High molecular weight compounds having an indenodibenzoheterole structure as a partial structure, and organic electroluminescent devices 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 an electron blocking capability, 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 that has an organic layer (thin film) formed via the polymer material and exhibits high light-emission efficiency and a long service life.　The present invention is a high molecular weight compound comprising, as a repeating unit, a triarylamine structure represented by general formula (1) below. (In the formula, R1 and R2 each independently represent a substituted or unsubstituted alkyl group having 1-40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3-40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1-40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3-40 carbon atoms, or a substituted or unsubstituted polyether group having 1-40 carbon atoms.)

Description

[Technical Field]

[0001] The present invention relates to a high-molecular-weight compound suitable for organic electroluminescence elements (organic EL elements), which are self-luminous elements suitable for various display devices, and to an organic EL element containing the same. [Background technology]

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

[0003] Organic EL elements are constructed by sandwiching a thin film (organic layer) of organic compounds between an anode and a cathode. Thin film formation methods can be broadly divided into vacuum deposition and coating methods. Vacuum deposition is a technique that mainly uses low-molecular-weight compounds to form a thin film on a substrate in a vacuum, and is a technology that has already been put to practical use. On the other hand, coating is a technique that mainly uses high-molecular-weight compounds to form a thin film on a substrate using a solution, such as inkjet or printing. It is highly efficient in the use of materials and is suitable for larger areas and higher resolution, 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 substrate 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 devices using polymer materials have been investigated to date, but there has been a problem that device characteristics such as luminous efficiency and life span are not necessarily sufficient (see, for example, Patent Documents 1 to 5).

[0007] A fluorene polymer called TFB has been known as a typical hole transport material used in polymer organic EL devices (see Patent Documents 6 and 7). However, TFB has insufficient hole transport properties and 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 achieving a long life. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] US Patent Application Publication No. 2008 / 0274303 [Patent Document 2] Japanese Patent Application Laid-Open No. 2007-119763 [Patent Document 3] US Patent Application Publication No. 2010 / 0176377 [Patent Document 4] Japanese Patent Application Laid-Open No. 2007-177225 [Patent Document 5] U.S. Patent No. 7,651,746 [Patent Document 6] International Publication No. 1999 / 054385 [Patent Document 7] International Publication No. 2005 / 059951 Summary of the Invention

[0009] An object of the present invention is to provide a polymer material that has excellent hole injection and transport properties, electron blocking ability, and high stability in a thin film state. An object of the present invention is to provide an organic EL device having an organic layer (thin film) formed from the polymer material, which has high luminous efficiency and a long life.

[0010] The present inventors have noticed that triarylamines containing an indenodibenzoheterole 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 triarylamine compounds containing an indenodibenzoheterole structure, they have discovered a high molecular weight compound with a novel structure that not only has hole injection / transport capabilities but also a wide gap, excellent heat resistance, and thin film stability, and have completed the present invention.

[0011] According to the present invention, there is provided a high molecular weight compound containing a triarylamine structure represented by the following general formula (1) as a repeating unit.

[0012] According to the present invention, there is provided an organic EL device having a pair of electrodes and at least one organic layer sandwiched between them, wherein the organic layer contains the above-mentioned high molecular weight compound as a constituent material.

[0013] In the organic EL device of the present invention, the organic layer is preferably a hole transport layer, an electron blocking layer, a hole injection layer or a light emitting layer.

[0014] That is, the present invention is as follows.

[0015] [1] A high molecular weight compound containing, as a repeating unit, a triarylamine structural unit having an indenodibenzoheterole structure represented by the following general formula (1) as a partial structure:

[0016] [ka] (In the formula, R1 and R2 each independently represent a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, or a substituted or unsubstituted polyether group having 1 to 40 carbon atoms; X represents an oxygen atom or a sulfur atom; R3~R 11 each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; R 12 and R 16 each independently represents a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, or a substituted or unsubstituted aryloxy group; R 12 and R 16 may be bonded to each other via a single bond, an optionally substituted methylene group, an oxygen atom or a sulfur atom, R 13 ~R 15 , R 17 ~R 19 each independently represents a hydrogen atom or a deuterium atom, L represents a substituted or unsubstituted arylene group having 5 to 40 carbon atoms; n represents an integer of 0 to 3.

[0017] [2] The high molecular weight compound according to [1], which contains a repeating unit represented by the following general formula (2):

[0018] [ka] (In the formula, R1~R 19 , X, L, and n are the same as in equation (1), R 20 ~R 22 each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, or a substituted or unsubstituted aryloxy group; Y represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; m and p represent mole fractions; m indicates 0.1 to 0.9, p indicates a value between 0.1 and 0.9.

[0019] [3] The high molecular weight compound according to [1] or [2], wherein X is an oxygen atom.

[0020] [4]R 12 ~R 19 The high molecular weight compound according to any one of [1] to [3], wherein is a hydrogen atom.

[0021] [5] R3~R 11The high molecular weight compound according to any one of [1] to [4], wherein is a hydrogen atom.

[0022] [6] R3~R 22 The high molecular weight compound according to any one of [2] to [5], wherein is a hydrogen atom.

[0023] [7] The high molecular weight compound according to any one of [2] to [6], wherein Y 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.

[0024] [8] The high molecular weight compound according to any one of [1] to [7], wherein R1 and R2 are each independently an alkyl group, an alkyloxy group, or a polyether group.

[0025] [9] The high molecular weight compound according to any one of [1] to [8], which contains a thermally crosslinkable structural unit as a repeating unit.

[0026]

[10] The high molecular weight compound according to [9], wherein the thermally crosslinkable structural unit is one or more types of thermally crosslinkable structural units selected from the group consisting of general formulae (3aa) to (3bd):

[0027] [ka]

[0028] [ka] (In the formula, R each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; The wavy line indicates cis or trans. The dotted line indicates the bond to the main chain; a represents an integer of 0 to 4; b represents an integer of 0 to 3.

[0029]

[11] An organic electroluminescence element having a pair of electrodes and at least one organic layer sandwiched between them, wherein the organic layer contains the high molecular weight compound according to any one of [1] to

[10] .

[0030]

[12] The organic electroluminescence device according to

[11] , wherein the organic layer is a hole transport layer.

[0031]

[13] The organic electroluminescence device according to

[11] , wherein the organic layer is an electron blocking layer.

[0032]

[14] The organic electroluminescence device according to

[11] , wherein the organic layer is a hole injection layer.

[0033]

[15] The organic electroluminescence device according to

[11] , wherein the organic layer is a light-emitting layer.

[0034] A high molecular weight compound containing a triarylamine structural unit having an indenodibenzoheterole structure as a partial structure, represented by general formula (1), as a repeating unit, is (1) Good hole injection characteristics. (2) The mobility of holes is large. (3) It has a wide gap and is excellent in electron blocking ability. (4) The thin film state is stable. (5) Excellent heat resistance. It has the following characteristics.

