High molecular weight triarylamine compounds, and organic electroluminescent elements containing these high molecular weight compounds

Abstract

The purpose of the present invention is to provide a polymer material that exhibits excellent hole injection and transport performance, has electron blocking capabilities, and has high stability when in the form of a thin film. Another purpose of the present invention is to provide an organic EL element which has an organic layer (a thin film) formed from the polymer material, which has high luminous efficiency, and which has a long service life.　This high molecular weight compound contains a repeating unit represented by general formula (1) and a repeating unit represented by general formula (2), and has a weight average molecular weight of at least 10,000 but less than 1,000,000 in terms of polystyrene equivalent.

Description

Triarylamine polymeric compounds and organic electroluminescent devices containing these polymeric compounds

[0001] The present invention relates to a high molecular weight compound suitable for an organic electroluminescence element (organic EL element), which is a self-luminous element suitable for various display devices, and to said element.

[0002] Organic EL elements are self-luminous elements, and therefore are brighter and more visible than liquid crystal elements, and are capable of producing clearer displays, and therefore have been the subject of vigorous research.

[0003] Organic EL elements have a structure in which a thin film (organic layer) of an organic compound is sandwiched between an anode and a cathode. Thin film formation methods are broadly divided into vacuum deposition and coating methods. Vacuum deposition is a technique in which a thin film is formed on a substrate in a vacuum using mainly low-molecular-weight compounds, and is a technology that has already been put to practical use. On the other hand, coating is a technique in which a thin film is formed on a substrate using a solution, such as inkjet printing, mainly using high-molecular-weight compounds. This method is highly efficient in the use of materials and is suitable for larger areas and higher definition, making it an essential technology for future large-area organic EL displays.

[0004] The vacuum deposition method using low-molecular-weight materials has extremely low material utilization efficiency, and as the size increases, the shadow mask bends more, making uniform deposition on large substrates difficult. It also has other problems, such as high manufacturing costs.

[0005] On the other hand, polymeric materials can be dissolved in organic solvents and applied to form uniform films on large substrates, allowing for application methods such as inkjet printing and printing to be used, thereby increasing the efficiency of material use and significantly reducing the manufacturing costs of devices.

[0006] Various organic EL elements using polymer materials have been investigated to date, but there have been problems in that the element characteristics, such as luminous efficiency and life span, are not necessarily sufficient (see, for example, Patent Documents 1 to 5).

[0007] Furthermore, a fluorene polymer called TFB has been known as a typical hole transport material that has been used in polymer organic EL devices (see Patent Documents 6 and 7). However, TFB has insufficient hole transport properties and insufficient electron blocking properties, which means that some electrons pass through the light-emitting layer, preventing improvements in luminous efficiency. Furthermore, TFB has poor film adhesion with adjacent layers, preventing the device from having a long life.

[0008] JP 2005-272834 A JP 2007-119763 A JP 2007-162009 A JP 2007-177225 A US7651746 B2 WO 1999 / 054385 WO 2005 / 059951

[0009] The present invention aims to provide a polymeric material that has excellent hole injection and transport properties, electron blocking ability, and high stability in a thin film state, and further aims to provide an organic EL device that has an organic layer (thin film) formed from the polymeric material, has high luminous efficiency, and has a long life.

[0010] The present inventors have noticed that high molecular weight compounds containing repeating units having a triarylamine structure including a fluorene structure have high hole injection / transport capabilities and are also expected to have a wide gap. As a result of synthesizing and examining various high molecular weight compounds containing repeating units having a triarylamine structure (hereinafter also referred to as "triarylamine repeating units"), they have completed the present invention.

[0011] That is, the present invention is as described below.

[0012] [1] A high molecular weight compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and having a weight average molecular weight of 10,000 or more but less than 1,000,000 in terms of polystyrene:

[0013]

[0014]

[0015] In the formula, R １and R ３ may be the same or different and represent a deuterium atom, a cyano group, a nitro group, a halogen atom; or an alkyl group, a cycloalkyl group, an alkyloxy group, a cycloalkyloxy group, an alkenyl group, or an aryloxy group, each of which has 40 or less carbon atoms. １ and R in general formula (2) １ may be the same or different, but R ３ and R in general formula (2) ３ represents the same group. a represents an integer of 0 to 3, and b represents an integer of 0 to 4. R ２ represents an alkyl group, a cycloalkyl group, or an alkyloxy group, each having 3 to 40 carbon atoms. L represents a phenylene group, and n represents an integer of 0 to 3. X represents a hydrogen atom, an amino group, a monovalent aryl group, or a monovalent heteroaryl group. However, X in general formula (1) and X in general formula (2) represent the same group. Y and Z may be the same or different and represent a hydrogen atom, a monovalent aryl group, or a monovalent heteroaryl group.

[0016] [2] The high molecular weight compound according to [1], wherein a and b are 0 in the general formulas (1) and (2).

[0017] [3] In the general formula (1), R ２ is an alkyl group having 3 to 40 carbon atoms.

[0018] [4] The high molecular weight compound according to any one of [1] to [3], wherein in the general formulae (1) and (2), X is 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.

[0019] [5] The high molecular weight compound according to [1], which contains a repeating unit containing a thermally crosslinkable structural unit Q represented by the following general formula (3):

[0020]

[0021] In the formula, R ３, X, and a are all the same as those shown in general formula (1).

[0022] [6] The high molecular weight compound according to [5], wherein the thermally crosslinkable structural unit Q is a structural unit represented by any one of general formulas (4a) to (4z) shown in Figures 10 and 11.

[0023] [7] An organic electroluminescence element having a pair of electrodes and an organic layer sandwiched therebetween, wherein the high-molecular-weight compound according to any one of [1] to [6] is used as a constituent material of the organic layer.

[0024] [8] The organic electroluminescence device according to [7], wherein the organic layer is a hole transport layer.

[0025] [9] The organic electroluminescence device according to [7], wherein the organic layer is an electron blocking layer.

[0026]

[10] The organic electroluminescence element according to [7], wherein the organic layer is a hole injection layer.

[0027]

[11] The organic electroluminescence element according to [7], wherein the organic layer is a light-emitting layer.

[0028] The high molecular weight compound of the present invention has a weight average molecular weight in the range of 10,000 or more and less than 1,000,000 in terms of polystyrene as measured by GPC (gel permeation chromatography).

[0029] The high molecular weight compound of the present invention has the following properties: (1) good hole injection properties, (2) high hole mobility, and (3) a wide gap and excellent electron blocking ability.

[0030] The organic layer formed from the high molecular weight compound of the present invention can be suitably used as a hole transport layer, an electron blocking layer, a hole injection layer, or a light emitting layer, and an organic EL device formed by sandwiching the organic layer between a pair of electrodes has the following advantages: (1) high luminous efficiency and power efficiency, (2) low practical driving voltage, and (3) long life.

[0031] Chemical structure of structural units 1-1 to 1-6 suitable as repeating units represented by general formula (1) Chemical structure of structural units 1-7 to 1-12 suitable as repeating units represented by general formula (1) Chemical structure of structural units 1-13 to 1-20 suitable as repeating units represented by general formula (1) Chemical structure of structural units 1-21 to 1-28 suitable as repeating units represented by general formula (1) Chemical structure of structural units 2-1 to 2-9 suitable as repeating units represented by general formula (2) Chemical structure of structural units 2-10 to 2-21 suitable as repeating units represented by general formula (2) Chemical structure of structural units 2-34 to 2-48 suitable as a repeating unit represented by general formula (2) Chemical structure of structural units 2-49 to 2-58 suitable as a repeating unit represented by general formula (2) Chemical structure of structural units (4a) to (4p) of thermally crosslinkable structural unit Q Chemical structure of structural units (4q) to (4z) of thermally crosslinkable structural unit Q Chemical structure of substituents 1 to 24 suitable as substituent X in general formulas (1 to 3) Chemical structure of substituents 25 to 44 suitable as substituent X in general formulas (1 to 3) An example of the layer structure of an organic EL element of the present invention An example of the layer structure of an organic EL element of the present invention High molecular weight compound I of Example 1 １ H-NMR chart of high molecular weight compound II in Example 2 １ H-NMR chart of high molecular weight compound III in Example 3 １ H-NMR chart of high molecular weight compound IV in Example 4 １ H-NMR chart of high molecular weight compound V in Example 5 １ H-NMR chart of high molecular weight compound VI in Example 6 １ H-NMR chart of high molecular weight compound VII of Example 7 １ H-NMR chart of high molecular weight compound VIII of Example 8 １ H-NMR chart of high molecular weight compound IX of Example 9 １ H-NMR chart of high molecular weight compound X of Example 10 １ H-NMR chart of high molecular weight compound XI of Example 11 １ H-NMR chart

[0032] <Triarylamine Repeating Unit> The two types of triarylamine repeating units contained in the high molecular weight compound of the present invention have structures represented by the following general formulas (1) and (2), respectively.

[0033]

[0034]

[0035] In the general formulas (1) and (2), R １ and R ３ may be the same or different and represent a deuterium atom, a cyano group, a nitro group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; or an alkyl group, a cycloalkyl group, an alkyloxy group, a cycloalkyloxy group, an alkenyl group, or an aryloxy group, each of which has 40 or less carbon atoms. １ and R ３ is preferably an alkyl group or alkyloxy group having 1 to 8 carbon atoms, a cycloalkyl group or cycloalkyloxy group having 5 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryloxy group, in terms of excellent hole injection / transport capability.

