JP2000087027A - Material for organic electroluminescence element and organic electroluminescence element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject material excellent in light emitting characteristics by employing a specific compound bearing an aromatic ring. SOLUTION: There is provided a compound containing at least one recurring unit represented by formula I. In formula I, Q1 is a group of atoms necessary for forming a 5- or 6-membered aromatic ring; X is O, S, N-R1 or CR2(R3); R1-3 are each H, an aliphatic hydrocarbyl, an aryl or a heterocyclyl; R is H, an alkyl or an aryl; and (m) is at least 1, preferably 10-100,000. As examples of the compounds having at least one recurring unit represented by formula I, there can be cited a compound of formula II and the like. In an organic electroluminescence element wherein a light emitting layer or plural thin films of organic compounds containing a light emitting layer are formed between a pair of electrodes, at least one compound containing at least one recurring unit of formula I is incorporated into at least one layer, or at least one layer is composed of a film formed by coating at least one of the compounds containing at least one recurring unit of formula I, which gives an element excellent in stability enough for repeated use.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a material for a light emitting device (organic electroluminescence (EL) device) and a light emitting device which can emit light by converting electric energy into light, and relates to a display device, a display, a backlight, an electrophotograph, Illumination light source, recording light source, reading light source, signs, signs,
The present invention relates to a light-emitting element that can be suitably used in a field such as interior.

[0002]

2. Description of the Related Art At present, research and development on various display elements are active, and among them, organic EL elements are attracting attention as promising display elements because they can obtain high-luminance light emission at low voltage. For example, an EL element that forms an organic thin film by vapor deposition of an organic compound is known (Applied
Physics Letters, 51, 913, 1987
Year). However, EL involving an organic compound vapor deposition operation
Device fabrication has a problem in productivity, simplification of the manufacturing process,
From the viewpoint of processability and a large area, it is desirable to manufacture a device by a coating method.

[0003] As an EL element material used for producing a coating type EL element which is advantageous in productivity, for example, a π-conjugated polymer typified by paraphenylene vinylene is known. Therefore, there are problems that it is difficult to control the concentration of the light emitting material, and it is difficult to finely control the color tone and the light emission intensity. Similarly, as an EL element using a coating method, for example, an element in which a low-molecular-weight fluorescent compound is dispersed in poly (N-vinylcarbazole) (Japanese Patent Laid-Open No. 4-2)
12286). In this method, the type of fluorescent compound can be changed arbitrarily, so the color tone and emission intensity can be adjusted relatively easily.However, when driven after a long time lapse or when driven continuously, layer separation easily occurs, However, there was a problem that light emission was not obtained and light emission characteristics were not excellent. In addition, a device using a polymer for organic EL which has been conventionally developed does not always have sufficient durability. One of the causes is considered to be separation of the interface between the organic layer and the cathode due to heat generation during driving or the like. In order to suppress this, it is desired to develop a material for improving the adhesion at the layer interface.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a material for an organic EL device and an organic EL device which have good light emission characteristics and excellent stability upon repeated use.

[0005]

This object has been achieved by the following means.

(1) An organic electroluminescent device material comprising a compound containing at least one repeating unit represented by the following general formula (I):

[0007]