[0035] An organic EL device in which an organic layer formed of such a high molecular weight compound, for example, a hole transport layer, an electron blocking layer, a hole injection layer, or a light emitting layer is formed between a pair of electrodes, is (1) High luminous efficiency and power efficiency. (2) The practical driving voltage is low. (3) It has a long life. This has the advantage that: [Brief explanation of the drawings]

[0036] [Figure 1] FIG. 1 is a diagram showing an example of a layer structure of an organic EL element of the present invention. [Figure 2] FIG. 1 is a diagram showing an example of a layer structure of an organic EL element of the present invention. [Figure 3] 1H-NMR chart of the high molecular weight compound A of the present invention synthesized in Example 1. [Figure 4] 1H-NMR chart of the high molecular weight compound B of the present invention synthesized in Example 2. [Figure 5] 1H-NMR chart of the high molecular weight compound C of the present invention synthesized in Example 3. DETAILED DESCRIPTION OF THE INVENTION

[0037] <High molecular weight compounds> The high molecular weight compound of the present invention is a high molecular weight compound containing, as a repeating unit, a triarylamine structural unit having an indenodibenzoheterole structural unit as a partial structure.

[0038] <<Triarylamine structural unit>> The triarylamine structural unit contained in the high molecular weight compound has an indenodibenzoheterole structure as a partial structure, and is represented by the following general formula (1).

[0039] [ka] (In the formula, R1 and R2 each independently represent a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, or a substituted or unsubstituted polyether group having 1 to 40 carbon atoms; X represents an oxygen atom or a sulfur atom; R3~R 11 each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group. R 12 and R 16 each independently represents a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, or a substituted or unsubstituted aryloxy group; R 12and R 16 may be bonded to each other via a single bond, an optionally substituted methylene group, an oxygen atom or a sulfur atom, R 13 ~R 15 , R 17 ~R 19 each independently represents a hydrogen atom or a deuterium atom, L represents a substituted or unsubstituted arylene group having 5 to 40 carbon atoms; n represents an integer of 0 to 3.

[0040] Examples of the alkyl group, cycloalkyl group, alkyloxy group, cycloalkyloxy group and polyether group represented by R1 and R2 include the following groups. Alkyl groups (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, and the like. Alkyloxy group (1 to 8 carbon atoms); Examples of such groups include a methyloxy group, an ethyloxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, a tert-butyloxy group, an n-pentyloxy group, an n-hexyloxy group, an n-heptyloxy group, and an n-octyloxy group. cycloalkyl groups (5 to 10 carbon atoms); A cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, and the like. Cycloalkyloxy group (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, and the like. Polyether groups; Examples of such groups include an n-1,3-dioxabutyl group, an n-2,4-dioxapentyl group, an n-1,3,5-trioxahexyl group, an n-2,4,6-trioxaheptyl group, an n-1,3,5,7-tetraoxaoctyl group, and an n-2,4,6,8-tetraoxanonane group.

[0041] In order to improve solubility, R1 and R2 are preferably alkyl groups, alkyloxy groups or polyether groups having 1 to 8 carbon atoms, and from the viewpoint of synthesis, are most preferably alkyl groups having 1 to 8 carbon atoms.

[0042] X represents an oxygen atom or a sulfur atom, and in the present invention, it is preferably an oxygen atom from the viewpoint of hole injection and transport properties.

[0043] R3~R 11 Examples of the alkyl group, cycloalkyl group, alkyloxy group, cycloalkyloxy group, and polyether group represented by the formula (I) include the same groups as those shown in the description of R1 and R2, and examples of the alkenyl group, aryloxy group, aryl group, and heteroaryl group include the following groups. Alkenyl group (2 to 6 carbon atoms); Vinyl group, allyl group, isopropenyl group, 2-butenyl group, etc. aryloxy groups; Phenyloxy group, tolyloxy group, naphthyloxy group, and the like. aryl groups; Examples of such groups include a phenyl group, a naphthyl group, an anthracenyl group, a phenanthrenyl group, a fluorenyl group, an indenyl group, a pyrenyl group, a perylenyl group, and a fluoranthenyl group. heteroaryl groups; A pyridinyl group, a pyrimidinyl group, a triazinyl group, a furyl group, a pyrrolyl group, a thienyl group, a quinolyl group, an isoquinolyl group, a benzofuranyl group, a benzothienyl group, an indolyl group, a carbazolyl group, an indenocarbazolyl group, a benzoxazolyl group, a benzothiazolyl group, a quinoxalinyl group, a benzimidazolyl group, a pyrazolyl group, a dibenzofuranyl group, a dibenzothienyl group, a naphthyridinyl group, a phenanthrolinyl group, an acridinyl group, a carbolinyl group, and the like.

[0044] R3~R 11 is preferably an aryl group, a hydrogen atom, or a deuterium atom, and is most preferably a hydrogen atom from a synthetic standpoint.

[0045] R 12 and R 16 Examples of the alkyl group, polyether group, cycloalkyl group, alkyloxy group, cycloalkyloxy group, alkenyl group and aryloxy group represented by the formula (I) include R1, R2, R3 to R 11 Examples include the same groups as those shown in the description of .

[0046] R 12 and R 16 is preferably a hydrogen atom or a deuterium atom, and is most preferably a hydrogen atom from a synthesis standpoint. Also, R 13 ~R 15 , R 17 ~R 19 is preferably a hydrogen atom or a deuterium atom, and is most preferably a hydrogen atom from a synthesis standpoint. That is, R 12 ~R 19 is most preferably a hydrogen atom.

[0047] Furthermore, examples of the substituent that the alkyl group, cycloalkyl group, alkyloxy group, cycloalkyloxy group, polyether group, alkenyl group, aryloxy group, aryl group, and heteroaryl group may have include a deuterium atom, a cyano group, a nitro group, and the following groups: Halogen atoms, such as fluorine, chlorine, bromine, and iodine atoms; Alkyl groups, particularly those having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, n-heptyl, isoheptyl, neoheptyl, n-octyl, isooctyl, and neooctyl groups; Alkyloxy groups, particularly those having 1 to 8 carbon atoms, such as a methyloxy group, an ethyloxy group, or a propyloxy group; Alkenyl groups, for example, vinyl groups, allyl groups; Aryloxy groups, for example, phenyloxy groups, tolyloxy groups, naphthyloxy groups; Aryl groups, for example, phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, and triphenylenyl groups; Heteroaryl groups, such as pyridinyl, pyrimidinyl, triazinyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, indenocarbazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, and carbolinyl groups; Aryl vinyl groups, such as styryl groups and naphthyl vinyl groups; Acyl groups, for example, acetyl group, benzoyl group, and the like.

[0048] These substituents may further have the substituents exemplified above. Furthermore, it is preferable that these substituents 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.

[0049] 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.

[0050] L represents a divalent arylene group, and examples of the arylene group include the following groups. arylene groups; Phenylene group, naphthalenediyl group, phenanthrenediyl group, fluorenediyl group, indenediyl group, pyrenediyl group, and the like. In the present invention, from the viewpoint of hole injection and transport properties, L is preferably a phenylene group.

[0051] From the viewpoint of synthesis, n is preferably an integer of 0 to 2, and more preferably 0 or 1.

