JP2001226469A - New polymer, luminescent element material and luminescent element using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a material which has a good electron transport property, is suitable for forming luminescent elements by a coating process, and is useful the luminescent elements that can be driven at a low voltage, has good luminescent characteristics, can be applied to a wide wavelength region, and has excellent stability, when repeatedly used, and to provide a luminescent element. SOLUTION: This luminescent element material using a polymer having structural units represented by the general formula (I) [Ar is a conjugated unsaturated group, provided that nitrogen-containing heterogeneous rings containing two or more nitrogen atoms are excluded; (m) and (n) are each a molar fraction in the polymer; (m)+(n)=100; (n) is a numerical value of 0 to <100; R is hydrogen atom or a substituent, provided that when Ar is a substituted fruorene ring or an alkoxy-substituted benzene ring, (n) is not a numerical value of 50].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer having a high electron affinity, a material for a light emitting device capable of converting electric energy into light and emitting light, and a display device, a display, a backlight, an electrophotograph, and an illumination light source. The present invention relates to a light emitting element which can be suitably used in fields such as a recording light source, a reading light source, a sign, a signboard, and an interior.

[0002]

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

[0003] As a light emitting device material used for producing a light emitting device of a coating method which is advantageous in productivity, for example, a π-conjugated polymer represented by polyparaphenylenevinylene (PPV) is known. There are many problems for practical use, such as strength and durability. Similarly, as a light-emitting element using a coating method, for example, there is an element in which a low-molecular-weight fluorescent compound is dispersed in poly (N-vinylcarbazole) (JP-A-4-212286). In this method, since the kind of the fluorescent compound can be arbitrarily changed, it is relatively easy to adjust the color tone and the emission intensity.However, when the driving voltage is high, and when driving after a long time lapse or when driving continuously,
There was also a problem in terms of durability, such as a tendency for luminance to drop.

It is believed that these problems are due in part to poor electron injecting and electron transporting properties from the cathode, and attempts have been made to develop various electron injecting and electron transporting polymers. However, it has not yet shown satisfactory physical properties and performance. For example, polyacetylene or the like, which is famous for an electron-transporting (conductive) polymer, has problems in solubility and film-forming properties, and is not suitable for element production by a coating process. Also, J.I. P
hys. : Condens. Matter 10 (199
8) Poly (2,5-pyridinediyl) as reported in 5171-5178, Synthetic
In a polymer such as poly (p-pyridylvinylene) as reported in Metals 85 (1997) 1179-1182, the electron transporting material has a narrow band gap and cannot be used for a blue light emitting element and a green light emitting element. The conventional problems such as insufficient injectability, poor conductivity, poor solubility in general-purpose organic solvents, and solubility only in special solvents such as formic acid, etc. were not reached.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide a light emitting device having a good electron transporting property, suitable for producing a light emitting device by a coating process, capable of being driven at a low voltage, and having good light emitting characteristics.
An object of the present invention is to provide a light-emitting element material and a light-emitting element which can be applied to a wide wavelength range and have excellent stability upon repeated use.

[0006]

This object has been achieved by the following means. [1] A polymer having at least one structure represented by the following general formula (I).

[0007]

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(In the formula, Ar represents a conjugated unsaturated group, provided that a nitrogen-containing heterocyclic ring having two or more nitrogen atoms is excluded.
m and n represent the mole fraction in the polymer, and m + n = 1
00. n represents a numerical value of 0 or more and less than 100. R represents a hydrogen atom or a substituent. However, when Ar is a substituted fluorene ring or an alkoxy-substituted benzene ring, n does not take a value of 50. [2] In the general formula (I), Ar is a conjugated unsaturated group other than a nitrogen-containing heterocyclic ring having two or more nitrogen atoms, a substituted fluorene ring, and an alkoxy-substituted benzene ring. ] The novel polymer as described above. [3] A light emitting device material comprising a polymer having at least one structure represented by the following general formula (I).

