JP5279377B2 - Novel polyalkoxykinkphenyl derivative, host material comprising the same, and organic electroluminescence device using the same - Google Patents

Description

  The present invention relates to a novel polyalkoxy kink phenyl derivative, a host material comprising the same, and an organic electroluminescence device using the same.

Research and development for practical application of organic EL elements (organic electroluminescence elements) is being promoted mainly by domestic and foreign electric manufacturers and material manufacturers. Reduction of power consumption and extension of the life of the device are listed as indispensable issues in order to be handled equally with displays such as liquid crystal display devices and light emitting diodes that are already known in the world.
In order to solve this problem, an organic EL element using a phosphorescent material has recently been studied (Non-Patent Document 1).
Unlike conventional fluorescent materials, phosphorescent materials have a very high quantum efficiency because they can use triplet excited states, and there is almost no energy deactivation, and the internal emission quantum yield reaches almost 100%. .
However, since this phosphorescent material easily causes concentration quenching, it is necessary to use it together with a host material in the same manner as a fluorescent material.
In order to obtain high-efficiency light emission, it is necessary to optimize transport materials and host materials. However, unlike phosphor materials, phosphorescent materials cannot obtain satisfactory effects unless triplet energy is completely confined. Especially for blue materials, the energy level is very high. Therefore, 4,4'-di (N-carbazolyl) -1,1'-biphenyl (CBP) that has been used so far cannot sufficiently confine energy. Unfortunately, there have been few wide-gap host materials that can confine this blue phosphorescent energy satisfactorily, and this has been one factor that hinders the development of blue phosphorescent materials.

Appl. Phys. Lett. , 75 (1) 4 (1999)

  An object of the present invention is to provide a novel polyalkoxykinkphenyl derivative, a host material comprising the same, and an organic electroluminescence device using the same, which are necessary for providing a high-efficiency device that enables low-voltage driving of the device. There is in point to do.

The first of the present invention is the following general formula (1)
Wherein R is a linear or branched alkoxy group having 1 to 6 carbon atoms, r is a group independently selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 6 carbon atoms. R ^{20 to} R ³¹ and R ^{40 to} R ⁴² are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a straight chain having 1 to 6 carbon atoms. Each is a group independently selected from the group consisting of a chain or branched alkylamino group and a fluorine atom, m is an integer of 1 or 2, n is an integer of 3 or 4, and m + n = 5. )
It is related with the polyalkoxy kink phenyl derivative characterized by these.
The second of the present invention is the following general formula (2)
Wherein R is a linear or branched alkoxy group having 1 to 6 carbon atoms, r is a group independently selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 6 carbon atoms. R ^{20 to} R ³¹ and R ^{40 to} R ⁴² are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a straight chain having 1 to 6 carbon atoms. Each is a group independently selected from the group consisting of a chain or branched alkylamino group and a fluorine atom, m is an integer of 1 or 2, n is an integer of 3 or 4, and m + n = 5. )
It is related with the polyalkoxy kink phenyl derivative characterized by these.
3rd of this invention is related with the host material which consists of a polyalkoxy kink phenyl derivative of Claim 1 or 2.
4th of this invention is related with the organic electroluminescent element using the polyalkoxy kink phenyl derivative of Claim 1 or 2.

As R, r and R ^{20 to} R ³¹ and R ^{40 to} R ⁴² in the present invention, a linear or branched alkyl group having 1 to 6 carbon atoms (in the case of R, an alkyl moiety in alkoxy) is methyl , Ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl, 2,2-dimethylpropyl, n-hexyl, 2-methylpentyl , 3-methylpentyl, 4-methylpentyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl and the like.
Regarding also the alkyl moiety in the alkoxy and alkylamino group in ^R 20 ^{to R 31} and ^R 40 ^{to R 42,} it can be exemplified alkyl groups described above.

The compound of the present invention can be produced by the following reaction.
[Wherein, R is a linear or branched alkoxy group having 1 to 6 carbon atoms, r is a group independently selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 6 carbon atoms. R ^{20 to} R ³¹ and R ^{40 to} R ⁴² are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a straight chain having 1 to 6 carbon atoms. Each is a group independently selected from the group consisting of a chain or branched alkylamino group and a fluorine atom, m is an integer of 1 or 2, n is an integer of 3 or 4, and m + n = 5. X is a halogen (eg, Cl, Br, I). ]