[0052] Furthermore, L may have a substituent, which may include a deuterium atom, a cyano group, a nitro group, and the following groups. Halogen atoms, such as fluorine, chlorine, bromine, and iodine atoms; Alkyl groups, particularly those having 1 to 8 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, neohexyl, n-heptyl, isoheptyl, neoheptyl, n-octyl, isooctyl, and neooctyl groups; Alkyloxy groups, particularly those having 1 to 8 carbon atoms, such as a methyloxy group, an ethyloxy group, or a propyloxy group; Alkenyl groups, for example, vinyl groups, allyl groups; Aryloxy groups, for example, phenyloxy groups, tolyloxy groups, naphthyloxy groups; Aryl groups, for example, phenyl, biphenylyl, terphenylyl, naphthyl, anthracenyl, phenanthrenyl, fluorenyl, indenyl, pyrenyl, perylenyl, fluoranthenyl, and triphenylenyl groups; Heteroaryl groups, such as pyridinyl, pyrimidinyl, triazinyl, thienyl, furyl, pyrrolyl, quinolyl, isoquinolyl, benzofuranyl, benzothienyl, indolyl, carbazolyl, indenocarbazolyl, benzoxazolyl, benzothiazolyl, quinoxalinyl, benzimidazolyl, pyrazolyl, dibenzofuranyl, dibenzothienyl, and carbolinyl groups; Aryl vinyl groups, such as styryl groups and naphthyl vinyl groups; Acyl groups, for example, acetyl group, benzoyl group, and the like.

[0053] 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.

[0054] <<Average molecular weight>> As already mentioned, the high molecular weight compound of the present invention, which contains the triarylamine structural unit represented by the general formula (1) as a repeating unit, has excellent properties such as hole injection characteristics, hole mobility, electron blocking ability, thin film stability, and heat resistance. From the viewpoint of further enhancing these properties and ensuring film formability, for example, the weight average molecular weight, measured by GPC in terms of polystyrene, is preferably 10,000 or more and less than 1,000,000, more preferably 10,000 or more and less than 500,000, and even more preferably 10,000 or more and less than 200,000.

[0055] <<Other structural units>> The high molecular weight compound of the present invention is preferably a copolymer containing other structural units as repeating units in order to ensure coatability, adhesion to other layers, and durability when applied to form an organic layer in an organic EL device by coating, for example. Examples of such other structural units include a thermally crosslinkable structural unit, a triarylamine structural unit different from that represented by the general formula (1), and a linking structural unit represented by the following general formula (4):

[0056] <<<Consolidated structural unit>>> The high molecular weight compound of the present invention may contain a linking structural unit represented by the following general formula (4) as a repeating unit.

[0057] [ka] (In the formula, R 20 ~R 22 each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, or a substituted or unsubstituted aryloxy group; Y represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0058] R 20 ~R 22 Examples of the alkyl group, polyether group, cycloalkyl group, alkyloxy group, cycloalkyloxy group, alkenyl group and aryloxy group represented by the formula (I) include R1, R2, R3 to R 11 Examples include the same groups as those shown in the description of .

[0059] R 20 ~R 22 is preferably a hydrogen atom or a deuterium atom, and is most preferably a hydrogen atom from a synthesis standpoint.

[0060] Examples of the aryl and heteroaryl groups represented by Y include the above-mentioned R3 to R 11 Examples of the aryl and heteroaryl groups are the same as those shown in the above.

[0061] The amino group, aryl group, and heteroaryl group represented by Y may have the same substituent as that of the aforementioned L. These substituents may further have the same substituent as that of the aforementioned L.

[0062] Y 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.

[0063] Specific examples of linking structural units are shown below as chemical formulas (4aa) to (4bp). In chemical formulas (4aa) to (4bp), dotted lines indicate bonds to adjacent structural units, and solid lines extending from rings with free ends indicate that the free ends are methyl groups. Although preferred specific examples of linking structural units are shown, the linking structural units used in the present invention are not limited to these structural units.

[0064] [ka]

[0065] [ka]

[0066] <<<Thermal crosslinkable structural unit>>> The thermally crosslinkable structural unit is a structural unit having a reactive functional group such as a vinyl group or a cyclobutane ring within the structural unit. The high molecular weight compound of the present invention may contain two or more types of thermally crosslinkable structural units as repeating units. Specific examples of the thermally crosslinkable structural unit are shown in formulas (3aa) to (3bd). These are preferred specific examples of the thermally crosslinkable structural unit, but the thermally crosslinkable structural unit used in the present invention is not limited to these structural units.

[0067] [ka]

[0068] [ka] (In the formula, R each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; The wavy line indicates cis or trans. The dotted line indicates the bond to the main chain; a represents an integer of 0 to 4; b represents an integer of 0 to 3.

[0069] In the formulas (3aa) to (3bd), the dashed lines indicate bonds to adjacent structural units, the wavy lines indicate cis or trans, and the solid lines extending from the rings with free ends indicate that the ends are methyl groups.

[0070] Examples of the alkyl group, polyether group, cycloalkyl group, alkyloxy group, cycloalkyloxy group, alkenyl group, aryloxy group, aryl group, and heteroaryl group represented by R include R1, R2, R3 to R4 in the above-mentioned general formula (1). 11 Examples include the same groups as those shown in the description of .

[0071] R is preferably a hydrogen atom or a deuterium atom, and from a synthetic standpoint, is most preferably a hydrogen atom.

[0072] <<Combination of structural units>> The thermally crosslinkable structural unit and other structural units such as a triarylamine structural unit different from that represented by the general formula (1) may be contained in the high molecular weight compound as a repeating unit alone, or may be contained in the high molecular weight compound as a repeating unit together with the linking structural unit represented by the general formula (4) described above.

[0073] In the high molecular weight compound of the present invention, when the structural unit represented by general formula (1) is represented by A, the linking structural unit represented by general formula (4) is represented by B, and the thermally crosslinkable structural unit or the triarylamine structural unit different from that represented by general formula (1) is represented by C, the high molecular weight compound preferably contains the structural unit A at 1 mol% or more, particularly 20 mol% or more. Provided that the structural unit A is contained in such an amount, the structural unit B is preferably contained in an amount of 1 mol% or more, particularly 30 to 70 mol%, and further the structural unit C is preferably contained in an amount of 1 mol% or more, particularly 3 to 20 mol%. A terpolymer containing the structural units A, B, and C so as to satisfy these conditions is most suitable for forming an organic layer of an organic EL device.

[0074] The structural units preferably contain structural units A and B, and particularly preferably contain a repeating unit represented by the following general formula (2).

[0075] [ka] (In the formula, R1~R 19 , X, L, and n are the same as in general formula (1), R 20 ~R 22 each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, or a substituted or unsubstituted aryloxy group; Y represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; m and p represent mole fractions; m indicates 0.1 to 0.9, p indicates a value between 0.1 and 0.9.

[0076] The alkyl group, polyether group, cycloalkyl group, alkyloxy group, cycloalkyloxy group, alkenyl group, aryloxy group, aryl group, heteroaryl group and substituent in general formula (2) are the same as those in general formula (1) above.

[0077] <<Synthesis method>> The high molecular weight compound of the present invention can be 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, a unit compound having each structural unit is prepared, and the unit compound is appropriately borated or halogenated, followed by polycondensation using an appropriate catalyst, thereby synthesizing the high molecular weight compound.

[0078] For example, a triarylamine derivative represented by the following general formula (1a) can be used as a compound for introducing the structural unit of general formula (1).

[0079] [ka] (In the formula, Q is a hydrogen atom, a halogen atom, or a borate ester group; R1~R 19 , L, and n are the same as those shown in general formula (1).

[0080] That is, in the general formula (1a), those in which Q is a hydrogen atom are unit compounds for introducing the structural unit of general formula (1), and those in which Q is a halogen atom or a borate ester group are halides or borate ester compounds used to synthesize polymers, respectively. The halide is preferably a bromide.

[0081] For example, a copolymer containing 40 mol % of structural unit A represented by general formula (1), 50 mol % of structural unit B represented by general formula (4), and 10 mol % of thermally crosslinkable structural unit C (formula (3ai) in Figure 3) is represented by general formula (5) shown below.