[0036] Examples of the alkyl group, alkyloxy group, cycloalkyl group, cycloalkyloxy group, alkenyl group, and aryloxy group include the following groups: Alkyl group (having 1 to 8 carbon atoms): methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, neohexyl group, n-heptyl group, isoheptyl group, neoheptyl group, n-octyl group, isooctyl group, neooctyl group, etc. Alkyloxy group (having 1 to 8 carbon atoms): methyloxy group, ethyloxy group, n-propyloxy group, isopropyloxy group, n-butyloxy group, tert-butyloxy group, n-pentyloxy group, n-hexyloxy group, n-heptyloxy group, n-octyloxy group, etc. Cycloalkyl groups (having 5 to 10 carbon atoms): a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, etc. Cycloalkyloxy groups (having 5 to 10 carbon atoms): a cyclopentyloxy group, a cyclohexyloxy group, a cycloheptyloxy group, a cyclooctyloxy group, a 1-adamantyloxy group, a 2-adamantyloxy group, etc. Alkenyl groups (having 2 to 6 carbon atoms): a vinyl group, an allyl group, an isopropenyl group, a 2-butenyl group, etc. Aryloxy groups: a phenyloxy group, a tolyloxy group, etc.

[0037] In the general formulae (1) and (2), a represents an integer of 0 to 3, and b represents an integer of 0 to 4.

[0038] In the high molecular weight compound of the present invention, it is preferable that the aforementioned a and b are 0 from the viewpoint of synthesis.

[0039] In the general formula (1), R ２ R represents an alkyl group, a cycloalkyl group, or an alkyloxy group, each having 3 to 40 carbon atoms. ２ is preferably an alkyl group or alkyloxy group having 1 to 8 carbon atoms, or a cycloalkyl group or cycloalkyloxy group having 5 to 10 carbon atoms, in view of excellent hole injection and transport capabilities.

[0040] R ２Examples of the alkyl group, alkyloxy group, cycloalkyl group, and cycloalkyloxy group represented by the formula R １ , R ３ Examples of the groups include the same groups as those shown in the above.

[0041] In the high molecular weight compound of the present invention, the R ２ is most preferably an n-hexyl group or an n-octyl group in order to enhance solubility in organic solvents.

[0042] In the general formulae (1) and (2), the substituent X represents a hydrogen atom, an amino group, a monovalent aryl group, or a monovalent heteroaryl group.

[0043] Examples of the monovalent aryl group and monovalent heteroaryl group represented by X include the following groups: Aryl group: phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, indenyl group, pyrenyl group, perylenyl group, fluoranthenyl group, etc. Heteroaryl group: 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, benzoxazolyl group, benzothiazolyl group, quinoxalinyl group, benzimidazolyl group, pyrazolyl group, dibenzofuranyl group, dibenzothienyl group, naphthyridinyl group, phenanthrolinyl group, acridinyl group, carbolinyl group, etc.

[0044] The amino group, aryl group, and heteroaryl group may have a substituent. Examples of the substituent include a deuterium atom, a cyano group, a nitro group, and the following groups: a halogen atom, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; an alkyl group, particularly one having 1 to 8 carbon atoms, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, an isohexyl group, a neohexyl group, an n-heptyl group, an isoheptyl group, a neoheptyl group, an n-octyl group, an isooctyl group, and a neooctyl group; an alkyloxy group, particularly one having 1 to 8 carbon atoms, such as a methyloxy group, an ethyloxy group, and a propyloxy group; an alkenyl group, such as a vinyl group and an allyl group; an aryloxy group, such as a phenyloxy group and a tolyloxy group; Aryl groups, for example, phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, and triphenylenyl groups; heteroaryl groups, for example, pyridyl, pyrimidinyl, triazinyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, indenocarbazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, and carbolinyl groups; arylvinyl groups, for example, styryl and naphthylvinyl groups; acyl groups, for example, acetyl and benzoyl groups;

[0045] These substituents may further have the substituents exemplified above. Furthermore, these substituents preferably exist independently of each other, but these substituents may be bonded to each other via a single bond, a methylene group which may have a substituent, an oxygen atom, or a sulfur atom to form a ring.

[0046] For example, the aryl group or heteroaryl group may have a phenyl group as a substituent, and the phenyl group may further have a phenyl group as a substituent, i.e., taking the aryl group as an example, the aryl group may be a biphenylyl group, a terphenylyl group, or a triphenylenyl group.

[0047] The substituent X in the general formulae (1) and (2) is preferably 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, in view of excellent hole injection and transport capabilities.

[0048] In the general formula (1), L represents a phenylene group, and n represents an integer of 0 to 3.

[0049] The above-mentioned L may have a substituent. Examples of the substituent include the same groups as the substituents that the above-mentioned substituent X may have, and these substituents may further have a substituent.

[0050] In the general formulae (1) and (2), Y and Z represent a hydrogen atom, a monovalent aryl group, or a monovalent heteroaryl group.

[0051] Examples of the monovalent aryl group and monovalent heteroaryl group represented by Y and Z include the same groups as those shown for X.

[0052] At least one of Y and Z is preferably a monovalent aryl group, and more preferably at least Y is a monovalent aryl group. The monovalent aryl group represented by Y and Z is preferably a phenyl group, a naphthyl group, a phenanthrenyl group, a biphenyl group, a naphthylphenyl group, or a (triphenyl)phenyl group, in view of excellent hole injection and transport capabilities.

[0053] The monovalent aryl group or monovalent heteroaryl group represented by Y and Z may have a substituent (e.g., a phenyl group) shown in X. Y and Z may be bonded to each other via a single bond, a methylene group which may have a substituent, an oxygen atom, or a sulfur atom to form a ring.

[0054] In the present invention, specific examples of repeating units represented by the above-mentioned general formula (1) are shown in Figures 1 to 4 as repeating units 1-1 to 1-28. Specific examples of repeating units represented by the above-mentioned general formula (2) are shown in Figures 5 to 9 as repeating units 2-1 to 2-58. In the chemical formulae shown in Figures 1 to 9, dashed lines indicate bonds to adjacent repeating units, and solid lines extending from a ring with a free end indicate that the free end is a methyl group. While preferred specific examples of repeating units are shown, the repeating units used in the present invention are not limited to these examples.

[0055] In the present invention, specific examples of the substituent X in the above-mentioned general formulas (1) to (3) are shown as substituents 1 to 44 in Figures 12 and 13. In the chemical formulas shown in Figures 12 and 13, wavy lines indicate bonding sites. Although these figures show preferred specific examples of the substituent X, the substituent X in the present invention is not limited to these examples.

[0056] <High-Molecular-Weight Compound> The high-molecular-weight compound of the present invention, which is composed of the repeating unit represented by the general formula (1) and the repeating unit represented by the general formula (2), has, from the viewpoint of further improving properties such as hole injection characteristics, hole mobility, electron blocking ability, thin film stability, and heat resistance, and also ensuring film-formability, a weight-average molecular weight, as measured by GPC in terms of polystyrene, of from 10,000 to less than 1,000,000, more preferably from 10,000 to less than 500,000, and even more preferably from 10,000 to less than 300,000.

[0057] In order to enhance stability in a thin film state, the high molecular weight compound of the present invention preferably contains a repeating unit containing a thermally crosslinkable structural unit Q represented by the following general formula (3).

[0058]

[0059] In the general formula (3), R ３ , X, and a are all the same as those shown in general formula (1).

[0060] The thermally crosslinkable structural unit Q is a structural unit having a thermally crosslinkable functional group. Examples of the thermally crosslinkable functional group include a vinyl group, an ethynyl group, an acryloyl group, a methacryloyl group, a conjugated diene, and a cyclobutane ring. Specific examples of the thermally crosslinkable structural unit Q are shown in Figures 10 and 11 as general formulas (4a) to (4z).

[0061] In the general formulae (4a) to (4z), the dashed lines indicate bonds to adjacent structural units, and the solid lines extending from the rings with free ends indicate that the ends are methyl groups.

[0062] In addition, in the general formulae (4a) to (4z), R １ , R ２ , a and b are the same as those shown in general formula (1).

[0063] In the high molecular weight compound of the present invention, when the repeating unit represented by general formula (1) is represented by A, the repeating unit represented by general formula (2) is represented by B, and the repeating unit represented by general formula (3) is represented by C, it is preferable that the repeating unit A is contained in an amount of 1 mol % or more, particularly 30 mol % or more, of all the repeating units. Provided that the repeating unit A is contained in such an amount, it is preferable that the repeating unit B is contained in an amount of 1 mol % or more, particularly 10 to 60 mol %, and further that the repeating unit C is contained in an amount of 1 mol % or more, particularly 10 to 20 mol %. A high molecular weight compound containing repeating units A, B, and C so as to satisfy these conditions is most suitable for forming an organic layer of an organic EL device.

[0064] The high molecular weight compound of the present invention is synthesized by linking the structural units through the Suzuki polymerization reaction or the Hartwig-Buchwald polymerization reaction to form a C-C bond or a C-N bond, respectively. Specifically, the high molecular weight compound of the present invention can be synthesized by preparing a unit compound having each structural unit, appropriately converting this unit compound into a boric acid ester or halogenating it, and then subjecting it to a polycondensation reaction using a catalyst.

[0065] For example, a high molecular weight compound containing 30 mol % of repeating unit A represented by general formula (1), 60 mol % of repeating unit B represented by general formula (2), and 10 mol % of repeating unit C for enhancing thermal crosslinkability is represented by general formula (5) shown below.

[0066]

[0067] The high molecular weight compound of the present invention described above can be dissolved in an aromatic organic solvent such as benzene, toluene, xylene, or anisole to prepare a coating solution, which can then be coated on a predetermined substrate and dried by heating to form a thin film excellent in properties such as hole injection, hole transport, and electron blocking properties. The thin film thus formed has good heat resistance and also good adhesion to other layers.

[0068] 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. The hole injection layer and hole transport layer formed from such a high-molecular-weight compound have higher hole injection properties, higher mobility, and higher electron blocking properties than those formed from conventional materials, and can confine excitons generated in the light-emitting layer, and can further improve the probability of hole and electron recombination, thereby achieving high luminous efficiency and reducing the driving voltage, thereby improving the durability of the organic EL device.