[0009]

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(In the formula, Ar represents a conjugated unsaturated group, provided that a nitrogen-containing heterocyclic ring having two or more nitrogen atoms is excluded.
m and n represent the mole fraction in the polymer, and m + n = 1
00. n represents a numerical value of 0 or more and less than 100. R represents a hydrogen atom or a substituent. However, when Ar is a substituted fluorene ring or an alkoxy-substituted benzene ring, n does not take a value of 50. [4] In the general formula (I), Ar is a conjugated unsaturated group other than a nitrogen-containing heterocycle having two or more nitrogen atoms, a substituted fluorene ring, and an alkoxy-substituted benzene ring. ] The light emitting device material according to the above. [5] A light-emitting element having a light-emitting layer or a plurality of organic compound thin layers including the light-emitting layer formed between a pair of electrodes, wherein at least one layer contains at least one polymer according to the above [3]. Light emitting element. [6] In a light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, at least one film is formed by applying at least one polymer described in the above [3]. A light-emitting element, which is a layer. [7] A light-emitting element having a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer formed between a pair of electrodes, wherein at least one layer contains at least one polymer according to the above [4]. Light emitting element. [8] In a light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer are formed between a pair of electrodes, at least one layer is formed by applying at least one polymer described in the above [4]. A light-emitting element, which is a layer.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polymer of the present invention is a compound containing at least one structure represented by the general formula (I), and preferably has the structure represented by the general formula (I) in a polymer main chain and / or a side chain. Things. The polymer having at least the structure represented by the general formula (I) has high electron affinity, good solubility in water and an organic solvent, and has good electron injection, electron transport,
This is extremely effective for producing a light emitting device by a coating process.

In the general formula (I), Ar may have a double bond, a triple bond, and / or an aromatic ring in its conjugated system, and is selected depending on various physical properties when polymerized. Ar may also have two or more skeletons,
The entire polymer may be a multi-component copolymer. Ar
As a substituted or unsubstituted arylene group having up to 20 total atoms, a substituted or unsubstituted heteroarylene group having up to 20 total atoms having no more than 2 nitrogen atoms,
And tertiary arylamines are preferred, among which phenylene, biphenylene, terphenylene, naphthylene,
Fluorene, acenaphthene, phenanthrene, anthracene, fluoranthene, pyrene, perylene, rubrene,
Chrysene, furan, thiophene, pyrrole, oxazole, isoxazole, thiazole, isothiazole,
Imidazole, pyridine, benzoxazole, benzothiazole, quinoline, isoquinoline, phenanthridine, acridine, carbazole, diphenylene oxide, triphenylamine, N, N'-diphenylbenzidine, N, N'-diphenyl-1,4-phenylene Diamine, diphenylnaphthylamine, tetraarylsilane, diaryldivinylsilane, dialkyldiarylsilane, dialkyldivinylsilane are more preferred, phenylene, biphenylene, fluorene, anthracene,
Particularly preferred are pyrrole, oxazole, pyridine and quinoline, which may have one or more substituents. Examples of the substituent include an alkyl group having up to 20 carbon atoms, an aryl group having up to 20 carbon atoms, an aralkyl group having up to 20 carbon atoms, a (thio) alkoxy group having up to 20 carbon atoms, and a (thio) up to 20 carbon atoms. A) an aryloxy group, a cyano group, a fluoro group, a chloro group, an alkoxycarbonyl group having up to 20 carbon atoms, an aryloxycarbonyl group having up to 20 carbon atoms, a polyalkyleneoxy group, an alkylsulfonyl group, and an arylsulfonyl group; so,
Alkyl group, alkoxy group, polyalkyleneoxy group,
A cyano group is particularly preferred, and an alkyl group and an alkoxy group are more preferred. Examples of R include a hydrogen atom and carbon number 20.
Alkyl group of up to, aryl groups of up to 20 carbon atoms, an aralkyl group having up to 20 carbon atoms or a polyalkyleneoxy group of up to 20 carbon atoms is preferable, in this, an alkyl group, polyalkyleneoxy groups are more preferred, C ₁ alkyl group -C ₆ (methyl, ethyl, propyl, n- butyl, n- hexyl) is particularly preferred.