[0082] [ka]

[0083] Such copolymers can be synthesized by a polycondensation reaction between a borate ester and a halogenated borate, but it is necessary that the intermediate for introducing structural units A and C is a borate ester, while the intermediate for introducing structural unit B is a halogenated borate, or that the intermediate for introducing structural units A and C is a halogenated borate, while the intermediate for introducing structural unit B is a borate ester. In other words, the molar ratio of the halogenated borate to the halogenated borate must be equal.

[0084] 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 obtained has good heat resistance and also good adhesion to other layers.

[0085] The high-molecular-weight compound of the present invention can be used as a constituent material for the hole injection layer and / or hole transport layer of an organic EL device. The hole injection layer and hole transport layer formed from the 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. Furthermore, they can 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.

[0086] 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.

[0087] <Organic EL element> The organic EL device of the present invention, which includes an organic layer formed using the above-described high-molecular-weight compound of the present invention, has, for example, the structure shown in Fig. 1. 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 such as a transparent resin substrate).

[0088] Of course, the organic EL device to which the high molecular weight compound is applied is not limited to the layer structure described above. A hole-blocking layer may be provided between the light-emitting layer 5 and the electron-transporting layer 6. Alternatively, as shown in FIG. 2, an electron-blocking layer may be provided between the hole-transporting layer 11 and the light-emitting layer 13. Furthermore, although not shown in FIG. 2, an electron-injection layer may be provided between the cathode 15 and the electron-transporting layer 14. Furthermore, some layers may be omitted. For example, the hole-injection layer 3 may be omitted from the structure shown in FIG. 1, and a simple layer structure may be adopted 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 used.

[0089] The high molecular weight compound is suitable for use as a material for forming an organic layer (e.g., a hole injection layer 3, a hole transport layer 4, an emitting layer 5, or an electron blocking layer) provided between the anode 2 and the cathode 7, taking advantage of its properties such as hole injection property and hole transport property.

[0090] 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 a glass substrate 1 (which may be a transparent substrate such as a transparent resin substrate).

[0091] 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, or anisole. That is, 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.

[0092] In an organic EL device having an organic layer formed using the high-molecular-weight compound, the hole injection layer 3 can also be formed using a conventionally known material, such as the following material, without using the high-molecular-weight compound. Porphyrin compounds, such as copper phthalocyanine; Starburst triphenylamine derivatives; Arylamines having structures linked by single bonds or divalent groups that do not contain heteroatoms (e.g., triphenylamine trimers and tetramers); Acceptor heterocyclic compounds such as hexacyanoazatriphenylene; Coating-type polymer materials, such as poly(3,4-ethylenedioxythiophene) (PEDOT) and poly(styrene sulfonate) (PSS).

[0093] The hole injection layer 3 (thin film) can be formed using these materials by vapor deposition and coating using spin coating, inkjet, etc., depending on the type of film-forming material. The thin film is formed in the same manner for the other layers, and is formed by vapor deposition or coating depending on the type of film-forming material.

[0094] The hole transport layer 4 provided on the hole injection layer 3 can also be formed by coating using the high molecular weight compound of the present invention by spin coating, inkjet coating, or the like, similar to the hole injection layer 3.

[0095] In the organic EL device of the present invention having an organic layer formed using the high molecular weight compound, 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, for example: 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, for example: 1,1-bis[4-(di-4-tolylamino)phenyl]cyclohexane (hereinafter abbreviated as TAPC); various triphenylamine trimers and tetramers; Coating polymer materials that are also used for hole injection layers.

[0096] The compounds used in the hole transport layer 4, including the high-molecular-weight compounds, may be used alone or in combination to form a film. Alternatively, one or more of the compounds may be used to form a plurality of layers, and the hole transport layer 4 may be a multilayer film formed by laminating such layers.

[0097] In an organic EL device having an organic layer formed using the high molecular weight compound, the hole injection layer 3 and the hole transport layer 4 may be combined, and such a hole injection / transport layer may be formed by coating using a polymer material such as PEDOT.

[0098] In addition, for the hole transport layer 4 (as well as the hole injection layer 3), materials typically used for this layer can also be used that are P-doped with trisbromophenylaminehexachloroantimony and radialene derivatives (see, for example, WO2014 / 009310).The hole transport layer 4 (as well as the hole injection layer 3) can also be formed using a polymer compound having a TPD basic skeleton.

[0099] Furthermore, the electron blocking layer 12 (which can be provided between the hole transport layer 11 and the light-emitting layer 13 as shown in Figure 2) can also be formed by coating using the high molecular weight compound of the present invention by spin coating, inkjet, or the like.

[0100] In an organic EL device having an organic layer formed using the high-molecular-weight compound, the electron-blocking layer 12 can also be formed using a known electron-blocking compound having an electron-blocking effect, such as a carbazole derivative or a compound 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 4,4',4''-tri(N-carbazolyl)triphenylamine (hereafter abbreviated as TCTA); 9,9-bis[4-(carbazol-9-yl)phenyl]fluorene; 1,3-bis(carbazol-9-yl)benzene (hereafter abbreviated as mCP); 2,2-bis(4-carbazol-9-ylphenyl)adamantane (hereinafter abbreviated as Ad-Cz) Examples of compounds with a triarylamine structure 9-[4-(carbazol-9-yl)phenyl]-9-[4-(triphenylsilyl)phenyl]-9H-fluorene

[0101] The compounds used in the electron-blocking layer 12, including the high-molecular-weight compound of the present invention, may be used alone or in combination to form a film. Alternatively, multiple layers may be formed using one or more of the compounds, and the electron-blocking layer 12 may be a multilayer film formed by stacking such layers.

[0102] In an organic EL device having an organic layer formed using the above-described high molecular weight compound, the light-emitting layer 5 can be formed using light-emitting materials such as metal complexes of quinolinol derivatives such as Alq3, as well as various metal complexes of zinc, beryllium, and aluminum, anthracene derivatives, bisstyrylbenzene derivatives, pyrene derivatives, oxazole derivatives, and polyparaphenylenevinylene derivatives.

[0103] 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, and polydialkylfluorene derivatives can be used as the host material, and the high-molecular-weight compounds of the present invention described above can also be used. As the dopant material, quinacridone, coumarin, rubrene, perylene, and their derivatives, benzopyran derivatives, rhodamine derivatives, aminostyryl derivatives, and the like can be used.

[0104] The compounds used in the light-emitting layer 5, 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, one or more of the compounds may be used to form a plurality of layers, and the light-emitting layer 5 may be a multilayer film formed by laminating such layers.

[0105] Furthermore, the light-emitting layer 5 can be formed using a phosphorescent material as the light-emitting material. Examples of phosphorescent materials that can be used include phosphorescent emitters of metal complexes such as iridium and platinum. For example, green phosphorescent emitters such as Ir(ppy)3, blue phosphorescent emitters such as FIrpic and FIr6, and red phosphorescent emitters such as Btp2Ir(acac) can be used. These phosphorescent materials are used by doping into a hole-injecting / transporting host material or an electron-transporting host material.

[0106] 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.

[0107] It is also possible to use materials that emit delayed fluorescence, such as CDCB derivatives such as PIC-TRZ, CC2TA, PXZ-TRZ, and 4CzIPN, as light-emitting materials (see Appl. Phys. Let., 98, 083302 (2011)).

