WO2023182377A1 - トリアリールアミン高分子量化合物および有機エレクトロルミネッセンス素子 - Google Patents

トリアリールアミン高分子量化合物および有機エレクトロルミネッセンス素子 Download PDF

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WO2023182377A1
WO2023182377A1 PCT/JP2023/011302 JP2023011302W WO2023182377A1 WO 2023182377 A1 WO2023182377 A1 WO 2023182377A1 JP 2023011302 W JP2023011302 W JP 2023011302W WO 2023182377 A1 WO2023182377 A1 WO 2023182377A1
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group
molecular weight
high molecular
weight compound
structural unit
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French (fr)
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優太 三枝
和法 富樫
秀良 北原
美香 篠田
由香 吉澤
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Hodogaya Chemical Co Ltd
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Priority to JP2024509175A priority patent/JPWO2023182377A1/ja
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    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
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    • H10K85/111—Organic polymers or oligomers comprising aromatic, heteroaromatic, or aryl chains, e.g. polyaniline, polyphenylene or polyphenylene vinylene
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    • C08G2261/10—Definition of the polymer structure
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    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
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    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
    • C08G2261/3162—Arylamines
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    • C08G2261/50—Physical properties
    • C08G2261/52—Luminescence

Definitions

  • the present invention relates to a high molecular weight compound suitable for an organic electroluminescent device (organic EL device), which is a self-luminous device suitable for various display devices, and the device.
  • organic EL device organic electroluminescent device
  • organic EL devices are self-luminous devices, they are brighter and have better visibility than liquid crystal devices, allowing for clearer display, and have therefore been actively researched.
  • An organic EL element has a structure in which a thin film (organic layer) of an organic compound is sandwiched between an anode and a cathode.
  • Methods for forming thin films are broadly classified into vacuum evaporation methods and coating methods.
  • the vacuum evaporation method is a method of forming a thin film on a substrate in vacuum, mainly using a low-molecular compound, and is a technology that has already been put into practical use.
  • the coating method is a method that mainly uses high molecular weight compounds to form a thin film on a substrate using a solution such as inkjet or printing.It has high material usage efficiency and is suitable for large areas and high definition. This technology will be essential for future large-area organic EL displays.
  • Vacuum deposition methods using low-molecular materials have extremely low material usage efficiency, and as the size increases, the shadow mask will bend more, making uniform deposition on large substrates difficult. It also has the problem of high manufacturing costs.
  • TFB fluorene polymer
  • An object of the present invention is to provide a polymer material that has excellent hole injection and transport performance, has electron blocking ability, and is highly stable in a thin film state.
  • Another object of the present invention is to provide an organic EL element that has an organic layer (thin film) formed of the polymeric material, has high luminous efficiency, and has a long life.
  • the present inventors focused on the fact that triarylamines containing a terphenyl structure in the molecular main chain have high hole injection and transport ability, and are also expected to have a wide gap.
  • triarylamine high molecular weight compounds containing structural units we discovered a high molecular weight compound with a novel structure that has a wide gap, excellent heat resistance, and thin film stability, in addition to hole injection and transport capabilities.
  • the present invention has now been completed.
  • a repeating unit represented by the following general formula (3) consisting of a triarylamine structural unit represented by the following general formula (1) and a connecting structural unit represented by the general formula (2); , and a thermally crosslinkable structural unit.
  • an organic EL element including an organic layer formed using the above-mentioned high molecular weight compound is provided.
  • the organic layer is preferably a hole transport layer, an electron blocking layer, a hole injection layer, or a light emitting layer.
  • a repeating structural unit represented by the following general formula (3) consisting of a triarylamine structural unit represented by the following general formula (1) and a connecting structural unit represented by the following general formula (2). , a thermally crosslinkable structural unit, and has a weight average molecular weight of 10,000 or more and less than 1,000,000 in terms of polystyrene.
  • R 1 each independently represents a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkyl group having 3 to 40 carbon atoms, a cyclo It represents an alkyl group, an alkyloxy group, a cycloalkyloxy group, an alkenyl group, or an aryloxy group.
  • R 2 each independently represents an alkyl group, a cycloalkyl group, or an alkyloxy group having 3 to 40 carbon atoms.
  • X represents a hydrogen atom, an amino group, a monovalent aryl group, or a monovalent heteroaryl group.
  • L represents a divalent phenyl group, and n represents an integer of 0 to 3.
  • thermoly crosslinkable structural unit is a structural unit represented by the following general formulas (4-1) to (4-112).
  • R is each independently a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group, a cycloalkyl group, or an alkyl group having 3 to 40 carbon atoms. Indicates an oxy group, cycloalkyloxy group, alkenyl group, or aryloxy group.
  • R is each independently a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or an alkyl group, a cycloalkyl group, or an alkyl group having 3 to 40 carbon atoms. Indicates an oxy group, cycloalkyloxy group, alkenyl group, or aryloxy group.
  • An organic electroluminescent device comprising an organic layer formed using the high molecular weight compound according to any one of [1] to [7].
  • the high molecular weight compound of the present invention is composed of a triarylamine structural unit (divalent group) represented by the above-mentioned general formula (1) and a connecting structural unit (bivalent group) represented by general formula (2). It is a polymer containing a repeating structural unit represented by the general formula (3) and a thermally crosslinkable structural unit, and preferably has a weight average molecular weight in terms of polystyrene measured by GPC (gel permeation chromatography). is in the range of 10,000 or more and less than 1,000,000.
  • GPC gel permeation chromatography
  • the high molecular weight compound of the present invention is (1) Good hole injection characteristics; (2) High hole mobility; (3) wide gap and excellent electron blocking ability; (4) The thin film state is stable; (5) Excellent heat resistance; It has the following characteristics.
  • An organic EL device in which an organic layer formed of such a high molecular weight compound, such as a hole transport layer, an electron blocking layer, a hole injection layer, or a light emitting layer, is formed between a pair of electrodes, (1) High luminous efficiency and power efficiency; (2) Low practical driving voltage; (3) Long lifespan; It has the advantage of
  • FIG. 1 is a 1 H-NMR chart of high molecular weight compound A synthesized in Example 1.
  • FIG. 1 is a 1 H-NMR chart of high molecular weight compound B synthesized in Example 2.
  • FIG. 3 is a 1 H-NMR chart of high molecular weight compound C synthesized in Example 3.
  • FIG. 3 is a 1 H-NMR chart of high molecular weight compound D synthesized in Example 4.