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(Wherein Q ₁ represents an atom group necessary for forming a 5- or 6-membered aromatic ring. X is an oxygen atom, a sulfur atom, NR ₁ , CR ₂ (R ₃ ) ( R ₁ , R ₂ , and R ₃ each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, or a heterocyclic group.) R represents a hydrogen atom, an alkyl group, or an aryl group. (2) An organic electroluminescent device material, which is a compound containing a polymer having m of 10 to 100,000 described in (1) as a constituent component. (3) In an organic electroluminescence device in which a light emitting layer or a plurality of organic compound thin films including the light emitting layer are formed between a pair of electrodes, at least one layer contains at least one of the compounds described in (1) and (2). Characteristic organic electroluminescent element. (4) In an organic electroluminescent device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes, at least one layer is coated with at least one of the compounds described in (1) and (2). An organic electroluminescent device, which is a layer formed.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. First, general formula (I) will be described in detail. Q
₁ represents an atom group necessary for forming a 5- or 6-membered aromatic ring. The aromatic ring formed by Q ₁ is an aryl group or an aromatic heterocyclic group, for example, benzene, pyrrole, imidazole, pyrazole, pyridine, pyrazine,
Pyrimidine, pyridazine, thiazole, isothiazole, oxazole, isoxazole, selenazole,
Triazine and the like. It is preferably a 6-membered aromatic ring, more preferably benzene, pyridine, pyrazine, pyrimidine and pyridazine, further preferably benzene and pyridine, and particularly preferably benzene. The 5- or 6-membered aromatic ring formed by Q ₁ may have a substituent, for example, an alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably carbon atom Formulas 1 to 10, for example, methyl, ethyl,
iso-propyl, tert-butyl, n-octyl,
n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 10 carbon atoms, and examples thereof include propargyl and 3-pentynyl), and an aryl group (preferably). Is 6 to 30 carbon atoms, more preferably 6 carbon atoms
-20, particularly preferably 6-12 carbon atoms, for example, phenyl, p-methylphenyl, naphthyl and the like. ), Amino group (preferably 0 to 30 carbon atoms, more preferably 0 to 20 carbon atoms, particularly preferably 0 to 0 carbon atoms)
10, for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino, diphenylamino, ditolylamino and the like. ), An alkoxy group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms,
For example, methoxy, ethoxy, butoxy, 2-ethylhexyloxy and the like can be mentioned. ), An aryloxy group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 2 carbon atoms)
0, particularly preferably 6 to 12 carbon atoms, for example, phenyloxy, 1-naphthyloxy, 2-naphthyloxy and the like. ), An acyl group (preferably having 1 carbon atom)
-30, more preferably 1-20 carbon atoms, particularly preferably 2-12 carbon atoms, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and particularly preferably having 2 to 2 carbon atoms.
12, for example, methoxycarbonyl, ethoxycarbonyl and the like. ), An aryloxycarbonyl group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 12 carbon atoms, and examples thereof include phenyloxycarbonyl).
Acyloxy group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, and particularly preferably having 2 to 10 carbon atoms)
And examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably having 2 to 2 carbon atoms)
30, more preferably 2 to 20 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetylamino and benzoylamino. ), An alkoxycarbonylamino group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, particularly preferably having 2 to 12 carbon atoms, for example, methoxycarbonylamino and the like), aryloxycarbonylamino Group (preferably having 7 to 30 carbon atoms, more preferably having 7 to 20 carbon atoms, particularly preferably having 7 to 12 carbon atoms, such as phenyloxycarbonylamino, etc.), and a sulfonylamino group (preferably having a carbon number of 7). 1-30, more preferably 1-20 carbon atoms, particularly preferably 1-12 carbon atoms, such as methanesulfonylamino, benzenesulfonylamino, etc.), sulfamoyl group (preferably 0-30 carbon atoms, More preferably 0 to 2 carbon atoms
0, particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like. ), Carbamoyl group (preferably having 1 to 30 carbon atoms,
More preferably, it has 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl. ), An alkylthio group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as methylthio and ethylthio, etc.), and an arylthio group (preferably carbon Number 6 to 30, more preferably carbon number 6 to 20,
Particularly preferably, it has 6 to 12 carbon atoms, such as phenylthio. ), A sulfonyl group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl). It has 1 to 30, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include methanesulfinyl and benzenesulfinyl.
A ureido group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 20 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as ureide, methylureide, and phenylureide), and a phosphoric amide group (Preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoramide, phenylphosphoramide, etc.), hydroxy group, mercapto Group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group,
An imino group, a heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom, specifically, for example, imidazolyl, pyridyl, Quinolyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzthiazolyl, etc.). These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, the rings may be linked.

