Organic film forming material, organic film forming composition, method for manufacturing organic film, organic semiconductor element, organic electroluminescent element, organic el display, and organic el lighting

Abstract

To provide an organic electroluminescent element with high luminous efficiency and long driving lifetime, comprising an organic film forming material with high hole injection transport capability and high durability, and a hole transport layer containing the organic film forming material.SOLUTION: An organic film forming material contains polymer 1 containing a repeating unit represented by formula (50) and polymer 2 containing a repeating unit represented by formula (40), and the polymer 1 does not contain the repeating unit represented by formula (40).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a material for forming an organic film, and more particularly to an organic semiconductor and an organic electroluminescent element. Organic film-forming material useful as a charge transport material, and organic film-forming composition containing said material - Patents.com a method for producing an organic film formed using the composition; and a method for producing an organic film having an organic layer containing an organic film-forming material. The present invention relates to an organic semiconductor element and an organic electroluminescent element. [Background technology]

[0002] The organic layers of organic electroluminescent devices can be formed by vacuum deposition and wet deposition. The vacuum deposition method is easy to laminate, and therefore, it is possible to improve the charge injection from the anode and / or cathode. On the other hand, the wet film formation method has the advantage that it is easy to confine excitons in the light-emitting layer. No pre-processing is required, large areas can be easily produced, and multiple materials with various functions can be mixed and coated. By using a liquid, it is possible to easily form a layer containing multiple materials with various functions. This has the advantage of being able to However, since the wet film formation method is difficult to laminate, it is difficult to achieve a high-performance element compared to elements formed by vacuum deposition. The current situation is that they have poor driving stability and, with a few exceptions, are not yet at a practical level.

[0003] Therefore, in order to perform lamination by a wet film formation method, a charge transport polymer having a crosslinkable group is used. For example, Patent Documents 1 to 3 disclose specific repeating The organic electroluminescent device contains a polymer having a methyl group unit and is laminated by a wet film formation method. It has been disclosed.

[0004] In Patent Documents 4 and 5, a fluorene ring or a carbazole ring and a substituent are added to the main chain of a polymer. A hole injection / transport material having a structure in which a phenylene ring is bonded without any aryl group is disclosed.

[0005] In Patent Document 6, a polymer having a triarylamine repeating unit is described, in which the main chain It is described that it is preferable that the polymer contains a fluorene ring, and further, the polymer main chain contains a substituted The inclusion of a phenylene group with a group generates a twist, increasing the triplet energy of the polymer. It is stated that it should be added. In Patent Document 7, a compound is described in which a hydroxyl group is bonded between nitrogen atoms of the main chain amine of an arylamine polymer or oligomer. The present invention discloses a compound in which a phenylene group having a substituent is linked. In Patent Document 8, an arylamine polymer or oligomer having a polymerizable substituent is used. Furthermore, it is disclosed that a mixed layer containing a polymer or oligomer is used as a hole transport layer. It has been found that the thermal stability of the layer can be improved by polymerizing The effect described is that the polymerized layer does not dissolve when a light-emitting layer is applied thereon.

[0006] Patent documents 9 to 12 describe polymers having an arylamine structure with a carbazoline structure in the side chain structure. Patent documents 9 to 11 disclose polymers having a carbazole side chain structure. In Patent Documents 9 and 12, the carbazole in the side chain structure is directly attached to the main chain. The compound in Patent Document 12 has two carbazoles in the side chain structure. A structure is disclosed.

[0007] Patent Document 13 describes a compound having a twisted bond structure in a main chain having an arylamine structure, and a side chain A polymer with enhanced durability of carbazole structure is disclosed.

[0008] Patent documents 5, 8 to 11, 14 to 18 disclose polymers having a carbazole structure in the main chain. The carbazole skeleton has a deeper ionization potential than the aromatic amine skeleton. Patent documents 5 and 8 to 11 show a carbazole bonded to a position other than the 9-position. Patent Document 14 discloses a structure having two carbazoles connected to the main chain at the 3-position. Patent Document 16 describes a structure having one carbazole connected to the main chain at the 9-position. References 15 and 17 disclose structures having two carbazoles connected to the main chain at the 9-position. It has been done. Patent Document 18 describes a dicarbazone bonded to the main chain at the 9-position as part of a material for forming a light-emitting layer. The polymer containing dicarbazole was added with a low molecular weight dicarbazole compound, and the transport between the polymer chains was investigated. Methods for supplementing transport with small molecules have been disclosed. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] International Publication No. 2009 / 123269 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-045986 [Patent Document 3] International Publication No. 2013 / 191088 [Patent Document 4] Japanese Patent Application Laid-Open No. 2016-084370 [Patent Document 5] Japanese Patent Application Publication No. 2017-002287 [Patent Document 6] Special Publication No. 2007-520858 [Patent Document 7] Special Publication No. 2013-531658 [Patent Document 8] Japanese Patent Application Laid-Open No. 2010-034496 [Patent Document 9] International Publication No. 2011 / 099531 [Patent Document 10] International Publication No. 2016 / 031639 [Patent Document 11] International Publication No. 2009 / 110360 [Patent Document 12] International Publication No. 2008 / 126393 [Patent Document 13] International Publication No. 2019 / 177175 [Patent Document 14] Japanese Patent Application Laid-Open No. 2003-012777 [Patent Document 15] Japanese Patent Application Laid-Open No. 2013-216789 [Patent Document 16] Japanese Patent Application Laid-Open No. 2018-104675 [Patent Document 17] Japanese Patent Application Laid-Open No. 2011-144375 [Patent Document 18] Patent Publication No. 2021-061316 Summary of the Invention [Problem to be solved by the invention]

[0010] However, through investigations by the present inventors, the techniques disclosed in the above Patent Documents 1 to 17 are as follows: It was found that each of them has the following problems. The organic electroluminescent devices described in Patent Documents 1 to 3 have problems such as low brightness and short driving life. Therefore, there is a demand for improvement in the charge injection and transport properties and durability of charge transport materials.

[0011] The polymers described in Patent Documents 4 and 5 have a π-conjugated system in the main chain, and therefore, are single-excited. The single-state energy level (S1) and the excited triplet energy level (T1) are low, making them suitable for use as luminescent materials. There is a problem that quenching occurs due to energy transfer from photoexcitons, resulting in a decrease in luminescence efficiency. Therefore, charge transport materials with high S1 and T1 levels are required.

[0012] Patent Document 6 lists F as an example of an arylamine polymer containing a fluorene ring in the main chain. Although 8-TFB (fluorene + triphenylamine system) is described, F8-TF B is not twisted because the phenylene between the nitrogen atom of the fluorene and the amine has no substituent. In addition, the LUMO extends to the vicinity of the nitrogen atom of the amine, which causes poor electron durability. There is. The compound disclosed in Patent Document 7 has a fluorene ring or a carbazole structure in the main chain. Since it does not contain silicon, there is a problem of poor electronic durability. Patent Document 8 describes an arylamine having a fluorenyl group or a carbazole group in the main chain. Although polymers or oligomers are disclosed, the durability of organic electroluminescent devices to which these materials are applied is unclear. The sex was insufficient.

[0013] In addition, the polymers disclosed in Patent Documents 9 to 12 have carbazole in the side chain. However, since the two carbazoles are not connected via a linking group between their nitrogen atoms, As will be described later, the durability of the organic electroluminescent device using this material was insufficient. The polymer disclosed in Patent Document 13 has excellent durability and charge transport properties, but it emits green light. The luminous efficiency of the device and the blue light-emitting device was insufficient.

[0014] The polymers disclosed in Patent Documents 5, 8 to 11 and 14 have a π-conjugated structure in the main chain. In order to have an excited singlet energy level (S1) and an excited triplet energy level (T1 ) is low, and there is a risk that the luminous efficiency of an organic electroluminescent device using this material will be low.

[0015] The polymers disclosed in Patent Documents 15 to 17 are large because they are connected to the main chain at the 9-position. The excited singlet energy level (S1) and excited triplet energy level (T1) are shown. However, the ionization potential of the thin film is equivalent to that of a material with carbazole only in the side chain. On the other hand, the hole transport performance is inferior to that of a material having carbazole only in the side chain. The organic electroluminescent device used in this case requires a high driving voltage and may have a short driving life.

[0016] In addition, the low molecular weight polymer mixture disclosed in Patent Document 18 has a hole transport distance of 100 nm. This is effective for the light-emitting layer, where the exciton absorption by the light-emitting material suppresses deterioration. In addition, low molecular weight materials are easily eluted by immersion in a solvent, and low molecular weight polymers are not suitable for use as a transport layer. It is difficult to insolubilize a layer formed from a molecular mixture. For this reason, coating methods are used for subsequent laminations. If this mixture was used, it might not be possible to use it.

[0017] Therefore, the present invention provides a material for forming an organic film having high hole injection and transport ability and high durability, and Another object of the present invention is to provide a composition for forming an organic film, which comprises: The present invention aims to provide an organic electroluminescent device that is stable and has a long driving life. [Means for solving the problem]

[0018] The arylamine repeating unit with a carbazole side chain (structure) as shown in Patent Document 13 High durability and low driving current of organic electroluminescent devices obtained by polymers of the type A and a carbazole bonded to the main chain at the 9-position, as shown in Patent Documents 15 to 17. High efficiency organic electroluminescent devices obtained by polymers with repeating units (referred to as Structure B type) In order to simultaneously obtain these, several methods were tried.

[0019] When a polymer containing both structure A and structure B was synthesized, the charge transport property was higher than that of structure B. The luminous efficiency was close to that of the structure A type. A method of mixing a polymer of structure A and a polymer of structure B to form a film as one layer is also available. Generally, the smaller S1 and T1 become the relaxation paths for excitons, so the effect of the B-type structure cannot be obtained. It was estimated that high efficiency could not be expected.

[0020] In addition, an organic layer made of a polymer containing structure A species is placed on the anode side, and an organic layer made of a polymer containing structure B species is placed on the cathode side. The organic layer was placed on the light-emitting layer side to form a laminated structure element. The driving voltage of the device increases depending on the layer thickness of the B-type structure, showing the influence of the low charge transport property of the B-type structure. It was suggested that the voltage can be kept low by thinning the layer thickness of Structure B type. The solvent resistance of the thin film deteriorates in proportion to the amount of reduction in the film thickness. When forming the film by this method, the underlayer cannot be made sufficiently insoluble, the device characteristics become unstable, and mass production becomes difficult. is also thought to have a negative impact.

[0021] As a result of extensive investigation, the present inventors have discovered a specific compound containing a carbazole skeleton connected to the main chain at the 9-position. a polymer having a specific repeating unit and a polymer not having the repeating unit and having a specific aromatic amine structure; The above problem can be solved by using a material in which a polymer having a specific repeating unit containing The present invention has been completed based on the discovery that the above problem can be solved.

[0022] That is, the gist of the present invention is as follows [1] to

[21] . [1] A polymer 1 having a repeating unit represented by the following formula (50) and a polymer 2 having a repeating unit represented by the following formula (40) and polymer 2 containing a repeating unit represented by the formula (I), The polymer 1 is an organic film-forming material that does not contain a repeating unit represented by the following formula (40): Fee.

[0023] [ka]

[0024] (In formula (50), Ar 51 is an aromatic hydrocarbon group which may have a substituent and a substituted a group to which one or more groups selected from the group consisting of aromatic heterocyclic groups are linked, Ar 52 is a divalent aromatic hydrocarbon group which may have a substituent and and a divalent aromatic heterocyclic group, The linkage is made directly or via a linking group. Ar 51 and Ar 52 may be bonded directly or via a linking group to form a ring.

[0025] [ka]

[0026] (In formula (40), Ar 1 and Ar 2 each independently represents a divalent aromatic hydrocarbon which may have a substituent. a divalent aromatic heterocyclic group optionally having a substituent, and a divalent aromatic heterocyclic group optionally having a substituent; represents a divalent group to which a group or a plurality of groups are linked, and the linkage is made directly or via a linking group. There are. R 1 ~R 18 each independently represents a direct bond, a hydrogen atom, a deuterium atom, a halogen atom, or a substituted It represents an aromatic ring group which may have one or more groups, and a group formed by linking 2 to 8 such aromatic rings. p and q each independently represent an integer of 0 to 1, and p+q is 1 or more. Ar 3 is Ar in the formula (50). 51 is the same as: r represents an integer of 0 to 1. G is a direct bond, a divalent aromatic ring group which may have a substituent, or the aromatic ring is bonded to a ring having 2 to 1 carbon atoms. It represents a divalent group formed by linking four groups. s and t each independently represent an integer of 0 to 1. However, this does not apply when s is 0, t is 1, p is 0, and r is 1. R 1 ~R 8 and R 9 are respectively, Ar 1 , N-Ar 3 Nitrogen atom of , G, R 10 ~R 18 One of Ar 2 or directly bonded to the main chain of polymer 2 , R 10 ~R 17 and R 18 One of them is G or R 1 ~R 9 of One is directly bonded to the other, and the other is bonded to Ar 2 or directly bonded to the main chain of polymer 2 (I'm doing it.)