  • FIG. 1 is a 1 H-NMR chart of high molecular weight compound E synthesized in Example 5.
  • FIG. 3 is a 1 H-NMR chart of high molecular weight compound F synthesized in Example 6.
  • FIG. 3 is a 1 H-NMR chart of high molecular weight compound G synthesized in Example 7.
  • FIG. 1 is a 1 H-NMR chart of high molecular weight compound A synthesized in Example 1.
  • FIG. 1 is a 1 H-NMR chart of high molecular weight compound B synthesized in Example 2.
  • Triarylamine structural unit and linking structural unit are both divalent groups, and are represented by the following general formulas (1) and (2), respectively.
  • R 1 is each independently a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a group having 1 to 1 carbon atoms.
  • R 1 is each independently a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a group having 1 to 1 carbon atoms.
  • alkyl group, alkyloxy group, cycloalkyl group, cycloalkyloxy group, alkenyl group, and aryloxy group represented by R 1 include the following groups.
  • alkyl groups include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, Examples include neopentyl group, n-hexyl group, isohexyl group, neohexyl group, n-heptyl group, isoheptyl group, neoheptyl group, n-octyl group, isooctyl group, neooctyl group, and the like.
  • alkyloxy groups (having 1 to 8 carbon atoms) include methyloxy, ethyloxy, n-propyloxy, isopropyloxy, n-butyloxy, tert-butyloxy, n-pentyloxy, n- -hexyloxy group, n-heptyloxy group, n-octyloxy group, etc.
  • Examples of the cycloalkyl group (having 5 to 10 carbon atoms) include a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, and the like.
  • Examples of the cycloalkyloxy group include cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, cyclooctyloxy group, 1-adamantyloxy group, 2-adamantyloxy group, etc. .
  • Examples of the alkenyl group include vinyl group, allyl group, isopropenyl group, and 2-butenyl group.
  • Examples of the aryloxy group (having 6 to 10 carbon atoms) include phenyloxy group and tolyloxy group.
  • R 1 is preferably a deuterium atom. Synthetically, it is most preferable that a and b are 0.
  • R 2 each independently represents an alkyl group, a cycloalkyl group, or an alkyloxy group having 3 to 40 carbon atoms.
  • Examples of the alkyl group, cycloalkyl group, and alkyloxy group represented by R 2 include the same groups as those shown for R 1 .
  • R 2 is preferably an alkyl group having 3 to 40 carbon atoms, most preferably an n-hexyl group or an n-octyl group, in order to improve solubility. It is.
  • X represents a hydrogen atom, an amino group, a monovalent aryl group, or a monovalent heteroaryl group.
  • Examples of the monovalent aryl group and monovalent heteroaryl group include the following groups.
  • aryl group examples include phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, and fluoranthenyl group.
  • heteroaryl groups include pyridyl group, pyrimidinyl group, triazinyl group, furyl group, pyrrolyl group, thienyl group, quinolyl group, isoquinolyl group, benzofuranyl group, benzothienyl group, indolyl group, carbazolyl group, indenocarbazolyl group. group, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, naphthyridinyl group, phenanthrolinyl group, acridinyl group, and carbolinyl group.
  • the above-mentioned amino group, aryl group, and heteroaryl group may have a substituent.
  • Substituents include deuterium atoms, cyano groups, nitro groups, etc.
  • Halogen atoms such as fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms;
  • Alkyl groups especially those having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, Neopentyl group, n-hexyl group, isohexyl group, neohexyl group, n-heptyl group, isoheptyl group, neoheptyl group, n-octyl group, isooctyl group, and neooc
  • these substituents may further have the substituents exemplified above. Furthermore, it is preferable that these substituents exist independently, but if these substituents exist through a single bond, a methylene group that may have a substituent, an oxygen atom, or a sulfur atom, may be bonded to each other to form a ring.
  • X is a hydrogen atom, a diphenylamino group, a phenyl group, a naphthyl group, a dibenzofuranyl group, a dibenzothienyl group, a phenanthrenyl group, a fluorenyl group, a carbazolyl group, an indenocarbazolyl group, or an acridinyl group.
  • a hydrogen atom is particularly preferable.
  • the above-mentioned aryl group and heteroaryl group may have a phenyl group as a substituent, and this phenyl group may further have a phenyl group as a substituent. That is, taking an aryl group as an example, this aryl group may be a biphenylyl group, a terphenylyl group, or a triphenylenyl group.
  • L represents a divalent phenylene group or a naphthylene group
  • n represents an integer of 0 to 3.
  • n is preferably 0.
  • the above L may have a substituent.
  • the substituent is the same as the substituent that X described above may have, and these substituents may further have a substituent.
  • connecting structural units 1 to 31 in FIGS. 1 to 6 specific examples of the connecting structural units represented by the above-mentioned general formula (2) are shown as structural units 1 to 31 in FIGS. 1 to 6.
  • the broken lines indicate bonds to adjacent structural units, and the solid lines with free tips extending from the ring indicate that the free tips are methyl groups. It shows.
  • the connecting structural unit used in the present invention is not limited to these structural units.
  • the thermally crosslinkable structural unit possessed by the high molecular weight compound of the present invention may be any structural unit that can undergo a thermal crosslinking reaction, but preferable structural units are those represented by the general formulas (4-1) to (4-112).
  • the structural unit shown (thermally crosslinkable structural unit 4) is exemplified.
  • R is each independently a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, or a carbon atom.
  • alkyl group, cycloalkyl group, alkyloxy group, cycloalkyloxy group, alkenyl group, and aryloxy group represented by R include the same groups as those shown for R 1 .
  • thermally crosslinkable structural units 4 those represented by general formulas (4-34), (4-36), (4-37), (4-45), (4-47) and (4-48) Structural units are preferred. Further, in these structural units, a and b are preferably 0.
  • the thermally crosslinkable structural unit 4 preferably includes a terphenyl structure in which three benzene rings are connected.
  • the high molecular weight compound of the present invention containing From the viewpoint of further enhancing these properties and ensuring film formability, the weight average molecular weight in terms of polystyrene measured by GPC is preferably 10,000 or more and less than 1,000,000, more preferably 10,000. It is in the range of 10,000 or more and less than 200,000, more preferably 10,000 or more and less than 200,000.
  • the high molecular weight compound of the present invention preferably contains the thermally crosslinkable structural unit 4 as a thermally crosslinkable structural unit, but the coating property when applied to the formation of an organic layer in an organic EL element by coating, for example,
  • the thermally crosslinkable structural unit 4 may be further included in order to ensure adhesion with other layers and durability.