[0108] By forming the light-emitting layer 5 by carrying a fluorescent or phosphorescent light-emitting material, or a material that emits delayed fluorescence, which is called a dopant, on the high molecular weight compound, an organic EL element with reduced driving voltage and improved luminous efficiency can be realized.

[0109] In an organic EL device having an organic layer formed using the high-molecular-weight compound, 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.

[0110] In addition, in an organic EL device having an organic layer formed using the high molecular weight compound, p-bis(triphenylsilyl)benzene (hereinafter abbreviated as UGH2) and 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.

[0111] In an organic EL device having an organic layer formed using the above-described high-molecular-weight compound, a hole-blocking layer (not shown) provided between the light-emitting layer 5 and the electron-transporting layer 6 can be formed using a compound known per se having a hole-blocking effect. Examples of such known compounds having a hole-blocking effect include the following: phenanthroline derivatives such as bathocuproine (hereafter 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; Oxadiazole derivatives, etc.

[0112] 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 6.

[0113] The compounds used in the hole-blocking layer may be used alone or in combination of two or more. Alternatively, one or more of the compounds may be used to form multiple layers, and the hole-blocking layer may be a multilayer film formed by stacking such layers.

[0114] In an organic EL device having an organic layer formed using the high-molecular-weight compound, the electron transport layer 6 is formed using a known electron transport compound, such as a metal complex of a quinolinol derivative, such as Alq3 or BAlq, as well as various metal complexes, pyridine derivatives, pyrimidine derivatives, triazole derivatives, triazine derivatives, oxadiazole derivatives, thiadiazole derivatives, carbodiimide derivatives, quinoxaline derivatives, phenanthroline derivatives, silole derivatives, and benzimidazole derivatives.

[0115] The compounds used in the electron transport layer 6 may be used alone or in combination of two or more. Alternatively, one or more of the compounds may be used to form a plurality of layers, and a multilayer film formed by stacking such layers may be used as the hole blocking layer.

[0116] Furthermore, in an organic EL device having an organic layer formed using the above-mentioned high molecular weight compound, an electron injection layer (not shown) that is provided as needed can also be formed using a known material, 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.

[0117] For the cathode 7 of an organic EL device having an organic layer formed using the high molecular weight compound, 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.

[0118] As described above, by forming at least one of the hole injection layer, hole transport layer, light-emitting layer, and electron blocking layer 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, reduced driving voltage, improved current resistance, and improved maximum luminous brightness. [Example]

[0119] The present invention will be described below with reference to the following experimental examples, but the present invention is not limited to the following examples. In the following description, the structural unit represented by general formula (1) contained in the high molecular weight compound of the present invention is referred to as "structural unit A," the linking structural unit represented by general formula (4) is referred to as "structural unit B," the thermally crosslinkable structural unit is referred to as "structural unit C," and the structural unit consisting of a triarylamine other than general formula (1) is referred to as "structural unit D."

[0120] The synthesized compounds were purified by column chromatography and solvent crystallization, and identified by NMR analysis.

[0121] To produce high molecular weight compounds, the following intermediates 1 to 14 were synthesized.

[0122] <Synthesis of Intermediate 1>

[0123] [ka]

[0124] The following components were added to a reaction vessel whose atmosphere had been replaced with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes. Methyl 2-bromobenzoate: 25.0g Dibenzofuran-4-boronic acid: 27.1g Potassium carbonate: 32.1g Toluene: 200 mL Ethanol: 100 mL Water: 75mL Next, 1.3 g of tetrakistriphenylphosphine palladium(0) was added, and the mixture was heated and stirred at 78°C for 6 hours. After cooling to room temperature, water and toluene were added, and the organic layer was collected by separation. This organic layer was dehydrated with anhydrous sodium sulfate, purified by adsorption using 175 g of silica gel, and concentrated under reduced pressure to obtain 32.8 g (93.2% yield) of pale yellow oil, intermediate 1.

[0125] <Synthesis of intermediate 2>

[0126] [ka]

[0127] The following components were added to a reaction vessel purged with nitrogen and cooled to 0°C. Intermediate 1: 25.4g THF: 245 mL Next, 100 mL of a 2 M n-octylmagnesium bromide diethyl ether solution was slowly added dropwise, and the mixture was then warmed to room temperature. After stirring for a total of 27 hours, 10 wt % aqueous ammonium chloride solution and toluene 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 purified by column chromatography (n-hexane / chloroform) to obtain 11.4 g (28.3% yield) of Intermediate 2 as a white solid.

[0128] <Synthesis of intermediate 3>

[0129] [ka]

[0130] The following components were added to a reaction vessel purged with nitrogen and cooled to -65°C. Intermediate 2: 12.8g Dichloromethane: 130 mL Next, 4.0 g of boron trifluoride diethyl ether complex was added, and the mixture was slowly warmed to room temperature and stirred for a total of 8 hours. Saturated aqueous sodium bicarbonate solution was slowly 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 purified by column chromatography (n-hexane) to obtain 11.9 g of colorless oil, intermediate 3 (yield 96.4%).

[0131] <Synthesis of intermediate 4>

[0132] [ka]

[0133] The following components were added to a reaction vessel purged with nitrogen and cooled to 0°C. Intermediate 3: 11.8g Dichloromethane: 120 mL Next, 1.3 mL of bromine was added and the mixture was stirred for 7 hours. A 10 wt% aqueous solution of sodium thiosulfate was added, and the mixture was separated to collect the organic layer. This organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 13.1 g (95.3% yield) of a white solid, intermediate 4.

[0134] <Synthesis of Intermediate 5>

[0135] [ka]

[0136] The following components were added to a reaction vessel whose atmosphere had been replaced with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes. Intermediate 4: 12.9g Triphenylamine-4-boronic acid pinacol: 9.4g 2M potassium carbonate aqueous solution: 18mL Toluene: 57 mL Ethanol: 14 mL Next, 0.27 g of tetrakistriphenylphosphine palladium(0) was added, and the mixture was heated and stirred under reflux for 16 hours. After cooling to room temperature, water and toluene 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 purified by column chromatography (n-hexane / toluene) to obtain 17.8 g of colorless oil, intermediate 5 (yield 106%).

[0137] <Synthesis of intermediate 6>

[0138] [ka]

[0139] The following ingredients were added to a nitrogen-purged reaction vessel: Intermediate 5: 16.0g THF: 160 mL Next, 7.9 mg of N-bromosuccinimide was added and the mixture was stirred for 10 hours. Water and toluene were added, and the mixture was separated to collect the organic layer. This organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 20.9 g (107% yield) of colorless oil, intermediate 6.

[0140] <Synthesis of intermediate 7>

[0141] [ka]

[0142] The following components were added to a reaction vessel whose atmosphere had been replaced with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes. Intermediate 6: 19.4g Bis(pinacolato)diboron: 12.3g Potassium acetate: 6.5g 1,4-dioxane: 200 mL Next, 0.36 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 6 hours. After cooling to room temperature, water and toluene 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 purified by column chromatography (toluene) to obtain 10.7 g (49.1% yield) of white powder of intermediate 7.