[0069] Furthermore, the high molecular weight compound of the present invention having the above-described electrical properties has a wider gap than conventional materials and is effective in confining excitons, and therefore can naturally be suitably used in electron blocking layers and light-emitting layers.

[0070] <Organic EL Device> The organic EL device of the present invention, which is provided with an organic layer formed using the above-described high-molecular-weight compound of the present invention, has a pair of electrodes and at least one organic layer sandwiched between them, and has a structure, for example, as shown in Fig. 14. 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 provided on a glass substrate 1 (which may be a transparent substrate other than glass, such as a transparent resin substrate).

[0071] Of course, the organic EL device of the present invention is not limited to the above-described layer structure. A hole-blocking layer may be provided between the light-emitting layer 5 and the electron-transporting layer 6. Alternatively, as shown in FIG. 15 , an electron-blocking layer may be provided between the hole-transporting layer 4 and the light-emitting layer 5, or an electron-injection layer may be provided between the cathode 7 and the electron-transporting layer 6. Furthermore, some layers may be omitted. For example, a simple layer structure may be employed in which an anode 2, a hole-transporting layer 4, a light-emitting layer 5, an electron-transporting layer 6, and a cathode 7 are provided on a glass substrate 1. Alternatively, a two-layer structure in which layers having the same function are stacked may be employed.

[0072] The high molecular weight compound of the present invention is suitably used as a material for forming an organic layer, such as the hole injection layer 3, the hole transport layer 4, the light-emitting layer 5, or the electron blocking layer, provided between the anode 2 and the cathode 7, by taking advantage of its properties such as hole injection property and hole transport property.

[0073] In the organic EL element, the transparent anode 2 may be formed from a known electrode material, and is formed by depositing an electrode material with a large work function, such as ITO or gold, on the glass substrate 1 (transparent substrate).

[0074] The hole injection layer 3 provided on the transparent anode 2 can be formed using a coating liquid prepared by dissolving the high molecular weight compound of the present invention in an aromatic organic solvent such as toluene, xylene, anisole, etc. Specifically, the hole injection layer 3 can be formed by coating the transparent anode 2 with this coating liquid by spin coating, inkjet printing, or the like.

[0075] Furthermore, in the organic EL device of the present invention, the hole injection layer 3 can be formed using conventionally known materials, such as the following materials, without using the high-molecular-weight compound of the present invention: porphyrin compounds typified by copper phthalocyanine; starburst-type triphenylamine derivatives; arylamines having a structure linked by a single bond or a divalent group not containing a heteroatom (e.g., triphenylamine trimer and tetramer); acceptor heterocyclic compounds such as hexacyanoazatriphenylene; and coating-type polymer materials, such as poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(styrenesulfonate) (PSS).

[0076] Formation of layers (thin films) using such materials can be carried out by vapor deposition or coating using a spin coating method, inkjet method, etc. This also applies to other layers, and films are formed by vapor deposition or coating depending on the type of film-forming material.

[0077] Like the hole injection layer 3, the hole transport layer 4 provided on the hole injection layer 3 can also be formed by coating using a coating solution prepared by dissolving the high molecular weight compound of the present invention in an organic solvent, such as spin coating or inkjet coating.

[0078] Furthermore, in an organic EL device having an organic layer formed using the high molecular weight compound of the present invention, the hole transport layer 4 can also be formed using a conventionally known hole transport material. Representative examples of such hole transport materials are as follows: benzidine derivatives, such as N,N'-diphenyl-N,N'-di(m-tolyl)benzidine (hereinafter abbreviated as TPD); N,N'-diphenyl-N,N'-di(α-naphthyl)benzidine (hereinafter abbreviated as NPD); N,N,N',N'-tetrabiphenylylbenzidine; amine derivatives, such as 1,1-bis[4-(di-4-tolylamino)phenyl]cyclohexane (hereinafter abbreviated as TAPC); various triphenylamine trimers and tetramers; and coating-type polymer materials also used for hole injection layers.

[0079] The above-mentioned hole transport layer materials, including the high molecular weight compound of the present invention, may be used alone to form a film, or two or more of them may be mixed to form a film. Alternatively, a multilayer film in which multiple layers are formed using one or more of the compounds, and such layers are stacked, can be used as the hole transport layer.

[0080] In the organic EL element of the present invention shown in FIG. 14, the hole injection layer 3 and the hole transport layer 4 may be formed as a single hole injection / transport layer having the functions of these layers, and such a hole injection / transport layer may be formed by coating using a polymer material such as PEDOT.

[0081] The hole transport layer 4 (and the hole injection layer 3) may be formed by doping a material typically used for the layer with trisbromophenylaminehexachloroantimony or a radialene derivative (see, for example, WO 2014 / 009310) or the like with P. Alternatively, the hole transport layer 4 (or the hole injection layer 3) may be formed using a polymer compound having a TPD basic skeleton.

[0082] 15, an electron blocking layer 12 can be provided between the hole transport layer 11 and the light emitting layer 13. The electron blocking layer 12 can be formed by coating using a coating solution prepared by dissolving the high molecular weight compound of the present invention in an organic solvent, such as by spin coating or inkjet coating.

[0083] Furthermore, in the organic EL device of the present invention, the electron-blocking layer can be formed using known electron-blocking compounds having an electron-blocking effect, such as carbazole derivatives and compounds having a triphenylsilyl group and a triarylamine structure. Specific examples of carbazole derivatives and compounds having a triarylamine structure are as follows. Examples of carbazole derivatives include 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 include 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene;

[0084] The electron-blocking layer may be formed using a single compound, including the high-molecular-weight compound of the present invention, or a mixture of two or more compounds. Alternatively, a multilayer film formed by laminating multiple layers using one or more of the compounds may be used as the electron-blocking layer.

[0085] In the organic EL element of the present invention, the light-emitting layer 5 is ３ In addition to metal complexes of quinolinol derivatives such as those mentioned above, various metal complexes of zinc, beryllium, aluminum, etc., anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, polyparaphenylenevinylene derivatives, etc. can be used to form the light-emitting material.

[0086] The light-emitting layer 5 can also be composed of a host material and a dopant material. In this case, in addition to the light-emitting materials described above, thiazole derivatives, benzimidazole derivatives, polydialkylfluorene derivatives, etc. can be used as the host material, and the high-molecular-weight compound of the present invention described above can also be used. As the dopant material, quinacridone, coumarin, rubrene, perylene, and derivatives thereof, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, etc. can be used.

[0087] Such a light-emitting layer 5 may also have a single layer structure using one or more kinds of light-emitting materials, or may have a multi-layer structure in which a plurality of layers are laminated.

[0088] Furthermore, a phosphorescent material can be used as the light-emitting material to form the light-emitting layer 5. As the phosphorescent material, a phosphorescent emitter of a metal complex such as iridium or platinum can be used. For example, Ir(ppy) ３ green phosphorescent emitters such as FIrpic and FIr6; blue phosphorescent emitters such as Btp ２ A red phosphorescent material such as Ir(acac) can be used, and these phosphorescent materials are used by doping into a hole-injecting / transporting host material or an electron-transporting host material.

[0089] In order to avoid concentration quenching, the phosphorescent light-emitting material is preferably doped into the host material by co-evaporation in a range of 1 to 30 weight percent based on the entire light-emitting layer.

[0090] Furthermore, materials that emit delayed fluorescence, such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, can also be used as light-emitting materials (see Appl. Phys. Let., 98, 083302 (2011), Chem. Commun., 48, 11392 (2012), Nature, 492, 234 (2012)).

[0091] By forming the light-emitting layer 5 by carrying the high molecular weight compound of the present invention with a fluorescent light-emitting material, a phosphorescent light-emitting material, or a material that emits delayed fluorescence, which is called a dopant, an organic EL element with reduced driving voltage and improved luminous efficiency can be realized.

[0092] In an organic EL device having an organic layer formed using the high-molecular-weight compound of the present invention, the high-molecular-weight compound of the present invention can be used as a hole-injecting / transporting host material. In addition, carbazole derivatives such as 4,4'-di(N-carbazolyl)biphenyl (hereinafter abbreviated as CBP), TCTA, and mCP can also be used.

[0093] In an organic EL device having an organic layer formed using the high molecular weight compound of the present invention, p-bis(triphenylsilyl)benzene (hereinafter abbreviated as UGH2) or 2,2′,2″-(1,3,5-phenylene)-tris(1-phenyl-1H-benzimidazole) (hereinafter abbreviated as TPBI) can be used as an electron-transporting host material.

[0094] In an organic EL device having an organic layer formed using the high-molecular-weight compound of the present invention, the hole-blocking layer (not shown in FIG. 14 ) provided between the light-emitting layer 5 and the electron-transporting layer 6 can be formed using a known compound having hole-blocking properties. Examples of such known compounds having hole-blocking properties 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-quinolinato)-4-phenylphenolate (hereinafter abbreviated as BAlq); various rare-earth complexes; triazole derivatives; triazine derivatives; and oxadiazole derivatives.

[0095] These materials can also be used to form the electron transport layer 6 described below, and can also be used as a hole blocking layer and electron transport layer.

[0096] Such a hole-blocking layer may also have a single layer structure or a multi-layer laminate structure, and each layer is formed using one or more of the above-mentioned compounds having hole-blocking properties.

[0097] In the organic EL device having an organic layer formed using the high molecular weight compound of the present invention, the electron transport layer 6 is formed using a compound having electron transport properties known per se, for example, Alq ３ In addition to metal complexes of quinolinol derivatives such as BAlq, 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.

[0098] The electron transport layer 6 may also have a single layer structure or a multi-layer laminate structure. Each layer is formed using one or more of the above-mentioned electron transport compounds.

[0099] Furthermore, in an organic EL device having an organic layer formed using the high molecular weight compound of the present invention, an electron injection layer (not shown in Figures 14 and 15) that is provided as needed can also be formed using a compound known per se, for example, an alkali metal salt such as lithium fluoride or cesium fluoride, an alkaline earth metal salt such as magnesium fluoride, a metal oxide such as aluminum oxide, or an organometallic complex such as lithium quinoline.