[0027] [2] Ar in the formula (50) 52 has a divalent aromatic hydrocarbon group and a substituent a divalent group in which a plurality of groups selected from the group consisting of divalent aromatic heterocyclic groups, There is, said Ar 52 The compound contains a structure in which a plurality of benzene ring structures are linked at para positions, At least one of the benzene ring structures has a carbon atom bonded to an adjacent benzene ring structure. The compound according to [1], wherein at least one of two adjacent carbon atoms has a substituent. Mechanical film forming material. [3] The repeating unit represented by the formula (50) is represented by the following formula (54), the following formula (55), Or the organic film-type according to [1] or [2], which is a repeating unit represented by the following formula (57): material for construction.

[0028] [ka]

[0029] (In formula (54), Ar 51 is Ar in the formula (50). 51 is the same as X is -C(R 207 )(R 208 )-, -N(R 209 )- or -C(R 211 )( R 212 )-C(R 213 )(R 214 )- and R 201 , R 202 , R 221 and R 222 may each independently have a substituent. It is a good alkyl group, R 207 ~R 209 and R 211 ~R 214 are each independently a hydrogen atom, a group having a substituent, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted an aromatic hydrocarbon group which may be optionally substituted, a and b each independently represent an integer of 0 to 4; c is an integer from 0 to 3, d is an integer from 0 to 4, R201 If there are multiple R 201 may be the same or different, R 202 If there are multiple R 202 may be the same or different, R 221 If there are multiple R 221 may be the same or different, R 222 If there are multiple R 222 may be the same or different, i and j are each independently an integer of 0 to 3.

[0030] [ka]

[0031] (In formula (55), Ar 51 is Ar in the formula (50). 51 is the same as R 303 and R 306 are each independently an alkyl group which may have a substituent, , R 304 and R 305 each independently represents an alkyl group which may have a substituent, a substituted an alkoxy group which may have one or more groups or an aralkyl group which may have one or more groups, l is 0 or 1; m is 1 or 2; n is 0 or 1 a5 is 0 or 1, b5 is 0 or 1.

[0032] [ka]

[0033] (In formula (57), Ar51 is Ar in the formula (50). 51 is the same as R 517 ~R 519 each independently represents an alkyl group which may have a substituent; an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, f, g, and h each independently represent an integer of 0 to 4; e represents an integer of 0 to 3; However, if g is 1 or greater, e is 1 or greater.)

[0034] [4] The polymer 2 is represented by the following formula (54), the following formula (55), or the following formula (57): The material for forming an organic film according to any one of [1] to [3], which contains a repeating unit represented by the formula:

[0035] [ka]

[0036] (In formula (54), Ar 51 is Ar in the formula (50). 51 is the same as X is -C(R 207 )(R 208 )-, -N(R 209 )- or -C(R 211 )( R 212 )-C(R 213 )(R 214 )- and R 201 , R 202 , R 221 and R 222 may each independently have a substituent. It is a good alkyl group, R 207 ~R 209 and R 211 ~R 214are each independently a hydrogen atom, a group having a substituent, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted an aromatic hydrocarbon group which may be optionally substituted, a and b each independently represent an integer of 0 to 4; c is an integer from 0 to 3, d is an integer from 0 to 4, R 201 If there are multiple R 201 may be the same or different, R 202 If there are multiple R 202 may be the same or different, R 221 If there are multiple R 221 may be the same or different, R 222 If there are multiple R 222 may be the same or different, i and j are each independently an integer of 0 to 3.

[0037] [ka]

[0038] (In formula (55), Ar 51 is Ar in the formula (50). 51 is the same as R 303 and R 306 are each independently an alkyl group which may have a substituent, , R 304 and R 305 each independently represents an alkyl group which may have a substituent, a substituted an alkoxy group which may have one or more groups or an aralkyl group which may have one or more groups, l is 0 or 1; m is 1 or 2; n is 0 or 1 a5 is 0 or 1, b5 is 0 or 1.

[0039] [ka]

[0040] (In formula (57), Ar 51 is Ar in the formula (50). 51 is the same as R 517 ~R 519 each independently represents an alkyl group which may have a substituent; an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, f, g, and h each independently represent an integer of 0 to 4; e represents an integer of 0 to 3; However, if g is 1 or greater, e is 1 or greater.)

[0041] [5] Ar in the formula (40) 1 and Ar 2 At least one of the following formula (41) Or the material for forming an organic film according to any one of [1] to [4], represented by the following formula (42):

[0042] [ka]

[0043] (In formula (41), R 201 , R 202 , a to d, and X are the same as in formula (54), and are independent of polymer 1. m4 represents an integer between 1 and 2.)

[0044] [ka]

[0045] (In formula (42), R 23 and R 25 each independently represents an alkyl group which may have a substituent, R 24 represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent. represents a group or an aralkyl group which may have a substituent, u and w each independently represent an integer of 0 to 2; v represents an integer of 1 or 2; x, y, and z each independently represent an integer of 0 to 2, and x+z is 1 or more.

[0046] [6] The repeating unit represented by the formula (40) is a repeating unit represented by the following formula (43): The organic film-forming material according to any one of [1] to [5], which is a unit.

[0047] [ka]

[0048] (In formula (43), R 1 ~R 6 , R 8 , R 10 , R 12 ~R 17 are each independently a hydrogen atom, a deuterium atom, A halogen atom, an aromatic ring group which may have a substituent, and a group in which 2 to 8 such aromatic rings are linked together represents a group represented by the formula: Ar 1 ~Ar 3 , G, p, q, r, s, and t are the same as in equation (40).

[0049] [7] The compound according to any one of [1] to [5], wherein in the formula (40), t is 1. Mechanical film forming material. [8] The compound according to any one of [1] to [5], wherein in the formula (40), r is 1. Mechanical film forming material. [9] The content ratio of the polymer 1 to the total content of the polymer 1 and the polymer 2. The material for forming an organic film according to any one of [1] to [8], wherein the content is 10 to 90 mass %.

[10] Ar in the formula (40) 3 and Ar in the formula (50) 51 Less One of the compounds according to any one of [1] to [5] contains a structure represented by the following formula (51): Material for organic film formation.

[0050] [ka]

[0051] (In formula (51), * represents a bond to the nitrogen atom of the main chain of formula (50), Ar 53 and Ar 54 are each independently optionally substituted divalent aromatic hydrocarbon groups, optionally substituted aromatic hydrocarbon groups, Heterocyclic group, or aromatic hydrocarbon group which may have a substituent or represents a divalent group in which a plurality of aromatic heterocyclic groups are linked together directly or via a linking group, and Ar 55 is an aromatic hydrocarbon group which may have a substituent and an aromatic hydrocarbon group which may have a substituent. A monovalent group having one or more groups linked together selected from at least one of aromatic heterocyclic groups The linkage is direct or via a linking group. Ar 56 represents a hydrogen atom or a substituent.

[0052]

[11] Ar in the formula (40) 3 and Ar in the formula (50) 51Less One of the compounds according to any one of [1] to [5] contains a structure represented by the following formula (52): Material for organic film formation.

[0053] [ka]

[0054] (In formula (52), Ar 61 and Ar 62 are each independently an optionally substituted divalent aromatic hydrocarbon group or an optionally substituted divalent is an aromatic heterocyclic group, Ar 63 ~Ar 65 are each independently a hydrogen atom or a substituent. * indicates the bond position.)

[0055]

[12] The weight average molecular weight (Mw) of the polymer 1 and the polymer 2 is 15,000 or more. The material for forming an organic film according to any one of [1] to

[11] , which has a molecular weight of 50,000 or less.

[13] The polydispersity (Mw / Mn) of the polymer 1 and the polymer 2 is 3.5 or less. The organic film-forming material according to any one of [1] to

[12] .

[14] The polymer 1 and the polymer 2 each have a crosslinking group, a polymerizable group, and a leaving solubilizing group. The organic film-forming material according to any one of [1] to

[13] .

[15] An organic film comprising the organic film-forming material according to any one of [1] to

[14] and a solvent. Forming composition.

[16] An organic film formed by a wet film-forming method using the organic film-forming composition according to

[15] . Manufacturing method.

[17] An organic layer containing the organic film-forming material according to any one of [1] to

[14] . , organic semiconductor devices.

[18] An organic electroluminescent device having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate. The organic layer includes a hole transport layer and a light emitting layer adjacent to the hole transport layer. death, The hole transport layer contains the organic film-forming material according to any one of [1] to

[14] . Electroluminescent device.

[19] The organic electroluminescent device according to

[18] , which has an emission peak wavelength of 500 nm or less. .

[20] A hole injection layer is provided between the anode and the hole transport layer, and the hole injection layer is a tetragon. The organic electroluminescent device according to

[18] , which contains a diarylborate ion.

[21] An organic electroluminescence display device comprising the organic electroluminescence element according to

[18] .

[22] An organic electroluminescent lighting device comprising the organic electroluminescent element according to

[18] . [Effects of the Invention]

[0056] According to the present invention, there is provided a material for forming an organic film having high hole injection and transport ability and high durability, and It is possible to provide an organic film-forming composition containing a film-forming material. In this way, an organic electroluminescent device having a long driving life can be provided.

[0057] The organic film-forming material according to the first embodiment of the present invention is a polymer having an aromatic amine in the main chain. The polymer (referred to as polymer 1) and the repeating unit containing a carbazole skeleton connected to the main chain at the 9-position It also includes a polymer having a unit (referred to as polymer 2). In the organic film-forming material of the present invention, the charge transfer in the bulk part of the organic film is Charge transport along the main chain is the main factor, and the low charge transport capacity of the main chain of polymer 2 is a factor. On the other hand, in the charge injection region near the light-emitting layer, the carbazole in polymer 2 Through this, it becomes easier for holes moving within the main chain to move to a deeper HOMO. When rubazolyl is included, the movement between the main chain and the side chain becomes easy. As a result, the adjacent deep HOMO It is believed that charge injection into the material in the light-emitting layer having The charge balance within the layer is improved, and the luminous efficiency is increased. Therefore, the organic electroluminescent device using the organic film-forming material of this embodiment has high luminous efficiency. stomach.

[0058] In addition, in the organic film-forming material of the present invention, the electron affinity of polymer 2 is deeper than that of polymer 1. Electrons easily enter polymer 2, and deterioration of polymer 1 is suppressed. Even if the main chain of polymer 2 deteriorates, its role in bulk transport is small from the beginning. In addition, the effect of the main chain length is small even in short-distance hole migration near the light-emitting layer, so the device characteristics are It is assumed that this is unlikely to lead to deterioration. As a result, the organic electroluminescent device using the organic film-forming material of this embodiment has a long driving life. stomach. [Brief explanation of the drawings]

[0059] [Figure 1] 1 is a schematic cross-sectional view showing an example of the structure of an organic electroluminescent device of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0060] The following describes an organic film-forming material according to one embodiment of the present invention, an organic film-forming material according to another embodiment of the present invention, and an organic film-forming material according to another embodiment of the present invention. organic film-forming composition containing organic film-forming material, organic semiconductor having organic layer containing organic film-forming material - Patents.com element, organic electroluminescent element having hole transport layer containing organic film-forming material, said organic electroluminescent element The embodiments of the organic EL display device having the element, the organic EL lighting, and the method for manufacturing the organic film are described in detail. It should be noted that the following description is an example (typical example) of an embodiment of the present invention, and the present invention does not limit the scope of the present invention. Unless otherwise stated, the contents of this document are not limited to these terms.

[0061] The organic film-forming material of the present invention is a polymer 1 containing a repeating unit represented by the following formula (50): and a polymer 2 containing a repeating unit represented by the following formula (40).

[0062] <Polymer 1> Polymer 1 is an arylamine polymer and contains a repeating unit represented by formula (50): and does not contain a repeating unit represented by the following formula (40).

[0063] [ka]

[0064] (In formula (50), Ar 51 is an aromatic hydrocarbon group which may have a substituent and a substituted a group to which one or more groups are linked, selected from at least one of aromatic heterocyclic groups represents Ar 52 is a divalent aromatic hydrocarbon group which may have a substituent and and one or more groups selected from at least one of the following divalent aromatic heterocyclic groups: The linkage is made directly or via a linking group. Ar 51 and Ar 52 may be bonded directly or via a linking group to form a ring.