The reaction used in this reaction is generally called the Suzuki coupling reaction, and details are described in Miyaura, N .; Suzuki, A .; Chem. Rev. 1995, 95, 2457, and the like.
As the solvent to be used, a mixture of an aromatic hydrocarbon solvent and an alcohol solvent or an ether solvent can be used. Examples of the aromatic hydrocarbon solvent in the mixture include toluene, xylene, ethylbenzene, and trimethylbenzene. Examples of the alcohol solvent include methanol, ethanol, propanol, and butanol. Examples of ether solvents include cyclic ethers such as tetrahydrofuran and 1,4-dioxane, methyl cellosolve, ethyl cellosolve, ethylene glycol dimethoxy ether, and ethylene glycol diethoxy ether.
Since the solubility of the raw material in the solvent is the key to the progress of the reaction, it is preferably a mixed solvent of toluene and alcohol, more preferably a mixed solvent of toluene and ethanol.
The bases used in the reaction (K ₂ CO ₃ in the above formula) are not particularly limited as long as they contain an alkali metal. Examples include hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, alkali metal carbonates such as cesium carbonate, lithium hydrogen carbonate, Organic bases such as alkali metal bicarbonates such as sodium hydrogen carbonate, potassium hydrogen carbonate and cesium hydrogen carbonate, alkali metal alcoholates such as lithium, sodium, potassium and cesium or alkali metal acetates. Preferred is an alkali metal carbonate or bicarbonate, and more preferred is potassium carbonate.
About palladium used for reaction, since it is a coupling reaction of a halogen compound and a boric acid compound, the thing of Pd (0) can be used similarly. Tetrakis (triphenylphosphine) palladium [Pd (PPh ₃ ) ₄ ] or tris (dibenzylideneacetone) dipalladium is preferable, and tetrakis (triphenylphosphine) palladium is more preferable because of the reactivity of the palladium compound.

Specific examples of the compound of the present invention are illustrated below. In the exemplified compounds below, the methyl group can be replaced with another alkyl group such as an ethyl group or a propyl group.

  The polyalkoxy kink phenyl derivative of the present invention has high carrier transport performance. Therefore, it can be used as a host material. In any case, it is desirable to form a layer by vapor deposition.

  When the polyalkoxykink phenyl derivative of the present invention is used in an organic electroluminescence device, it can be used in combination with a suitable light emitting material.

  When the polyalkoxykink phenyl derivative of the present invention is used for a light emitting layer, the compound of the present invention can be used as a host material.

  Next, the organic electroluminescence element (organic EL element) of the present invention will be described. The organic EL device of the present invention is a device in which a plurality of layers of organic compounds are laminated between an anode and a cathode, and contains the polyalkoxykinkphenyl derivative of the present invention as a host material of the light emitting layer. The light emitting layer is composed of a light emitting material and a host material. Examples of the configuration of the multilayer organic EL device include, for example, an anode (for example, ITO) / hole transport layer / light emitting layer / electron transport layer / cathode, ITO / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode. ITO / hole transport layer / light-emitting layer / hole block layer / electron transport layer / cathode, ITO / hole transport layer / light-emitting layer / hole block layer / electron transport layer / electron injection layer / cathode, ITO / hole injection layer (positive And a multilayer structure such as hole injection layer) / hole transport layer / light emitting layer / hole block layer / electron transport layer / electron injection layer / cathode. Moreover, you may have a sealing layer on a cathode as needed.

  Each of the hole transport layer, the electron transport layer, and the light-emitting layer preferably has a multilayer structure in which each function is separated. In addition, the hole transport layer and the electron transport layer can be provided separately with a layer responsible for the injection function (hole injection layer and electron injection layer) and a layer responsible for the transport function (hole transport layer and electron transport layer).

  Hereinafter, the constituent elements of the organic EL element of the present invention will be described by taking as an example an element structure composed of an anode / hole transport layer / light emitting layer / electron transport layer / cathode. The organic EL element of the present invention is preferably supported on a substrate.

  There is no restriction | limiting in particular about the raw material of a board | substrate, For example, what is conventionally used for the conventional organic EL element can be used, For example, what consists of glass, quartz glass, a transparent plastic etc. can be used.

As an anode of the organic EL device of the present invention, it is preferable to use a single metal having a high work function (4 eV or more), an alloy of metals having a high work function (4 eV or more), a conductive substance, or a mixture thereof as an electrode material. . Specific examples of such electrode materials include metals such as gold, silver, and copper, conductive transparent materials such as ITO (indium-tin oxide), tin oxide (SnO ₂ ), and zinc oxide (ZnO), polypyrrole, and polythiophene. Examples thereof include conductive polymer materials such as For the anode, these electrode materials can be formed by a method such as vapor deposition, sputtering, or coating. The sheet electrical resistance of the anode is preferably several hundred Ω / cm ² or less. The thickness of the anode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm.