  • thermally crosslinkable structural units examples include the structural units represented by the general formulas (5-1) to (5-31) (thermally crosslinkable structural unit 5).
  • R in the general formulas (5-1) to (5-31) is the same as R in the general formulas (4-1) to (4-112).
  • thermally crosslinkable structural units 5 structural units represented by general formulas (5-5) and (5-7) are preferred. Further, in these structural units, a and b are preferably 0. Although preferred specific examples of the thermally crosslinkable structural unit have been shown, the thermally crosslinkable structural unit used in the present invention is not limited to these structural units.
  • the triarylamine structural unit represented by general formula (1) is "structural unit A”
  • the connecting structural unit represented by general formula (2) is “structural unit B”
  • thermal crosslinking When the structural unit is represented by "structural unit C”, it is preferable that the structural unit A is contained in 1 mol% or more, particularly 20 mol% or more, and the condition is that the structural unit A is contained in such an amount.
  • structural unit B preferably contains structural unit B in an amount of 1 mol% or more, particularly 30 to 70 mol%, and further preferably contains structural unit C in an amount of 1 mol% or more, particularly 5 to 20 mol%,
  • a ternary copolymer containing structural units A, B, and C that satisfies these conditions is most suitable for forming the organic layer of an organic EL device.
  • the high molecular weight compound of the present invention is synthesized by forming a carbon-carbon bond or a carbon-nitrogen bond and linking each structural unit by Suzuki polymerization reaction or HARTWIG-BUCHWALD polymerization reaction, respectively.
  • the high molecular weight compound of the present invention is prepared by preparing a unit compound having each structural unit, appropriately boric acid esterifying or halogenating the unit compound, and performing a polycondensation reaction using an appropriate catalyst. Can be synthesized.
  • a triarylamine derivative represented by the following general formula (1a) can be used as a compound for introducing the triarylamine structural unit represented by the general formula (1).
  • Q is a hydrogen atom or a halogen atom (Br is particularly preferred), and R 1 , R 2 , and L are all the same as those shown in the general formula (1).
  • a compound in which Q is a hydrogen atom is a unit compound for introducing the structural unit of general formula (1), and a compound in which Q is a halogen atom is a unit compound for synthesizing a polymer. It is a halide used for
  • the intermediate for introducing structural unit A and structural unit C is a boric acid ester
  • the intermediate for introducing structural unit B is a halogenated product
  • the intermediate for introducing unit A and structural unit C is a halogenated product
  • the intermediate for introducing structural unit B needs to be a boric acid ester. That is, the molar ratio of the halogenated product and the boric acid esterified product must be equal.
  • the above-described high molecular weight compound of the present invention is dissolved in an aromatic organic solvent such as benzene, toluene, xylene, and anisole to prepare a coating solution, and this coating solution is coated on a predetermined substrate and dried by heating.
  • an aromatic organic solvent such as benzene, toluene, xylene, and anisole
  • a coating solution is coated on a predetermined substrate and dried by heating.
  • a thin film having excellent properties such as hole injection properties, hole transport properties, and electron blocking properties can be formed.
  • the formed thin film has good heat resistance and also has good adhesion to other layers.
  • the high molecular weight compound can be used as a constituent material of a hole injection layer and/or a hole transport layer of an organic EL device.
  • a hole injection layer or a hole transport layer formed from such a high molecular weight compound has higher hole injection properties, higher mobility, and electron blocking properties compared to those formed from conventional materials. It is possible to confine excitons generated in the light-emitting layer, and to improve the probability of holes and electrons recombining, resulting in high luminous efficiency and lower driving voltage. It is possible to realize the advantage that the durability of the element is improved.
  • the high molecular weight compound of the present invention having the electrical properties described above has a wider gap than conventional materials and is effective in confining excitons, so it is naturally suitable for use in electron blocking layers and light emitting layers. can do.
  • An organic EL element including an organic layer formed using the above-described high molecular weight compound of the present invention has a structure shown in FIG. 7, for example. That is, a transparent anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6 and a cathode 7 are formed on a glass substrate 1 (any transparent substrate such as a transparent resin substrate). It is provided.
  • the organic EL device to which the high molecular weight compound of the present invention is applied is not limited to the above-mentioned layer structure, and a hole blocking layer can be provided between the light emitting layer 5 and the electron transport layer 6.
  • a hole blocking layer can be provided between the hole transport layer 4 and the light emitting layer 5.
  • an electron injection layer may be provided between the cathode 7 and the electron transport layer 6.
  • some layers can also be omitted.
  • a simple layered structure in which an anode 2, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, and a cathode 7 are provided on the substrate 1 may be used. It is also possible to have a two-layer structure in which layers having the same function are stacked.
  • the high molecular weight compound of the present invention takes advantage of its properties such as hole injection and hole transport properties to provide an organic layer (for example, hole injection layer 3, positive It is suitably used as a material for forming the hole transport layer 4, the light emitting layer 5, and the electron blocking layer.
  • organic layer for example, hole injection layer 3, positive It is suitably used as a material for forming the hole transport layer 4, the light emitting layer 5, and the electron blocking layer.
  • the transparent anode 2 may be formed of a known electrode material, and an electrode material with a high work function such as ITO or gold is formed on the substrate 1 (a transparent substrate such as a glass substrate). It is formed by vapor deposition.
  • the hole injection layer 3 provided on the transparent anode 2 is formed using a coating liquid in which the high molecular weight compound of the present invention is dissolved in an aromatic organic solvent such as toluene, xylene, or anisole.
  • an aromatic organic solvent such as toluene, xylene, or anisole.
  • the hole injection layer 3 can be formed by coating the transparent anode 2 with this coating liquid by spin coating, inkjet, or the like.
  • the hole injection layer 3 may be made of a conventionally known material, such as the following, without using the high molecular weight compound of the present invention. It can also be formed using the following materials.
  • PEDOT poly(3,4-ethylenedioxythiophene)
  • PSS poly(styrene sulfonate)
  • a layer (thin film) using such a material can be formed by a coating method such as vapor deposition, spin coating, or inkjet. The same applies to other layers, and the film is formed by a vapor deposition method or a coating method depending on the type of film-forming material.
  • the hole transport layer 4 provided on the hole injection layer 3 is also formed using the high molecular weight compound of the present invention by a coating method such as spin coating or inkjet. be able to.
  • the hole transport layer 4 can also be formed using a conventionally known hole transport material.