[0100] For the cathode 7 of an organic EL device having an organic layer formed using the high molecular weight compound of the present invention, an electrode material having a low work function such as aluminum, or an alloy having an even lower work function such as a magnesium-silver alloy, a magnesium-indium alloy, or an aluminum-magnesium alloy is used as the electrode material.

[0101] As described above, by forming at least one of the hole injection layer, hole transport layer, light-emitting layer, and electron blocking layer shown in Fig. 15 using the high molecular weight compound of the present invention, an organic EL device having high luminous efficiency and power efficiency, low practical driving voltage, low light-emission onset voltage, and extremely excellent durability can be obtained. In particular, this organic EL device has high luminous efficiency, a reduced driving voltage, improved current resistance, and an increased maximum luminous brightness.

[0102] The present invention will be described below with reference to the following experimental examples. In the following description, the repeating unit represented by general formula (1) contained in the high molecular weight compound of the present invention will be referred to as "repeating unit A," the repeating unit represented by general formula (2) will be referred to as "repeating unit B," and the repeating unit represented by general formula (3) introduced to enhance thermal crosslinkability will be referred to as "repeating unit C."

[0103] The synthesized compounds were purified by column chromatography and crystallization using solvents, and the compounds were identified by NMR analysis.

[0104] In order to prepare the high molecular weight compounds of the present invention, the following intermediates 1 to 10 were synthesized.

[0105] <Synthesis of Intermediate 1>

[0106]

[0107] Intermediate 1 is used to introduce a partial structure of structural unit 1-1, which is a repeating unit shown in FIG.

[0108] The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. N,N-bis(4-bromophenyl)-9,9-di-n-octyl-9H-fluoren-2-amine: 16.7 g, bis(pinacolato)diboron: 11.9 g, potassium acetate: 5.7 g, and 1,4-dioxane: 170 ml. Next, 0.19 g of the dichloromethane adduct of {1,1'-bis(diphenylphosphino)ferrocene}palladium(II) dichloride was added, and the mixture was heated and stirred at 100°C for 7 hours. After cooling to room temperature, water and toluene were added, and the organic layer was separated and collected. This organic layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (ethyl acetate / n-hexane = 1 / 20) to obtain 7.6 g of Intermediate 1 as a white powder (yield 40%).

[0109] <Synthesis of Intermediate 2>

[0110]

[0111] Intermediate 2 is used to introduce the partial structure of the thermally crosslinkable structural unit Q (general formula (4e) in FIG. 10) into the repeating unit represented by general formula (3).

[0112] The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. N,N-bis(4-bromophenyl)-N-(benzocyclobuten-4-yl)amine: 8.0 g, bis(pinacolato)diboron: 9.9 g, potassium acetate: 4.6 g, and 1,4-dioxane: 80 ml. Next, 0.3 g of the dichloromethane adduct of {1,1'-bis(diphenylphosphino)ferrocene}palladium(II) dichloride was added, and the mixture was heated and stirred at 90°C for 11 hours. After cooling to room temperature, tap water and toluene were added, and the organic layer was separated and collected. This organic layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized from a 1 / 2 mixture of toluene and methanol to obtain 3.4 g of Intermediate 2 as a white powder (yield: 35%).

[0113] <Synthesis of Intermediate 3>

[0114]

[0115] Intermediate 3 is used to introduce the partial structure of structural unit 2-1, which is a repeating unit shown in FIG.

[0116] The following components were added to a nitrogen-purged reaction vessel and nitrogen gas was bubbled through for 30 minutes: bis(p-bromophenyl)[p-(2-naphthyl)phenyl]amine: 7.3 g, bis(pinacolato)diboron: 7.4 g, potassium acetate: 4.1 g, and 1,4-dioxane: 50 ml. Next, 0.11 g of the dichloromethane adduct of {1,1'-bis(diphenylphosphino)ferrocene}palladium(II) dichloride was added, heated, and stirred at 100°C for 11 hours. After cooling to room temperature, methanol was added, and the mixture was stirred for 1 hour and filtered. The resulting solid was dissolved in chloroform, 40 g of silica gel was added, and adsorption purification was performed. The mixture was then concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized from a 1 / 6 mixture of chloroform and methanol to obtain 3.9 g of Intermediate 3 as a white powder (yield: 45%).

[0117] <Synthesis of Intermediate 4>

[0118]

[0119] Intermediate 4 is used to introduce the partial structure of structural unit 2-3, which is a repeating unit shown in FIG.

[0120] The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. bis(p-bromophenyl)[p-(9-phenanthrenyl)phenyl]amine: 20.0 g, bis(pinacolato)diboron: 18.4 g, potassium acetate: 10.2 g, and 1,4-dioxane: 100 ml. Next, 0.28 g of the dichloromethane adduct of {1,1'-bis(diphenylphosphino)ferrocene}palladium(II) dichloride was added, and the mixture was heated and stirred at 96°C for 7 hours. After cooling to room temperature, the mixture was filtered. The resulting solid was dissolved in chloroform, and 100 g of silica gel was added for adsorption purification. The mixture was then concentrated under reduced pressure to obtain a crude product. The crude product was washed with toluene by hot dispersion, yielding 12.9 g of Intermediate 4 as a white powder (yield: 55%).

[0121] <Synthesis of Intermediate 5>

[0122]

[0123] Intermediate 5 is used to introduce the partial structure of structural unit 2-18, which is a repeating unit shown in FIG.

[0124] The following components were added to a nitrogen-purged reaction vessel and nitrogen gas was bubbled through for 30 minutes: bis(p-bromophenyl){p-[o-(p-octylphenyl)phenyl]phenyl}amine: 15.8 g, bis(pinacolato)diboron: 12.6 g, potassium acetate: 7.0 g, and 1,4-dioxane: 100 ml. Next, 0.19 g of the dichloromethane adduct of {1,1'-bis(diphenylphosphino)ferrocene}palladium(II) dichloride was added, and the mixture was heated and stirred at 96°C for 10 hours. After cooling to room temperature, water and toluene were added, and the organic layer was separated and collected. This organic layer was dehydrated with anhydrous magnesium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (toluene / ethyl acetate = 40 / 1) to obtain 4.7 g of Intermediate 5 as a white powder (yield 26%).

[0125] <Synthesis of Intermediate 6>

[0126]

[0127] Intermediate 6 is used to introduce a partial structure of the thermally crosslinkable structural unit Q (general formula (4g) in FIG. 10) into the repeating unit represented by general formula (3).

[0128] The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. N-(benzocyclobuten-4-yl)-3,6-dibromocarbazole: 19.6 g, bis(pinacolato)diboron: 24.5 g, potassium acetate: 13.5 g, and 1,4-dioxane: 120 ml. Next, 0.4 g of the dichloromethane adduct of {1,1'-bis(diphenylphosphino)ferrocene}palladium(II) dichloride was added, and the mixture was heated and stirred at 97°C for 5 hours. After cooling to room temperature, tap water and toluene were added, and the organic layer was separated and collected. This organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized from a 1 / 5 mixture of toluene and methanol to obtain 14.5 g of Intermediate 6 as a white powder (yield: 61%).

[0129] <Synthesis of Intermediate 7>

[0130]

[0131] Intermediate 7 is used to introduce the partial structure of the thermally crosslinkable structural unit Q (general formula (4a) in FIG. 10) into the repeating unit represented by general formula (3).

[0132] The following components were placed in a nitrogen-purged reaction vessel and cooled to 0°C. 11.5 g of methyltriphenylphosphonium bromide and 75 ml of tetrahydrofuran were then added. 3.6 g of potassium t-butoxide was then added and stirred for 1 hour, and 11.3 g of 4-(bis(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amino)benzaldehyde was dissolved in 75 ml of tetrahydrofuran. The solution was slowly added, and the mixture was stirred for 5 hours while slowly warming to room temperature. Tap water and toluene were added, and the organic layer was separated and collected. This organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was purified by column chromatography (toluene / ethyl acetate = 40 / 1) to obtain 3.6 g of Intermediate 7 as a pale yellowish white powder (yield 32%).

[0133] <Synthesis of Intermediate 8>

[0134]

[0135] Intermediate 8 is used to introduce the partial structure of structural unit 2-21, which is a repeating unit shown in FIG.

[0136] The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. Bis(p-bromophenyl)[p-(2,4,6-triphenylphenyl)phenyl]amine: 23.9 g, bis(pinacolato)diboron: 18.0 g, potassium acetate: 9.9 g, and 1,4-dioxane: 120 ml. Next, 0.3 g of the dichloromethane adduct of {1,1'-bis(diphenylphosphino)ferrocene}palladium(II) dichloride was added, and the mixture was heated and stirred at 98°C for 4 hours. After cooling to room temperature, tap water and toluene were added, and the organic layer was separated and collected. This organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized from toluene to obtain 13.3 g of Intermediate 8 as a white powder (yield: 49%).

[0137] <Synthesis of Intermediate 9>

[0138]

[0139] Intermediate 9 is used to introduce the partial structure of structural unit 2-22, which is a repeating unit shown in FIG.

[0140] The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. bis(p-bromophenyl)[3-phenyl-4-(p-phenylphenyl)phenyl]amine: 17.0 g, bis(pinacolato)diboron: 14.4 g, potassium acetate: 7.9 g, and 1,4-dioxane: 85 ml. Next, 0.2 g of the dichloromethane adduct of {1,1'-bis(diphenylphosphino)ferrocene}palladium(II) dichloride was added, and the mixture was heated and stirred at 99°C for 6 hours. After cooling to room temperature, tap water and toluene were added, and the organic layer was separated and collected. This organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was recrystallized from toluene to obtain 7.0 g of off-white powder of Intermediate 9 (yield: 36%).