[0065] (Ar 51 ) Ar in the above formula (50) 51 represents an aromatic hydrocarbon group which may have a substituent, and one or more groups selected from the group consisting of optionally substituted aromatic heterocyclic groups; represents a group to which the Ar group is linked. 51 and Ar 52 are bonded directly or via a linking group to form a ring It may be possible.

[0066] The aromatic hydrocarbon group preferably has 6 to 60 carbon atoms. Zene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring , pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluorine ring A monovalent group of a 6-membered ring such as a lanthene ring or a fluorene ring, or a group of 2 to 5 condensed rings thereof For example, a "monovalent group of a benzene ring" refers to a "monovalent "a benzene ring having a free valence of 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31,

[0067] The aromatic heterocyclic group preferably has 3 or more and 60 or less carbon atoms, and specifically, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, Imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolyl imidazoline pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzo a diisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, Pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxalin quinazoline ring, quinanthridine ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazoline ring a monovalent group of a 5- or 6-membered monocyclic ring or 2- to 4-condensed ring such as a zolinone ring or an azulene ring, or Examples include groups in which a plurality of these are linked together.

[0068] Ar 51 may have a substituent in view of excellent charge transport properties and durability. Aromatic hydrocarbon groups having a low molecular weight are preferred, and among them, benzene rings or fluoro groups which may have a substituent are preferred. Monovalent groups of phenyl rings, i.e., optionally substituted phenyl or fluorenyl groups is more preferred, and an optionally substituted fluorenyl group is even more preferred, The optionally contained 2-fluorenyl group is particularly preferred.

[0069] Ar 51 The aromatic hydrocarbon group and aromatic heterocyclic group may have a substituent, which may be a polymerizable group. There are no particular limitations on the substituents as long as they do not significantly impair the properties of the compound 1. Examples of the substituents include a group selected from the group Z of substituents described below, such as an alkyl group, an alkoxy group, an aromatic group, and the like. A hydrocarbon group or an aromatic heterocyclic group is more preferred, and an alkyl group is even more preferred.

[0070] Ar 51 In terms of solubility in coating solvents, the A fluorenyl group is preferred, and in particular, a 2-fluoro group substituted with an alkyl group having 4 to 12 carbon atoms is preferred. Further, a 9-fluorenyl group in which the 9-position of a 2-fluorenyl group is substituted with an alkyl group is preferred. Alkyl-2-fluorenyl groups are preferred, and in particular 9,9-disubstituted alkyl groups. Alkyl-2-fluorenyl groups are preferred.

[0071] A fluorenyl group substituted with an alkyl group at least at the 9-position or the 9'-position This tends to improve the solubility in solvents and the durability of the fluorene ring. The fluorenyl group substituted with an alkyl group at both the 9- and 9'-positions allows for solvent The solubility in water and the durability of the fluorene ring tend to be further improved.

[0072] Also, Ar 51 is a spirobifluorenyl group from the viewpoint of solubility in coating solvents. is also preferred.

[0073] Polymer 1 is a repeating unit represented by the formula (50) 51 Less and one of the benzene rings has 2 to 10 carbon atoms, each of which may have a substituent selected from the substituent group Z described below. A group containing five linked monovalent or divalent groups, a group represented by the following formula (51), a group represented by the following formula (52): or a group represented by the following formula (53): In the repeating unit represented by the formula (50) contained in the polymer 1, 51 , and the following Polymer 2 contains the repeating unit represented by formula (40) 3 At least one of Preferably, the group is a group represented by the following formula (51): This tends to suppress the electrons from reaching the periphery of the amine skeleton, improving the durability of the polymer main chain. In polymer 1, the energy is The structure with close levels allows the charge that has moved along the main chain to be smoothly transported to the side chain. Furthermore, side chains with similar energy levels in both polymer 1 and polymer 2 are When using HO, it has excellent hole transport between side chains, and many side chains can be used to transport deep HO molecules such as light-emitting materials. This allows for hole injection into the material having MO, thereby improving the efficiency of the organic electroluminescent device of the present invention. This is thought to improve career balance.

[0074] In addition, the repeating unit represented by the formula (50) contained in the polymer 1 is 51 , and The Ar in the repeating unit represented by formula (40) contained in polymer 2 described later 3 At least One of them is preferably a group represented by the following formula (52): The group represented by formula (52) has a higher effect of stabilizing the LUMO than the group represented by formula (51). It is believed that this improves the durability of polymers having the carbazole structure on the main chain to the side chain. Charge transfer between the polymers, charge transfer between the side chains of both polymers, and charge transfer from the polymer to the light-emitting material, etc. The reason why the group represented by formula (52) is preferred is that the group represented by formula (51) The reasons for this are similar to those for the preferred reasons.

[0075] (Formula (51))

[0076] [ka]

[0077] In formula (51), * represents a bond to the nitrogen atom of the main chain of formula (50), Ar 53 , Ar 54 each independently represents a divalent aromatic hydrocarbon which may have a substituent. a group, an aromatic heterocyclic group which may have a substituent, or an aromatic carbon atom which may have a substituent a hydroxyl group or an aromatic heterocyclic group which may have a substituent, directly or via a linking group; represents a divalent group in which a plurality of groups are linked together, Ar 55 represents an aromatic hydrocarbon group which may have a substituent; Aromatic heterocyclic group, or an aromatic hydrocarbon group or aromatic heterocyclic group which may have a substituent represents a monovalent group in which a plurality of groups are linked together directly or via a linking group, Ar 56 represents a hydrogen atom or a substituent.

[0078] Here, the substituents that each aromatic hydrocarbon group and each aromatic heterocyclic group may have, and the Ar when it is a group 56 may have a crosslinking group. A group selected from group T can be used.

[0079] (Ar 53 , Ar 54 ) In the repeating unit represented by the formula (51), Ar 53 , Ar 54 are independent of each other a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic hydrocarbon group which may have a substituent, or an aromatic hydrocarbon group which may have a substituent or a divalent group in which a plurality of aromatic heterocyclic groups, which may be bonded together directly or via a linking group, Preferably, it is a divalent aromatic hydrocarbon group which may have a substituent or a divalent aromatic hydrocarbon group which has a substituent. It is a group in which a plurality of optionally divalent aromatic hydrocarbon groups are linked together. The aromatic heterocyclic group and the substituent that the aromatic heterocyclic group may have may have a crosslinking group, and The same groups as those in the group Z of substituents are preferred. The bridging group is a group selected from the group T of bridging groups described below. can be used.

[0080] Ar 53 and Ar 54 The aromatic hydrocarbon group and aromatic heterocyclic group are 52 Similar to Aromatic hydrocarbon groups and aromatic heterocyclic groups such as those listed above can be used.

[0081] An aromatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent The divalent group in which a plurality of heterocyclic groups are linked directly or via a linking group is a group in which a plurality of the same groups are linked. It may be a group in which two or more groups are linked together, or a group in which two or more different groups are linked together.

[0082] When a plurality of the above divalent groups are linked together, examples include a divalent group in which 2 to 10 groups are linked together, It is preferably a divalent group in which 2 to 5 groups are linked together.

[0083] Ar 53 is a group consisting of 1 to 6 optionally substituted divalent aromatic hydrocarbon groups linked together. A group in which 2 to 4 optionally substituted divalent aromatic hydrocarbon groups are linked is preferred. Among them, a group in which 1 to 4 phenylene rings which may have a substituent are linked is more preferable. A group having two phenylene rings linked together, which may have a substituent, is more preferred. is particularly preferred.

[0084] In addition, when a plurality of these divalent aromatic hydrocarbon groups or divalent aromatic heterocyclic groups are linked together, Preferably, the divalent aromatic hydrocarbon groups are linked together in such a way that they do not conjugate. Specifically, the 1,3-phenylene group or the substituted group have a twist due to the steric effect of the substituent. It is preferred that the compound contains a group that forms the structure.

[0085] Ar 53 The substituents which may be possessed by are preferably the same as those in the group Z of substituents described below. For more details, see Ar 53 has no substituents.

[0086] Ar 54 are excellent in charge transport properties and durability, so they are A group in which one or more optionally divalent aromatic hydrocarbon groups are linked is preferred, and the divalent aromatic The hydrocarbon group may have a substituent. When a plurality of hydrocarbon groups are linked, the number of the linked hydrocarbon groups is preferably 2 to 10. A value of 6 or less is more preferable, and a value of 3 or less is particularly preferable from the viewpoint of film stability. Aromatic hydrocarbon structures include benzene ring, naphthalene ring, anthracene ring, and fluorene ring. and more preferably a benzene ring or a fluorene ring. a group in which 1 to 4 phenylene rings which may have a substituent are linked together, or a group in which A group in which an optionally substituted phenylene ring and an optionally substituted fluorene ring are linked is preferred. In view of broadening the LUMO, it is preferable that two phenylene rings which may have a substituent are linked. Biphenylene is particularly preferred.

[0087] Ar 54 The substituents which may be possessed by the group include any one of the substituents in the group Z described below, or A combination of these groups can be used. N-carbazolyl group, indolocarbazolyl group The substituent is preferably other than an indenocarbazolyl group, and more preferably, It is also preferred that the alkyl group has no substituent. .

[0088] (Ar 55 ) Ar 55 represents an aromatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, Aromatic heterocyclic groups, or aromatic hydrocarbon groups which may have a substituent, and A plurality of groups selected from the aromatic heterocyclic groups which may be optionally substituted are linked directly or via a linking group. Preferably, it is a monovalent aromatic hydrocarbon group which may have a substituent, or It is a group in which a plurality of monovalent aromatic hydrocarbon groups, which may have a substituent, are linked together.

[0089] Here, the substituents that the aromatic hydrocarbon group and the aromatic heterocyclic group may have are those that do not include a bridging group. The bridging group may have a substituent, and is preferably the same as the substituent group Z described later. A group selected from the group T of bridging groups can be used.

[0090] When a plurality of groups are linked together, the group is a divalent group of 2 to 10 groups linked together, and a monovalent group of 2 to 5 groups linked together is preferable. As the aromatic hydrocarbon and aromatic heterocycle, the Ar group is preferable. 51 Similar to Aromatic hydrocarbon groups and aromatic heterocyclic groups such as those listed above can be used.

[0091] Ar 55 It is preferable that the compound has a structure represented by any one of the following schemes 2: Furthermore, from the viewpoint of distributing the LUMO of the molecules, a-1 to a-4, b-1 to b-9, c- A structure selected from the group consisting of 1 to c-4, d-1 to d-16, and e1 to e4 is preferred. From the viewpoint of promoting the broadening of the LUMO of the molecule by having an electron-withdrawing group, a-1 A structure selected from a-1 to a-4, b-1 to b-9, d-1 to d-12, and e1 to e4 is preferred. Furthermore, from the viewpoint of the effect of confining excitons formed in the light-emitting layer, which has a high triplet level, it is preferable. , a-1 to a-4, d-1 to d-12, and e1 to e4 are preferred. In addition, d-1 and d-10 are more preferable from the viewpoint of easy synthesis and excellent stability. The benzene ring structures of d-1 and d-2 are particularly preferred. These structures may further have a substituent. In the figure, "-*" indicates Ar 54 If there are multiple "-*"s, One of them is Ar 54represents the bonding position with

[0092] [ka]

[0093] [ka]

[0094] [ka]

[0095] (R 31 and R 32 ) R in Scheme 2 31 and R 32 each independently represents a linear or branched group which may have a substituent; The number of carbon atoms in the alkyl group is not particularly limited, but In order to maintain the solubility of the polymer, the number of carbon atoms is preferably 1 or more and 6 or less, and more preferably 3 or less. A methyl group or an ethyl group is more preferred.

[0096] R 31 and R 32 may be the same or different, but the charge is uniformly distributed between the nitrogen atoms. Since it can be distributed around and is easy to synthesize, all R 31 and R 32 teeth It is preferred that they are the same groups.

[0097] Ar 55 The substituents which may be possessed by the group include any one of the substituents in the group Z described below, or From the viewpoint of durability and charge transportability, the above-mentioned A r 54 It is preferable that the substituents are selected from the same substituents that may be possessed by the group.

[0098] (Ar 56 ) Ar 56 represents a hydrogen atom or a substituent. 56 When is a substituent, the specific limitation is Preferably, the aromatic hydrocarbon group may have a substituent, but is not limited to a substituted aromatic hydrocarbon group. A preferred structure is an aromatic heterocyclic group such as the Ar 53 ~Ar 54 Listed in It is a monovalent structure similar to the aromatic hydrocarbon structure and aromatic heterocyclic structure mentioned above.