  • Typical such hole transport materials are as follows.
  • Benzidine derivatives e.g. N,N'-diphenyl-N,N'-di(m-tolyl)benzidine (hereinafter abbreviated as TPD); N,N'-diphenyl-N,N'-di( ⁇ -naphthyl)benzidine (hereinafter abbreviated as NPD); N,N,N',N'-tetrabiphenylylbenzidine; Amine derivatives, e.g.
  • TAPC 1,1-bis[4-(di-4-tolylamino)phenyl]cyclohexane
  • TAPC 1,1-bis[4-(di-4-tolylamino)phenyl]cyclohexane
  • triphenylamine trimers and tetramers A coated polymer material that is also used as a hole injection layer.
  • the above-mentioned compounds for the hole transport layer may each be formed into a film alone, or two or more thereof may be mixed and formed into a film. Moreover, a plurality of layers can be formed using one or more of the above compounds, and a multilayer film in which such layers are laminated can be used as a hole transport layer.
  • the layer can also serve as both the hole injection layer 3 and the hole transport layer 4.
  • the hole injection/transport layer can be formed by a coating method using a polymeric material such as PEDOT.
  • hole transport layer 4 (same as the hole injection layer 3), trisbromophenylamine hexachloroantimony or a radialene derivative (for example, see WO2014/009310) is added to the material normally used for this layer. Doped materials can be used. Further, the hole transport layer 4 (or hole injection layer 3) can be formed using a high molecular weight compound having a TPD basic skeleton.
  • an electron blocking layer (which can be provided between the hole transport layer 4 and the light emitting layer 5 as shown in FIG. 8) is also formed by spin coating, inkjet coating, etc. using the high molecular weight compound of the present invention. can do.
  • an organic EL device having an organic layer formed using the high molecular weight compound of the present invention a known electron blocking compound having an electron blocking effect, such as a carbazole derivative or a triphenylsilyl group, may be used.
  • the electron blocking layer can also be formed using a compound having a triarylamine structure. Specific examples of carbazole derivatives and compounds having a triarylamine structure are as follows.
  • carbazole derivatives 4,4',4''-tri(N-carbazolyl)triphenylamine (hereinafter abbreviated as TCTA); 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene; 1,3-bis(carbazol-9-yl)benzene (hereinafter abbreviated as mCP); 2,2-bis(4-carbazol-9-ylphenyl)adamantane (hereinafter abbreviated as Ad-Cz); Examples of compounds having a triarylamine structure 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene.
  • TCTA 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene
  • mCP 1,3-bis(carbazol-9-yl)benzene
  • Ad-Cz 2,2-bis(4-carbazol-9-y
  • the electron blocking layer may also be formed individually, including the high molecular weight compound of the present invention, but it can also be formed as a mixture of two or more types. Alternatively, a plurality of layers may be formed using one or more of the above compounds, and a multilayer film in which such layers are laminated can be used as an electron blocking layer.
  • the light-emitting layer is a metal complex of a quinolinol derivative such as Alq 3 ; various metal complexes such as zinc, beryllium, and aluminum; It can be formed using luminescent materials such as anthracene derivatives; bisstyrylbenzene derivatives; pyrene derivatives; oxazole derivatives; polyparaphenylene vinylene derivatives.
  • a quinolinol derivative such as Alq 3
  • various metal complexes such as zinc, beryllium, and aluminum
  • luminescent materials such as anthracene derivatives; bisstyrylbenzene derivatives; pyrene derivatives; oxazole derivatives; polyparaphenylene vinylene derivatives.
  • the light-emitting layer can also be composed of a host material and a dopant material.
  • the host material in addition to the above-mentioned luminescent materials, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, etc. can be used, and furthermore, the above-mentioned high molecular weight compound of the present invention can also be used.
  • the dopant material quinacridone, coumarin, rubrene, perylene, and derivatives thereof; benzopyran derivatives; rhodamine derivatives; aminostyryl derivatives, etc. can be used.
  • Such a light emitting layer 5 can also have a single layer structure using one or more types of each light emitting material, or can have a multilayer structure in which a plurality of layers are laminated.
  • the light emitting layer 5 can also be formed using a phosphorescent material as the light emitting material.
  • a phosphorescent material phosphorescent emitters of metal complexes such as iridium and platinum can be used.
  • green phosphorescent emitters such as Ir(ppy) 3 ; blue phosphorescent emitters such as FIrpic and FIr6; red phosphorescent emitters such as Btp 2 Ir(acac), etc.
  • These phosphorescent materials are used by doping them into a hole-injecting/transporting host material or an electron-transporting host material.
  • doping of the phosphorescent light-emitting material into the host material is preferably carried out by co-evaporation in a range of 1 to 30 weight percent based on the entire light-emitting layer.
  • the driving voltage is lowered and the luminous efficiency is increased.
  • An improved organic EL device can be realized.
  • the high molecular weight compound of the present invention can be used as a host material with hole injection/transport properties.
  • carbazole derivatives such as 4,4'-di(N-carbazolyl)biphenyl (hereinafter abbreviated as CBP), TCTA, and mCP can also be used.
  • p-bis(triphenylsilyl)benzene (hereinafter abbreviated as UGH2) is used as an electron transporting host material.
  • TPBI 2,2',2''-(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole)
  • the hole blocking layer (not shown in the figure) provided between the light emitting layer 5 and the electron transport layer 6 is as follows: It can be formed using a compound having a hole blocking effect that is known per se. Examples of known compounds having such a hole blocking effect include the following. Phenanthroline derivatives such as bathocuproine (hereinafter abbreviated as BCP); Metal complexes of quinolinol derivatives such as aluminum (III) bis(2-methyl-8-quinolinate)-4-phenylphenolate (hereinafter abbreviated as BAlq); Various rare earth complexes; Triazole derivative; Triazine derivative; Oxadiazole derivative.
  • BCP bathocuproine
  • BAlq Metal complexes of quinolinol derivatives such as aluminum (III) bis(2-methyl-8-quinolinate)-4-phenylphenolate
  • These materials can also be used to form the electron transport layer 6 described below, and can also be used as the hole blocking layer and electron transport layer 6.
  • Such a hole-blocking layer can also have a single-layer or multilayer stacked structure, and each layer is formed using one or more of the above-mentioned compounds having a hole-blocking effect.
  • the electron transport layer 6 is made of a known electron transporting compound such as a quinolinol derivative such as Alq 3 and BAlq. Formation using metal complexes, various metal complexes, pyridine derivatives, pyrimidine derivatives, triazole derivatives, triazine derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silole derivatives, benzimidazole derivatives, etc. I can do it.
