forming a light-emitting layer was 30% by mass, and the weighted average glass transition temperature of all the non-light-emitting materials was 139 ° C.
  • Example 10 (Example 10) In Example 7, compounds (HH-1), (LH-1) and (D-1) as a non-light-emitting material and a light-emitting material included in the composition for forming a light-emitting layer were mixed at a mass ratio of 70:30:15. An organic electroluminescent element was produced in the same manner as in Example 7 except that the mixture was changed to a mixed one.
  • the content rate of the low Tg compound with respect to the total amount of all non-light-emitting materials contained in the composition for forming a light-emitting layer was 30% by mass, and the weighted average glass transition temperature of all the non-light-emitting materials was 138 ° C.
  • Example 7 (Comparative Example 3) In Example 7, compounds (HH-1), (LH-4) and (D-1) as a non-light emitting material and a light emitting material contained in the composition for forming a light emitting layer in a mass ratio of 70:30:15 An organic electroluminescent element was produced in the same manner as in Example 7 except that the mixture was changed to a mixed one.
  • Compound (LH-4) was a compound having the structure shown below, Tg was 95 ° C., and molecular weight was 930.2. Moreover, the weighted average glass transition temperature of all the non-light-emitting materials was 140 ° C.
  • Example 7 (Comparative Example 4) In Example 7, compounds (HH-1), (LH-5) and (D-1) as a non-light-emitting material and a light-emitting material contained in the composition for forming a light-emitting layer were mixed at a weight ratio of 70:30:15. An organic electroluminescent element was produced in the same manner as in Example 7 except that the mixture was changed to a mixed one.
  • Compound (LH-5) was a compound having the structure shown below, Tg was 86 ° C., and molecular weight was 612.8. Moreover, the weighted average glass transition temperature of all the non-light-emitting materials was 137 ° C.
  • Example 7 Comparative Example 5
  • compounds (HH-1), (LH-1) and (D-1) as a non-light-emitting material and a light-emitting material contained in the composition for forming a light-emitting layer were used at a mass ratio of 95: 5: 15.
  • An organic electroluminescent element was produced in the same manner as in Example 7 except that the mixture was changed to a mixed one.
  • the weighted average glass transition temperature of all non-light emitting materials was 156 ° C.
  • Comparative Examples 3 and 4 which do not include any of the material having a pyrimidine skeleton and the material having a triazine skeleton as the non-light emitting material have a small LT85 after heating. Moreover, although the material which has a pyrimidine frame
  • the present invention relates to various fields in which an organic electroluminescent element is used as a composition for forming a light emitting layer of an organic electroluminescent element, for example, as a flat panel display (for example, for OA computers and wall-mounted televisions) and a surface light emitter. It can be suitably used in the fields of light sources that make use of features (for example, light sources of copiers, backlight light sources of liquid crystal displays and instruments), display boards, marker lamps, and illumination devices.

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Abstract

Le but de la présente invention est de fournir un élément électroluminescent organique qui a une longue durée de vie et une excellente stabilité au stockage; et la présente invention concerne une composition pour former une couche électroluminescente, qui est appropriée pour l'élément électroluminescent organique. La présente invention concerne spécifiquement une composition pour former une couche électroluminescente d'un élément électroluminescent organique, qui contient un matériau électroluminescent, un matériau non électroluminescent et un solvant organique, et qui est caractérisée en ce que : le matériau électroluminescent peut être composé d'un ou plusieurs matériaux; le matériau non électroluminescent contient un composé à Tg élevée ayant une température de transition vitreuse non inférieure à 130 °C et un composé à faible Tg ayant une température de transition vitreuse inférieure ou égale à 100 °C; le rapport de teneur du composé à faible Tg par rapport à tous les matériaux non électroluminescents étant de 10 à 70 % en poids; et au moins l'un des matériaux non électroluminescents ayant un squelette pyrimidine ou un squelette triazine.
PCT/JP2018/001764 2017-01-23 2018-01-22 Composition pour former une couche électroluminescente et élément électroluminescent organique contenant ladite composition pour former une couche électroluminescente WO2018135656A1 (fr)

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