[0141] <Synthesis of Intermediate 10>

[0142]

[0143] Intermediate 10 is used to introduce the partial structure of structural unit 2-7, which is a repeating unit shown in FIG.

[0144] The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. bis(p-bromophenyl)-2-triphenylenylamine: 31.7 g, bis(pinacolato)diboron: 30.6 g, potassium acetate: 16.9 g, and 1,4-dioxane: 160 ml. Next, 0.5 g of a dichloromethane adduct of {1,1'-bis(diphenylphosphino)ferrocene}palladium(II) dichloride was added, and the mixture was heated and stirred at 100°C for 10 hours. After cooling to room temperature, tap water and chloroform were added, and the organic layer was collected by separation. This organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was washed with toluene to obtain 16.0 g of an off-white powder of Intermediate 10 (yield: 43%).

[0145] Example 1 Synthesis of High Molecular Weight Compound I: The following components were added to a nitrogen-purged reaction vessel and nitrogen gas was bubbled through for 30 minutes. Intermediate 1: 3.6 g Intermediate 3: 1.4 g Intermediate 2: 0.4 g 1,3-dibromobenzene: 1.8 g Tripotassium phosphate: 7.5 g Toluene: 9 ml Water: 5 ml 1,4-dioxane: 27 ml Next, 1.5 mg of palladium(II) acetate and 12.5 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 86°C for 9.5 hours. After this, 19 mg of phenylboronic acid was added and stirred for 1 hour, followed by 264 mg of bromobenzene and stirring for 1 hour. 50 ml of toluene and 50 ml of a 5 wt % aqueous solution of sodium N,N-diethyldithiocarbamate were added, and the mixture was heated and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was collected by separation and washed three times with saturated brine. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, silica gel was added, and the polymer was purified by adsorption. The silica gel was then removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 ml of toluene. The solution was then added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated three times and the resulting mixture was dried to obtain 2.5 g (yield 57%) of high molecular weight compound I.

[0146] The average molecular weight and dispersity of the high molecular weight compound I measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 65,000 Weight average molecular weight Mw (polystyrene equivalent): 170,000 Dispersity (Mw / Mn): 2.6

[0147] In addition, NMR measurement was performed on the high molecular weight compound I. １ From the results of H-NMR measurement, the chemical formula of high molecular weight compound I was found to be as follows:

[0148]

[0149] As can be seen from the chemical composition, this high molecular weight compound I contains 60 mol % of repeating unit A represented by general formula (1), 30 mol % of repeating unit B represented by general formula (2), and 10 mol % of repeating unit C represented by general formula (3), which is introduced to enhance thermal crosslinking properties. The molar ratio of each structural unit is １ This is an estimated value obtained from the results of H-NMR measurement.

[0150] Example 2 Synthesis of High Molecular Weight Compound II: The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. Intermediate 1: 4.2 g Intermediate 4: 1.0 g Intermediate 2: 0.4 g 1,3-dibromobenzene: 1.8 g Tripotassium phosphate: 7.4 g Toluene: 9 ml Water: 5 ml 1,4-dioxane: 27 ml Next, 1.5 mg of palladium(II) acetate and 12.4 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 86°C for 8.5 hours. After this, 19 mg of phenylboronic acid was added and stirred for 1 hour, followed by 262 mg of bromobenzene and stirring for 1 hour. 50 ml of toluene and 50 ml of a 5 wt % aqueous solution of sodium N,N-diethyldithiocarbamate were added, and the mixture was heated and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was collected by separation and washed three times with saturated brine. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, silica gel was added, and the polymer was purified by adsorption. The silica gel was then removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 ml of toluene. The solution was then added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated three times and the resulting mixture was dried to obtain 2.8 g (yield 62%) of high molecular weight compound II.

[0151] The average molecular weight and dispersity of the high molecular weight compound II measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 55,000 Weight average molecular weight Mw (polystyrene equivalent): 94,000 Dispersity (Mw / Mn): 1.7

[0152] Furthermore, NMR measurement was carried out on polymer compound II. １ From the results of H-NMR measurement, the chemical formula of polymer compound II was found to be as follows:

[0153]

[0154] As can be seen from the chemical composition, this polymer compound II contains 70 mol % of repeating unit A represented by general formula (1), 20 mol % of repeating unit B represented by general formula (2), and 10 mol % of repeating unit C represented by general formula (3), which is introduced to enhance thermal crosslinking property. The molar ratio of each structural unit is １ This is an estimated value obtained from the results of H-NMR measurement.

[0155] Example 3 Synthesis of High Molecular Weight Compound III: The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. Intermediate 1: 1.8 g Intermediate 5: 3.4 g Intermediate 2: 0.4 g 1,3-dibromobenzene: 1.8 g Tripotassium phosphate: 7.5 g Toluene: 9 ml Water: 5 ml 1,4-dioxane: 27 ml Next, 1.5 mg of palladium(II) acetate and 12.5 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 90°C for 9 hours. After this, 19 mg of phenylboronic acid was added and stirred for 1 hour, followed by 263 mg of bromobenzene and stirring for 1 hour. 50 ml of toluene and 50 ml of a 5 wt % aqueous solution of sodium N,N-diethyldithiocarbamate were added, and the mixture was heated and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was collected by separation and washed three times with saturated brine. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, silica gel was added, and the polymer was purified by adsorption. The silica gel was then removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 ml of toluene. The solution was then added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated three times and the resulting mixture was dried to obtain 3.3 g (71% yield) of high molecular weight compound III.

[0156] The average molecular weight and dispersity of the high molecular weight compound III measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 71,500 Weight average molecular weight Mw (polystyrene equivalent): 143,000 Dispersity (Mw / Mn): 2.0

[0157] In addition, NMR measurement was carried out on the high molecular weight compound III. １ From the results of H-NMR measurement, the chemical formula of the high molecular weight compound III was found to be as follows:

[0158]

[0159] As can be seen from the chemical composition, this polymer compound III contains 30 mol % of repeating unit A represented by general formula (1), 60 mol % of repeating unit B represented by general formula (2), and 10 mol % of repeating unit C represented by general formula (3), which is introduced to enhance thermal crosslinking properties. The molar ratio of each structural unit is １ This is an estimated value obtained from the results of H-NMR measurement.

[0160] Example 4 Synthesis of High Molecular Weight Compound IV: The following components were added to a nitrogen-purged reaction vessel and nitrogen gas was bubbled through for 30 minutes. Intermediate 1: 3.6 g Intermediate 8: 1.8 g Intermediate 2: 0.4 g 1,3-dibromobenzene: 1.8 g Tripotassium phosphate: 7.5 g Toluene: 9 ml Water: 5 ml 1,4-dioxane: 27 ml Next, 1.5 mg of palladium(II) acetate and 12.5 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 85°C for 9 hours. After this, 19 mg of phenylboronic acid was added and stirred for 1 hour, followed by 264 mg of bromobenzene and stirring for 1 hour. 50 ml of toluene and 50 ml of a 5 wt % aqueous solution of sodium N,N-diethyldithiocarbamate were added, and the mixture was heated and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was collected by separation and washed three times with saturated brine. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, silica gel was added, and the polymer was purified by adsorption. The silica gel was then removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 ml of toluene. The solution was then added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated three times and the resulting mixture was dried to obtain 3.2 g (72% yield) of high molecular weight compound IV.

[0161] The average molecular weight and dispersity of the high molecular weight compound IV measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 72,000 Weight average molecular weight Mw (polystyrene equivalent): 122,000 Dispersity (Mw / Mn): 1.7

[0162] In addition, NMR measurement was carried out on the high molecular weight compound IV. １ From the results of H-NMR measurement, the chemical formula of high molecular weight compound IV was found to be as follows:

[0163]

[0164] As can be seen from the chemical composition, this polymer compound IV contains 60 mol % of repeating unit A represented by general formula (1), 30 mol % of repeating unit B represented by general formula (2), and 10 mol % of repeating unit C represented by general formula (3), which is introduced to enhance thermal crosslinking properties. The molar ratio of each structural unit is １ This is an estimated value obtained from the results of H-NMR measurement.

[0165] Example 5 Synthesis of High Molecular Weight Compound V: The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. Intermediate 1: 3.8 g Intermediate 9: 1.7 g Intermediate 2: 0.4 g 1,3-dibromobenzene: 1.8 g Tripotassium phosphate: 7.8 g Toluene: 9 ml Water: 5 ml 1,4-dioxane: 27 ml Next, 1.6 mg of palladium(II) acetate and 13 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 87°C for 10 hours. After this, 19 mg of phenylboronic acid was added and stirred for 1 hour, followed by 276 mg of bromobenzene and stirring for 1 hour. 50 ml of toluene and 50 ml of a 5 wt % aqueous solution of sodium N,N-diethyldithiocarbamate were added, and the mixture was heated and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was collected by separation and washed three times with saturated brine. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, silica gel was added, and the polymer was purified by adsorption. The silica gel was then removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 ml of toluene. The solution was then added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated three times and the resulting mixture was dried to obtain 3.5 g (72% yield) of high molecular weight compound V.

[0166] The average molecular weight and dispersity of the high molecular weight compound V measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 65,000 Weight average molecular weight Mw (polystyrene equivalent): 123,000 Dispersity (Mw / Mn): 1.9

[0167] In addition, NMR measurement was performed on the high molecular weight compound V.１ From the results of H-NMR measurement, the chemical formula of high molecular weight compound V was found to be as follows:

[0168]

[0169] As can be seen from the chemical composition, this polymer compound V contains 60 mol % of repeating unit A represented by general formula (1), 30 mol % of repeating unit B represented by general formula (2), and 10 mol % of repeating unit C represented by general formula (3), which is introduced to enhance thermal crosslinking properties. The molar ratio of each structural unit is １ This is an estimated value obtained from the results of H-NMR measurement.