[0143] <Synthesis of intermediate 8>

[0144] [ka]

[0145] The following components were added to a reaction vessel whose atmosphere had been replaced with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes. N,N-bis(4-bromophenyl)-N-(benzocyclobuten-4-yl)-amine: 8.0 g Bis(pinacolato)diboron: 9.9g Potassium acetate: 4.6g 1,4-dioxane: 80 mL Next, 0.3 g of the dichloromethane adduct of [1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloride was added, 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 collected by separation. 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 toluene / methanol = 1 / 2 to obtain 3.4 g (35% yield) of a white powder of Intermediate 2.

[0146] <Synthesis of Intermediate 9>

[0147] [ka]

[0148] The following components were added to a reaction vessel purged with nitrogen and cooled on ice. Cerium(III) chloride: 118.9g THF: 500 mL Next, 482 mL of a 1 M n-hexylmagnesium bromide THF solution was slowly added dropwise, followed by stirring for 1 hour. Intermediate 1 dissolved in 200 mL of THF was then slowly added dropwise, and the mixture was allowed to warm to room temperature. After stirring for 2 hours at room temperature, 10 wt% aqueous ammonium chloride solution and toluene were added, and the mixture was separated to collect the organic layer. This organic layer was dehydrated over anhydrous sodium sulfate and then concentrated under reduced pressure to obtain a crude product. The crude product was washed with methanol to obtain 54.5 g (76.6% yield) of a white solid, Intermediate 9.

[0149] <Synthesis of Intermediate 10>

[0150] [ka]

[0151] The following components were added to a reaction vessel purged with nitrogen and cooled to -65°C. Intermediate 9: 63.6g Dichloromethane: 640 mL Next, 22.6 g of boron trifluoride diethyl ether complex was added, and the mixture was slowly warmed to room temperature and stirred for a total of 13 hours. Saturated aqueous sodium bicarbonate solution was slowly 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 acetonitrile to obtain 56.6 g (92.8% yield) of a white solid, intermediate 10.

[0152] <Synthesis of intermediate 11>

[0153] [ka]

[0154] The following components were added to a reaction vessel purged with nitrogen and cooled to 0°C. Intermediate 10: 56.6g Dichloromethane: 560 mL Next, 7.2 mL of bromine was added and the mixture was stirred for 3 hours. A 10 wt % aqueous solution of sodium thiosulfate was added, and the mixture was separated to collect the organic layer. This organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 72.4 g (108.3% yield) of a pale yellow oil, Intermediate 11.

[0155] <Synthesis of intermediate 12>

[0156] [ka]

[0157] The following components were added to a reaction vessel whose atmosphere had been replaced with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes. Intermediate 11: 26.0g Triphenylamine-4-boronic acid pinacol: 22.1g 2M potassium carbonate aqueous solution: 40mL Toluene: 115 mL Ethanol: 28 mL Next, 0.60 g of tetrakistriphenylphosphine palladium(0) was added, and the mixture was heated and stirred under reflux for 23 hours. After cooling to room temperature, water and toluene 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 purified by column chromatography (n-hexane) to obtain 25.2 g (73.0% yield) of colorless oil, intermediate 12.

[0158] <Synthesis of intermediate 13>

[0159] [ka]

[0160] The following ingredients were added to a nitrogen-purged reaction vessel: Intermediate 12: 32.1g THF: 325 mL Next, 17.5 g of N-bromosuccinimide was added and the mixture was stirred at room temperature for 12 hours. Water and toluene were added, and the mixture was separated to collect the organic layer. This organic layer was dehydrated with anhydrous sodium sulfate and then concentrated under reduced pressure to obtain 41.7 g of a pale yellow oil, intermediate 13 (yield 105%).

[0161] <Synthesis of intermediate 14>

[0162] [ka]

[0163] The following components were added to a reaction vessel whose atmosphere had been replaced with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes. Intermediate 13: 41.0g Bis(pinacolato)diboron: 26.9g Potassium acetate: 14.2g 1,4-dioxane: 400 mL Next, 0.78 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 10 hours. After cooling to room temperature, water and toluene 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 purified by column chromatography (toluene) to obtain 13.8 g (31.2% yield) of a white solid, intermediate 14.

[0164] Example 1 (Synthesis of high molecular weight compound A) The following components were added to a reaction vessel whose atmosphere had been replaced with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes. Intermediate 7: 5.0g 1,3-dibromobenzene: 1.5g Intermediate 8: 0.7g Tripotassium phosphate: 5.7g Toluene: 9 mL Water: 5mL 1,4-dioxane: 27 mL Next, 1.2 mg of palladium(II) acetate and 9.5 mg of tri-o-tolylphosphine were added, heated, and stirred at 82°C for 11 hours. After this, 15 mg of phenylboronic acid was added and stirred for 1.5 hours, followed by 200 mg of bromobenzene and stirring for 1.5 hours. 50 mL of toluene and 50 mL of a 5 wt% aqueous solution of sodium N,N-diethyldithiocarbamate were added, heated, and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was separated and washed three times with saturated brine. The organic layer was dehydrated over anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, silica gel was added, and the mixture was purified by adsorption. The silica gel was removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dry residue was dissolved in 100 mL of toluene. The solution was added dropwise to 300 mL of n-hexane, and the resulting precipitate was collected by filtration. This procedure was repeated three times, and the mixture was dried to obtain 3.5 g of high molecular weight compound A (yield 77%).

[0165] The average molecular weight and dispersity of polymer compound A measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 30,000 Weight average molecular weight Mw (polystyrene equivalent): 52,000 Dispersity (Mw / Mn): 1.7

[0166] Furthermore, polymer compound A was subjected to NMR measurement. 1 The results of H-NMR measurement are shown in Figure 3. The chemical formula was as follows:

[0167] [ka]

[0168] As can be seen from the chemical composition, this polymer compound A contained 40 mol % of the structural unit A represented by general formula (1), 50 mol % of the structural unit B represented by general formula (4), and 10 mol % of the thermally crosslinkable structural unit C.

[0169] <Example 2> (Synthesis of high molecular weight compound B) The following components were added to a reaction vessel whose atmosphere had been replaced with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes. Intermediate 14: 6.4g 1,3-dibromobenzene: 1.8g Intermediate 8: 0.4g Tripotassium phosphate: 6.9g Toluene: 9 mL Water: 5mL 1,4-dioxane: 27 mL

[0170] Next, 1.5 mg of palladium(II) acetate and 11.4 mg of tri-o-tolylphosphine were added, heated, and stirred at 82°C for 19 hours. After this, 18 mg of phenylboronic acid was added and stirred for 2 hours, followed by 243 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, heated, and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was separated and washed three times with saturated brine. The organic layer was dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, silica gel was added, and the mixture was purified by adsorption. The silica gel was removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 mL of toluene. This 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 5.0 g of high molecular weight compound B (yield 91%).

[0171] The average molecular weight and dispersity of polymer compound B measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 22,000 Weight average molecular weight Mw (polystyrene equivalent): 37,000 Dispersity (Mw / Mn): 1.7

[0172] Furthermore, NMR measurement was carried out on polymer compound B. 1 The results of H-NMR measurement are shown in Figure 4. The chemical formula was as follows:

[0173] [ka]

[0174] As can be seen from the chemical composition, this polymer compound B contained 45 mol % of the structural unit A represented by general formula (1), 50 mol % of the structural unit B represented by general formula (4), and 5 mol % of the thermally crosslinkable structural unit C.