As the cathode, an electrode material is preferably a single metal having a low work function (4 eV or less), an alloy of metals having a low work function (4 eV or less), a conductive substance, or a mixture thereof. Specific examples of such electrode materials include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, magnesium, magnesium-silver alloy, magnesium-indium alloy, aluminum, aluminum-lithium alloy, and aluminum-magnesium alloy. Can be mentioned. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet electrical resistance of the cathode is preferably several hundred Ω / cm ² or less. The thickness of the cathode depends on the material, but is generally about 5 to 1,000 nm, preferably 10 to 500 nm. In order to efficiently extract light emitted from the organic EL device of the present invention, at least one of the anode and the cathode is preferably transparent or translucent.

The hole transport layer (hole transport layer) of the organic electroluminescence device of the present invention is composed of a hole (hole) transport compound and has a function of transmitting holes (holes) injected from the anode to the light emitting layer. doing. When a hole transfer compound is disposed between two electrodes to which an electric field is applied and holes are injected from the anode, a hole transfer material having a hole mobility of at least 10 ⁻⁶ cm ² / V · sec or more is preferable. The hole transfer material used for the hole transport layer of the organic electroluminescence device of the present invention is not particularly limited as long as it has the above-mentioned preferable performance. Any one of materials conventionally used as charge injection materials for holes in photoconductive materials and known materials used for hole transport layers of organic electroluminescence elements can be selected and used.

Examples of the hole transfer material include phthalocyanine derivatives such as copper phthalocyanine, N, N, N ′, N′-tetraphenyl-1,4-phenylenediamine, N, N′-di (m-tolyl) -N, Triarylamines such as N′-diphenyl-4,4-diaminophenyl (TPD) and N, N′-di (1-naphthyl) -N, N′-diphenyl-4,4-diaminophenyl (α-NPD) Derivatives, polyphenylenediamine derivatives, polythiophene derivatives, and water-soluble PEDOT-PSS (polyethylenedioxathiophene-polystyrene sulfonic acid). The hole transport layer may be composed of one or more of these other hole transport compounds, or may be a stack of hole transport layers composed of a compound different from the hole transport material.
Examples of the hole injection material include PEDOT-PSS (polymer mixture) and DNTPD represented by the following chemical formula.

Examples of the hole transport material include TPD, DTASi, and α-NPD represented by the following chemical formula.

The electron transport layer of the organic electroluminescent element of the present invention is made of an electron transport material and has a function of transmitting electrons injected from the cathode to the light emitting layer. When an electron transport material is arranged between two electrodes to which an electric field is applied and electrons are injected from the cathode, an electron transport material having an electron mobility of at least 10 ⁻⁶ cm ² / V · sec or more is preferable. The electron transport material used for the electron transport layer used in the organic EL device of the present invention is not particularly limited as long as it has the above-mentioned preferable performance. Any one of materials conventionally used as electron charge injection materials in photoconductive materials and known materials used for electron transport layers of organic electroluminescent elements can be selected and used.

Examples of the electron transporting material include quinoline complexes such as tris (8-hydroxyquinolinolato) aluminum complex (Alq ₃ ), 1-N-phenyl-2- (p-biphenylyl) -5- (p- triazine derivatives such as tert-butylphenyl) -1,3,5-triazine (TAZ), phenanthroline derivatives such as 1,4-di (1,10-phenanthroline-2-yl) benzene (DPB), fluoride Examples include alkali metal halides such as lithium. The electron transport layer may be composed of one or more of these other electron transport materials, and may be a stack of electron transport layers composed of a compound different from the electron transport material. .
Examples of the electron injection material include lithium fluoride (LiF) and 8-hydroxyquinolinolato lithium complex (Liq) represented by the following chemical formula, and phenanthroline according to Japanese Patent Application No. 2006-292032 of the present applicant. Derivative lithium complexes (LiPB) and phenoxypyridine lithium complexes (LiPP) listed in Japanese Patent Application No. 2007-29695 can also be used.
Examples of the electron transport material include Alq ₃ , TAZ, and DPB represented by the following chemical formula.

  There is no restriction | limiting in particular about the light emitting material used for the light emitting layer of the organic electroluminescent element of this invention, Arbitrary things can be selected and used.

Examples of the light-emitting material include perylene derivatives, naphthacene derivatives, quinacridone derivatives, coumarin derivatives (eg, coumarin 1, coumarin 540, coumarin 545), pyran derivatives (eg, DCM-1, DCM-2, DCJTB, etc.), organometallic complexes, Fluorescent materials such as (8-hydroxyquinolinolato) aluminum complex (Alq ₃ ) and tris (4-methyl-8-hydroxyquinolinolato) aluminum complex (Almq ₃ ), and [2- (4,6-difluorophenyl) Pyridyl-N, C2 ′] iridium (III) picolylate (FIrpic), tris {1- [4- (trifluoromethyl) phenyl] -1H-pyrazolate-N, C2 ′} iridium (III) (Irtfmpppz ₃ ), bis [2- (4 ′, 6′-difluorophenyl) pyridina -N, C2 '] iridium (III) tetrakis (1-pyrazolyl) borate (FIr6), tris (2-phenylpyridinato) iridium (III) (Irppy ₃₎ and the like phosphorescent material such as.