[0170] Example 6 Synthesis of High Molecular Weight Compound VI: The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. Intermediate 1: 3.7 g Intermediate 3: 1.4 g Intermediate 2: 0.4 g 9-(3,5-dibromophenyl)-9H-carbazole: 3.1 g Tripotassium phosphate: 6.9 g Toluene: 9 ml Water: 5 ml 1,4-dioxane: 27 ml Next, 1.4 mg of palladium(II) acetate and 11.5 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 85°C for 7 hours. After this, 17 mg of phenylboronic acid was added and stirred for 2 hours, followed by 242 mg of bromobenzene and stirring for 2 hours. 50 ml of toluene and 50 ml of a 5 wt % aqueous solution of sodium N,N-diethyldithiocarbamate were added, and the mixture was heated and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was separated and washed three times with saturated saline. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added for adsorption purification. The silica gel was then removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 ml of toluene. The solution was then added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated four times and dried to obtain 3.8 g (yield 69%) of high molecular weight compound VI.

[0171] The average molecular weight and dispersity of the high molecular weight compound VI measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 135,000 Weight average molecular weight Mw (polystyrene equivalent): 257,000 Dispersity (Mw / Mn): 1.9

[0172] In addition, NMR measurement was carried out on the high molecular weight compound VI. １ From the results of H-NMR measurement, the chemical formula of the high molecular weight compound VI was as follows:

[0173]

[0174] As can be seen from the chemical composition, this polymer compound VI contains 60 mol % of repeating unit A represented by general formula (1), 30 mol % of repeating unit B represented by general formula (2), and 10 mol % of repeating unit C represented by general formula (3), which is introduced to enhance thermal crosslinking properties. The molar ratio of each structural unit is １ This is an estimated value obtained from the results of H-NMR measurement.

[0175] Example 7 Synthesis of High Molecular Weight Compound VII: The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. Intermediate 1: 3.6 g Intermediate 3: 1.4 g Intermediate 6: 0.4 g 1,3-Dibromobenzene: 1.8 g Tripotassium phosphate: 7.5 g Toluene: 9 ml Water: 5 ml 1,4-Dioxane: 27 ml Next, 1.5 mg of palladium(II) acetate and 12.5 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 87°C for 9 hours. After this, 19 mg of phenylboronic acid was added and stirred for 1 hour, followed by 264 mg of bromobenzene and stirring for 1 hour. 50 ml of toluene and 50 ml of a 5 wt % aqueous solution of sodium N,N-diethyldithiocarbamate were added, and the mixture was heated and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was collected by separation and washed three times with saturated brine. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, silica gel was added, and the polymer was purified by adsorption. The silica gel was then removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 ml of toluene. The solution was then added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated five times, followed by drying to obtain 2.2 g (yield 50%) of high molecular weight compound VII.

[0176] The average molecular weight and dispersity of the high molecular weight compound VII measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 54,000 Weight average molecular weight Mw (polystyrene equivalent): 130,000 Dispersity (Mw / Mn): 2.4

[0177] In addition, NMR measurement was carried out on the high molecular weight compound VII. １ From the results of H-NMR measurement, the chemical formula of high molecular weight compound VII was found to be as follows:

[0178]

[0179] As can be seen from the chemical composition, this polymer compound VII contains 60 mol % of repeating unit A represented by general formula (1), 30 mol % of repeating unit B represented by general formula (2), and 10 mol % of repeating unit C represented by general formula (3), which is introduced to enhance thermal crosslinking properties. The molar ratio of each structural unit is １ This is an estimated value obtained from the results of H-NMR measurement.

[0180] Example 8 Synthesis of High Molecular Weight Compound VIII: The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. Intermediate 1: 3.7 g Intermediate 3: 1.4 g Intermediate 6: 0.4 g 9-(3,5-dibromophenyl)-9H-carbazole: 3.1 g Tripotassium phosphate: 6.9 g Toluene: 9 ml Water: 5 ml 1,4-dioxane: 27 ml Next, 1.4 mg of palladium(II) acetate and 11.5 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 85°C for 8 hours. After this, 17 mg of phenylboronic acid was added and stirred for 2 hours, followed by 242 mg of bromobenzene and stirring for 2 hours. 50 ml of toluene and 50 ml of a 5 wt % aqueous solution of sodium N,N-diethyldithiocarbamate were added, and the mixture was heated and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was separated and washed three times with saturated saline. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added for adsorption purification. The silica gel was then removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 ml of toluene. The solution was then added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated three times and dried to obtain 3.4 g (yield 61%) of high molecular weight compound VIII.

[0181] The average molecular weight and dispersity of the high molecular weight compound VIII measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 123,000 Weight average molecular weight Mw (polystyrene equivalent): 222,000 Dispersity (Mw / Mn): 1.8

[0182] In addition, NMR measurement was carried out on the high molecular weight compound VIII. １ From the results of H-NMR measurement, the chemical formula of the high molecular weight compound VIII was found to be as follows:

[0183]

[0184] As can be seen from the chemical composition, this polymer compound VIII contains 60 mol % of repeating unit A represented by general formula (1), 30 mol % of repeating unit B represented by general formula (2), and 10 mol % of repeating unit C represented by general formula (3), which is introduced to enhance thermal crosslinking properties. The molar ratio of each structural unit is １ This is an estimated value obtained from the results of H-NMR measurement.

[0185] Example 9 Synthesis of High Molecular Weight Compound IX: The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. Intermediate 1: 3.5 g Intermediate 10: 1.4 g Intermediate 2: 0.4 g 1,3-Dibromobenzene: 1.7 g Tripotassium phosphate: 7.2 g Toluene: 9 ml Water: 5 ml 1,4-Dioxane: 27 ml Next, 1.5 mg of palladium(II) acetate and 12.0 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 85°C for 6.5 hours. After this, 18 mg of phenylboronic acid was added and stirred for 1 hour, followed by addition of 255 mg of bromobenzene and stirring for 1 hour. 50 ml of toluene and 50 ml of a 5 wt % aqueous solution of sodium N,N-diethyldithiocarbamate were added, and the mixture was heated and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was collected by separation and washed three times with saturated brine. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, silica gel was added, and the polymer was purified by adsorption. The silica gel was then removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 ml of toluene. The solution was then added dropwise to 300 ml of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated six times and the resulting mixture was dried to obtain 2.6 g (yield 62%) of high molecular weight compound IX.

[0186] The average molecular weight and dispersity of the high molecular weight compound IX measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 55,000 Weight average molecular weight Mw (polystyrene equivalent): 127,000 Dispersity (Mw / Mn): 2.3

[0187] In addition, NMR measurement was carried out on the high molecular weight compound IX. １ From the results of H-NMR measurement, the chemical formula of high molecular weight compound IX was found to be as follows:

[0188]

[0189] As can be seen from the chemical composition, this polymer compound IX contains 60 mol % of repeating units A represented by general formula (1), 30 mol % of repeating units B represented by general formula (2), and 10 mol % of repeating units C represented by general formula (3), which are introduced to enhance thermal crosslinking properties. The molar ratio of each structural unit is １ This is an estimated value obtained from the results of H-NMR measurement.

[0190] Example 10 Synthesis of High Molecular Weight Compound X: The following components were added to a nitrogen-purged reaction vessel, and nitrogen gas was bubbled through for 30 minutes. Intermediate 1: 3.6 g Intermediate 3: 1.4 g Intermediate 2: 0.3 g Intermediate 7: 78 mg 1,3-Dibromobenzene: 1.8 g Tripotassium phosphate: 7.5 g Toluene: 9 ml Water: 5 ml 1,4-Dioxane: 27 ml Next, 1.5 mg of palladium(II) acetate and 12.5 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 88°C for 6 hours. After this, 19 mg of phenylboronic acid was added and stirred for 1 hour, followed by 264 mg of bromobenzene and stirring for 1 hour. 50 ml of toluene and 50 ml of a 5 wt % aqueous solution of sodium N,N-diethyldithiocarbamate were added, and the mixture was heated and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was separated and washed three times with saturated saline. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, and silica gel was added for adsorption purification, followed by filtration to remove the silica gel. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 ml of toluene. The solution was then added dropwise to 200 ml of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated four times and dried to obtain 3.1 g (yield 72%) of high molecular weight compound X.

[0191] The average molecular weight and dispersity of the high molecular weight compound X measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 88,000 Weight average molecular weight Mw (polystyrene equivalent): 352,000 Dispersity (Mw / Mn): 4.0

[0192] In addition, NMR measurement was carried out on the high molecular weight compound X. １ From the results of H-NMR measurement, the chemical formula of the high molecular weight compound X was as follows:

[0193]

[0194] As can be seen from the chemical composition, this polymer compound X contained 60 mol % of repeating units A represented by general formula (1), 30 mol % of repeating units B represented by general formula (2), 8 mol % of repeating units C represented by general formula (3) and containing partial structure (4e) which were introduced to enhance thermal crosslinking properties, and 2 mol % of repeating units C represented by general formula (3) and containing partial structure (4a) which were introduced to enhance thermal crosslinking properties. The molar ratio of each structural unit was １ This is an estimated value obtained from the results of H-NMR measurement.

[0195] Example 11 Synthesis of High Molecular Weight Compound XI The following components were added to a nitrogen-purged reaction vessel and nitrogen gas was bubbled through for 30 minutes. Intermediate 1: 3.6 g Intermediate 3: 1.4 g Intermediate 6: 0.3 g Intermediate 7: 78 mg 1,3-Dibromobenzene: 1.8 g Tripotassium phosphate: 7.5 g Toluene: 9 ml Water: 5 ml 1,4-Dioxane: 27 ml Next, 1.5 mg of palladium(II) acetate and 12.5 mg of tri-o-tolylphosphine were added, and the mixture was heated and stirred at 85°C for 6 hours. After this, 19 mg of phenylboronic acid was added and stirred for 1 hour, followed by 264 mg of bromobenzene and stirring for 1 hour. 50 ml of toluene and 50 ml of a 5 wt % aqueous solution of sodium N,N-diethyldithiocarbamate were added, and the mixture was heated and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was separated and washed three times with saturated saline. The organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, silica gel was added, and adsorption purification was performed. The silica gel was then removed by filtration. The resulting filtrate was concentrated under reduced pressure, and 100 ml of toluene was added to the dried product to dissolve it. The resulting solution was added dropwise to 200 ml of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated four times and dried to obtain 3.1 g of high molecular weight compound XI (yield 72%).