[0099] Ar 56 When is a substituent, it may have a crosslinking group. Examples of the crosslinking group include those described below. A group selected from the group T of bridging groups can be used.

[0100] Ar 56 When is a substituent, bonding to the 3-position of carbazole improves durability. It is preferable from the viewpoint of Ar 56 From the viewpoint of ease of synthesis and charge transport properties, It is preferable that Ar 56 From the viewpoint of improving durability and charge transportability, an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent; It is preferable that the alkyl group is an aromatic hydrocarbon group which may have a substituent. stomach.

[0101] Ar 56 is preferably a hydrogen atom from the viewpoint of ease of synthesis and charge transport properties. stomach.

[0102] Ar 56 is an aromatic hydrocarbon group which may have a substituent or an aromatic hydrocarbon group which may have a substituent In the case of an aromatic heterocyclic group, the substituents are the same as those listed in the substituent group Z described below. The same applies to the preferred substituents, and the substituents that these substituents may further have are also The same is true.

[0103] (Formula (52)) Ar in the repeating unit represented by the above formula (50) 51 At least one of the following formula The group represented by formula (52) is also preferred. The reason for this is that the two groups in formula (52) In the rubazole structure, the aromatic hydrocarbon group or aromatic heterocyclic group between the nitrogen atoms has L The distribution of UMO suppresses the influence on the main chain amine in formula (50), This is thought to be because the durability against electrons and excitons in the silicon is improved.

[0104] [ka]

[0105] (In formula (52), Ar 61 and Ar 62 each independently represents a divalent aromatic hydrocarbon which may have a substituent; a divalent aromatic heterocyclic group which may have a substituent, Ar 63 ~Ar 65 are each independently a hydrogen atom or a substituent. * indicates the bonding position to the nitrogen atom in formula (50).

[0106] (Ar 63 ~Ar 65 ) Ar 63 ~Ar 65 Each independently represents a hydrogen atom or a substituent. 63 ~Ar 6 5When is a substituent, the substituent is not particularly limited, but preferably has a substituent. The aromatic hydrocarbon group may be an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent. Preferred structures of the hydride group and aromatic heterocyclic group include the above-mentioned Ar 51 The groups listed in The same is true.

[0107] Ar 63 ~Ar 65 is a substituent, Ar 63 ~Ar 65 is the structure of each carbazole From the viewpoint of improving durability, it is preferable that the bond be at the 3-position or the 6-position.

[0108] Ar 63 ~Ar 65 From the viewpoint of ease of synthesis and charge transport properties, it is preferable that the It is preferable that:

[0109] Ar 63 ~Ar 65 From the viewpoint of improving durability and charge transportability, It is preferably an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. It is more preferable that the alkyl group is an aromatic hydrocarbon group which may have a substituent.

[0110] Ar 63 ~Ar 65 an aromatic hydrocarbon group which may have a substituent or In the case of an aromatic heterocyclic group, the substituents which may be present include those exemplified in the substituent group Z described below. The same applies to the substituents, and the preferred substituents are also the same. The same is true for good substituents.

[0111] (Ar 62 ) Ar 62is a divalent aromatic hydrocarbon group which may have a substituent or a divalent aromatic hydrocarbon group which has a substituent. It is a divalent aromatic heterocyclic group which may be

[0112] The aromatic hydrocarbon group preferably has 6 to 60 carbon atoms, more preferably 1 to 20 carbon atoms. The carbon number is preferably from 10 to 50, and more preferably from 12 to 40. Specific examples of the hydrogen hydride group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthane ring, and the like. Thylene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triflate ring six-membered monocyclic or monocyclic rings such as phenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring; Examples of such groups include divalent groups having 2 to 5 condensed rings and groups in which multiple such groups are linked together. In the case of conjugation, the group is preferably a group in which a plurality of linked divalent aromatic hydrocarbon groups are conjugated.

[0113] The aromatic heterocyclic group preferably has 3 to 60 carbon atoms, and specifically, a furan ring , benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, Midazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolyl midazo pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring , furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzo Isothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, Imidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazo a divalent group of a 5- or 6-membered monocyclic ring or 2- to 4-condensed ring such as a linone ring or an azulene ring, or and groups in which a plurality of these are linked together.

[0114] The substituents that these aromatic hydrocarbon groups or aromatic heterocyclic groups may have are the substituents described below. The group Z includes alkyl groups, aralkyl groups, and aromatic hydrocarbon groups. By the results Ar 62 In the case where the structure of the compound is twisted, it is preferable that the compound has no substituents. Due to the steric effect of Ar 62 If the structure of the compound does not become distorted, it is preferable that the compound has a substituent. I wish.

[0115] Ar 62 Preferred groups are a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring. or a group in which a plurality of these are linked together, and more preferably a divalent group of a benzene ring Or a group in which a plurality of such rings are linked, and particularly preferably a group in which the benzene rings are linked divalently at the 1- and 4-positions 1,4-phenylene group linked by divalent bonds at the 2,7-positions of the fluorene ring; It is a phenylene group or a group in which a plurality of such groups are linked together, and most preferably "1,4-phenylene" It is a group containing the group -2,7-fluorenylene group-1,4-phenylene group-”.

[0116] In these preferred structures, the phenylene group does not have a substituent other than at the linking position. , Ar due to the steric effect of the substituents 62 In addition, the fluorenylene group is preferably In terms of improving the solubility and durability of the fluorene structure, it is preferable to have a substituent at the 9,9' position. It is preferable from this point of view.

[0117] (Ar 61 ) Ar 61 is a divalent group that connects to the nitrogen atom of the main chain amine in formula (52). Ar 61is a divalent aromatic hydrocarbon group which may have a substituent or is also a divalent aromatic heterocyclic group.

[0118] Ar 61 The aromatic hydrocarbon group preferably has 6 or more and 60 or less carbon atoms, and more preferably Preferably, the number of carbon atoms is 10 or more and 50 or less, and particularly preferably 12 or more and 40 or less. Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, and an anthracene ring. , phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene six-membered rings such as a ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring; Examples of the divalent group include a monocyclic group or a divalent group having 2 to 5 condensed rings, and a group in which a plurality of these groups are linked together.

[0119] Ar 61 The aromatic heterocyclic group preferably has 3 to 60 carbon atoms. Furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazo ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolidine ring, Midazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienthio Phen ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring , benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoline ring Xaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring a divalent ring having a 5- or 6-membered monocyclic ring or 2 to 4 condensed rings, such as a quinazolinone ring or an azulene ring; groups or groups in which a plurality of such groups are linked together.

[0120] The substituents that these aromatic hydrocarbon groups or aromatic heterocyclic groups may have are the substituents described below. The group Z includes alkyl groups, aralkyl groups and aromatic hydrocarbon groups.

[0121] When a plurality of these divalent aromatic hydrocarbon groups or divalent aromatic heterocyclic groups are linked together, it is preferable that Or, it is a group in which multiple linked divalent aromatic hydrocarbon groups are bonded so as not to conjugate. The 1,3-phenylene group or the substituent group have a twisted structure due to the steric effect of the substituent. It is preferred that the group contains:

[0122] (Formula (53)) Ar in the repeating unit represented by the formula (50) 51 At least one of the following formula: A group represented by (53) is also preferred.

[0123] [ka]

[0124] In formula (53), * represents a bond to the nitrogen atom of the main chain of formula (50), Ar 71 represents a divalent aromatic hydrocarbon group which may have a substituent, Ar 72 and Ar 73 each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic carbon which may have a substituent; Two or more groups selected from a hydrogen fluoride group and an aromatic heterocyclic group which may have a substituent are directly bonded to the or a monovalent group in which a plurality of groups are linked via a linking group, Ring HA is an aromatic heterocycle containing a nitrogen atom, X 2 , Y 2 each independently represents a carbon atom or a nitrogen atom; X2 and Y 2 At least When one of them is a carbon atom, the carbon atom may have a substituent.

[0125] (Ar 71 ) Ar 71 is the Ar 53 is a group similar to Ar 71 is one divalent aromatic hydrocarbon group which may have a substituent, or A group in which 2 to 10 divalent aromatic hydrocarbon groups are linked together, which may have the following substituents, is preferred. one divalent aromatic hydrocarbon group optionally having one substituent, or A group in which 2 to 8 aromatic hydrocarbon groups are linked is more preferred, and among these, a group in which 2 It is preferable that the aromatic hydrocarbon group is a group in which two or more aromatic hydrocarbon groups are linked together.

[0126] Ar 71 As the group, particularly, a group in which 2 to 6 benzene rings which may have a substituent are linked is is preferred, and a quaterphenylene group in which four benzene rings which may have substituents are linked together. is most preferred.

[0127] Also, Ar 71 contains at least one benzene ring linked at the 1,3 position, which is a non-conjugated site. It is preferable that the number of the hydroxyl groups included in the total number of the hydroxyl groups is 1 or more, and more preferable that the number of the hydroxyl groups included in the total number of the hydroxyl groups is 2 or more.

[0128] Ar 71 is a group in which a plurality of optionally substituted divalent aromatic hydrocarbon groups are linked together. From the viewpoint of charge transportability or durability, it is preferable that all of the groups are directly bonded to each other.

[0129] For this reason, Ar 71 as the nitrogen atom of the main chain of the polymer and the ring HA in the formula (53) Preferred structures for connecting the two are shown in Scheme 2-1 and Scheme 2-2 below. "-*" indicates the bonding site with the nitrogen atom of the main chain of the polymer or the ring HA of the formula (53). Whichever of the two "-*" is bonded to the nitrogen atom of the polymer main chain, the ring H It may be bonded to A.

[0130] [ka]

[0131] [ka]

[0132] Ar 71 The substituents which may be possessed by the group include any one of the substituents in the group Z described below or A combination of Ar 71 Preferred range of substituents that may be possessed by is the same as the substituent that may be possessed when G is an aromatic hydrocarbon group.

[0133] (X 2 and Y 2 ) X 2 and Y 2 Each of X independently represents a carbon (C) atom or a nitrogen (N) atom. 2 and Y 2 When at least one of them is a C atom, it may have a substituent.

[0134] X is chosen to localize the LUMO more easily around the HA ring. 2 and Y 2 All of them are Nhara Preferably a child.

[0135] X 2 and Y 2When at least one of the groups is a C atom, the following substituents may be included: Any of the above-mentioned substituent groups Z or a combination thereof can be used. From the perspective of X 2 and Y 2 More preferably, has no substituent.

[0136] (Ar 72 and Ar 73 ) Ar 72 and Ar 73 each independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic carbon which may have a substituent; Two or more groups selected from a hydrogen fluoride group and an aromatic heterocyclic group which may have a substituent are directly bonded to the Alternatively, it is a monovalent group in which a plurality of groups are linked via a linking group.

[0137] From the viewpoint of distributing the LUMO of the molecule, Ar 72 and Ar 73 are each independently a-1 to a-4, b-1 to b-9, c-1 to c-4, d-1 to d-16 shown in scheme 2 and preferably has a structure selected from e-1 to e-4.

[0138] Furthermore, the presence of electron-withdrawing groups promotes the broadening of the LUMO of the molecule. , a-1~a-4, b-1~b-9, c-1~c-5, d-1~d-12, and e-1~ The structure selected from e-4 is preferred.

[0139] Furthermore, from the viewpoint of the effect of trapping excitons formed in the light-emitting layer, which has a high triplet level, A structure selected from -1 to a-4, d-1 to d-12, and e-1 to e-4 is preferred.

[0140] In order to prevent aggregation of molecules, a structure selected from d-1 to d-12 and e-1 to e-4 is Ar is more preferred from the viewpoint of easy synthesis and excellent stability. 72 =Ar 73 =d-1 again is preferably d-10, and the benzene ring structure of d-1 is particularly preferred.

[0141] These structures may also have a substituent. "-*" indicates the binding site to the cyclic HA. When there are multiple "-*", any one of them represents the site of binding to the ring HA.

[0142] Ar 72 and Ar 73 The substituent that may be possessed by the group may be any of the substituent group Z described below. From the viewpoint of durability and charge transportability, It is a substituent, and is preferably the same as the substituent group Z described below.