  • a quinolinol derivative such as Alq 3 and BAlq.
  • This electron transport layer 6 can also have a single layer or multilayer laminated structure, and each layer is formed using one or more of the above-mentioned electron transport compounds.
  • the electron injection layer (not shown in the figure) provided as necessary may also be of a known type, for example. , alkali metal salts such as lithium fluoride and cesium fluoride, alkaline earth metal salts such as magnesium fluoride, metal oxides such as aluminum oxide, and organometallic complexes such as lithium quinoline. .
  • an electrode material with a low work function such as aluminum, and a magnesium-silver alloy, a magnesium-indium alloy, or an aluminum-magnesium alloy can be used. Alloys with lower work functions, such as, are used as electrode materials.
  • the hole injection layer 3, the hole transport layer 4, the light emitting layer 5, and the electron blocking layer using the high molecular weight compound of the present invention.
  • An organic EL element with high efficiency and power efficiency, low practical driving voltage, low emission start voltage, and extremely excellent durability can be obtained.
  • this organic EL element has high luminous efficiency while reducing drive voltage, improving current tolerance, and increasing maximum luminance.
  • structural unit A the structural unit represented by general formula (1) possessed by the high molecular weight compound of the present invention
  • structural unit B the connecting structural unit represented by general formula (2)
  • structural unit C the thermally crosslinkable structural unit
  • synthesized compound was purified by column chromatography and crystallization using a solvent.
  • Compound identification was performed by NMR analysis.
  • intermediates 1 to 10 were synthesized.
  • intermediate 1 corresponds to "structural unit A”
  • intermediates 4, 5, 6, and 10 correspond to "structural unit C”.
  • intermediates 2 and 3 are intermediates for synthesizing intermediate 4
  • intermediates 7, 8, and 9 are intermediates for synthesizing intermediate 10.
  • Example 1 Synthesis of high molecular weight compound A; The following components were added to a reaction vessel purged with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes.
  • Intermediate 1 5.6g 1,3-dibromobenzene: 1.8g
  • Intermediate 4 0.5g Tripotassium phosphate: 6.9g Toluene: 9ml, water: 5ml, 1,4-dioxane: 27ml
  • 1.4 mg of palladium (II) acetate and 12 mg of tri-o-tolylphosphine were added, heated, and stirred at 88° C. for 8 hours.
  • the crude polymer was dissolved in toluene, silica gel was added thereto for adsorption purification, and the silica gel was removed by filtration.
  • the obtained filtrate was concentrated under reduced pressure, and 100 ml of toluene was added to the dried product to dissolve it, and the solution was added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This operation was repeated three times and 3.3 g (yield 69%) of high molecular weight compound A was obtained by drying.
  • the average molecular weight and dispersity of high molecular weight compound A measured by GPC were as follows. Number average molecular weight Mn (polystyrene equivalent): 76,000 Weight average molecular weight Mw (polystyrene equivalent): 175,000 Dispersity (Mw/Mn): 2.3
  • this high molecular weight compound A contained 45 mol% of structural unit A, 50 mol% of structural unit B, and 5 mol% of structural unit C.
  • Example 2 Synthesis of high molecular weight compound B; The following components were added to a reaction vessel purged with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes.
  • Intermediate 1 5.6g 1,3-dibromobenzene: 1.8g
  • Intermediate 5 0.5g Tripotassium phosphate: 6.8g Toluene: 9ml, water: 5ml, 1,4-dioxane: 27ml
  • 1.4 mg of palladium (II) acetate and 12 mg of tri-o-tolylphosphine were added, heated, and stirred at 88° C. for 12 hours.
  • the crude polymer was dissolved in toluene, silica gel was added thereto for adsorption purification, and the silica gel was removed by filtration.
  • the obtained filtrate was concentrated under reduced pressure, and 100 ml of toluene was added to the dried product to dissolve it, and the solution was added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This operation was repeated three times and 3.4 g (yield 71%) of high molecular weight compound B was obtained by drying.
  • the average molecular weight and dispersity of high molecular weight compound B measured by GPC were as follows. Number average molecular weight Mn (polystyrene equivalent): 40,000 Weight average molecular weight Mw (polystyrene equivalent): 65,000 Dispersity (Mw/Mn): 1.6
  • this high molecular weight compound B contained 45 mol% of structural unit A, 50 mol% of structural unit B, and 5 mol% of structural unit C.
  • Example 3 Synthesis of high molecular weight compound C; The following components were added to a reaction vessel purged with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes.
  • Intermediate 1 5.6g 1,3-dibromobenzene: 1.8g
  • Intermediate 6 0.5g Tripotassium phosphate: 6.8g Toluene: 9ml, water: 5ml, 1,4-dioxane: 27ml
  • 1.4 mg of palladium (II) acetate and 12 mg of tri-o-tolylphosphine were added, heated, and stirred at 88° C. for 12 hours.
  • the crude polymer was dissolved in toluene, silica gel was added thereto for adsorption purification, and the silica gel was removed by filtration.
  • the obtained filtrate was concentrated under reduced pressure, and 100 ml of toluene was added to the dried product to dissolve it, and the solution was added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This operation was repeated three times and 3.4 g (yield 65%) of high molecular weight compound C was obtained by drying.
  • the average molecular weight and dispersity of high molecular weight compound B measured by GPC were as follows. Number average molecular weight Mn (polystyrene equivalent): 44,000 Weight average molecular weight Mw (polystyrene equivalent): 80,000 Dispersity (Mw/Mn): 1.8
  • this high molecular weight compound C contained 45 mol% of structural unit A, 50 mol% of structural unit B, and 5 mol% of structural unit C.
  • Example 4 Synthesis of high molecular weight compound D; The following components were added to a reaction vessel purged with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes.
  • Intermediate 1 5.4g 1,3-dibromobenzene: 1.7g
  • Intermediate 10 0.7g Tripotassium phosphate: 7.4g Toluene: 9ml, water: 5ml, 1,4-dioxane: 27ml
  • 1.5 mg of palladium (II) acetate and 12 mg of tri-o-tolylphosphine were added, heated, and stirred at 86° C. for 9.5 hours.
  • the crude polymer was dissolved in toluene, silica gel was added thereto for adsorption purification, and the silica gel was removed by filtration.
  • the obtained filtrate was concentrated under reduced pressure, and 100 ml of toluene was added to the dried product to dissolve it, and the solution was added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This operation was repeated three times and 3.3 g (yield 63%) of high molecular weight compound D was obtained by drying.