[0196] The average molecular weight and dispersity of the high molecular weight compound XI measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 61,000 Weight average molecular weight Mw (polystyrene equivalent): 357,000 Dispersity (Mw / Mn): 5.9

[0197] In addition, NMR measurement was carried out on the high molecular weight compound XI. １ From the results of H-NMR measurement, the chemical formula of the high molecular weight compound XI was as follows:

[0198]

[0199] As can be seen from the chemical composition, this polymer compound XI contained 60 mol % of repeating units A represented by general formula (1), 30 mol % of repeating units B represented by general formula (2), 8 mol % of repeating units C represented by general formula (3) and containing partial structure (4g) which are introduced to enhance thermal crosslinking properties, and 2 mol % of repeating units C represented by general formula (3) and containing partial structure (4a) which are introduced to enhance thermal crosslinking properties. The molar ratio of each structural unit was １ This is an estimated value obtained from the results of H-NMR measurement.

[0200] Example 12 Using the high molecular weight compounds I to XI synthesized in Examples 1 to 11, a coating film having a thickness of 80 nm was formed on an ITO substrate, and the work function was measured using an ionization potential measurement device (PYS-202 model, manufactured by Sumitomo Heavy Industries, Ltd.). The results are as follows:

[0201]

[0202] It is clear that the high molecular weight compounds I to XI of the present invention have a preferable energy level compared with the work function of 5.4 eV of common hole transport materials such as NPD and TPD, and have good hole transport ability.

[0203] Example 13: Fabrication and evaluation of organic EL element An organic EL element having the layer structure shown in Fig. 14 was fabricated by the following method. A glass substrate 1 on which a 50 nm thick ITO film (transparent anode 2) was formed was cleaned with an organic solvent, and then the surface of the transparent anode 2 was cleaned by UV / ozone treatment. A 50 nm thick film of PEDOT / PSS (manufactured by Ossila) was formed by spin coating so as to cover the transparent anode 2 provided on the glass substrate 1, and the film was dried on a hot plate at 200°C for 10 minutes to form a hole injection layer 3.

[0204] A coating solution was prepared by dissolving 0.6 wt % of the high-molecular-weight compound I obtained in Example 1 in toluene. The substrate on which the hole injection layer 3 had been formed as described above was transferred into a glove box purged with dry nitrogen and dried on a hot plate at 230°C for 10 minutes. The coating solution was then spin-coated on the hole injection layer 3 to form a coating layer with a thickness of 25 nm. This was then further dried on a hot plate at 220°C for 30 minutes to form a hole transport layer 4.

[0205] The substrate on which the hole transport layer 4 was formed as described above was placed in a vacuum deposition machine, and the pressure was reduced to 0.001 Pa or less. On the hole transport layer 4, a 34 nm-thick light-emitting layer 5 was formed by binary deposition of a blue light-emitting material (EMD-1) having the following structural formula and a host material (EMH-1). In the binary deposition, the deposition rate ratio was EMD-1:EMH-1=4:96.

[0206]

[0207] As electron transport materials, compounds (ETM-1) and (ETM-2) having the following structural formulas were prepared.

[0208]

[0209] An electron transport layer 6 having a thickness of 20 nm was formed on the light-emitting layer 5 by binary deposition using the electron transport materials (ETM-1) and (ETM-2). In the binary deposition, the deposition rate ratio of ETM-1:ETM-2 was 50:50.

[0210] Finally, aluminum was vapor-deposited to a thickness of 100 nm to form a cathode 7. 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 were formed was moved into a glove box purged with dry nitrogen, and the glass substrate was bonded to another glass substrate for sealing using a UV-curable resin to form an organic EL device. The characteristics of the fabricated organic EL device were measured in the atmosphere at room temperature. Furthermore, the light-emitting characteristics of the fabricated organic EL device were measured when a DC voltage was applied. The measurement results are shown in Table 2.

[0211] Example 14 An organic EL device was fabricated in the same manner as in Example 13, except that the hole transport layer 4 was formed using a coating liquid prepared by dissolving 0.6 wt % of the compound of Example 2 (high molecular weight compound II) in toluene instead of high molecular weight compound I. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 13, and the results are shown in Table 2.

[0212] Example 15 An organic EL device was fabricated in the same manner as in Example 13, except that the hole transport layer 4 was formed using a coating liquid prepared by dissolving 0.6 wt % of the compound of Example 3 (high molecular weight compound III) in toluene instead of high molecular weight compound I. The fabricated organic EL device was evaluated for various properties in the same manner as in Example 13, and the results are shown in Table 2.

[0213] Example 16 An organic EL device was fabricated in the same manner as in Example 13, except that the hole transport layer 4 was formed using a coating liquid prepared by dissolving 0.6 wt % of the compound of Example 4 (high molecular weight compound IV) in toluene instead of high molecular weight compound I. The fabricated organic EL device was evaluated for various properties in the same manner as in Example 13, and the results are shown in Table 2.

[0214] Example 17 An organic EL device was fabricated in the same manner as in Example 13, except that the hole transport layer 4 was formed using a coating liquid prepared by dissolving 0.6 wt % of the compound of Example 5 (high molecular weight compound V) in toluene instead of high molecular weight compound I. The fabricated organic EL device was evaluated for various properties in the same manner as in Example 13, and the results are shown in Table 2.

[0215] Comparative Example 1 An organic EL device was produced in the same manner as in Example 13, except that the hole transport layer 4 was formed using a coating solution prepared by dissolving 0.6 wt % of the following TFB (hole transport polymer) in toluene instead of the high molecular weight compound I.

[0216]

[0217] The TFB (hole transport polymer) was poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl))diphenylamine] (American Dye Source, Hole Transport Polymer ADS259BE). The organic EL device of Comparative Example 1 was evaluated for various characteristics in the same manner as in Example 13, and the results are shown in Table 2.

[0218] In the evaluation of various characteristics, the voltage, brightness, luminous efficiency, and power efficiency were measured at a current density of 10 mA / cm ２ The value is the value when a current of 700 cd / m is applied. ２ When driven at a constant current, the luminance was 560 cd / m ２ The time required for the brightness to decay to 80% (corresponding to 80% when the initial brightness was 100%) was measured.

[0219]

[0220] As shown in Table 2, the current density was 10 mA / cm ２The luminous efficiency when a current of 100 cd / A was passed through the organic EL element of Example 14 was 9.03 cd / A, the organic EL element of Example 15 was 9.43 cd / A, the organic EL element of Example 16 was 9.92 cd / A, the organic EL element of Example 17 was 10.10 cd / A, and the organic EL element of Example 18 was 9.42 cd / A, all of which were high efficiencies, compared to 5.53 cd / A for the organic EL element of Comparative Example 1. Furthermore, the element lifetime (80% decay) was 123 hours for the organic EL element of Example 14, 97 hours for the organic EL element of Example 15, 9 hours for the organic EL element of Example 16, 14 hours for the organic EL element of Example 17, and 26 hours for the organic EL element of Example 18, all of which were long lifetimes, compared to 7 hours for the organic EL element of Comparative Example 1.

[0221] Example 18 An organic EL element having the layer structure shown in Fig. 15 was fabricated by the following method. A glass substrate 8 on which a 50-nm-thick ITO film (transparent anode 9) was formed was cleaned with an organic solvent, and then the surface of the transparent anode 9 was cleaned by UV / ozone treatment. A 50-nm-thick film of PEDOT / PSS (manufactured by Ossila) was formed by spin coating so as to cover the transparent anode 9 provided on the glass substrate 8, and the film was dried on a hot plate at 200°C for 10 minutes to form a hole injection layer 10.

[0222] 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 had been formed as described above was transferred into a glove box purged with dry nitrogen and dried on a hot plate at 230°C for 10 minutes. Then, a coating layer having a thickness of 15 nm was formed on the hole injection layer 10 by spin coating using the coating solution, and this was further dried on a hot plate at 220°C for 30 minutes to form a hole transport layer 11.

[0223]

[0224] A coating solution was prepared by dissolving 0.4 wt % of the high molecular weight compound I obtained in Example 1 in toluene. A coating layer having a thickness of 15 nm was formed on the hole transport layer 11 formed as described above by spin coating using the coating solution, and the layer was further dried on a hot plate at 220° C. for 30 minutes to form an electron blocking layer 12.

[0225] The substrate on which the electron-blocking layer 12 had been formed as described above was placed in a vacuum deposition machine, and the pressure was reduced to 0.001 Pa or less. A 34-nm-thick light-emitting layer 13 was formed on the electron-blocking layer 12 by binary deposition of a blue-emitting material (EMD-1) and a host material (EMH-1). In the binary deposition, the deposition rate ratio was EMD-1:EMH-1=4:96.

[0226] An electron transport layer 14 having a thickness of 20 nm was formed on the light-emitting layer 13 by binary deposition using electron transport materials (ETM-1) and (ETM-2). In the binary deposition, the deposition rate ratio of ETM-1:ETM-2 was 50:50.