[0143] (Ar 52 ) Ar 52 is a divalent aromatic hydrocarbon group which may have a substituent and and a divalent aromatic heterocyclic group, The linkage is made directly or via a linking group. Ar 52 is a divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group which may have a substituent. a divalent group in which a plurality of groups selected from the group consisting of cyclic groups are linked together, 52 Multiple in a structure in which the benzene ring structures are linked at the para position, At least one of the two carbon atoms is located next to the carbon atom that bonds to the adjacent benzene ring structure. It is preferred that at least one of the atoms has a substituent. Ar 52As the aromatic hydrocarbon group and aromatic heterocyclic group in the formula (50), Ar 51 In addition, Ar 52 Aromatic hydrocarbons in The substituents which the group and aromatic hydrocarbon group may have are preferably the same as those in the group Z of substituents described below. Ar 52 The linking group in is preferably the same as the linking group described below.

[0144] [Substituent group Z] The substituent group Z is an alkyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, group, alkoxycarbonyl group, dialkylamino group, diarylamino group, arylalkenyl group alkylamino group, acyl group, halogen atom, haloalkyl group, alkylthio group, arylthio group Aromatic hydrocarbon groups, silyl groups, siloxy groups, cyano groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups. These substituents may have any of straight-chain, branched and cyclic structures.

[0145] More specifically, the substituent group Z includes the following structures. For example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i- Butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group , dodecyl group, etc., usually have 1 or more carbon atoms, preferably 4 or more carbon atoms, and usually 24 or less carbon atoms. is preferably 12 or less, more preferably 8 or less, and even more preferably 6 A linear, branched, or cyclic alkyl group, which is: For example, the number of carbon atoms of a methoxy group, an ethoxy group, etc. is usually 1 or more and usually 24 or less. alkoxy groups, preferably 12 or less; For example, phenoxy group, naphthoxy group, pyridyloxy group, etc., which usually have 4 or more carbon atoms, Preferably, the number is 5 or more, usually 36 or less, preferably 24 or less. an aryloxy group or a heteroaryloxy group; For example, a methoxycarbonyl group, an ethoxycarbonyl group, or the like, usually has two or more carbon atoms. alkoxycarbonyl groups, typically 24 or less, preferably 12 or less; For example, a dimethylamino group, a diethylamino group, etc., usually has two or more carbon atoms, dialkylamino groups having 24 or less, preferably 12 or less; For example, the number of carbon atoms is usually 10 or more, such as a diphenylamino group or a ditolylamino group, Preferably, it is 12 or more, usually 36 or less, preferably 24 or less diaryl amines. Noki; For example, the number of carbon atoms is usually 7 or more and usually 36 or less, such as a phenylmethylamino group. an arylalkylamino group, preferably having a molecular weight of 24 or less; For example, acetyl groups, benzoyl groups, etc., usually have 2 or more carbon atoms and usually have 24 or less carbon atoms. acyl groups, preferably 12 or less; For example, halogen atoms such as fluorine atoms and chlorine atoms; For example, the number of carbon atoms is usually 1 or more and usually 12 or less, such as a trifluoromethyl group. haloalkyl groups, preferably 6 or less; For example, a methylthio group, an ethylthio group, etc., usually has 1 or more carbon atoms and usually has 24 or less carbon atoms. an alkylthio group, preferably having 12 or less carbon atoms; For example, a phenylthio group, a naphthylthio group, a pyridylthio group, etc., which usually have 4 or more carbon atoms and preferably 5 or more, usually 36 or less, preferably 24 or less. thio group; For example, a trimethylsilyl group, a triphenylsilyl group, etc., which usually have two or more carbon atoms silyl groups, preferably 3 or more and usually 36 or less, preferably 24 or less; For example, trimethylsiloxy groups, triphenylsiloxy groups, and other groups with carbon atoms of usually 2 or more Preferably, the number of silyl groups is 3 or more, and usually 36 or less, preferably 24 or less. Si group; cyano group; For example, the number of carbon atoms is usually 6 or more and usually 36 or less, such as a phenyl group and a naphthyl group. an aromatic hydrocarbon group, preferably having 24 or less aromatic hydrocarbon groups; For example, a thienyl group, a pyridyl group, etc., usually have 3 or more carbon atoms, preferably 4 or more carbon atoms. and the aromatic heterocyclic group has a ring structure of usually 36 or less, preferably 24 or less.

[0146] Among the above-mentioned substituent group Z, alkyl groups, alkoxy groups, diarylamido groups, From the viewpoint of charge transport properties, aromatic hydrocarbon groups are preferred. A substituted or unsubstituted aromatic hydrocarbon group is preferred, and an aromatic heterocyclic group is more preferred. From the viewpoint of improving solubility, it is more preferable that the hydroxyl group does not have an alkyl group or an alkoxy group. A silyl group is preferred.

[0147] Each of the substituents in the above-mentioned substituent group Z may further have a substituent. Examples of the substituents include the same as those in the above-mentioned substituent group Z. is preferably an alkyl group having no further substituents, an alkyl group having 8 or less carbon atoms, an alkyl group having 8 or less carbon atoms, an alkoxy group or a phenyl group, more preferably an alkyl group having 6 or less carbon atoms, Each of the substituents in the above substituent group Z has the following alkoxy group or phenyl group: From the viewpoint of functionality, it is more preferable that the group has no further substituents.

[0148] [Linking group] Specific examples of the linking group include an -O- group, a -C(=O)- group, and a hydrogen atom. 1 to 30 groups selected from optionally substituted -CH2- groups in any order, preferably is a divalent linking group formed by linking 1 to 5, more preferably 1 to 3, groups. Among them, those having a structure represented by the formula (40-χ) described later are preferred because they are excellent in hole injection into the light-emitting layer. It is preferable.

[0149] [Bridging group] The polymer 1 may have a crosslinking group, but the organic film-forming material of the present invention is When used in a layer adjacent to the light-emitting layer of a device, it is preferred that the compound does not have a crosslinking group. Here, the crosslinking group is a group that is formed in the vicinity of the crosslinking group by irradiation with heat and / or active energy rays. A crosslinking group is a group that reacts with another crosslinking group to form a new chemical bond. The corresponding group may be the same as the bridging group or may be different.

[0150] The crosslinking group may be a group containing an alkenyl group, a group containing a conjugated diene structure, or a group containing an alkynyl group. a group containing an oxirane structure, a group containing an oxetane structure, a group containing an aziridine structure, a group containing a maleic anhydride structure; a group containing an alkenyl group bonded to an aromatic ring; Specific examples of the bridging group include the following: Examples thereof include groups selected from the group T of bridging groups.

[0151] (Bridging group T)

[0152] [ka]

[0153] [ka]

[0154] In the above-mentioned bridging group T, R XL represents a methylene group, an oxygen atom, or a sulfur atom; n X L represents an integer from 0 to 5. XL If there are multiple, they may be the same or different. Well, n XL If there are multiple, they may be the same or different. *1 is a bond These bridging groups may have a substituent.

[0155] The repeating unit represented by the above formula (50) can be a repeating unit represented by the following formula (54), the following formula (55), or the following formula (56): The repeating unit is preferably represented by the formula (57).

[0156] Hereinafter, the repeating unit represented by the above formula (50) is more preferably "formula (54)" "Repeating units represented by formula (55)", "Repeating units represented by formula (57)", The repeating units are described in detail below.

[0157] The polymer 1 containing a triarylamine structure as a repeating unit is represented by the formula (54) or the formula (55) ) or the repeating unit represented by formula (57), in each formula, repeating units of different structures It is also preferred that the copolymer contains a plurality of types of repeat units.

[0158] <Repeating unit represented by formula (54)>

[0159] [ka]

[0160] (In formula (54), Ar 51 is Ar in the formula (50).51 is the same as X is -C(R 207 )(R 208 )-, -N(R 209 )- or -C(R 211 )( R 212 )-C(R 213 )(R 214 )- and R 201 , R 202 , R 221 and R 222 may each independently have a substituent. It is a good alkyl group, R 207 ~R 209 and R 211 ~R 214 are each independently a hydrogen atom, a group having a substituent, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted an aromatic hydrocarbon group which may be optionally substituted, a and b each independently represent an integer of 0 to 4; c is an integer from 0 to 3, d is an integer from 0 to 4, R 201 If there are multiple R 201 may be the same or different, R 202 If there are multiple R 202 may be the same or different, R 221 If there are multiple R 221 may be the same or different, R 222 If there are multiple R 222 may be the same or different, i and j are each independently an integer of 0 to 3.

[0161] (R 201 , R 202 , R 221 , R 222 ) R in the repeating unit represented by the above formula (54) 201 , R 202 , R 221 and R 22 2 are each independently an alkyl group which may have a substituent.

[0162] The alkyl group may be a straight-chain, branched, or cyclic alkyl group. There is no particular limitation on the number of carbon atoms in the alkyl group. However, in order to maintain the solubility of the polymer, it is preferably 1 or more and 8 or less. The alkyl group is preferably a methyl group or an ethylene group, more preferably 6 or less, and even more preferably 3 or less. A ethyl group is more preferred.

[0163] R 201 If there are multiple R 201 may be the same or different, and R 202 If there are multiple R 202 may be the same or different. They can be uniformly distributed around the nitrogen atom and are easy to synthesize. R 201 and R 202 are preferably the same group.

[0164] R 221 If there are multiple R 221 may be the same or different, and R 222 If there are multiple R 222 may be the same or different. They can be uniformly distributed around the nitrogen atom and are easy to synthesize. R 221 and R 222 are preferably the same group.

[0165] (R 207 ~R 209 and R 211~R 214 ) R 207 ~R 209 and R 211 ~R 214 are each independently a hydrogen atom, a group having a substituent, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted It is an aromatic hydrocarbon group which may be optionally substituted.

[0166] The alkyl group is not particularly limited, but is preferably a carbon-containing alkyl group since it tends to improve the solubility of the polymer. The number is preferably 1 or more, and is preferably 24 or less, more preferably 8 or less, and most preferably 6 or less. The alkyl group may have a linear, branched or cyclic structure.

[0167] Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group Examples of the alkyl group include an n-octyl group, a cyclohexyl group, and a dodecyl group.

[0168] The aralkyl group is not particularly limited, but carbon is preferred because it tends to improve the solubility of the polymer. The prime number is preferably 5 or more, and is preferably 60 or less, and more preferably 40 or less.

[0169] Specific examples of the aralkyl group include a 1,1-dimethyl-1-phenylmethyl group, a 1,1 -di(n-butyl)-1-phenylmethyl group, 1,1-di(n-hexyl)-1-phenyl phenylmethyl group, 1,1-di(n-octyl)-1-phenylmethyl group, phenylmethyl group, Phenylethyl group, 3-phenyl-1-propyl group, 4-phenyl-1-n-butyl group, 1-methyl-1-phenylethyl group, 5-phenyl-1-n-propyl group, 6-phenyl -1-n-hexyl group, 6-naphthyl-1-n-hexyl group, 7-phenyl-1-n-hexyl group butyl group, 8-phenyl-1-n-octyl group, 4-phenylcyclohexyl group, etc. can be done.

[0170] The aromatic hydrocarbon group is not particularly limited, but tends to improve the solubility of the polymer. Therefore, the number of carbon atoms is preferably 6 or more, and is preferably 60 or less, and more preferably 30 or less. stomach.

[0171] Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, an anthracene ring, Phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring 6-membered rings such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring Examples include monovalent groups of a single ring or 2 to 5 condensed rings, and groups in which a plurality of these are linked together.

[0172] From the viewpoint of improving charge transport properties and durability, R 207 and R 208 is a methyl group or an aromatic carbon A hydride group is preferred, and R 207 and R 208 is more preferably a methyl group, and R 2 09 is more preferably a phenyl group.

[0173] R 201 , R 202 , R 221 , R 222 alkyl group, R 207 ~R 209 and R 2 11 ~R 214 The alkyl group, aralkyl group and aromatic hydrocarbon group may have a substituent. The substituent may be any of the R 207 ~R 209 and R211 ~R 214 alkyl group, Examples of the preferred ralkyl group and aromatic hydrocarbon group include the groups mentioned above.

[0174] R 201 , R 202 , R 221 , R 222 alkyl group, R 207 ~R 209 and R 2 11 ~R 214 The alkyl group, aralkyl group and aromatic hydrocarbon group are preferred from the viewpoint of lowering voltage. Most preferably, they have no substituents.

[0175] (a, b, c and d) In the repeating unit represented by the above formula (54), a and b each independently represent 0 to 4. It is preferable that a+b is 1 or more, and further, a and b are each 2 or less. It is preferable that a and b are both 1, and it is more preferable that a is 1 or more. "Above" means that c is 1 or greater, and "b" means that d is 1 or greater. In addition, when b is 1 or more, it is preferable that d is also 1 or more. When d is 2 or more, the plural a's may be the same or different. When d is 2 or more, the plural a's may be the same or different. b may be the same or different.