The light emitting layer is formed of a host material and a light emitting material (dopant) [Appl. Phys. Lett. 65 3610 (1989)]. In particular, when a phosphorescent material is used for the light emitting layer, it is necessary to use a host material. As the host material used at this time, it is preferable to use the polyalkoxykinkphenyl derivative of the present invention. Other existing host materials 4,4′-di (N-carbazolyl) -1,1′-biphenyl (CBP), 1,4-di (N-carbazolyl) benzene-2,2′-di [4 ″-( N-carbazolyl) phenyl] -1,1′-biphenyl (4CzPBP) and the like can also be used.

The light emitting material is preferably 0.01 to 40% by weight, more preferably 0.1 to 20% by weight with respect to the host material. Examples of the light emitting material include conventionally known FIrpic, Irppy ₃ , Fir 6 and the like shown below.

  In the organic electroluminescence device of the present invention, a hole injection layer composed of an organic conductor may be further provided between the anode and the organic compound layer for the purpose of further improving the hole injection property. Examples of the hole injection material used here include phthalocyanine derivatives such as copper phthalocyanine, polyphenylenediamine derivatives, polythiophene derivatives, and PEDOT-PSS (polyethylenedioxythiophene-polystyrenesulfonic acid) in addition to the compounds of the present invention. .

  The method for forming the hole injection layer and the hole transport layer of the device containing the polyalkoxykink phenyl derivative of the present invention is not particularly limited. For example, a dry film forming method (for example, a vacuum vapor deposition method, an ionization vapor deposition method, etc.) or a wet film forming method [a solvent coating method (for example, a spin coating method, a casting method, an ink jet method, etc.)] can be used. The film formation of the electron transport layer is limited to a dry film formation method (for example, a vacuum vapor deposition method, an ionization vapor deposition method, etc.) because the lower layer may be eluted when the wet film formation method is used. For the production of the element, the above film forming method may be used in combination.

When forming each layer such as a hole transport layer, a light emitting layer, and an electron transport layer by a vacuum deposition method, the vacuum deposition conditions are not particularly limited. Usually, under a vacuum of about 10 ⁻⁵ Torr or less, a boat temperature (deposition source temperature) of about 50 to 500 ° C., a substrate temperature of about −50 to 300 ° C., and 0.01 to 50 nm / sec. Vapor deposition is preferred. When forming each layer of a positive hole transport layer, a light emitting layer, and an electron carrying layer using a some compound, it is preferable to co-evaporate the boat which put the compound, respectively controlling temperature.

  When forming the hole injection layer and the hole transport layer by a solvent coating method, the components constituting each layer are dissolved or dispersed in a solvent to obtain a coating solution. Solvents include hydrocarbon solvents (eg, heptane, toluene, xylene, cyclohexane, etc.), ketone solvents (eg, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), halogen solvents (eg, dichloromethane, chloroform, chlorobenzene, dichlorobenzene, etc.) Ester solvents (eg, ethyl acetate, butyl acetate, etc.), alcohol solvents (eg, methanol, ethanol, butanol, methyl cellosolve, ethyl cellosolve, etc.), ether solvents (eg, dibutyl ether, tetrahydrofuran, 1,4-dioxane, 1 , 2-dimethoxyethane, etc.), aprotic solvents (eg, N, N′-dimethylacetamide, dimethyl sulfoxide, etc.), water and the like. The solvent may be used alone, or a plurality of solvents may be used in combination.

  The thickness of each layer such as a hole transport layer, a light emitting layer, and an electron transport layer is not particularly limited, but is usually set to 5 to 5,000 nm.

  The organic electroluminescence device of the present invention can be protected by providing a protective layer (sealing layer) for the purpose of blocking contact with oxygen, moisture, etc., or by enclosing the device in an inert material. Examples of the inert substance include paraffin, silicon oil, and fluorocarbon. Examples of the material used for the protective layer include fluororesin, epoxy resin, silicone resin, polyester, polycarbonate, and photocurable resin.

  The organic electroluminescence device of the present invention can be used as a normal DC drive device. When a DC voltage is applied, light emission is usually observed when about 1.5 to 20 V is applied with the positive polarity of the anode and the negative polarity of the cathode. The organic EL element of the present invention can also be used as an AC drive element. When an AC voltage is applied, light is emitted when the anode is in a positive state and the cathode is in a negative state. The organic electroluminescence device of the present invention includes, for example, a flat light emitter such as an electrophotographic photosensitive member and a flat panel display, a copying machine, a printer, a backlight of a liquid crystal display, a light source such as an instrument, various light emitting devices, various display devices, and various signs. It can be used for various sensors and various accessories.