[0227] Finally, aluminum was evaporated to a thickness of 100 nm to form a cathode 15. The glass substrate on which the transparent anode 9, hole injection layer 10, hole transport layer 11, electron blocking layer 12, light-emitting layer 13, electron transport layer 14, and cathode 15 were formed was moved into a glove box purged with dry nitrogen, and another glass substrate for sealing was attached using a UV-curable resin to form an organic EL device. The characteristics of the fabricated organic EL device were measured in the atmosphere at room temperature. Furthermore, the light-emitting characteristics of the fabricated organic EL device were measured when a DC voltage was applied. The measurement results are shown in Table 3.

[0228] An organic EL device was fabricated in the same manner as in Example 18, except that a coating layer having a thickness of 15 nm was formed on the hole transport layer 11 by spin coating using a coating solution of high molecular weight compound I, and then heated on a hot plate at 210° C. for 30 minutes to form an electron blocking layer 12. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0229] An organic EL device was fabricated in exactly the same manner as in Example 18, except that a coating layer having a thickness of 15 nm was formed on the hole transport layer 11 by spin coating using a coating solution of high molecular weight compound I, and then heated on a hot plate at 220° C. for 20 minutes to form an electron blocking layer 12. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0230] Example 21 An organic EL device was fabricated in the same manner as in Example 18, except that the electron-blocking layer 12 was formed using a coating liquid prepared by dissolving 0.4 wt % of the compound of Example 2 (high-molecular-weight compound II) in toluene instead of high-molecular-weight compound I. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0231] Example 22 An organic EL device was fabricated in the same manner as in Example 18, except that the electron-blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt % of the compound of Example 3 (high-molecular-weight compound III) in toluene instead of high-molecular-weight compound I. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0232] Example 23 An organic EL device was fabricated in the same manner as in Example 18, except that the electron-blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt % of the compound of Example 4 (high-molecular-weight compound IV) in toluene instead of high-molecular-weight compound I. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0233] Example 24 An organic EL device was fabricated in the same manner as in Example 18, except that the electron-blocking layer 12 was formed using a coating liquid prepared by dissolving 0.4 wt % of the compound of Example 5 (high-molecular-weight compound V) in toluene instead of high-molecular-weight compound I. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0234] Example 25 An organic EL device was fabricated in the same manner as in Example 18, except that the electron-blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt % of the compound of Example 6 (high-molecular-weight compound VI) in toluene instead of high-molecular-weight compound I. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0235] Example 26 An organic EL device was fabricated in the same manner as in Example 18, except that the electron-blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt % of the compound of Example 7 (high-molecular-weight compound VII) in toluene instead of high-molecular-weight compound I. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0236] Example 27 An organic EL device was fabricated in the same manner as in Example 18, except that the electron-blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt % of the compound of Example 8 (high molecular weight compound VIII) in toluene instead of high molecular weight compound I. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0237] Example 28 An organic EL device was fabricated in the same manner as in Example 18, except that the electron-blocking layer 12 was formed using a coating liquid prepared by dissolving 0.4 wt % of the compound of Example 9 (high-molecular-weight compound IX) in toluene instead of high-molecular-weight compound I. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0238] Example 29 An organic EL device was fabricated in the same manner as in Example 18, except that the electron-blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt % of the compound of Example 10 (high-molecular-weight compound X) in toluene instead of high-molecular-weight compound I. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0239] Example 30 An organic EL device was fabricated in the same manner as in Example 18, except that the electron-blocking layer 12 was formed using a coating liquid prepared by dissolving 0.4 wt % of the compound of Example 11 (high-molecular-weight compound XI) in toluene instead of high-molecular-weight compound I. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 18, and the results are shown in Table 3.

[0240] Comparative Example 2 An organic EL device was fabricated in exactly the same manner as in Example 18, except that the electron-blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt % of TFB (a hole-transporting polymer) in toluene instead of the high-molecular-weight compound I. The organic EL device of Comparative Example 2 was evaluated for various properties in the same manner as in Example 18, and the results are shown in Table 3.

[0241] In the evaluation of various characteristics, the voltage, brightness, luminous efficiency, and power efficiency were measured at a current density of 10 mA / cm ２ The value is the value when a current of 700 cd / m is applied. ２ When driven at a constant current, the luminance was 560 cd / m ２ The time required for the brightness to decay to 80% (corresponding to 80% when the initial brightness was 100%) was measured.

[0242]

[0243] As shown in Table 3, the current density was 10 mA / cm ２ The luminous efficiency when a current of 100 mA was passed through the organic EL element of Example 18 was 8.09 cd / A, the organic EL element of Example 19 was 7.93 cd / A, and the organic EL element of Example 20 was 8.42 cd / A, all of which were high efficiencies, compared to 5.50 cd / A for the organic EL element of Comparative Example 2. Furthermore, the element lifetime (at 80% decay) was 204 hours for the organic EL element of Example 18, 338 hours for the organic EL element of Example 19, and 306 hours for the organic EL element of Example 20, all of which were long lifetimes, compared to 11 hours for the organic EL element of Comparative Example 2, and a tendency for the lifetime to be even longer was observed under low temperature or short-time heating conditions.

[0244] Also, as shown in Table 3, at a current density of 10 mA / cm ２The luminous efficiency when a current of 100 cd / A was passed through the organic EL element of Comparative Example 2 was 5.50 cd / A, whereas the luminous efficiency was 9.14 cd / A for the organic EL element of Example 21, 8.97 cd / A for the organic EL element of Example 22, 7.95 cd / A for the organic EL element of Example 23, 8.46 cd / A for the organic EL element of Example 24, 7.62 cd / A for the organic EL element of Example 25, 7.47 cd / A for the organic EL element of Example 26, 8.15 cd / A for the organic EL element of Example 27, 7.12 cd / A for the organic EL element of Example 28, 7.52 cd / A for the organic EL element of Example 29, and 6.86 cd / A for the organic EL element of Example 30, and all of them were highly efficient.

[0245] Furthermore, as shown in Table 3, the element lifetime (at 80% decay) was 11 hours for the organic EL element of Comparative Example 2, and was 265 hours for the organic EL element of Example 21, 214 hours for the organic EL element of Example 22, 258 hours for the organic EL element of Example 23, 242 hours for the organic EL element of Example 24, 52 hours for the organic EL element of Example 25, 229 hours for the organic EL element of Example 26, 105 hours for the organic EL element of Example 27, 122 hours for the organic EL element of Example 28, 218 hours for the organic EL element of Example 29, and 295 hours for the organic EL element of Example 30, all of which were long lifetimes.

[0246] The high molecular weight compound of the present invention has high hole transporting ability and excellent electron blocking ability, making it an excellent compound for use in coating-type organic EL devices. By using this compound to prepare coating-type organic EL devices, high luminous efficiency and power efficiency can be achieved, and durability can be improved. For example, this allows for applications in home appliances and lighting.

[0247] 1, 8: Glass substrate 2, 9: Transparent anode 3, 10: Hole injection layer 4, 11: Hole transport layer 5, 13: Light-emitting layer 6, 14: Electron transport layer 7, 15: Cathode 12: Electron blocking layer

Claims

1. A high molecular weight compound containing a repeating unit represented by the following general formula (1) and a repeating unit represented by the following general formula (2), and having a weight average molecular weight of 10,000 or more and less than 1,000,000 in terms of polystyrene: 【Chemistry 1】 【Chemistry 2】 During the ceremony, R １ and R ３ may be the same or different and represent a deuterium atom, a cyano group, a nitro group, a halogen atom; or an alkyl group, a cycloalkyl group, an alkyloxy group, a cycloalkyloxy group, an alkenyl group, or an aryloxy group, each of which has 40 or less carbon atoms. However, R in the general formula (1) １ and R in general formula (2) １ may be the same or different, but R ３ and R in general formula (2) ３ indicates the same group. a represents an integer of 0 to 3; b represents an integer of 0 to 4; R ２ represents an alkyl group, a cycloalkyl group, or an alkyloxy group, each of which has 3 to 40 carbon atoms. L represents a phenylene group; n represents an integer of 0 to 3. X represents a hydrogen atom, an optionally substituted amino group, a monovalent aryl group, or a monovalent heteroaryl group, and the substituents may be bonded to each other via a single bond, an optionally substituted methylene group, an oxygen atom, or a sulfur atom to form a ring. However, X in formula (1) and X in formula (2) represent the same group. Y represents a monovalent aryl group which may have a substituent, Z represents a hydrogen atom, a monovalent aryl group which may have a substituent, or a monovalent heteroaryl group, and Y and Z may be bonded to each other via a single bond, a methylene group which may have a substituent, an oxygen atom, or a sulfur atom to form a ring.

2. 2. The high molecular weight compound according to claim 1, wherein a and b are 0 in said general formulas (1) and (2).

3. In the general formula (1), R ２ The high molecular weight compound according to claim 1, wherein is an alkyl group having 3 to 40 carbon atoms.

4. 2. The high molecular weight compound according to claim 1, wherein in said general formulas (1) and (2), 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.

5. The high molecular weight compound according to claim 1 , comprising a repeating unit containing a thermally crosslinkable structural unit Q represented by the following general formula (3): 【Chemistry 3】 During the ceremony, R ３ , X, and a are all the same as those shown in general formula (1).

6. 6. The high molecular weight compound according to claim 5, wherein the thermally crosslinkable structural unit Q is a structural unit represented by the following general formulas (4a) to (4z): 【Chemistry 4】 【Chemistry 5】 During the ceremony, R １ , R ２ , a and b are the same as those shown in general formula (1).

7. An organic electroluminescence element having a pair of electrodes and an organic layer sandwiched between them, wherein the high molecular weight compound according to any one of claims 1 to 6 is used as a constituent material of the organic layer.

8. The organic electroluminescence device according to claim 7 , wherein the organic layer is a hole transport layer.

9. The organic electroluminescence device according to claim 7 , wherein the organic layer is an electron blocking layer.

10. The organic electroluminescence device according to claim 7 , wherein the organic layer is a hole injection layer.

11. The organic electroluminescence device according to claim 7 , wherein the organic layer is a light-emitting layer.

Images