The substituent is preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an acyloxy group, an acylamino group, or an alkoxy group. Carbonylamino group, aryloxycarbonylamino group, sulfonylamino group, sulfamoyl group, carbamoyl group, alkylthio group, arylthio group, sulfonyl group, halogen atom, cyano group, heterocyclic group or substituent linked to form a condensed ring And more preferably an alkyl group,
Alkenyl group, aryl group, halogen atom, cyano group,
Heterocyclic group, a substituent is linked to form a benzene ring, more preferably an alkyl group, an alkenyl group,
An aryl group, a heterocyclic group, and a substituent are linked to form a benzene ring, and particularly preferably an alkyl group, an alkenyl group, an aryl group, an aromatic heterocyclic group, and a substituent are linked to form a benzene ring. It was done.

X is an oxygen atom, a sulfur atom, NR ₁ , C
R ₂ (R ₃ ) (R ₁ , R ₂ and R ₃ are each a hydrogen atom,
Represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. ). The aliphatic hydrocarbon group represented by R ₁ , R ₂ and R ₃ may be linear, branched or cyclic, and is preferably an alkyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom). -12, particularly preferably 1-8 carbon atoms
For example, methyl, ethyl, iso-propyl, t
tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, and examples thereof include vinyl, allyl, 2-butenyl, and 3-pentenyl. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, and particularly preferably having 2 carbon atoms.
To 8, for example, propargyl, 3-pentynyl and the like. ), More preferably an alkyl group,
It is an alkenyl group, more preferably an alkyl group. The aryl groups represented by R ₁ , R ₂ and R ₃ are monocyclic or condensed aryl groups, and preferably have 6 to 3 carbon atoms.
0, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, 4-methylphenyl, 4-methoxyphenyl, 3-trifluoromethylphenyl, pentafluorophenyl, 1-naphthyl, 2
-Naphthyl and the like. The heterocyclic group represented by R ₁ , R ₂ and R ₃ is a monocyclic or condensed heterocyclic group (preferably having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, more preferably 2 to 2 carbon atoms). 10 heterocyclic groups), and is preferably an aromatic heterocyclic group containing at least one of a nitrogen atom, an oxygen atom, a sulfur atom and a selenium atom. R ₁ ,
Specific examples of the heterocyclic group represented by R ₂ and R ₃ include, for example, pyrrolidine, piperidine, pyrrole, furan, thiophene, imidazoline, imidazole, benzimidazole, naphthoimidazole, thiazolidine, thiazole, benzthiazole, naphthothiazole, Thiazole, oxazoline, oxazole, benzoxazole, naphthoxazole, isoxazole, selenazole, benzoselenazole, naphthoselenazole, pyridine, quinoline, isoquinoline, indole, indolenine, pyrazole, pyrazine, pyrimidine, pyridazine, triazine, indazole, purine, Phthalazine,
Naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, phenanthridine, pteridine, phenanthroline, tetrazaindene and the like, preferably furan, thiophene, pyridine, quinoline, pyrazine, pyrimidine, pyridazine, triazine, phthalazine, naphthyridine, quinoxaline, Quinazoline,
More preferred are furan, thiophene, pyridine and quinoline.

R ₁ is preferably a hydrogen atom, an alkyl group, an aryl group, or an aromatic heterocyclic group. R ₂ , R
₃ is preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, more preferably an alkyl group, and still more preferably a lower alkyl group. Preferably an oxygen atom as X, a sulfur atom, an N-R _1, and more preferably an oxygen atom, a N-R _1, more preferably N-R ₁
It is.

R represents a hydrogen atom, an alkyl group or an aryl group. Preferably, the alkyl group represented by R is
It has 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms, for example, methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl , Cyclopropyl,
Cyclopentyl, cyclohexyl and the like can be mentioned. R
The aryl group represented by preferably has 6 to 3 carbon atoms
It has 0, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl. The alkyl group and the aryl group represented by R may have a substituent, and examples of the substituent include those described as the substituent for the aromatic ring formed by Q ₁ . R is preferably a hydrogen atom,
It is an alkyl group, more preferably a hydrogen atom and a lower alkyl group, and further preferably a hydrogen atom and a methyl group.

M represents an integer of 1 or more, preferably 10
~ 100,000, more preferably 10-1000
0, and more preferably 10 to 5000.