  The preferable example of the organic electroluminescent element of this invention is shown in FIGS.

  FIG. 25 is a cross-sectional view showing an example of the organic EL element of the present invention. FIG. 25 shows a configuration in which an anode 2, a hole transport layer 5, a light emitting layer 3, and a cathode 4 are sequentially provided on a substrate 1. In this case, the light emitting layer is useful when it has an electron transporting function.

  FIG. 26 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 26 shows a configuration in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. This is a separation of the functions of carrier transport and light emission, and the degree of freedom in material selection increases, so that the efficiency of light emission and the degree of freedom in light emission color increase.

  FIG. 27 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 27 shows a structure in which an anode 2, a hole injection layer 7, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6 and a cathode 4 are sequentially provided on a substrate 1. In this case, by providing the hole injection layer 7, the adhesion between the anode 2 and the hole transport layer 5 is improved, and the injection of holes from the anode is improved. Effective for lowering voltage.

  FIG. 28 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 28 shows a configuration in which an anode 2, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, an electron injection layer 8 and a cathode 4 are sequentially provided on a substrate 1. In this case, injection of electrons from the cathode 4 is improved, which is effective for lowering the voltage of the light emitting element.

  FIG. 29 is a cross-sectional view showing another example of the organic electroluminescence element of the present invention. FIG. 29 shows a structure in which an anode 2, a hole injection layer 7, a hole transport layer 5, a light emitting layer 3, an electron transport layer 6, an electron injection layer 8 and a cathode 4 are sequentially provided on a substrate 1. belongs to. In this case, hole injection from the anode 2 is improved and electron injection from the cathode 4 is improved, which is the most effective for driving at a low voltage.

  30 to 33 are cross-sectional views of a device in which a hole block layer is inserted into the device. The hole blocking layer has an effect of preventing holes injected from the anode or excitons generated by recombination in the light emitting layer 3 from escaping to the cathode 4, and the organic electroluminescence element This is effective in improving the luminous efficiency. The hole blocking layer 9 can be inserted between the light emitting layer 3 and the cathode 4, between the light emitting layer 3 and the electron transport layer 6, or between the light emitting layer 3 and the electron injection layer 8. More preferred is between the light emitting layer 3 and the electron transport layer 6.

  30 to 33, each of a hole transport layer 5, a hole injection layer 7, an electron transport layer 6, an electron injection layer 8, a light emitting layer 3, and a hole block layer 9. May be a single layer structure or a multilayer structure.

  25 to 33 are basic device configurations to the last, and the configuration of the organic electroluminescence device using the compound of the present invention is not limited to this.

Unlike the conventional carbazole-substituted host material, the polyalkoxykink phenyl derivative of the present invention has a good hole and electron carrier balance, can efficiently give energy to the dopant in the light emitting layer, and has little film thickness dependency. . The energy gap is sufficiently wide as 3.6 eV to 4.0 eV, and a sufficient effect can be expected even in combination with a blue phosphorescent dopant that requires a lot of energy for light emission.
Therefore, the compound of the present invention is necessary for increasing the efficiency of the device and is extremely important industrially.

  Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited thereto.