[0176] When a+b is 1 or more, the aromatic rings in the main chain are twisted due to steric hindrance, and the polymer is difficult to dissolve in a solvent. In addition to excellent solubility, the coating film formed by the wet film-forming method and heat-treated has excellent insolubility in solvents. Therefore, if a+b is 1 or more, it is possible to form another organic film on this coating film by a wet film forming method. When forming a layer (for example, a light-emitting layer), the light-emitting layer forming composition used in the present invention contains an organic solvent. As a result, the influence on the formed light-emitting layer is reduced. This is expected to further extend the operating life of the organic electroluminescent device.

[0177] In the repeating unit represented by the above formula (54), c is an integer of 0 to 3, and d is 0. c and d are integers of 1 to 4. Preferably, c and d are each 2 or less, and c and d are equal. It is more preferred that both c and d are 1 or both c and d are 2. preferable.

[0178] In the repeating unit represented by the above formula (54), both c and d are 1 or both c and d are 1. If a is 2 and both a and b are 2 or 1, then R 201 and R 202 are mutual It is most preferred that the bond is symmetrical to the .

[0179] where R 201 and R 202 and bond to positions symmetric to each other means that in equation (54) For the fluorene ring, carbazole ring or 9,10 dihydrophenanthrene derivative structure Te, R 201 and R 202 In this case, the main chain is the axis. A 180 degree rotation is considered to be the same structure.

[0180] R 221 and R 222 are, if present, each independently a carbon atom of the benzene ring to which X is attached. It is preferably present at the 1st, 3rd, 6th, or 8th position relative to the atom. 221 and / or R 222 The existence of R 221 and / or R 222 is bonded The fused ring and the adjacent benzene ring on the main chain are twisted due to steric hindrance, and the polymer is dissolved in a solvent. The coating film formed by the wet film-forming method and then heat-treated tends to have excellent insolubility in solvents. This is favorable and in line with the trend.

[0181] (i and j) In the repeating unit represented by the above formula (54), i and j each independently represent 0 to 3. It is preferable that a and b are each 2 or less, and both a and b are 0 or 1. It is more preferable that:

[0182] (Ar 51 ) In the repeating unit represented by the above formula (54), Ar 51 is the formula (50) RuAr 51 and the aromatic hydrocarbon group which may have a substituent and the aromatic hydrocarbon group which has a substituent are the same as those of and a group or groups selected from the group consisting of optionally substituted aromatic heterocyclic groups, It is the base.

[0183] Aromatic hydrocarbon groups which may have a substituent and aromatic hetero groups which may have a substituent As the group to which one group or multiple groups selected from the group consisting of cyclic groups are linked, the group represented by the formula (5) 0) in Ar 51 The same substituents and preferred structures as those of the formula Ar in (50) 51 The same as in the case of

[0184] Ar in the repeating unit represented by the above formula (54) 51 At least one of the formula (51), a group represented by the formula (52) or the formula (53) is more preferable. In the two carbazole structures in the formula (51), the aromatic hydrocarbons between the nitrogen atoms are The distribution of the LUMO in the aromatic or heteroaromatic group improves the durability against electrons and excitons. It is thought to be on an upward trend.

[0185] (X) X in the above formula (54) is -C(R 207 ) (R 208 )- or -N(R 209 )-, and -C(R 207 )(R 2 08 )- is more preferred.

[0186] In addition, in the polymer containing the repeating unit represented by the above formula (54), Ar 51 , R 2 01 , R 202 , R 221 , R 222 If there are multiple Xs, they may be the same or different. Preferably, the repeating units of the polymer represented by formula (54) have the same structure. In this case, the polymer contains multiple repeating units of the same structure. By including multiple repeating units, the HOMO and LUMO of the repeating units become the same, so that a specific shallow quasi- It is believed that charges do not concentrate at the positions to form traps, and that the charge transport properties are excellent.

[0187] The repeating unit represented by the above formula (54) is any one of the following formulae (54-1) to (54-8): The repeating unit represented by any one of the following is particularly preferred.

[0188] [ka]

[0189] [ka]

[0190] In the above formula, R 201 and R 202 are identical and R 201 and R 202 Mutually The bonds are symmetrical.

[0191] The main chain structure excluding the nitrogen atom in the above formula (54) is not particularly limited, but may be, for example, the following: Examples of such structures include:

[0192] [ka]

[0193] [ka]

[0194] [ka]

[0195] [ka]

[0196] [ka]

[0197] [ka]

[0198] [ka]

[0199] [ka]

[0200] [Content of repeating unit represented by formula (54)] In the case where the polymer 1 contains a repeating unit represented by formula (54), The content of the repeating unit represented by formula (54) is not particularly limited. The content in the polymer is usually 10 mol % or more, preferably 30 mol % or more, and more preferably 40 mol % or more. It is more preferable that the content is 100 mol % or more, and further more preferable that the content is 50 mol % or more.

[0201] When polymer 1 contains a repeating unit represented by formula (54), polymer 1 has a repeating unit The organic electroluminescent element may be composed of only the repeating unit represented by formula (54). In order to balance the various properties when used as a repeating unit, the repeating unit represented by formula (54) In this case, the repeating unit represented by formula (54) in the polymer may be The content of repeating units is usually 99 mol % or less, preferably 95 mol % or less.

[0202] [Terminal group] In this specification, the term "terminal group" refers to a group formed by an end-capping agent used at the end of polymerization of the polymer. In polymer 1, the structure represented by formula (54) The end group of the polymer containing the repeating unit is preferably a hydrocarbon group. From the viewpoint of charge transportability, the group preferably has 1 to 60 carbon atoms, and more preferably has 1 to 40 carbon atoms. is more preferable, and 1 or more and 30 or less is even more preferable.

[0203] Examples of the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. , n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl The carbon number of the aryl group, such as a cyclohexyl group, a cyclohexyl group, a dodecyl group, etc. is usually 1 or more, preferably 4 or more. and the number of alkyl groups is usually 24 or less, preferably 12 or less, and is a linear, branched, or cyclic alkyl group. Kill group; The number of carbon atoms of the vinyl group or the like is usually 2 or more and usually 24 or less, preferably 12 or less. a linear, branched, or cyclic alkenyl group, The number of carbon atoms, such as an ethynyl group, is usually 2 or more and usually 24 or less, preferably 12 or less. a straight or branched alkynyl group; The carbon number of a phenyl group, a naphthyl group, etc. is usually 6 or more and usually 36 or less, and is preferably and aromatic hydrocarbon groups having 24 or less carbon atoms.

[0204] These hydrocarbon groups may further have a substituent. is preferably an alkyl group or an aromatic hydrocarbon group. When there are a plurality of such groups, they may be bonded to each other to form a ring.

[0205] The terminal group is preferably an alkyl group or an aromatic carbon group from the viewpoint of charge transportability and durability. It is preferably a hydrogen group, and more preferably an aromatic hydrocarbon group.

[0206] <Repeating unit represented by formula (55)>

[0207] [ka]

[0208] (In formula (55), Ar 51 is Ar in the formula (50). 51 is the same as R 303and R 306 are each independently an alkyl group which may have a substituent, , R 304 and R 305 each independently represents an alkyl group which may have a substituent, a substituted an alkoxy group which may have one or more groups or an aralkyl group which may have one or more groups, l is 0 or 1; m is 1 or 2; n is 0 or 1 a5 is 0 or 1, b5 is 0 or 1.

[0209] (R 303 , R 306 ) R in the repeating unit represented by the above formula (55) 303 and R 306 are each independently It is an alkyl group which may have a substituent. The alkyl group is R in the formula (54). 201 and R 202 Similar things are listed The substituents that may be present and the preferred structures are also shown in R 201 and R 202 and similar Examples include: R 303 If there are multiple R 303 may be the same or different, and R 306 If there are multiple R 306 may be the same or different.

[0210] (R 304 , R 305 ) R in the repeating unit represented by the above formula (55) 304 and R 305 are each independently an optionally substituted alkyl group, an optionally substituted alkoxy group, or a substituted An aralkyl group which may have a substituent is preferably an alkyl group which may have a substituent. It is a aryl group. R 304 and R 305 are preferably the same.

[0211] The alkyl group may be a straight-chain, branched, or cyclic alkyl group. There is no particular limitation on the number of carbon atoms in the alkyl group. However, it is preferable that the number is 1 or more because the solubility of the polymer tends to be improved. 24 or less is preferable, 8 or less is more preferable, and 6 or less is even more preferable.

[0212] Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, n-octyl group group, a cyclohexyl group, a dodecyl group, and the like.

[0213] The alkoxy group is not particularly limited, and may be an alkoxy group (-OR 10 )R 10 The group may be linear or branched. or cyclic structure, which tends to improve the solubility of the polymer, The number of carbon atoms is preferably 1 or more, and is preferably 24 or less, and more preferably 12 or less.

[0214] Specifically, methoxy, ethoxy, n-propoxy, n-butoxy, hexyl Examples of the alkoxy group include an oxy group, a 1-methylpentyloxy group, and a cyclohexyloxy group.

[0215] The aralkyl group is not particularly limited, but carbon is preferred because it tends to improve the solubility of the polymer. A prime number of 5 or greater is preferable, and a prime number of 60 or less is preferable, and a prime number of 40 or less is more preferable.

[0216] Specifically, 1,1-dimethyl-1-phenylmethyl group, 1,1-di(n-butyl)- 1-phenylmethyl group, 1,1-di(n-hexyl)-1-phenylmethyl group, 1,1- Di(n-octyl)-1-phenylmethyl group, phenylmethyl group, phenylethyl group, 3 -phenyl-1-propyl group, 4-phenyl-1-n-butyl group, 1-methyl-1-phenyl phenylethyl group, 5-phenyl-1-n-propyl group, 6-phenyl-1-n-hexyl group , 6-naphthyl-1-n-hexyl group, 7-phenyl-1-n-heptyl group, 8-phenyl Examples include a phenyl-1-n-octyl group and a 4-phenylcyclohexyl group.

[0217] (l, m and n) l represents 0 or 1, and n represents 0 or 1.

[0218] l and n are each independent, and l+n is preferably 1 or more, more preferably 1 or 2, and 2 When l+n is in the above range, the solubility of the polymer 1 is increased, and the polymer It also tends to be possible to suppress deposition from a composition for organic electroluminescent elements containing the compound.

[0219] m represents 1 or 2, and the organic electroluminescent device of the present invention can be driven at a low voltage and has hole injection and transport properties. It is preferable that the ratio is 1 because this tends to improve the performance and durability.

[0220] (a5 and b5) a5 represents 0 or 1, and a5 represents 0 or 1. When l=n=1, a5 and b5 are simultaneously When a5 and b5 do not become 0 at the same time, the solubility of the polymer is increased. Furthermore, precipitation from a composition containing the polymer also tends to be suppressed. If the ratio is 1 or more, the aromatic rings in the main chain are twisted due to steric hindrance, and the polymer has excellent solubility in solvents. At the same time, a coating film formed by a wet film-forming method and then heat-treated tends to have excellent insolubility in solvents. Therefore, if a5+b5 is 1 or more, it is possible to form another organic layer (e.g., When forming a layer (e.g., a light-emitting layer), the polymer is mixed with the organic solvent-containing composition for forming the other organic layer. Dissolution is suppressed.

[0221] (Ar 51 ) In the repeating unit represented by the above formula (55), Ar 51 is the formula (50) RuAr 51 and the aromatic hydrocarbon group which may have a substituent and the aromatic hydrocarbon group which has a substituent are the same as those of and a group or groups selected from the group consisting of optionally substituted aromatic heterocyclic groups, It is the base.

[0222] Aromatic hydrocarbon groups which may have a substituent and aromatic hetero groups which may have a substituent As the group to which one group or multiple groups selected from the group consisting of cyclic groups are linked, the group represented by the formula (5 0) in Ar 51 The same substituents and preferred structures as those of the formula Ar in (50) 51 The same as in the case of

[0223] The main chain structure excluding the N atom of the repeating unit represented by formula (55) is not particularly limited, but For example, the following structure can be given:

[0224] [ka]

[0225] [ka]

[0226] [ka]

[0227] [ka]

[0228] [ka]

[0229] [ka]

[0230] [ka]

[0231] [ka]

[0232] [Content of repeating unit represented by formula (55)] In the case where the polymer 1 contains a repeating unit represented by formula (55), The content of the repeating unit represented by formula (55) is not particularly limited. Usually, the content in the polymer is 10 mol % or more, preferably 30 mol % or more, and more preferably 40 mol % or more. It is more preferable that the content is 100 mol % or more, and particularly preferable that the content is 50 mol % or more.