The novel polymer having at least the structure represented by the general formula (I) of the present invention is useful as a conductive polymer, an electron transporting polymer, and an electron injecting polymer.

The polymer of the present invention having at least the structure represented by the general formula (I) may be a homopolymer or a copolymer with another monomer. Also,
The copolymer may be a random copolymer, an alternating copolymer, a block copolymer, or a graft copolymer. Further, a star burst type homopolymer or copolymer may be used. As described above, Ar may be a multi-component copolymer having two types of skeletons. The substance that controls light emission in the present invention may be a polymer having at least the structure represented by the general formula (I), or may be another light-emitting polymer or a light-emitting low-molecular compound.
Further, the polymer of the present invention may include a skeleton portion having a hole transporting function, an electron transporting function, or a light emitting function in the compound.

In the general formula (I), n is preferably a numerical value of 0 to 70, more preferably 0 to 50, and particularly preferably a numerical value of 0 to 30. In the case where Ar is only a substituted fluorene ring or only an alkoxy-substituted benzene ring, when n takes a value near 50, the effect of the pyridine ring contributing to the polymer properties is offset by the alkyl-substituted fluorene ring and the alkoxy-substituted benzene ring portion. However, not only is it undesirable in terms of the polymer electronic structure, applicability, film formability, and device characteristics, but also because it has low polarity, it cannot be laminated and applied on a luminescent material such as polyfluorene.

The average molecular weight of the polymer having at least the structure represented by the general formula (I) is not uniform since it varies depending on the type of the substituent, but is preferably from 500 to 10,000.
00, more preferably 700 to 700,000, still more preferably 1,000 to 500,000.

Specific examples of the polymer having at least the structure represented by the general formula (I) are shown below, but the present invention is not limited thereto.

[0018]

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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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[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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Although the polymerization method of the polymer of the present invention is not limited, for example, a reaction in the presence of a base of bishalomethylarylene,
Examples include a condensation reaction of dimethyl arylene and diformyl arylene, a Wittig reaction, a Suzuki coupling, and the like. Examples of polymerization are described in, for example, the method of WO94 / 20589, Polymer, 1994, vol. 35, No.
2, p391, the method of JP-A-7-300580, and the like. When these polymerization methods are used, hundreds to thousands of relatively low molecular weight polymers may be obtained, unlike radical polymerization.

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.), esters (eg, ethyl acetate, etc.), alcohols (eg, methanol, etc.), ketones (eg, acetone, cyclohexanone, etc.), nitromethane, water, and those containing two-phase solvents. A mixed solvent and the like can be mentioned. 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 solvent for dissolving the polymer of the present invention and the coating solvent can be freely selected depending on the structure of the polymer. For example, in the case of a highly polar polymer such as Exemplified Compound 1, various highly polar solvents such as water, methanol and other alcohols, formic acid, acetic acid, cellosolve-based solvents, glycol-based solvents, dioxane and the like, and mixed solvents thereof Can be dissolved. On the other hand, in the case of a low-polarity polymer such as Exemplified Compound 2, it can be dissolved in various low-polarity solvents such as tetrahydrofuran, a halogenated hydrocarbon solvent, and an aromatic hydrocarbon solvent. Taking advantage of this advantage, it is dissolved in a highly polar solvent on a low-polarity light-emitting polymer such as a (substituted) phenylene vinylene (co) polymer, a (substituted) fluorene (co) polymer, and a (substituted) phenylene (co) polymer. The polymer of the present invention can be laminated only by a coating process without mixing between layers. Further, a polymer of the present invention dissolved in chloroform or the like is laminated on a water-based coated thin film such as a PEDOT-PSS film (polyethylenedioxythiophene-polystyrenesulfonic acid-doped material) only by a coating process without mixing between layers. It is equally possible.
Preferred coating solvents are water, methanol, ethanol, propanol, isopropanol, butanol, formic acid, acetic acid, methyl cellosolve, ethyl cellosolve, ethylene glycol, propylene glycol, dioxane,
Benzene, toluene, xylene, chloroform, dichloromethane, dichloroethane, tetrahydrofuran and mixed solvents thereof are preferable, and water, methanol, ethanol, propanol, isopropanol, acetic acid, methyl cellosolve, ethyl cellosolve, ethylene glycol, dioxane, toluene, chloroform, dichloromethane, dichloromethane,
Dichloroethane, tetrahydrofuran and their mixed solvents are particularly preferred.