The compound of the present invention contains at least one repeating unit of the formula (I), and may be a homopolymer or a polymer with another monomer. Further, it may be a random copolymer or a block copolymer. The number average molecular weight (M) of a polymer containing at least one repeating unit represented by the general formula (I)
n) is not uniform because it differs depending on the type of the substituent,
Preferably 2000 to 500,000, more preferably 3000
３０300,000, and more preferably 3,000 to 200,000. The weight average molecular weight (Mw) also varies depending on the type of the substituent and is not uniform, but is preferably 2000 to 1.5 million, more preferably 3000 to 1,000,000, and still more preferably 300 to 1,000,000.
0 to 500,000.

Further, the polymer of the present invention may contain a skeleton having a hole transporting function, an electron transporting function or a luminescent function in the compound. Hereinafter, specific examples of the polymer of the present invention are shown, but the present invention is not limited thereto.

[0017]

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[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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The polymerization method of the polymer of the present invention is not limited, and examples thereof include a radical polymerization method and an ionic polymerization method, and the radical polymerization method is preferred. As the initiator of the radical polymerization method, for example, azo compounds, peroxides and the like,
Preferred are azobisisobutyronitrile, azobisisobutyric acid diester derivatives, and dibenzoyl peroxide.

Although the polymerization solvent is not particularly limited, for example, aromatic hydrocarbons (eg, benzene, toluene, etc.), halogenated hydrocarbons (eg, dichloroethane, chloroform, etc.), ethers (eg, tetrahydrofuran, dioxane, etc.), amides (Eg, dimethylformamide, dimethylacetamide, etc.), ester type (eg, ethyl acetate, etc.), alcohol type (eg, methanol, etc.), ketone type (eg, acetone, cyclohexanone, etc.). Depending on the selection of the solvent, solution polymerization in which polymerization is performed in a homogeneous system and precipitation polymerization in which the generated polymer precipitates can also be performed.

The light-emitting device of the present invention is a device in which a light-emitting layer or a plurality of organic compound thin films including the light-emitting layer is formed between a pair of anode and cathode electrodes. , An electron injection layer, an electron transport layer, a protective layer, and the like, and each of these layers may have another function. Various materials can be used for forming each layer.

The anode supplies holes to the hole injection layer, the hole transport layer, the light emitting layer, and the like. A metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof is used. It is possible to use a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), or metals such as gold, silver, chromium, and nickel, and furthermore, these metals and conductive metal oxides. Mixtures or laminates, inorganic conductive substances such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, and the like. Oxides,
In particular, ITO is preferable in terms of productivity, high conductivity, transparency, and the like. The thickness of the anode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 500 nm.

As the anode, a layer formed on a soda lime glass, an alkali-free glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass in order to reduce ions eluted from the glass. Further, when soda lime glass is used, it is preferable to use a glass coated with a barrier coat such as silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength. When glass is used, the thickness is usually 0.2 mm or more, preferably 0.7 mm or more. Various methods are used for producing the anode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating evaporation method, a chemical reaction method (such as a sol-gel method), and a coating of a dispersion of indium tin oxide are used. The film is formed by the method described above. The anode can be cleaned or otherwise treated to lower the device's drive voltage,
It is also possible to increase the luminous efficiency. For example, in the case of ITO, UV-ozone treatment or the like is effective.

The cathode supplies electrons to the electron injection layer, the electron transport layer, the light-emitting layer, and the like. The cathode has good adhesion, ionization potential, and the like between the negative electrode such as the electron injection layer, the electron transport layer, and the light-emitting layer. It is selected in consideration of stability and the like. As the material of the cathode, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used, and specific examples thereof include an alkali metal (eg, Li, Na, K, etc.) or a fluoride thereof, and an alkaline earth metal. Metals such as Mg, Ca
Etc.) or its fluorides, gold, silver, lead, aluminum,
Sodium-potassium alloy or a mixed metal thereof, lithium-aluminum alloy or a mixed metal thereof, magnesium-silver alloy or a mixed metal thereof, indium, rare earth metals such as ytterbium, and the like, preferably having a work function of 4 eV or less. The material is more preferably aluminum, a lithium-aluminum alloy or a mixed metal thereof, a magnesium-silver alloy or a mixed metal thereof, or the like. The thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 1 μm. A method such as an electron beam method, a sputtering method, a resistance heating evaporation method, or a coating method is used for manufacturing the cathode, and a metal can be evaporated alone or two or more components can be simultaneously evaporated. Further, an alloy electrode can be formed by depositing a plurality of metals at the same time, or an alloy prepared in advance may be deposited. The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