  • the average molecular weight and dispersity of high molecular weight compound D measured by GPC were as follows. Number average molecular weight Mn (polystyrene equivalent): 78,000 Weight average molecular weight Mw (polystyrene equivalent): 124,000 Dispersity (Mw/Mn): 1.6
  • this high molecular weight compound D contained 45 mol% of structural unit A, 50 mol% of structural unit B, and 5 mol% of structural unit C.
  • the crude polymer was dissolved in toluene, silica gel was added thereto for adsorption purification, and the silica gel was removed by filtration.
  • the obtained filtrate was concentrated under reduced pressure, and 100 ml of toluene was added to the dried product to dissolve it.
  • the solution was added dropwise to 200 ml of n-hexane, and the resulting precipitate was collected by filtration. This operation was repeated three times and 2.9 g (yield 57%) of high molecular weight compound E was obtained by drying.
  • the average molecular weight and dispersity of high molecular weight compound E measured by GPC were as follows. Number average molecular weight Mn (polystyrene equivalent): 91,000 Weight average molecular weight Mw (polystyrene equivalent): 155,000 Dispersity (Mw/Mn): 1.7
  • this high molecular weight compound E contains 44 mol% of structural unit A, 50 mol% of structural unit B, and is represented by general formula (4-45) as structural unit C. It contained 3 mol% of structural units, and 3 mol% of structural units represented by general formula (5-7).
  • the crude polymer was dissolved in toluene, silica gel was added thereto for adsorption purification, and the silica gel was removed by filtration.
  • the obtained filtrate was concentrated under reduced pressure, and 100 ml of toluene was added to the dried product to dissolve it.
  • the solution was added dropwise to 200 ml of n-hexane, and the resulting precipitate was collected by filtration. This operation was repeated three times and 3.3 g (yield 67%) of high molecular weight compound F was obtained by drying.
  • the average molecular weight and dispersity of high molecular weight compound F measured by GPC were as follows. Number average molecular weight Mn (polystyrene equivalent): 63,000 Weight average molecular weight Mw (polystyrene equivalent): 101,000 Dispersity (Mw/Mn): 1.6
  • this high molecular weight compound F contains 45 mol% of the structural unit A, 50 mol% of the structural unit B, and is represented by the general formula (4-45) as the structural unit C. It contained 2 mol% of structural units represented by general formula (5-7) and 3 mol% of structural units represented by general formula (5-7).
  • Example 7 Synthesis of high molecular weight compound G; The following components were added to a reaction vessel purged with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes.
  • Intermediate 1 3.8g 9-(3,5-dibromophenyl)carbazole: 3.1g
  • Intermediate 5 0.5g
  • Intermediate 12 1.4g Tripotassium phosphate: 6.9g Toluene: 9ml, water: 5ml, 1,4-dioxane: 27ml
  • 1.4 mg of palladium (II) acetate and 11 mg of tri-o-tolylphosphine were added, heated, and stirred at 86° C. for 12 hours.
  • the crude polymer was dissolved in toluene, silica gel was added thereto for adsorption purification, and the silica gel was removed by filtration.
  • the obtained filtrate was concentrated under reduced pressure, and 100 ml of toluene was added to the dried product to dissolve it, and the solution was added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This operation was repeated three times and 2.6 g (yield 46%) of high molecular weight compound G was obtained by drying.
  • the average molecular weight and dispersity of high molecular weight compound G measured by GPC were as follows. Number average molecular weight Mn (polystyrene equivalent): 67,000 Weight average molecular weight Mw (polystyrene equivalent): 97,000 Dispersity (Mw/Mn): 1.4
  • this high molecular weight compound G contained 30 mol% of structural unit A, 50 mol% of structural unit B, and 5 mol% of structural unit C.
  • Example 8> Using high molecular weight compounds A to G synthesized in Examples 1 to 7, a coating film with a thickness of 80 nm was prepared on an ITO substrate, and an ionization potential measuring device (manufactured by Sumitomo Heavy Industries, Ltd., PYS- 202 type) to measure the work function. The results were as follows. High molecular weight compound A: 5.67eV High molecular weight compound B: 5.62eV High molecular weight compound C: 5.64eV High molecular weight compound D: 5.66eV High molecular weight compound E: 5.62eV High molecular weight compound F: 5.62eV High molecular weight compound G: 5.70eV
  • the high molecular weight compounds A to G of the present invention exhibit a suitable energy level compared to the work function of 5.4 eV of general hole transport materials such as NPD and TPD, and have good hole transport. It is clear that you have the ability.
  • Example 9 Fabrication and evaluation of organic EL devices; An organic EL device having the layered structure shown in FIG. 7 was manufactured and its characteristics were evaluated. Specifically, the glass substrate 1 on which ITO with a thickness of 50 nm was formed was cleaned with an organic solvent, and then the ITO surface was cleaned with UV/ozone treatment. PEDOT/PSS (manufactured by Ossila) was formed into a film with a thickness of 50 nm by spin coating so as to cover the transparent anode 2 (ITO) provided on the glass substrate 1, and dried on a hot plate at 200°C for 10 minutes. Then, a hole injection layer 3 was formed.
  • PEDOT/PSS manufactured by Ossila
  • a coating solution was prepared by dissolving 0.6 wt% of the high molecular weight compound A obtained in Example 1 in toluene.
  • the substrate on which the hole injection layer 3 is formed as described above is transferred to a glove box purged with dry nitrogen, and dried on a hot plate at 230° C. for 10 minutes. Then, a coating layer with a thickness of 25 nm was formed by spin coating using the above coating solution, and further dried on a hot plate at 220° C. for 30 minutes to form a hole transport layer 4.
  • the substrate on which the hole transport layer 4 was formed as described above was placed in a vacuum evaporator and the pressure was reduced to 0.001 Pa or less.
  • a light emitting layer 5 having a thickness of 34 nm was formed on the hole transport layer 4 by binary vapor deposition of a blue light emitting material (EMD-1) having the following structural formula and a host material (EMH-1).
  • EMD-1:EMH-1 4:96.
  • ETM-1 and ETM-2 were prepared as electron transport materials.
  • an electron transport layer 6 with a thickness of 20 nm was formed by binary vapor deposition using the electron transport materials ETM-1 and ETM-2.