Example 1
2,2 ″ ″, 5,5 ″ ″-tetramethoxy-5 ″-[2 ′, 5′-dimethoxy (1,1′-biphenyl) -4-yl] -1,1 ′: 3 ′, 1 ″ : 3 ″, 1 ″ ′: Synthesis of 3 ″ ′, 1 ″ ″-kinkphenyl (abbreviation 2,5-DMPTPB)
1,3,5-tris- (m-bromophenyl) benzene (abbreviation TmBrPhB) 2.17 g (4.0 mmol), 2.84 g (15.6 mmol) of 2,5-dimethoxyphenylboronic acid, 2M aqueous potassium carbonate solution 9 0.0 ml, 80 ml of toluene and 40 ml of ethanol were added and nitrogen bubbling was performed for 1 hour. Tetrakis (triphenylphosphine) palladium [Pd (PPh ₃ ) ₄ ] 0.28 g (0.24 mmol) was added, and the mixture was refluxed for 22 hours. The organic layer was extracted with toluene and washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, filtered, concentrated, and purified by silica gel column chromatography (developing solvent: toluene) to obtain a white foamy solid. The target product was confirmed by ¹ H-NMR and mass spectrometry (hereinafter abbreviated as MS). (Yield 2.60 g, 91% yield)
Colorless transparent solid, ¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.87-7.86 (m, 6H), 7.68 (d, 3H, J = 7.3 Hz), 7.60-7.50 ( m, 6H), 6.98-6.86 (m, 9H), 3.81 (s, 9H), 3.77 (s, 9H) ppm. MS: m / z 716 [M + H] ^+. Elemental analysis: C ₄₈ H ₄₂ O ₆ calculated value is C, 80.65%; H, 5.92%, measured value is C, 80.79%: H, 5.91%.
A ¹ H-NMR chart of the obtained 2,5-DMPTPB is shown in FIG. 1, and an MS chart is shown in FIG. 2 (chromatogram) and FIG. 3 (spectrum). Moreover, the measurement result of the ultraviolet absorption spectrum (UV) and photoluminescence (PL) in the thin-film state of 2,5-DMPTPB is shown in FIG.
Further, Table 1 summarizes the thermochemical characteristics and electrochemical characteristics.
Td: decomposition temperature,
Tg: secondary transition temperature,
Tm: melting point,
Ip: ionization potential,
Eg: energy gap,
Ea: Electroaffinity (electron affinity),
n. d. : Not detected For Tg (secondary transition temperature), a sample is added into DSC (Differential Scanning Calorimeter), and the molten material is rapidly cooled. When this melting and rapid cooling are repeated 2 to 3 times, a curve indicating a glass point appears on the chart.
As for Tm (melting point), when a sample is similarly added to DSC and the temperature is raised, a rapid heating curve appears.
As for Td (decomposition temperature), when a sample is added to DTA (Differential Thermal Analyzer differential thermal analyzer) and heated, the sample is decomposed by heat and the weight starts to decrease. Read the temperature at which the decrease starts and decrease by 5% by weight, and let that point be Td.
Regarding the energy gap (Eg), an absorption curve of the thin film prepared with a vapor deposition machine is measured with an ultraviolet-visible absorptiometer. A tangent line is drawn at the short-wavelength rising edge of the thin film, and the target wavelength is obtained by substituting the obtained wavelength W (nm) of the intersection into the following equation. The value obtained thereby becomes Eg.
Eg = 1240 ÷ W
For example, if the value W (nm) obtained by drawing the tangent is 470 nm, the value of Eg at this time is
Eg = 1240 ÷ 470 = 2.63 (eV)
It will be said.
IP (ionization potential) is measured using an ionization potential measuring device (for example, Riken Keiki AC-3), and the value of the voltage (eV) at which the sample to be measured starts ionization is read.
Ea (electron affinity) is a value obtained by subtracting Eg from Ip.

Example 2
3,3 ″ ″, 5,5 ″ ″-tetramethoxy-5 ″-[3 ′, 5′-dimethoxy (1,1′-biphenyl) -4-yl] -1,1 ′: 3 ′, 1 ″ : 3 ″, 1 ″ ′: Synthesis of 3 ″ ′, 1 ″ ″-kinkphenyl (abbreviated 3,5-DMPTPB)
2.17 g (4.0 mmol) of TmBrPhB, 4.10 g (15.6 mmol) of 3,5-dimethoxyphenylboronic acid pinacol ester, 9.0 ml of 2M potassium carbonate aqueous solution, 80 ml of toluene and 40 ml of ethanol were added, and nitrogen bubbling was performed for 1 hour. . 0.28 g (0.24 mmol) of Pd (PPh ₃ ) ₄ was added and refluxed for 16 hours. The organic layer was extracted with toluene and washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, filtered, concentrated, and purified by silica gel column chromatography (developing solvent: toluene) to obtain a white foamy solid. The target product was confirmed by ¹ H-NMR and MS. (Yield 2.45 g, Yield 86%)
Colorless transparent solid, ¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.87 (s, 6H), 7.69 (d, 3H, J = 7.3 Hz) 7.61 to 7.52 (m, 6H), 6.78 (d, 6H, J = 2.2 Hz), 6.48 (t, 3H, J = 2.2 Hz), 3.84 (s, 18H) ppm. MS: m / z 716 [M + H] ^+. Elemental analysis: calculated for C ₄₈ H ₄₂ O ₆ is C, 80.65%; H, 5.92%. The measured value is C, 80.38%; H, 5.86%.
FIG. 5 shows a ¹ H-NMR chart of the obtained 3,5-DMPTPB, and FIGS. 6 (chromatogram) and 7 (spectrum) show MS charts. Moreover, the measurement result of the ultraviolet absorption spectrum (UV) and photoluminescence (PL) in a thin film form is shown in FIG.
Further, Table 2 summarizes thermochemical characteristics and electrochemical characteristics.