The material of the light emitting layer is capable of injecting holes from an anode or a hole injection layer or a hole transport layer and applying electrons from a cathode or an electron injection layer or an electron transport layer when an electric field is applied. Any material can be used as long as it can form a layer having a function, a function of transferring injected charges, and a function of providing a field of recombination of holes and electrons to emit light. Preferably, the light-emitting layer contains the compound of the present invention, but other light-emitting materials of the compound of the present invention can also be used. For example, benzoxazole derivatives,
Benzimidazole derivatives, benzothiazole derivatives,
Styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazine derivatives, pyrazine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, Quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, various metal complexes represented by metal complexes of 8-quinolinol derivatives and rare earth complexes, polythiophene, polyphenylene, polyphenylene And polymer compounds such as vinylene. Although the thickness of the light emitting layer is not particularly limited, it is usually 1n.
m to 5 μm, more preferably 5 to 5 μm.
nm to 1 μm, more preferably 10 nm to 500
nm. The method for forming the light-emitting layer is not particularly limited, but a method such as resistance heating evaporation, electron beam, sputtering, molecular lamination, coating (spin coating, casting, dip coating, etc.), and LB method And preferably a resistance heating evaporation and coating method.

The material of the hole injection layer and the hole transport layer has one of a function of injecting holes from the anode, a function of transporting holes, and a function of blocking electrons injected from the cathode. Anything should do. Specific examples thereof include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, and styryl anthracene derivatives , Fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidin compound, porphyrin compound, polysilane compound,
Examples thereof include poly (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, and conductive polymer oligomers such as polythiophene. The thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 5 μm.
00 nm. The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the hole injection layer and the hole transport layer include a vacuum deposition method, an LB method, and a method in which the hole injection / transport agent is dissolved or dispersed in a solvent and coated (spin coating method, casting method, dip coating method). Etc.) are used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinyl carbazole), hydrocarbon resins, ketone resins, phenoxy resins, polyamides, ethyl cellulose, vinyl acetate, ABS resins, polyurethanes, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, and the like.

The material of the electron injecting layer and the electron transporting layer is not limited as long as it has a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. Good. Specific examples thereof include triazole derivatives, oxazole derivatives, oxadiazole derivatives,
Heterocyclic tetracarboxylic anhydrides such as fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene perylene, and phthalocyanine derivatives And various metal complexes typified by metal complexes of 8-quinolinol derivatives, metal phthalocyanines, and metal complexes having benzoxazole or benzothiazole as ligands. The thickness of the electron injection layer and the electron transport layer is not particularly limited, but is usually 1 nm to 5 μm.
m, more preferably 5 nm to 1
μm, and more preferably 10 nm to 500 nm. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-mentioned materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the electron injection layer and the electron transport layer include a vacuum deposition method, an LB method, and a method in which the electron injection and transport agent is dissolved or dispersed in a solvent and coated (spin coating, casting, dip coating, and the like). Is used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection transport layer can be applied.