[0175] Example 3 (Synthesis of high molecular weight compound C) The following components were added to a reaction vessel whose atmosphere had been replaced with nitrogen, and nitrogen gas was bubbled through the vessel for 30 minutes. Intermediate 14: 4.1g [p-(2-naphthyl)phenyl]bis[p-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]amine: 1.4g 1,3-dibromobenzene: 1.7g Intermediate 8: 0.4g Tripotassium phosphate: 6.5g Toluene: 9 mL Water: 5mL 1,4-dioxane: 27 mL Next, 1.4 mg of palladium(II) acetate and 10.6 mg of tri-o-tolylphosphine were added, heated, and stirred at 82°C for 21 hours. After this, 17 mg of phenylboronic acid was added and stirred for 2 hours, followed by 243 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, heated, and stirred under reflux for 2 hours. After cooling to room temperature, the organic layer was separated and washed three times with saturated brine. The organic layer was dehydrated with anhydrous sodium sulfate and concentrated under reduced pressure to obtain a crude polymer. The crude polymer was dissolved in toluene, silica gel was added, and the mixture was purified by adsorption. The silica gel was removed by filtration. The resulting filtrate was concentrated under reduced pressure, and the dried product was dissolved in 100 mL of toluene. This 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 3.8 g of high molecular weight compound C (84% yield).

[0176] The average molecular weight and dispersity of polymer compound C measured by GPC were as follows: Number average molecular weight Mn (polystyrene equivalent): 17,000 Weight average molecular weight Mw (polystyrene equivalent): 35,000 Dispersity (Mw / Mn): 2.1

[0177] Furthermore, NMR measurements were carried out on polymer compound C. 1 The results of H-NMR measurement are shown in Figure 5. The chemical formula was as follows:

[0178] [ka]

[0179] As can be seen from the chemical composition, this polymer compound C contained 30 mol % of structural units A represented by general formula (1), 50 mol % of structural units B represented by general formula (4), 5 mol % of thermally crosslinkable structural units C, and 15 mol % of structural units D consisting of a triarylamine other than general formula (1).

[0180] Example 4 (Work function measurement) Using the high molecular weight compounds A to C synthesized in Examples 1 to 3, coating films with a thickness of 100 nm were formed on ITO substrates, and the work functions were measured using an ionization potential measurement device (PYS-202 model, manufactured by Sumitomo Heavy Industries, Ltd.). The results are shown in Table 1.

[0181] [Table 1]

[0182] It is clear that the high molecular weight compounds A to C of the present invention exhibit a suitable energy level compared to the work function of 5.4 eV of common hole transport materials such as NPD and TPD, and have good hole transport ability.

[0183] <Example 5> (Fabrication and evaluation of organic EL devices) An organic EL device having the layer structure shown in Figure 1 was fabricated and its characteristics were evaluated. Specifically, a glass substrate 1 on which a 50-nm-thick ITO film was formed was washed with an organic solvent, and then the ITO surface was cleaned by UV / ozone treatment. A 50-nm-thick film of PEDOT / PSS (manufactured by HERAEUS) was formed by spin coating to cover the transparent anode 2 (ITO) provided on the glass substrate 1, and dried on a hot plate at 200°C for 10 minutes to form a hole injection layer 3.

[0184] A coating solution was prepared by dissolving 0.6 wt % of the high molecular weight compound A obtained in Example 1 in toluene. The substrate on which the hole injection layer 3 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 onto 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.

[0185] 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.

[0186] [ka]

[0187] As electron transport materials, compounds ETM-1 and ETM-2 having the following structural formulas were prepared.

[0188] [ka]

[0189] On the light-emitting layer 5 formed above, an electron-transporting layer 6 having a thickness of 20 nm was formed by binary deposition using the electron-transporting materials ETM-1 and ETM-2. In the binary deposition, the deposition rate ratio was ETM-1:ETM-2=50:50.

[0190] Finally, aluminum was evaporated to a thickness of 100 nm to form a cathode 7 . The glass substrate having the transparent anode 2, the hole injection layer 3, the hole transport layer 4, the light-emitting layer 5, the electron transport layer 6, and the cathode 7 formed thereon was moved into a glove box purged with dry nitrogen, and another glass substrate for sealing was attached thereto using a UV-curable resin, thereby completing an organic EL device. The characteristics of the fabricated organic EL device were measured in air at room temperature. Furthermore, the light-emitting characteristics were measured when a DC voltage was applied to the fabricated organic EL device. The results of the measurements are shown in Table 2.

[0191] Example 6 An organic EL device was fabricated in the same manner as in Example 5, except that the hole transport layer 4 was formed using a coating liquid prepared by dissolving 0.6 wt % of the high molecular weight compound B obtained in Example 2 in toluene instead of the high molecular weight compound A. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 5, and the results are shown in Table 2.

[0192] Example 7 An organic EL device was fabricated in the same manner as in Example 5, except that the hole transport layer 4 was formed using a coating liquid prepared by dissolving 0.6 wt % of the high molecular weight compound C obtained in Example 3 in toluene instead of the high molecular weight compound A. The various properties of the fabricated organic EL device were evaluated in the same manner as in Example 5, and the results are shown in Table 2.

[0193] <Comparative Example 1> An organic EL device was fabricated in the same manner as in Example 5, 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 A.

[0194] [ka]

[0195] The TFB (hole transport polymer) was poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N-(4-sec-butylphenyl))diphenylamine] (Hole Transport Polymer ADS259BE, manufactured by American Dye Source). The organic EL device of Comparative Example 1 was evaluated for various characteristics in the same manner as in Example 5, and the results are shown in Table 2.

[0196] In evaluating various characteristics, 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 / m2 The time it took for the brightness to decay to 80% (equivalent to 80% of the initial brightness of 100%) was measured.

[0197] [Table 2]

[0198] As shown in Table 2, a current density of 10 mA / cm 2 The luminous efficiency when a current of 100 kJ / s was passed through the organic EL element of Example 5 was 9.74 cd / A, the organic EL element of Example 6 was 9.57 cd / A, and the organic EL element of Example 7 was 9.37 cd / A, all of which were high efficiencies, compared to 5.52 cd / A for the organic EL element of Comparative Example 1. Furthermore, the element lifetime (at 80% decay) was 13 hours for the organic EL element of Example 5, 35 hours for the organic EL element of Example 6, and 38 hours for the organic EL element of Example 7, all of which were long lifetimes, compared to 6 hours for the organic EL element of Comparative Example 1.

[0199] Example 8 An organic EL device having the layer structure shown in Figure 2 was fabricated and its characteristics were evaluated. Specifically, a glass substrate 8 on which a 50 nm thick ITO film was formed was washed with an organic solvent, and then the ITO surface was cleaned by UV / ozone treatment. A 50 nm thick PEDOT / PSS (manufactured by HERAEUS) film was formed by spin coating so as to cover the transparent anode 9 (ITO) provided on this glass substrate 8, and dried on a hot plate at 200°C for 10 minutes to form a hole injection layer 10.

[0200] 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. The coating solution was then spin-coated onto the hole injection layer 10 to form a 15-nm-thick coating layer, which was then further dried on a hot plate at 220°C for 30 minutes to form a hole transport layer 11.

[0201] [ka]

[0202] A coating solution was prepared by dissolving 0.4 wt % of the high molecular weight compound A obtained in Example 1 in toluene. The coating solution was spin-coated onto the hole transport layer 11 to form a coating layer with a thickness of 15 nm, and the resulting layer was dried on a hot plate at 220°C for 30 minutes to form an electron blocking layer 12.

[0203] 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.