  • the glass substrate on which the transparent anode 2, hole injection layer 3, hole transport layer 4, light emitting layer 5, electron transport layer 6, and cathode 7 are formed was placed in a glove box purged with dry nitrogen. Then, another glass substrate for sealing was bonded using a UV curing resin to form an organic EL element. Characteristics of the produced organic EL device were measured in the atmosphere at room temperature. Furthermore, the light emitting characteristics of the manufactured organic EL device when a DC voltage was applied were measured. The measurement results are shown in Table 1.
  • Example 10 Example except that the hole transport layer 4 was formed using a coating solution prepared by dissolving 0.6 wt% of the high molecular weight compound B obtained in Example 2 in toluene instead of the high molecular weight compound A.
  • An organic EL device was produced in exactly the same manner as in Example 9. Regarding the produced organic EL element, various characteristics were evaluated in the same manner as in Example 9, and the results are shown in Table 1.
  • Example 11 Example except that the hole transport layer 4 was formed using a coating solution prepared by dissolving 0.6 wt% of the high molecular weight compound C obtained in Example 3 in toluene instead of the high molecular weight compound A.
  • An organic EL device was produced in exactly the same manner as in Example 9. Regarding the produced organic EL element, various characteristics were evaluated in the same manner as in Example 9, and the results are shown in Table 1.
  • Example 12 Example except that the hole transport layer 4 was formed using a coating solution prepared by dissolving 0.6 wt% of the high molecular weight compound D obtained in Example 4 in toluene instead of the high molecular weight compound A.
  • An organic EL device was produced in exactly the same manner as in Example 9. Regarding the produced organic EL element, various characteristics were evaluated in the same manner as in Example 9, and the results are shown in Table 1.
  • Example 9 except that instead of the high molecular weight compound A, the hole transport layer 4 was formed using a coating solution prepared by dissolving 0.6 wt% of the following TFB (hole transporting polymer) in toluene.
  • TFB hole transporting polymer
  • TFB hole transporting polymer
  • voltage, luminance, luminous efficiency, and power efficiency are values when a current with a current density of 10 mA/cm 2 is passed.
  • the device life is determined when the luminance at the start of light emission (initial luminance) is 700 cd/m 2 and constant current driving is performed, and the luminance is 560 cd/m 2 (80% of the initial luminance as 100%). It was measured as the time required to attenuate to (equivalent to: 80% attenuation).
  • the driving voltage of the organic EL elements produced in Examples 9 to 12 was 3.88 V to 3.91 V, which was lower than the driving voltage of 4.08 V of the organic EL element of Comparative Example 1. It was voltage. Furthermore, when a current with a current density of 10 mA/cm 2 was applied, the luminous efficiency of the organic EL element of Example 9 was 8.33 cd/A, compared to 5.52 cd/A of the organic EL element of Comparative Example 1.
  • the organic EL device of Example 10 had a high efficiency of 8.47 cd/A
  • the organic EL device of Example 11 had a high efficiency of 8.86 cd/A
  • the organic EL device of Example 12 had a high efficiency of 8.47 cd/A.
  • the organic EL element of Example 9 had a 44 hour life span, and the organic EL element of Example 10 had a life span of 54 hours.
  • the organic EL device of Example 11 had a long life of 13 hours, and the organic EL device of Example 12 had a long life of 29 hours.
  • Example 13 An organic EL device having the layered structure shown in FIG. 8 was manufactured and its characteristics were evaluated. Specifically, the glass substrate 8 on which ITO was deposited with a thickness of 50 nm was cleaned with an organic solvent, and then the ITO surface was cleaned with UV/ozone treatment. PEDOT/PSS (manufactured by Ossila) was formed into a film with a thickness of 50 nm by spin coating so as to cover the transparent anode 9 (ITO) provided on the glass substrate 8, and dried on a hot plate at 200°C for 10 minutes. Then, a hole injection layer 10 was formed.
  • PEDOT/PSS manufactured by Ossila
  • a coating solution was prepared by dissolving 0.4 wt% of a high molecular weight compound HTM-1 having the following structural formula in toluene.
  • the substrate on which the hole injection layer 10 is formed as described above is transferred to a glove box purged with dry nitrogen, and dried on a hot plate at 230° C. for 10 minutes. Then, a coating layer with a thickness of 15 nm was formed by spin coating using the above coating solution, and the hole transport layer 11 was further dried on a hot plate at 220° C. for 30 minutes.
  • a coating solution was prepared by dissolving 0.4 wt% of the high molecular weight compound A obtained in Example 1 in toluene.
  • a coating layer with a thickness of 15 nm was formed on the hole transport layer 11 by spin coating using the coating solution described above, and was further dried on a hot plate at 220° C. for 30 minutes to form an electron blocking layer 12. .
  • the substrate on which the electron blocking layer 12 was formed as described above was placed in a vacuum evaporator and the pressure was reduced to 0.001 Pa or less.
  • an electron transport layer 14 with a thickness of 20 nm was formed by binary vapor deposition using electron transport materials ETM-1 and ETM-2.
  • Example 13 except that the electron blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt% of the high molecular weight compound B obtained in Example 2 in toluene instead of the high molecular weight compound A.
  • An organic EL device was produced in exactly the same manner as above. Regarding the produced organic EL element, various characteristics were evaluated in the same manner as in Example 13, and the results are shown in Table 2.
  • Example 15 Example 13 except that the electron blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt% of the high molecular weight compound C obtained in Example 3 in toluene instead of the high molecular weight compound A.
  • An organic EL device was produced in exactly the same manner as above. Regarding the produced organic EL element, various characteristics were evaluated in the same manner as in Example 13, and the results are shown in Table 2.
  • Example 16 except that the electron blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt% of the high molecular weight compound D obtained in Example 4 in toluene instead of the high molecular weight compound A.
  • An organic EL device was produced in exactly the same manner as above. Regarding the produced organic EL element, various characteristics were evaluated in the same manner as in Example 13, and the results are shown in Table 2.
  • Example 13 except that the electron blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt% of the high molecular weight compound E obtained in Example 5 in toluene instead of the high molecular weight compound A.
  • An organic EL device was produced in exactly the same manner as above. Regarding the produced organic EL element, various characteristics were evaluated in the same manner as in Example 13, and the results are shown in Table 2.
  • Example 13 except that the electron blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt% of the high molecular weight compound F obtained in Example 6 in toluene instead of the high molecular weight compound A.
  • An organic EL device was produced in exactly the same manner as above. Regarding the produced organic EL element, various characteristics were evaluated in the same manner as in Example 13, and the results are shown in Table 2.