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 are 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, etc., and can be made of a metal, an alloy, a metal oxide, a conductive compound, or a mixture thereof. , Preferably 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. It is an oxide, and ITO is particularly preferable in terms of productivity, high conductivity, transparency, and the like. The thickness of the anode can be appropriately selected depending on the material.
It is preferably in the range of nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 1 μm.
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. 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 to form 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 dispersion of indium tin oxide are used. The film is formed by a method such as coating. 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, plasma treatment and the like are 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 a material for the cathode, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specific examples thereof include an alkali metal (for example, L
i, Na, K, etc.) and their fluorides, alkaline earth metals (eg, Mg, Ca, etc.) and their fluorides, gold, silver,
Lead, alnium, 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 a work function Is 4 eV or less, 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 cathode can have not only a single-layer structure of the compound and the mixture, but also a stacked structure including the compound and the mixture. The thickness of the cathode can be appropriately selected depending on the material, but is usually from 10 nm to 5 nm.
μm is preferable, and more preferably 50 nm
To 1 μm, and 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 15Ω / □ 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 a conjugated unsaturated compound, but the polymer of the present invention or another light emitting material may be used. For example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives,
Diphenylbutadiene derivative, tetraphenylbutadiene derivative, naphthalimide derivative, coumarin derivative, perylene derivative, perinone derivative, oxadiazole derivative, aldazine derivative, pyrazine derivative, cyclopentadiene derivative, bisstyrylanthracene derivative, quinacridone derivative, pyrrolopyridine derivative, (Substituted) polythiophene, (substituted) polyphenylene, (substituted), etc., such as asiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, various metal complexes represented by 8-quinolinol derivatives and rare earth complexes. Polymer compounds such as polyfluorene and (substituted) polyphenylenevinylene are exemplified. The thickness of the light emitting layer is not particularly limited, but is 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 1 μm.
500 nm.

The method for forming the light emitting layer is not particularly limited, but includes resistance heating evaporation, electron beam, sputtering, molecular lamination, coating (spin coating, casting, dip coating, etc.), and ink jetting. , A printing method, an LB method and the like, and preferably a resistance heating evaporation and a coating method.

The material of the hole injection layer and the hole transport layer has any of a function of injecting holes from the anode, a function of transporting holes, and a function of blocking electrons injected from the cathode. Any material may be used, and the polymer of the present invention or another material may be used. 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,
Conductive polymer oligomers such as poly (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, polythiophenes, (substituted) polythiophene-polystyrenesulfonic acid mixtures, and the like. The thickness of the hole injection layer and the hole transport layer is not particularly limited, but is 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 1 μm.
nm to 500 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.

As a method for forming the hole injection layer and the hole transport layer, a vacuum deposition method, an LB method, an ink jet method, a printing method,
A method of coating by dissolving or dispersing the hole injecting and transporting agent in a solvent (spin coating, casting, dip coating, etc.) is 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, and polysulfone.
Polyphenylene oxide, polybutadiene, poly (N-
Vinyl carbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, silicone resin, 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 a compound of the present invention or a triazole derivative, an oxazole derivative, an oxadiazole derivative, a fluorenone derivative, an anthraquinodimethane derivative, an anthrone derivative, a diphenylquinone derivative, a thiopyrandioxide derivative, a carbodiimide derivative, a fluorenide derivative. Representative metal complexes of heterocyclic tetracarboxylic anhydrides such as redenemethane derivatives, distyrylpyrazine derivatives, and naphthalene perylene, phthalocyanine derivatives, and 8-quinolinol derivatives, and metal complexes having metal phthalocyanine, benzoxazole, and benzothiazole as ligands Metal complexes to be used. The thickness of the electron injecting layer and the electron transporting layer is not particularly limited, but is 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 1 μm.
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.