[0233] When polymer 1 contains a repeating unit represented by formula (55), polymer 1 has a repeating unit The organic electroluminescent element may be composed of only the repeating unit represented by formula (55). In order to balance the various properties when used as a repeating unit, the repeating unit represented by formula (55) In this case, the repeating unit represented by formula (55) in the polymer may be The content of repeating units is usually 99 mol % or less, preferably 95 mol % or less.

[0234] [Terminal group] In polymer 1, the terminal group of the polymer containing the repeating unit represented by formula (55) is It is a hydrocarbon group, similar to the terminal group of the polymer containing the repeating unit represented by formula (54). The preferred hydrocarbon group and the substituents that may be possessed are also represented by the above formula (54). It is similar to the end group of a polymer containing repeating units.

[0235] <Repeating unit represented by formula (57)>

[0236] [ka]

[0237] (In formula (57), Ar 51 is Ar in the formula (50). 51 is the same as R 517 ~R 519 each independently represents an alkyl group which may have a substituent; an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, f, g, and h each independently represent an integer of 0 to 4; e represents an integer of 0 to 3; However, if g is 1 or greater, e is 1 or greater.)

[0238] (R 517 ~R 519 ) R 517 ~R 519The aromatic hydrocarbon group and aromatic heterocyclic group in Ar 51 The substituents which these groups may have are the same as those listed in The same groups as those in the above-mentioned substituent group Z are preferred.

[0239] R 517 ~R 519 The alkyl group and aralkyl group in the R 207 The ones mentioned in The same groups as those in R are preferred, and the substituents that may be further substituted are also the same as those in R 207 A group similar to I wish.

[0240] R 517 ~R 519 The alkoxy group in the formula (I) is any of the alkoxy groups exemplified in the above-mentioned substituent group Z. The preferred substituents that may be further possessed are the same as those in the group Z of substituents.

[0241] (f, g, h) f, g, and h each independently represent an integer of 0 to 4. When e is 2 or more, multiple g's may be the same or different. It is preferable that f+g+h is 1 or more. f+h is preferably 1 or greater, It is more preferable that f+h is 1 or more, and f, g, and h are 2 or less. It is more preferable that f+h is 1 or more, and f and h are 1 or less. Most preferably, f and h are both 1.

[0242] When f and h are both 1, R 517 and R 519 are bonded at symmetric positions to each other It is preferable that Also, R 517 and R 519 are preferably identical to

[0243] More preferably, g is 2. If g is 2, then two R 518 are most preferably bonded to each other in the para position. , If g is 2, then two R 518 are most preferably the same.

[0244] where R 517 and R 519 are bonded at positions symmetric to each other, the following bond positions are However, for the purposes of notation, a 180-degree rotation around the main chain is considered to be the same structure.

[0245] [ka]

[0246] The repeating unit represented by the formula (57) may be a repeating unit represented by the following formula (58): It is preferable that the unit is a unit.

[0247] (Repeating unit represented by formula (58))

[0248] [ka]

[0249] (In formula (58), Ar 51 is Ar in the formula (50). 51 is similar to R 517 ~R 519 ,f, g, h, and e are R in the formula (57) 517 ~R 519 , f, g, h, e are the same. .)

[0250] In the case of the repeating unit represented by the formula (58), g is preferably 0 or 2. When g=2, the binding positions are 2 and 5. When g=0, that is, R518 by When there is no steric hindrance, and g=2 and the bonding positions are 2 and 5, Two R's with obstacles 518 When the bond is diagonal to the benzene ring, R 517 and R 51 9 and can be bonded at positions symmetrical to each other.

[0251] The repeating unit represented by the formula (58) is represented by the following formula (59) where e=3: It is more preferable that the repeating unit is a repeating unit containing the above-mentioned repeating unit.

[0252] (Repeating unit represented by formula (59))

[0253] [ka]

[0254] (In formula (59), Ar 51 is Ar in the formula (50). 51 is similar to R 517 ~R 519 ,f, g and h are R in the formula (57) 517 ~R 519 , f, g, h.)

[0255] In the case of the repeating unit represented by the formula (59), g is preferably 0 or 2. When g=2, the binding positions are 2 and 5. When g=0, that is, R 518 by When there is no steric hindrance, and g=2 and the bonding positions are the 2nd and 5th positions, Physical disability is two R 518 When the bond is diagonal to the benzene ring, R 517 and R 5 19and can be bonded at positions symmetrical to each other.

[0256] <Specific examples of the main chain of the repeating unit represented by formula (57)> The main chain structure excluding the N atom of the repeating unit represented by formula (57) is not particularly limited, but For example, the following structure can be given:

[0257] [ka]

[0258] [Content of repeating unit represented by formula (57)] In the case where the polymer 1 contains a repeating unit represented by formula (57), The content of the repeating unit is not particularly limited, but the repeating unit represented by formula (57) Usually, the content in the polymer is 10 mol % or more, preferably 30 mol % or more, and more preferably 40 mol % or more. It is more preferable that the content is 100 mol % or more, and particularly preferable that the content is 50 mol % or more.

[0259] When polymer 1 contains a repeating unit represented by formula (57), polymer 1 has a repeating unit The organic electroluminescent element may be composed of only the repeating unit represented by formula (57). In order to balance the various properties when used as a repeating unit, the repeating unit represented by formula (57) In this case, the repeating unit represented by formula (57) in the polymer may be The content of repeating units is usually 99 mol % or less, preferably 95 mol % or less.

[0260] [Terminal group] In polymer 1, the terminal group of the polymer containing the repeating unit represented by formula (57) is It is a hydrocarbon group, similar to the terminal group of the polymer containing the repeating unit represented by formula (54). The preferred hydrocarbon group and the substituents that may be possessed are also represented by the above formula (54). It is similar to the end group of a polymer containing repeating units.

[0261] The repeating units represented by any of the formulas (50) to (55) and the formulas (57) to (59) include In the case where the crosslinking group is not contained, heating after the wet film formation is preferable. This is preferable because polymer chain distortion is unlikely to occur upon drying or baking (heating and baking). This is because when the groups react, a volume change can occur, causing distortion of the polymer chains. In addition, even if no volume change occurs, distortion of the polymer chain occurs.

[0262] [Preferred repeating units] As described above, the repeating unit represented by formula (50) is a repeating unit represented by formula (54). repeating unit, repeating unit represented by the formula (55) or repeating unit represented by the formula (57) Preferably, the unit is . Among these, A repeating unit represented by formula (54) containing a partial structure represented by formula (61): A repeating unit represented by the formula (55) containing a partial structure represented by the following formula (61): or a repeating unit represented by the formula (57) containing a partial structure represented by the following formula (61): It is preferable that:

[0263] [ka]

[0264] (In formula (61) and formula (61'), R 601 is R in Eq. (54) 201 or R 202 , R in Eq. (55) 303 , R304 , R 305 , or R 406 , R in Eq. (57) 517 , R 518 or R 5 19 and -* indicates a bond to the adjacent atom. When formula (61) is a partial structure of formula (54), Ring B is a part of a fused ring. Good too. The partial structures represented by formula (61) and formula (61') are R 601 In addition to Ring A and and Ring B, when it is a partial structure of formula (54), R 201 or R 202 , formula (5 If it is a partial structure of 5), R 303 , R 304 , R 305 , or R 406 , equation (57) If it is a partial structure of 517 , R 518 or R 519 It may have.)

[0265] (Repeating unit represented by formula (62)) As the repeating unit contained in the polymer 1, the repeating unit of the formula (54) is particularly preferred. The repeating unit represented by the formula (54) is preferably a repeating unit represented by the following formula (62): It is preferable that the unit is a unit.

[0266] [ka]

[0267] (In formula (62), Ar 51 , X, R 201 , R 202 , R 221 , R 222 , a, b, c, and d are the same as those in the formula Ar in (54) 51 , X, R201 , R 202 , R 221 , R 222 , a, b, c , d, and a 1 , a 2 , b 1 , b 2 , i 1 , i 2 , j 1 , j 2 are each independently 0 or 1. However, either of the following conditions (1) or (2) must be met. (1)a 1 , a 2 and at least one of a is 1 or greater; b 1 , b 2 and at least one of b is 1 or greater; c and d are 1 or greater, and If c is 1, then a 1 or a 2 At least one of is 1, If d is 1, then b 1 or b 2 At least one of them is 1. (2)i 1 , i 2 , j 1 and j 2 At least one of is 1. Ring B1 is R 201 and Ring B2 is R 201 a divalent group having c-1 benzene rings linked together, which may have When c=1, it refers to a single bond, Ring B3 refers to a divalent fused ring in which a biphenyl structure is further bonded with X. Ring B4 is R 202 a divalent group having d-1 benzene rings linked together, which may have However, when d=1, it refers to a single bond, Ring B5 is R 202 It refers to a divalent benzene ring which may have

[0268] Here, a in formula (54) being 1 or more means that a 1 , a 2 and at least one of a is 1 or more, and b in formula (54) is 1 or more. The above means that in equation (62), b 1 , b 2 and at least one of b is 1 or greater This is synonymous with

[0269] As shown below, the formula (62) is a compound represented by the formula (61) or the formula (61') as a partial structure. include. a 1 , a 2 and at least one of a is 1 or greater, a 1 or a 2 If at least one of is 1, When c is 2 or more, Ring B1 and Ring B2, or When c is 1, Ring B1 and Ring B3 are containing the formula (61) or the formula (61') as a partial structure, If a is 1 or more, in this case c is 2 or more, then Ring B2 and Ring B1 Or, Ring B2 and Ring B3 are represented by the formula (61) or the formula (61 ') as a substructure, Alternatively, when c is 3 or more and a is 1 or more, the ring B2 has the formula (61) or may contain the above formula (61') as a partial structure.

[0270] Similarly, b 1 , b 2 and b are each 1 or more. It can be seen that the formula (61') is included as a partial structure.

[0271] Also, i1 , i 2 , j 1 and j 2 If at least one of is 1, i 1 and i 2 If either or both of these are 1, then R in Ring B3 221 The ring to which and the benzene ring of Ring B2 or Ring B1, the partial structure is represented by the formula (61') formed, j 1 and j 2 If either or both of these are 1, then R in Ring B3 222 The ring to which and the benzene ring of Ring B4 or Ring B5, the partial structure of formula (61) is formed. It is clear that this will be achieved.

[0272] That is, Ring B3 and Ring B2 or Ring B1, or Ri It was found that Ring B3 and Ring B4 or Ring B5 have a twisted structure. R Therefore, since formula (62) contains a twisted structure of the aromatic ring of the main chain, for the reasons mentioned above, This is preferable because it is easier to obtain a flatter film.

[0273] The polymer 1 does not contain a repeating unit represented by the formula (40) described below. As a result, the HOMO of polymer 1 spreads around the N atoms of the main chain and the repeating units of the main chain The HOMO is distributed among the N atoms of the carbazoline, resulting in a carbazoline with a deeper HOMO in the main chain. The charge transport property is superior to that of polymer 2 containing a hexol structure, and the organic thin film formed using the organic thin film forming material of the present invention is This is responsible for the main charge transport within the film. As a result, the organic film has low electrical resistance, and the use of the organic film It is believed that this will improve the carrier balance of organic electroluminescent devices and achieve high luminous efficiency. In addition, even after the degradation of polymer 2 due to charge injection, the high molecular weight of the main chain of polymer 1 remains. Since the charge transport property is maintained, the organic electroluminescent device using the organic film is not susceptible to deterioration due to electrical conduction of the organic film. The change in carrier balance due to the change is small, resulting in a long operating life.

[0274] <Polymer 2> Polymer 2 contains a repeating unit represented by the following formula (40).

[0275] [ka]

[0276] (In formula (40), Ar 1 and Ar 2 each independently represents a divalent aromatic hydrocarbon which may have a substituent. a divalent aromatic heterocyclic group optionally having a substituent, and a divalent aromatic heterocyclic group optionally having a substituent; represents a divalent group to which a group or a plurality of groups are linked, and the linkage is made directly or via a linking group. There are. R 1 ~R 18 each independently represents a direct bond, a hydrogen atom, a deuterium atom, a halogen atom, or a substituted It represents an aromatic ring group which may have one or more groups, and a group formed by linking 2 to 8 such aromatic rings. p and q each independently represent an integer of 0 to 1, and p+q is 1 or more. Ar 3 is an aromatic hydrocarbon group which may have a substituent and an aromatic hydrocarbon group which may have a substituent. A group to which one or more groups selected from the group consisting of aromatic heterocyclic groups are linked, The linkage may be direct or via a linking group. r represents an integer of 0 to 1. G is a direct bond, a divalent aromatic ring group which may have a substituent, or the aromatic ring is bonded to a ring having 2 to 1 carbon atoms. It represents a divalent group formed by linking four groups. s and t each independently represent an integer of 0 to 1. However, this does not apply when s is 0, t is 1, p is 0, and r is 1. R 1 ~R 8 and R 9 are respectively Ar 1 , N-Ar 3 Nitrogen atom of , G, R 10 ~R 18 One of Ar 2 or directly bonded to the main chain of polymer 2 , R 10 ~R 17 and R 18 One of them is G or R 1 ~R 9 of One is directly bonded to the other, and the other is bonded to Ar 2 or directly bonded to the main chain of polymer 2 (I'm doing it.)