[0204] On the light-emitting layer 13 thus formed, an electron-transporting layer 14 having a thickness of 20 nm was formed by binary deposition using electron-transporting materials ETM-1 and ETM-2. In the binary deposition, the deposition rate ratio of ETM-1:ETM-2 was set to 50:50.

[0205] Finally, aluminum was evaporated to a thickness of 100 nm to form a cathode 15 . The glass substrate having 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 formed thereon was transferred 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.

[0206] Example 9 An organic EL device was fabricated in exactly the same manner as in Example 8, except that the electron-blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt % of the high-molecular-weight compound B obtained in Example 2 in toluene instead of the high-molecular-weight compound A. The characteristics of the fabricated organic EL device were measured in the atmosphere at room temperature. The measurement results of the light-emitting characteristics when a DC voltage was applied to the fabricated organic EL device are summarized in Table 3.

[0207] Example 10 An organic EL device was fabricated in exactly the same manner as in Example 8, except that the electron-blocking layer 12 was formed using a coating solution prepared by dissolving 0.4 wt % of the high-molecular-weight compound C obtained in Example 3 in toluene instead of the high-molecular-weight compound A. The characteristics of the fabricated organic EL device were measured in the atmosphere at room temperature. The measurement results of the light-emitting characteristics when a DC voltage was applied to the fabricated organic EL device are summarized in Table 3.

[0208] <Comparative Example 2> An organic EL device having the layer structure shown in Figure 1 was fabricated and its characteristics were evaluated. Specifically, a glass substrate 1 on which a 50-nm-thick ITO film was formed was washed with an organic solvent, and then the ITO surface was cleaned by UV / ozone treatment. A 50-nm-thick film of PEDOT / PSS (manufactured by HERAEUS) was formed by spin coating to cover the transparent anode 2 (ITO) provided on the glass substrate 1, and dried on a hot plate at 200°C for 10 minutes to form a hole injection layer 3.

[0209] A coating solution was prepared by dissolving 0.6 wt % of the high molecular weight compound HTM-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 the coating solution was spin-coated onto the hole injection layer 3 to form a coating layer with a thickness of 25 nm. This was then dried on a hot plate at 220°C for 30 minutes to form a hole transport layer 4.

[0210] 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. An emitting layer 5 having a thickness of 34 nm was formed on the hole transport layer 4 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.

[0211] An electron transport layer 6 having a thickness of 20 nm was formed on the light-emitting layer 5 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.

[0212] Finally, aluminum was evaporated to a thickness of 100 nm to form a cathode 7 . The glass substrate having the transparent anode 2, hole injection layer 3, hole transport layer 4, light-emitting layer 5, electron transport layer 6, and cathode 7 formed thereon was transferred 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 air 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.

[0213] In evaluating various characteristics, 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 it took for the brightness to decay to 80% (equivalent to 80% of the initial brightness of 100%) was measured.

[0214] [Table 3]

[0215] As shown in Table 3, a current density of 10 mA / cm 2The luminous efficiency when a current of 100 kJ / s was passed through the organic EL element of Example 8 was 9.30 cd / A, the organic EL element of Example 9 was 8.88 cd / A, and the organic EL element of Example 10 was 8.55 cd / A, all of which were high efficiencies, compared to 7.56 cd / A for the organic EL element of Comparative Example 2. Furthermore, the element lifetime (at 80% decay) was 20 hours for the organic EL element of Comparative Example 2, and was 41 hours for the organic EL element of Example 8, 73 hours for the organic EL element of Example 9, and 63 hours for the organic EL element of Example 10, all of which were long lifetimes.

[0216] As described above, it was found that an organic EL device having an organic layer formed using the high molecular weight compound of the present invention can realize an organic EL device with higher luminous efficiency and longer life compared to conventional organic EL devices. [Industrial Applicability]

[0217] The high molecular weight compound of the present invention has high hole transport capability, excellent electron blocking capability, and good thermal crosslinkability, 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. This allows for a wide range of applications, such as in home appliances and lighting. [Explanation of symbols]

[0218] 1, 8... Glass substrate 2, 9...Transparent anode 3, 10...Hole injection layer 4, 11···Hole transport layer 5, 13···Emitting layer 6, 14...electron transport layer 7, 15... cathode 12...Electron blocking layer

Claims

1. A high molecular weight compound containing, as a repeating unit, a triarylamine structural unit having an indenodibenzoheterole structure represented by the following general formula (1) as a partial structure: 【Chemistry 1】 (In the formula, R １ and R ２ each independently represent a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, or a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, X represents an oxygen atom or a sulfur atom; R ３ ~R １１ each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; R １２ and R １６ each independently represents a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, or a substituted or unsubstituted aryloxy group; R １２ and R １６ may be bonded to each other via a single bond, an optionally substituted methylene group, an oxygen atom or a sulfur atom, R １３ ~R １５ , R １７ ~R １９ each independently represents a hydrogen atom or a deuterium atom, L represents a substituted or unsubstituted arylene group having 5 to 40 carbon atoms; n represents an integer of 0 to 3.

2. The high molecular weight compound according to claim 1, comprising a repeating unit represented by the following general formula (2): 【Chemistry 2】 (In the formula, R １ ~R １９ , X, L, and n are the same as in general formula (1), R ２０ ~R ２２ each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, or a substituted or unsubstituted aryloxy group, Y represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted amino group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; m and p represent mole fractions; m is 0.1 to 0.9, p represents a value of 0.1 to 0.

9.

3. 3. The high molecular weight compound according to claim 1, wherein X is an oxygen atom.

4. R １２ ~R １９ The high molecular weight compound according to any one of claims 1 to 3, wherein is a hydrogen atom.

5. R ３ ~R １１ The high molecular weight compound according to any one of claims 1 to 4, wherein is a hydrogen atom.

6. R ３ ~R ２２ The high molecular weight compound according to any one of claims 2 to 5, wherein is a hydrogen atom.

7. 7. The high molecular weight compound according to claim 2, wherein Y 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.

8. R １ and R ２ and each independently represent an alkyl group, an alkyloxy group, or a polyether group.

9. The high molecular weight compound according to any one of claims 1 to 8, which contains a thermally crosslinkable structural unit as a repeating unit.

10. The high molecular weight compound according to claim 9, wherein the pre-thermally crosslinkable structural unit is one or more thermally crosslinkable structural units selected from the group consisting of the following general formulae (3aa) to (3bd): 【Transformation 3】 【Chemistry 4】 (In the formula, R's each independently represent a hydrogen atom, a deuterium atom, a cyano group, a nitro group, a halogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted polyether group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 40 carbon atoms, a substituted or unsubstituted alkyloxy group having 1 to 40 carbon atoms, a substituted or unsubstituted cycloalkyloxy group having 3 to 40 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 40 carbon atoms, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group; The wavy line indicates cis or trans. The dotted line indicates the bond to the main chain; a represents an integer of 0 to 4; b represents an integer of 0 to 3.

11. An organic electroluminescence element having a pair of electrodes and at least one organic layer sandwiched between them, wherein the organic layer comprises the high molecular weight compound according to any one of claims 1 to 10.

12. The organic electroluminescence device according to claim 11 , wherein the organic layer is a hole transport layer.

13. 12. The organic electroluminescent device according to claim 11, wherein the organic layer is an electron blocking layer.

14. The organic electroluminescence device according to claim 11 , wherein the organic layer is a hole injection layer.

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

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