Example 3
4,4 ″ ″-dimethoxy-5 ″-[4′-methoxy (1,1′-biphenyl) -4-yl] -1,1 ′: 3 ′, 1 ″: 3 ″, 1 ″ ″: 3 ″ Synthesis of ', 1 ""-kinkphenyl (abbreviation 4-MeOPTPB)
2.17 g (4.0 mmol) of TmBrPhB, 2.37 g (15.6 mmol) of 4-methoxyphenylboronic acid, 9.0 ml of 2M potassium carbonate aqueous solution, 80 ml of toluene and 40 ml of ethanol were added, and nitrogen bubbling was performed for 1 hour. 0.28 g (0.24 mmol) of Pd (PPh ₃ ) ₄ was added and refluxed for 19 hours. The organic layer was extracted with toluene and washed with saturated brine. The organic layer was dried over anhydrous magnesium sulfate, filtered, concentrated, and purified by silica gel column chromatography (developing solvent: toluene) to obtain a white solid. The target product was confirmed by ¹ H-NMR and MS. (Yield 2.0 g, Yield 80%)
Colorless transparent solid, ¹ H-NMR (400 MHz, CDCl ₃ ) δ 7.88 (s, 3H), 7.87 (s, 3H), 7.66-7.49 (m, 15H), 7.00 (d , 6H, J = 8.2 Hz), 3.85 (s, 9H) ppm. MS: m / z 626 [M + H] ^+.
FIG. 9 shows a ¹ H-NMR chart of the obtained 4-MeOPTPB, and FIGS. 10 and 11 show MS charts. Moreover, the measurement result of the ultraviolet absorption spectrum (UV) and photoluminescence (PL) in a thin film form is shown in FIG.
Further, Table 3 summarizes thermochemical characteristics and electrochemical characteristics.

Examples 4 to 6 and Comparative Example 1
Green phosphors using the host materials 2,5-DMPTPB, 3,5-DMPTPB and 4-MeOPTPB synthesized in Examples 1, 2, and 3 were prepared. As Comparative Example 1, a device using 4,4′-di (carbazol-9-yl) -1,1′-biphenyl (abbreviation CBP) was prepared, and the performance of each device was evaluated.
An energy diagram of each of these elements is shown in FIG.
The configuration of each element is shown below.
Example 4: [ITO / TPDPES: 10 wt% TBPAH (20 nm) / TAPC (30 nm) / 3,5-DMPTPB: 8 wt% Ir (ppy) ₃ (10 nm) / BmPyPB (50 nm) / LiF (0.5 nm) / Al (100 nm)]
Example 5: [ITO / TPDPES: 10 wt% TBPAH (20 nm) / TAPC (30 nm) / 2,5-DMPTPB: 8 wt% Ir (ppy) ₃ (10 nm) / BmPyPB (50 nm) / LiF (0.5 nm) / Al (100 nm)]
Example 6: [ITO / TPDPES: 10 wt% TBPAH (20 nm) / TAPC (30 nm) / 4-MeOPTPB: 8 wt% Ir (ppy) ₃ (10 nm) / BmPyPB (50 nm) / LiF (0.5 nm) / Al ( 100 nm)]
Comparative Example 1: [ITO / TPDPES: 10 wt% TBPAH (20 nm) / TAPC (30 nm) / CBP: 8 wt% Ir (ppy) ₃ (10 nm) / BmPyPB (50 nm) / LiF (0.5 nm) / Al (100 nm) ]
The current density-voltage characteristics are shown in FIG.
The luminance-voltage characteristics are shown in FIG.
The luminous efficiency vs. voltage characteristics are shown in FIG.
The current efficiency vs. voltage characteristics are shown in FIG.
The electroluminescence (EL) spectrum is shown in FIG.
Each is shown.
Table 4 shows the luminous efficiency and external quantum efficiency characteristics of the green phosphor elements of Examples 4 to 6 and Comparative Example 1 at 100 cd / m ² and 1000 cd / m ² .

Examples 7 to 9 and Comparative Example 2
Blue phosphorescent devices using the host materials 2,5-DMPTPB, 3,5-DMPTPB and 4-MeOPTPB synthesized in Examples 1, 2, and 3 were prepared. Moreover, the element using CBP was created as the comparative example 2, and the performance of each element was evaluated.
An energy diagram of each of these elements is shown in FIG.
The configuration of each element is shown below.
Example 7: [ITO / TPDPES: 10 wt% TBPAH (20 nm) / 3DTAPBP (20 nm) / 3,5-DMPTPB: 11 wt% FIrpic (10 nm) / BmPyPB (50 nm) / LiF (0.5 nm) / Al (100 nm) ]
Example 8: [ITO / TPDPES: 10 wt% TBPAH (20 nm) / 3DTAPBP (20 nm) / 2,5-DMPTPB: 11 wt% FIrpic (10 nm) / BmPyPB (50 nm) / LiF (0.5 nm) / Al (100 nm) ]
Example 9: [ITO / TPDPES: 10 wt% TBPAH (20 nm) / 3DTAPBP (20 nm) / 4-MeOPTPB: 11 wt% FIrpic (10 nm) / BmPyPB (50 nm) / LiF (0.5 nm) / Al (100 nm)]
Comparative Example 2: [ITO / TPDPES: 10 wt% TBPAH (20 nm) / 3DTAPBP (20 nm) / CBP: 11 wt% FIrpic (10 nm) / BmPyPB (50 nm) / LiF (0.5 nm) / Al (100 nm)]
The current density-voltage characteristics are shown in FIG.
The luminance-voltage characteristics are shown in FIG.
The luminous efficiency vs. voltage characteristics are shown in FIG.
The current efficiency vs. voltage characteristics are shown in FIG.
The electroluminescence (EL) spectrum is shown in FIG.
Each is shown.
Table 5 shows the luminous efficiency and external quantum efficiency characteristics of the blue phosphors of Examples 7 to 9 and Comparative Example 2 at 100 cd / m ² and 1000 cd / m ² .
As seen in FIG. 21, there is almost no difference between each example and comparative example on the low voltage side, but each example compound emits light in a higher luminance region than the comparative example on the high voltage side. There is a trend.