  • Example 13 except that the electron blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt% of the high molecular weight compound G obtained in Example 7 in toluene instead of the high molecular weight compound A.
  • An organic EL device was produced in exactly the same manner as above. Regarding the produced organic EL element, various characteristics were evaluated in the same manner as in Example 13, and the results are shown in Table 2.
  • PEDOT/PSS manufactured by Ossila
  • a coating solution was prepared by dissolving 0.6 wt% of high molecular weight compound HTM-1 in toluene.
  • the substrate on which the hole injection layer 3 has been formed as described above is transferred to a glove box purged with dry nitrogen, and a 25 nm thick film is applied onto the hole injection layer 3 by spin coating using the coating solution described above.
  • a coating layer having a thickness of 200° C. was formed, and further dried on a hot plate at 220° C. for 30 minutes to form a hole transport layer 4.
  • the substrate on which the hole transport layer 4 was formed as described above was placed in a vacuum evaporator and the pressure was reduced to 0.001 Pa or less.
  • an electron transport layer 6 having a thickness of 20 nm was formed by binary vapor deposition using electron transport materials ETM-1 and ETM-2.
  • the glass substrate on which the transparent anode 2, hole injection layer 3, hole transport layer 4, light emitting layer 5, electron transport layer 6, and cathode 7 are formed was placed in a glove box purged with dry nitrogen. Then, another glass substrate for sealing was bonded using a UV curing resin to form an organic EL element. Characteristics of the produced organic EL device were measured in the atmosphere at room temperature. Furthermore, the light emitting characteristics of the manufactured organic EL device when a DC voltage was applied were measured. The measurement results are shown in Table 2.
  • voltage, luminance, luminous efficiency, and power efficiency are values when a current with a current density of 10 mA/cm 2 is passed.
  • the device life is determined when the luminance at the start of light emission (initial luminance) is 700 cd/m 2 and constant current driving is performed, and the luminance is 560 cd/m 2 (80% of the initial luminance as 100%). It was measured as the time required to attenuate to (equivalent to: 80% attenuation).
  • the luminous efficiency of the organic EL element of Example 13 is 8.56 cd/A, compared to 7.56 cd/A of the organic EL element of Comparative Example 2. .27 cd/A, 8.30 cd/A for the organic EL device of Example 14, 8.54 cd/A for the organic EL device of Example 15, 8.34 cd/A for the organic EL device of Example 16, Example 19
  • the organic EL device had a high efficiency of 8.13 cd/A.
  • the organic EL device of Example 13 had a lifetime of 376 hours
  • the organic EL device of Example 14 had a lifetime of 336 hours
  • the organic EL device of Example 15 had a lifetime of 336 hours.
  • 264 hours for the organic EL device of Example 16 274 hours for the organic EL device of Example 17, 280 hours for the organic EL device of Example 18, 604 hours for the organic EL device of Example 19, and 185 hours for the organic EL device of Example 19. Both had a long lifespan.
  • the organic EL device including the organic layer formed using the high molecular weight compound of the present invention can realize an organic EL device with high luminous efficiency and long life compared to conventional organic EL devices. I understand.
  • the high molecular weight compound of the present invention has high hole transport ability, excellent electron blocking ability, and good thermal crosslinkability, so it is excellent as a compound for coating type organic EL devices.
  • a coated organic EL device using this compound high luminous efficiency and power efficiency can be obtained, and durability can be improved. This has enabled its use in a wide range of applications, such as home appliances and lighting.

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010108921A (ja) * 2008-09-30 2010-05-13 Mitsubishi Chemicals Corp 有機薄膜パターニング用基板、有機電界発光素子およびその製造方法、並びに有機ｅｌ表示装置および有機ｅｌ照明
JP2011253722A (ja) * 2010-06-02 2011-12-15 Mitsubishi Chemicals Corp 有機電界発光素子、有機ｅｌ照明及び有機ｅｌ表示装置
WO2013180036A1 (ja) * 2012-05-28 2013-12-05 三菱化学株式会社 導電性薄膜積層体の製造方法
WO2020009069A1 (ja) * 2018-07-03 2020-01-09 保土谷化学工業株式会社 分子主鎖にターフェニル構造を含むトリアリールアミン高分子量化合物およびこれらの高分子量化合物を含む有機エレクトロルミネッセンス素子
WO2021070878A1 (ja) * 2019-10-09 2021-04-15 保土谷化学工業株式会社 高分子量化合物からなる有機層を有する有機エレクトロルミネッセンス素子

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6309763B1 (en) 1997-05-21 2001-10-30 The Dow Chemical Company Fluorene-containing polymers and electroluminescent devices therefrom
CN1894199B (zh) 2003-11-14 2011-04-13 住友化学株式会社 卤代双二芳基氨基多环芳族化合物及其聚合物
GB0329364D0 (en) 2003-12-19 2004-01-21 Cambridge Display Tech Ltd Optical device
JP4736471B2 (ja) 2004-02-26 2011-07-27 住友化学株式会社 高分子化合物およびそれを用いた高分子発光素子
JP2007119763A (ja) 2005-09-29 2007-05-17 Sumitomo Chemical Co Ltd 高分子材料及び高分子発光素子
JP5217153B2 (ja) 2005-11-18 2013-06-19 住友化学株式会社 高分子化合物およびそれを用いた高分子発光素子
JP5018043B2 (ja) 2005-12-01 2012-09-05 住友化学株式会社 高分子化合物およびそれを用いた高分子発光素子

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010108921A (ja) * 2008-09-30 2010-05-13 Mitsubishi Chemicals Corp 有機薄膜パターニング用基板、有機電界発光素子およびその製造方法、並びに有機ｅｌ表示装置および有機ｅｌ照明
JP2011253722A (ja) * 2010-06-02 2011-12-15 Mitsubishi Chemicals Corp 有機電界発光素子、有機ｅｌ照明及び有機ｅｌ表示装置
WO2013180036A1 (ja) * 2012-05-28 2013-12-05 三菱化学株式会社 導電性薄膜積層体の製造方法
WO2020009069A1 (ja) * 2018-07-03 2020-01-09 保土谷化学工業株式会社 分子主鎖にターフェニル構造を含むトリアリールアミン高分子量化合物およびこれらの高分子量化合物を含む有機エレクトロルミネッセンス素子
WO2021070878A1 (ja) * 2019-10-09 2021-04-15 保土谷化学工業株式会社 高分子量化合物からなる有機層を有する有機エレクトロルミネッセンス素子

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