As the material of the protective layer, any material may be used as long as it has a function of preventing the element which promotes the element deterioration such as moisture and oxygen from entering the element. As a specific example,
In, Sn, Pb, Au, Cu, Ag, Al, Ti, N
metal such as i, MgO, SiO, SiO ₂ , Al ₂ O ₃ ,
GeO, NiO, CaO, BaO, Fe 2 O 3, Y 2 O
_3, a metal oxide such as TiO _2, MgF _2, LiF, Al
F ₃ , metal fluoride such as CaF ₂ , polyethylene, polypropylene, polymethyl methacrylate, polyimide,
Polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer Copolymer obtained, a fluorine-containing copolymer having a cyclic structure in the copolymer main chain, a water-absorbing substance having a water absorption of 1% or more,
A moisture-proof substance having a water absorption of 0.1% or less can be used. There is no particular limitation on the method for forming the protective layer. For example, a vacuum deposition method, a sputtering method, a reactive sputtering method,
BE (molecular beam epitaxy) method, cluster ion beam method, ion plating method, plasma polymerization method (high frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating method Applicable.

[0036]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Comparative Example 1 39 mg of poly (N-vinylcarbazole), PBD (t
-Butylphenyldiphenyloxadiazole) 12 m
g and 1 mg of compound A in 3 ml of 1,2-dichloroethane
And spin-coated on the washed ITO substrate.
The thickness of the generated organic thin film was about 110 nm. Mask patterned on organic thin film (light emitting area is 5mm
X5 mm), and magnesium: silver = 10: 1 was co-deposited at 250 nm in a vapor deposition apparatus.
00 nm was deposited (8 × 10 ⁻⁶ to 1 × 10 ⁻⁵ Torr).
r).

[0037]

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Comparative Example 2 37 mg of poly (N-vinylcarbazole), PBD12
mg and compound B3m in 1,2-dichloroethane 3 ml
, And the same operation as in Comparative Example 1 was performed to produce a device.

[0039]

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Example 1 A device was prepared by dissolving 40 mg of Exemplified Compound 23 of the present invention and 12 mg of PBD in 3 ml of 1,2-dichloroethane, and performing the same operation as in Comparative Example 1. Example 2 39 mg of Exemplified Compound 5 of the present invention, 12 mg of PBD and 1 mg of Compound A were dissolved in 3 ml of 1,2-dichloroethane, and the same operation as in Comparative Example 1 was performed to produce a device. Example 3 37 mg of Exemplified Compound 5 of the present invention, 12 mg of PBD and 233 mg of Exemplified Compound of the present invention were treated with 1,2-dichloroethane 3
The resultant was dissolved in the same solution as in Comparative Example 1, and the same operation as in Comparative Example 1 was performed to produce a device. Example 4 39 mg of Exemplified Compound 14 of the present invention and 1 mg of Compound A were dissolved in 3 ml of 1,2-dichloroethane, and the same operation as in Comparative Example 1 was carried out to produce a device. Example 5 39 mg of Exemplified Compound 15 of the present invention, 12 mg of PBD and 1 mg of Compound A were dissolved in 3 ml of 1,2-dichloroethane, and the same operation as in Comparative Example 1 was carried out to produce a device. Example 6 40 mg of Exemplified Compound 22 of the present invention was dissolved in 2.5 ml of 1,2-dichloroethane and spin-coated on a washed ITO substrate. The thickness was about 80 nm. The substrate was set in a vacuum deposition apparatus, and zinc complex C was vacuum-deposited by about 20 nm. A mask (a mask having a light-emitting area of 5 mm × 5 mm) patterned on the organic thin film was provided, and magnesium: silver = 10: 1 was co-evaporated at 250 nm in an evaporation apparatus, and then 300 nm of silver was evaporated (8 × 10 ^{−). 6} to 1 × 10 ^-5
Torr).

[0041]

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Table 1 shows the emission characteristics of the fabricated device. The emission characteristics were measured as follows. Using Toyo Technica Source Measure Unit Model 2400, ITO was used as anode and M
g: A DC constant voltage was applied to the EL element using Ag as a cathode to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation, and the emission wavelength was measured using a spectrum analyzer P manufactured by Hamamatsu Photonics.
It was measured using MA-11. In addition, the fabricated device
Evaluate the relative luminance (luminance after lapse of time assuming that the luminance immediately after device production is 100) expressed as a relative value (drive voltage 15 V) after leaving for 3 hours under the condition of 0 ° C. and 20% RH. did. Table 1 shows the results.