The method for forming the electron injection layer and the electron transport layer includes a vacuum deposition method, an LB method, an ink jet method, a printing method, and the like.
For example, a method of dissolving or dispersing the electron injecting / transporting agent in a solvent and coating (eg, spin coating, casting, dip coating, etc.) 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 a substance which promotes 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.

The method for forming the protective layer is not particularly limited. For example, a vacuum deposition method, a sputtering method, a reactive sputtering method, an MBE (molecular beam epitaxy) method, a cluster ion beam method, an ion plating method, a plasma polymerization method ( High-frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, inkjet method, printing method, and coating method can be applied.

[0055]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Example 1 (Synthesis of Exemplified Compound 1) 60 ml of dried tetrahydrofuran (THF) and 2.20 g of tBuOK were placed in a 200 ml flask under a nitrogen stream.
(19.60 mmol, 6.9 equivalents) was added and dissolved by stirring. Then, a THF solution of 2,6-bis (chloromethyl) pyridine (0.5 g, 2.84 mmol) (10 m
l) was added dropwise over 20 minutes. Thereafter, the mixture was stirred at room temperature for 20 hours. Then, the reaction mixture was dropped into a mixed solvent of ethyl acetate and THF. The resulting precipitate was separated by filtration and vacuum dried to obtain 0.19 g of a polymer of Exemplified Compound 1. Yield 65
%. As a result of measuring the molecular weight of this polymer by gel permeation chromatography (GPC) (polystyrene standard conversion; MeOH / water aeration), the weight average molecular weight was 12,000, and the number average molecular weight was 980.
It was 0. This polymer was soluble in water and MeOH.

Example 2 (Synthesis of Exemplified Compound 2) 2,6-bis (chloromethyl) pyridine (0.5 g,
(2.48 mmol) in THF was added to 2,6-bis (chloromethyl) pyridine (0.375 g, 2.13 mmol).
l) and 2,5-bis (chloromethyl) -1- (2-
Ethylhexyloxy) -4-methoxybenzene (0.
237 g (0.71 mmol) of a THF solution was obtained in the same manner as in Example 1 except for obtaining a polymer of Exemplified Compound 2 (0.35 g). Yield 70%. As a result of measuring the molecular weight of this polymer by GPC (in terms of polystyrene standard; THF aeration), the weight average molecular weight was 130.
The number average molecular weight was 11,000. This polymer was soluble in chloroform.

Example 3 (Synthesis of Exemplified Compound 23) In a 100 ml three-necked flask, 2,5-
0.956 g of a phosphonium salt obtained by reacting bis (chloromethyl) -1,4-di-n-octyloxybenzene with triphenylphosphine, 0.915 g
mmol, 0.0268 g of isophthalaldehyde, 0.1.
200 mmol, 0.108 g of 2,6-pyridinedicarboxaldehyde, 0.798 mmol, ethanol 2
5 ml was added and the mixture was stirred at room temperature. Next, an ethanol solution of sodium ethoxide (sodium ethoxide 3 mmol)
1 and ethanol (5 ml) were added dropwise, followed by stirring at room temperature for 15 hours. The produced gummy precipitate was taken out and washed with ethanol, and the precipitate was dissolved in chloroform and reprecipitated into ethanol for purification. Then, it was dried under vacuum to obtain 0.25 g of the target polymer. 55% yield. Weight average molecular weight 7200, number average molecular weight 24500.