1 shows a ¹ H-NMR chart of 2,5-DMPTPB of Example 1. 2 shows a MS chart (chromatogram) of 2,5-DMPTPB of Example 1. FIG. 2 shows an MS chart (spectrum) of 2,5-DMPTPB of Example 1. FIG. 2 shows a UV-PL curve of 2,5-DMPTPB of Example 1. ¹ shows a ¹ H-NMR chart of 3,5-DMPTPB of Example 2. The chart (chromatogram) of 3,5-DMPTPB MS of Example 2 is shown. The chart (spectrum) of 3,5-DMPTPB MS of Example 2 is shown. The UV-PL curve of 3, 5-DMPTPB of Example 2 is shown. The ¹ H-NMR chart of 4-MeOPTPB of Example 3 is shown. The chart (chromatogram) of 4-MeOPTPB of Example 3 is shown. The chart (spectrum) of 4-MeOPTPB of Example 3 is shown. The UV-PL curve of 4-MeOPTPB of Example 3 is shown. The energy diagram of Examples 4-6 and the comparative example 1 is shown. The current density-voltage characteristics of Examples 4 to 6 and Comparative Example 1 are shown. The luminance-voltage characteristics of Examples 4 to 6 and Comparative Example 1 are shown. The luminous efficiency-voltage characteristic of Examples 4-6 and the comparative example 1 is shown. The current efficiency-voltage characteristics of Examples 4 to 6 and Comparative Example 1 are shown. The electroluminescence (EL) spectrum of Examples 4-6 and the comparative example 1 is shown. The energy diagram of Examples 7-9 and the comparative example 2 is shown. The current density-voltage characteristics of Examples 7 to 9 and Comparative Example 2 are shown. The luminance-voltage characteristics of Examples 7 to 9 and Comparative Example 2 are shown. The luminous efficiency-voltage characteristic of Examples 7-9 and Comparative Example 2 is shown. The current efficiency-voltage characteristics of Examples 7 to 9 and Comparative Example 2 are shown. The electroluminescence (EL) spectrum of Examples 7-9 and Comparative Example 2 is shown. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention. It is sectional drawing which shows an example of the organic electroluminescent element in this invention.

Explanation of symbols

1 Substrate 2 Anode (ITO)
DESCRIPTION OF SYMBOLS 3 Light emitting layer 4 Cathode 5 Hole transport layer 6 Electron transport layer 7 Hole injection layer 8 Electron injection layer 9 Hole block layer

Claims (4)

The following general formula (1)
Wherein R is a linear or branched alkoxy group having 1 to 6 carbon atoms, r is a group independently selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 6 carbon atoms. R ^{20 to} R ³¹ and R ^{40 to} R ⁴² are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a straight chain having 1 to 6 carbon atoms. Each is a group independently selected from the group consisting of a chain or branched alkylamino group and a fluorine atom, m is an integer of 1 or 2, n is an integer of 3 or 4, and m + n = 5. )
A polyalkoxykinkphenyl derivative characterized by being represented by: The following general formula (2)
Wherein R is a linear or branched alkoxy group having 1 to 6 carbon atoms, r is a group independently selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 6 carbon atoms. R ^{20 to} R ³¹ and R ^{40 to} R ⁴² are hydrogen, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched alkoxy group having 1 to 6 carbon atoms, and a straight chain having 1 to 6 carbon atoms. Each is a group independently selected from the group consisting of a chain or branched alkylamino group and a fluorine atom, m is an integer of 1 or 2, n is an integer of 3 or 4, and m + n = 5. )
A polyalkoxykinkphenyl derivative characterized by being represented by:   A host material comprising the polyalkoxy kink phenyl derivative according to claim 1.   The organic electroluminescent element using the polyalkoxy kink phenyl derivative of Claim 1 or 2.