[0043]

[Table 1]

From the results shown in Table 1, it can be seen that the use of the compound of the present invention makes it possible to reduce the minimum driving voltage and to emit light with high luminance. In addition, it can be seen that the luminance decrease after storage at high temperature is small and the durability is excellent.

[0045]

According to the present invention, it is possible to obtain an organic EL device which can emit light with high luminance and has good durability. In particular, good light-emitting characteristics can be obtained even by a coating method with low luminance, and an element can be produced which is advantageous in terms of manufacturing cost.

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[Procedure amendment]

[Submission date] November 24, 1998 (1998.11.
24)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0025

[Correction method] Change

[Correction contents]

[0025]

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[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0040

[Correction method] Change

[Correction contents]

Example 1 A device was prepared by dissolving 40 mg of Exemplified Compound 23 of the present invention and 12 mg of PBD in 3 ml of 1,2-dichloroethane, and performing the same operation as in Comparative Example 1. Example 2 39 mg of Exemplified Compound 5 of the present invention, 12 mg of PBD and 1 mg of Compound A were dissolved in 3 ml of 1,2-dichloroethane, and the same operation as in Comparative Example 1 was performed to produce a device. Example 3 37 mg of Exemplified Compound 5 of the present invention, 12 mg of PBD and 233 mg of Exemplified Compound of the present invention were treated with 1,2-dichloroethane 3
The resultant was dissolved in the same solution as in Comparative Example 1, and the same operation as in Comparative Example 1 was performed to produce a device. Example 4 39 mg of Exemplified Compound 14 of the present invention and 1 mg of Compound A were dissolved in 3 ml of 1,2-dichloroethane, and the same operation as in Comparative Example 1 was carried out to produce a device. Example 5 39 mg of Exemplified Compound 15 of the present invention, 12 mg of PBD and 1 mg of Compound A were dissolved in 3 ml of 1,2-dichloroethane, and the same operation as in Comparative Example 1 was carried out to produce a device. Example 6 40 mg of Exemplified Compound 22 of the present invention was dissolved in 2.5 ml of 1,2-dichloroethane and spin-coated on a washed ITO substrate. The thickness was about 80 nm. The substrate was set in a vacuum deposition apparatus, and zinc complex C was vacuum-deposited by about 20 nm. A mask (a mask having a light-emitting area of 5 mm × 5 mm) patterned on the organic thin film was provided, and magnesium: silver = 10: 1 was co-evaporated at 250 nm in an evaporation apparatus, and then 300 nm of silver was evaporated (8 × 10 ^{−). 6} to 1 × 10 ^-5
Torr).

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 3K007 AB00 AB02 AB06 AB12 AB13 AB18 BB00 CA01 CA05 CB01 DA00 DB03 EB00 FA01 4J100 AB07Q AB07R AL08Q AM21R AQ06Q AQ15P AQ19P AQ28P BA02Q BA05Q BA05R BA11Q BA28Q BC43P BCBC BCBC BCBC BCBC BCBC BC BC BC73Q BC73R BC79P BC79Q BC83P CA01 CA04 CA05 DA01 JA32 JA43

Claims (4)

[Claims] 1. An organic electroluminescent device material comprising a compound containing at least one repeating unit represented by the following general formula (I). Embedded image (In the formula, Q ₁ represents an atomic group necessary for forming a 5- or 6-membered aromatic ring. X represents an oxygen atom, a sulfur atom, NR
₁ and CR ₂ (R ₃ ) (R ₁ , R ₂ and R ₃ each represent a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group). R represents a hydrogen atom, an alkyl group or an aryl group. m represents an integer of 1 or more. ) 2. The method according to claim 1, wherein m is 10 to 100,000.
An organic electroluminescent device material, characterized in that it is a compound containing a polymer as a constituent component. 3. An organic electroluminescence device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes, wherein at least one layer contains at least one compound according to claim 1 or 2. Characteristic organic electroluminescent element. 4. An organic electroluminescence device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes, at least one layer is coated with at least one of the compounds according to claim 1 or 2. An organic electroluminescent device, which is a layer formed.