Example 4 A PPV precursor solution (manufactured by Cambridge Display Technology Co., Ltd.) was spin-coated on a washed ITO substrate, followed by vacuum drying at 150 ° C. for 2 hours to form a PPV film (about 100 nm thick). A solution prepared by dissolving 20 mg of the polymer of Exemplified Compound 1 in 2 ml of methanol was spin-coated thereon (3000 rpm, 20 seconds) (film thickness: about 20 nm). Next, a mask patterned on this organic thin film (a mask having a light emitting area of 5 mm × 5 mm)
It was placed, magnesium in a vapor deposition apparatus: silver = 10: 1 was deposited 250nm co were deposited silver ^{300nm (1.0 × 10 -3 Pa~1.3 ×} 10 -3 Pa). The emission characteristics were measured as follows. Using Toyo Technica Source Measure Unit Model 2400, ITO as anode, Mg: A
g is used as a cathode, a DC constant voltage is applied to the EL element to emit light, the luminance of which is measured by a luminance meter BM-8 manufactured by Topcon, and the emission wavelength is measured by a spectrum analyzer PMA manufactured by Hamamatsu Photonics.
It measured using -11. In addition, the fabricated device was
The relative luminance (luminance after lapse of time assuming that the luminance immediately after device production was 100, expressed as a relative value (driving voltage: 10 V)) was evaluated after leaving the device for 3 hours under conditions of 20 ° C. and 20% RH. . As a result, light emission was observed from 3 V, and 10
It shows a current density of 35 mA / cm ² and 501 Cd / sq
m emitted green light. The emission wavelength λmax is 500 nm
Met. The relative luminance after aging was 78.

Example 5 In the same manner as in Example 4, ITO / PPV (100 nm) /
A device of Exemplified Compound 2 (50 nm) / Mg-Ag was prepared. The light emission characteristics were measured in the same manner as in Example 4. as a result,
It shows a current density of 300 mA / cm ^{2 at} 16 V and 953
It emitted Cd / sqm green light. The emission wavelengths λmax were 575 nm and 617 nm. The relative luminance after aging was 82.

Example 6 Baytron P (PED) was placed on a cleaned ITO substrate.
OT-PSS solution (polyethylenedioxythiophene-
(Polystyrene sulfonic acid dope) / Bayer) was spin-coated at 2000 rpm for 60 seconds, and then 100
Vacuum drying was performed at 1 ° C. for 1 hour to form a hole transporting film (film thickness: about 100 nm). A solution obtained by dissolving 20 mg of poly (9,9-dioctylfluorene) in 2 ml of chloroform was spin-coated thereon (1000 rpm, 20 seconds) (film thickness: about 70 nm). A solution obtained by dissolving 20 mg of the polymer of Exemplified Compound 1 in 2 ml of methanol was spin-coated thereon (5000 rpm, 20 seconds) (film thickness: about 10 n).
m). Next, a mask (a mask having a light emitting area of 5 mm × 5 mm) patterned on the organic thin film is provided,
400 nm of aluminum was deposited in a deposition apparatus. The light emission characteristics were measured in the same manner as in Example 4. As a result, it showed a current density of 657 mA / cm ^{2 at} 10 V and 5180 Cd /
It emitted blue light of sqm. The emission wavelength λmax is 430
nm. The relative luminance after aging was 77.

Example 7 In the same manner as in Example 6, ITO / poly (9,9-dioctylfluorene) (100 nm) / Exemplified Compound 9 (30n)
m) / Al device was prepared. The light emission characteristics were measured in the same manner as in Example 4. As a result, it showed a current density of 200 mA / cm ^{2 at} 5 V and emitted blue light of 1126 Cd / sqm. The emission wavelength λmax was 431 nm. The relative luminance after aging was 85.

Comparative Example 1 In the same manner as in Example 4, an element of ITO / polyphenylenevinylene (50 nm) / Mg-Ag was prepared, and the light emission characteristics were measured. As a result, light emission was observed from 4 V and 8 V
When the voltage was applied, a current value of 2025 mA / cm ² was exhibited, and only a luminance of 120 Cd / sqm was exhibited. The emission wavelength λmax was 500 nm. The relative luminance after aging was 28.

Comparative Example 2 In the same manner as in Example 5, ITO / polyphenylenevinylene (50 nm) / poly (2,5-pyridinediyl) (3
0 nm) / Mg-Ag device was prepared, and the emission characteristics were measured. As a result, when a voltage of 8 V was applied, 25 mA
/ Cm ² and a luminance of only 135 Cd / sqm. Emission wavelength λmax is 540 nm
No light emission from polyphenylenevinylene was obtained. The relative luminance after aging was 28.

Comparative Example 3 In the same manner as in Example 6, ITO / poly (9,9-dioctylfluorene) (100 nm) / Comparative compound 1 (30 n
m) / Al device, but poly (9, 9)
-Dioctylfluorene) is similar in polarity to the coating solvent system (halogenated hydrocarbon or THF) of Comparative Compound 1 because of the similarity in polarity between the coating solvent system (halogenated hydrocarbon or THF) and layer mixing occurs during lamination coating. However, an element having a laminated structure could not be produced. The light emitting characteristics of the device obtained by mixing the layers were measured in the same manner as in the above example, but no light was emitted.

[0065]

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Comparative Example 4 In the same manner as in Example 6, ITO / poly (9,9-dioctylfluorene) (100 nm) / Comparative compound 2 (30 n)
m) / Al device, but poly (9, 9)
-Dioctylfluorene) coating solvent system (halogenated hydrocarbon or THF) and Comparative Compound 2 coating solvent system (halogenated hydrocarbon or THF) have similar polarities, so layer mixing occurs during lamination coating. However, an element having a laminated structure could not be produced. The light emitting characteristics of the device obtained by mixing the layers were measured in the same manner as in the above example, but no light was emitted.

[0067]

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From these results, it is understood that the device using the compound of the present invention can function not only as an electron transporting material in both green light emission and blue light emission, but also as a light emitting material itself. In addition, it is possible to form a laminated film only by a coating process using the difference in polarity between polymers. Further, it can be seen that the minimum driving voltage is low, high-luminance light emission is possible, and the luminance decrease after storage at high temperature is small and the durability is excellent.

[0069]

According to the present invention, a polymer having a high electron affinity can be provided. Further, the electron transport layer is laminated on the low-polarity light-emitting polymer without mixing the layers only by the coating process, so that an organic light-emitting device that can emit light with high luminance and has excellent durability can be obtained. 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.

Claims (8)

[Claims] 1. A polymer having at least one structure represented by the following general formula (I). Embedded image (In the formula, Ar represents a conjugated unsaturated group. However, a nitrogen-containing heterocyclic ring having two or more nitrogen atoms is excluded. M and n each represent a mole fraction in the polymer, and m + n = 100.)
n represents a numerical value of 0 or more and less than 100. R represents a hydrogen atom or a substituent. However, when Ar is a substituted fluorene ring or an alkoxy-substituted benzene ring, n does not take a value of 50. ) 2. In the general formula (I), Ar is a nitrogen-containing heterocyclic ring having two or more nitrogen atoms, a substituted fluorene ring,
And a conjugated unsaturated group other than an alkoxy-substituted benzene ring. 3. A light emitting device material comprising a polymer having at least one structure represented by the following general formula (I). Embedded image (In the formula, Ar represents a conjugated unsaturated group. However, a nitrogen-containing heterocyclic ring having two or more nitrogen atoms is excluded. M and n each represent a mole fraction in the polymer, and m + n = 100.)
n represents a numerical value of 0 or more and less than 100. R represents a hydrogen atom or a substituent. However, when Ar is a substituted fluorene ring or an alkoxy-substituted benzene ring, n does not take a value of 50. ) 4. In the general formula (I), Ar is a nitrogen-containing heterocyclic ring having two or more nitrogen atoms, a substituted fluorene ring,
4. The light emitting device material according to claim 3, which is a conjugated unsaturated group other than an alkoxy-substituted benzene ring. 5. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, wherein at least one layer contains at least one polymer according to claim 3. Light emitting element. 6. A light-emitting element having a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer formed between a pair of electrodes, wherein at least one layer is formed by applying at least one polymer according to claim 3. A light-emitting element characterized in that it is a layer formed. 7. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, wherein at least one layer contains at least one polymer according to claim 4. Light emitting element. 8. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, wherein at least one layer is formed by applying at least one polymer according to claim 4. A light-emitting element characterized in that it is a layer formed.