[0277] The polymer having the repeating unit represented by the above formula (40) has a moiety containing a carbazole group. The LUMO of the arylamine becomes deeper, making it easier to accept electrons from the surrounding arylamine moieties. The Ar atom is closer to the N atom in the carbazole structure. 1 or Ar 2 The LUMO spreads to the polymer molecule. It is thought that the molecule has excellent redox resistance. The HOMO of the polymer does not extend along the main chain, so the excited singlet energy level (S1) , keeping the excited triplet energy level (T1) high. Furthermore, the electron holes flowing along the main chain are transported to the deep HOMO By trapping holes in the luminescent layer and transporting them to other materials deeper inside the luminescent layer efficiently, This is advantageous for charge injection.

[0278] (Ar 1 and Ar 2 ) Ar in formula (40) 1 and Ar 2 each independently represents a divalent group optionally having a substituent. and optionally substituted divalent aromatic heterocyclic groups, represents a divalent group to which one or more selected groups are linked, and the linkage is direct or via a linking group This is done through. Examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, an anthracene ring, a phenyl ring, and a phenyl ring. a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, Six-membered rings such as triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene ring Examples include groups derived from a single ring or 2 to 5 condensed rings. Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzo Thiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring Dole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thieno Furan ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring , a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, Isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, Examples of the quinazolinone ring include a 5- or 6-membered monocyclic ring or a group derived from 2 to 4 condensed rings, such as a quinazolinone ring and a quinazolinone ring. It can be obtained. Among these, Ar is preferred from the viewpoint of solubility in organic solvents and heat resistance. 1 and Ar 2 is benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, triphenylene ring, pyrene ring, A group derived from a ring selected from the group consisting of a thiophene ring, a pyridine ring, and a fluorene ring is preferred. . Ar 1 and Ar 2 represents a divalent aromatic hydrocarbon group which may have a substituent and a substituent a divalent aromatic heterocyclic group having a plurality of groups linked together selected from the group consisting of a divalent aromatic heterocyclic group which may have Specifically, a group formed by linking 2 to 8 aromatic rings can be mentioned. Examples of the aromatic ring include the above-mentioned aromatic hydrocarbon ring and aromatic heterocycle.

[0279] The aromatic hydrocarbon group and aromatic heterocyclic group may have a substituent, which may be a substituent having the characteristics of the polymer 2. There are no particular limitations on the substituents as long as they do not significantly reduce the and the substituent Z is an alkyl group, an alkoxy group, an aromatic hydrocarbon group, or the like. , an aromatic heterocyclic group is more preferred, and an alkyl group is even more preferred. When a plurality of groups are linked via a linking group, the linking group is preferably a group having outstanding properties of the polymer 2. There are no particular limitations as long as the linking group does not significantly reduce the molecular weight. 40-χ).

[0280] Ar 1 and Ar 2 may contain a structure represented by the following formula (40-χ):

[0281] [ka]

[0282] (In formula (40-χ), R 1901 and R 1902 are each independently a hydrogen atom, a group having 1 to 20 carbon atoms, Alkyl groups, aralkyl groups having 7 to 40 carbon atoms, heteroaralkyl groups having 4 to 40 carbon atoms, an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 30 carbon atoms; These groups may further have a substituent, and χ represents an integer of 1 to 8.

[0283] The substituents which these groups may further have include the aforementioned substituent group Z or From the viewpoint of thermal and electron durability, the substituents in the substituent group Z are preferably selected from the group consisting of aryl, aryl, aryls ... However, biphenyl, triphenyl, fluorenyl, and phenyl groups are also included in the fluorenyl group. is particularly preferred.

[0284] Ar 1 Or Ar 2 If the structure represented by formula (40-χ) is included, the main chain contains sp3 carbon atoms. By including the atoms, the singlet and triplet excited levels can be maintained high, and the excitons are not deactivated. Therefore, the luminous efficiency of the resulting organic electroluminescent device tends to be high.

[0285] (R 1 ~R 18 ) R 1 ~R 18 each independently represents a direct bond, a hydrogen atom, a deuterium atom, a halogen atom, or a substituted It represents an aromatic ring group which may have one or more groups, and a group formed by linking 2 to 8 such aromatic rings. R 1 ~R 8 and R 9 are respectively Ar 1 , N-Ar 3 Nitrogen atom of , G, R 10 ~R 18 One of Ar 2 or directly bonded to the main chain of polymer 2 , R 10 ~R 17 and R 18 One of them is G or R 1~R 9 of One is directly bonded to the other, and the other is bonded to Ar 2 or directly bonded to the main chain of polymer 2 are. The aromatic ring group which may have a substituent is (Ar 1 and Ar 2 (About the fragrance) The aromatic ring group may have a substituent selected from the group consisting of an aromatic hydrocarbon group and an aromatic heterocyclic group. The aforementioned Ar 1 and Ar 2 The same applies to the preferred embodiments.

[0286] In the repeating unit represented by the above formula (40), Ar 1 and Ar 2 At least one of It is preferable that the above formula be expressed by the following formula (41) or (42).

[0287] [ka]

[0288] (In formula (41), R 201 , R 202 , a to d, and X are the same as in formula (54), and are independent of polymer 1. m4 represents an integer between 1 and 2.

[0289] In the repeating unit represented by formula (40) in polymer 2, Ar 1 and Ar 2 Few At least one of them has a structure represented by the following formula (41), so that polymer 2 has a structure represented by the following formula (54) The preferred embodiment and effect of the formula (41) in polymer 2 is The preferred embodiments and effects are similar to those of formula (54) in the above. In addition, by including a structure similar to the main chain of polymer 1 and the main chain of polymer 2, the main chains of both polymers It is believed that this can facilitate the movement of the electric field between the electrodes.

[0290] Specific examples of the structure represented by formula (41) are shown below, but the structures used in the present invention are not limited to these. * indicates the bond position.

[0291] [ka]

[0292] [ka]

[0293] (In formula (42), R 23 and R 25 each independently represents an alkyl group which may have a substituent, R 24 represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent. represents a group or an aralkyl group which may have a substituent, u and w each independently represent an integer of 0 to 2; v represents an integer of 1 or 2; x, y, and z each independently represent an integer of 0 to 2, and x+z is 1 or more.

[0294] R 23 and R 25 The alkyl group, alkoxy group, and aralkyl group that may be contained in R in formula (55) 304 The substituents and preferred structures are the same as those shown in the above. Also, R in the formula (55) 304 is the same as: R 24 The alkyl group that may be contained in R 201 It is the same as The substituents that may be possessed and the preferred structures are also described in R 201 Same as It seems that

[0295] x and z are each independent, and x+z is 1 or more, more preferably 1 or 2. +z is 1 or more, preferably 2 or more. x+y+z is 6 or less, preferably 5 or less. x When y and z are within the above ranges, the solubility of polymer 2 is increased, and the amount of the polymer containing the polymer is increased. There is also a tendency that deposition from the composition for organic electroluminescent devices can be suppressed.

[0296] When x is 2, each u may be the same or different; When y is 2, each v may be the same or different; When z is 2, each w may be the same or different. Preferably, u+w is 1 or greater; It is more preferable that u+w is 1 or more, and u and w are 1 or less, It is most preferable that u and w are both 1.

[0297] If u and w are both 1, then R 23 and R 25 are bonded at symmetric positions to each other It is preferable. Also, R 23 and R 25 are preferably identical to

[0298] More preferably, v is 2. If v is 2, then two R 24 are most preferably linked to each other in the para position, If v is 2, then two R 24 are most preferably the same.

[0299] Specific examples of the structure represented by formula (42) are shown below, but the structures used in the present invention are not limited to these. * indicates the bond position.

[0300] [ka]

[0301] A specific example of the structure represented by formula (42) is the repeating structure represented by formula (57) described above. Among the examples of the main chain of the α-alkyl unit, examples shown in the main chain structure excluding the N atom are also preferably used. .

[0302] (Ar 3 ) In the above formula (40), Ar 3 is Ar in the formula (50). 51 is the same as The same is true for what is preferred.

[0303] (r, t) In the above formula (40), t is preferably 1. By including the HOMO, the HOMO tends to broaden and the charge mobility tends to increase. In the above formula (40), r is preferably 1. The carrier density is improved by including aromatic amines in the main chain of polymer 1. The charge transport between the main chains of the polymer 2 also tends to be improved.

[0304] (p, q) In the above formula (40), p and q each independently represent an integer of 0 to 1, and p+q is It is greater than or equal to 1. t is 1, and R of the carbazole group 18 Ar 2 If a direct bond to It is preferable to improve the oxidation-reduction resistance around the nitrogen of the carbazole group and to prevent degradation of the polymer 2. can be suppressed. Also, when t is 1 and r is 1, q is preferably 1. The amine skeleton of the zole and another repeating unit is not adjacent, which leads to a local deep HOMO level. This material can maintain a high singlet excitation energy level and improve the efficiency of light-emitting devices using this material. can.

[0305] (G, s) In the above formula (40), G is a direct bond or a divalent aromatic ring which may have a substituent. group, or a divalent group formed by linking 2 to 4 of the aromatic rings. The aromatic ring group is (Ar 1 and Ar 2 The aromatic hydrocarbon groups and aromatic heterocyclic groups described in The substituents that the aromatic ring group may have are selected from the above-mentioned Ar 1 and Ar 2 and The same applies to the preferred embodiments. G is more preferably a structure in which x+y+z is 4 or less in the formula (42). It's nice. When G exists, both s and t are 1, and G is always sandwiched between two carbazole groups. do. When G is bonded to the 9-position of the carbazole group, G is a redox-resistant group around the nitrogen of the carbazole group. It shows the effect of improving sexuality. When G is bonded to a position other than the 9-position of the carbazole group, the HOMO localized in the carbazole group However, the aromatic ring group of G is adjacent to the main chain. When the adjacent rings have a substituent that causes a twist, the HOMO spread is It is thought that this has the effect of stopping the charge transport and enhancing the injection effect into deep levels. can be done. By adjusting the structure of G, the hole transport level and localization of polymer 2 can be adjusted, and the polymerization The difference in charge transport property and hole transport level between polymer 1 and polymer 2 can be optimized, and the organic electric field of the present invention can be It is believed that the balance between the luminous efficiency and the life span of the light-emitting element can be adjusted.

[0306] (Repeating unit represented by formula (43)) The repeating unit represented by the formula (40) is a repeating unit represented by the following formula (43): It is preferable that there is.

[0307] [ka]

[0308] (In formula (43), R 1 ~R 6 , R 8 , R 10 , R 12 ~R 17 are each independently a hydrogen atom , a deuterium atom, a halogen atom, an aromatic ring group which may have a substituent, and the aromatic ring It represents a group formed by linking 2 to 8 units. Ar 1 ~Ar 3 , G, p, q, r, s, and t are the same as in equation (40).

[0309] In the repeating unit represented by formula (43), the HOMO extends from the 3-position of the carbazole, The HOMO is widely distributed between the nitrogen atoms of the two carbazole groups. This allows the charge transport of polymer 2 to be This tends to improve transmission. In addition, the charge flowing along the main chain is stabilized in the deep HOMO of the carbazole group, and the side chains and It is believed that this tends to improve injection into the deeper HOMO levels of the light-emitting material.

[0310] In the repeating unit represented by formula (43), it is more preferable that p is 1 and q is 1. Ar is added to the nitrogen of carbazole. 1 Or Ar 2 are adjacent to each other, which increases redox resistance. This increases the lifetime of the resulting organic electroluminescent device. In the repeating unit represented by formula (43), Ar 1 ~Ar 3 ,G,r,s,t's preferred The new aspect is the same as in equation (40).

[0311] (Specific examples of repeating units represented by formula (43)) Specific examples of the repeating unit represented by formula (43) are shown below. ) is not limited to these.

[0312] [ka]

[0313] Polymer 2 contains a repeating unit represented by the following formula (54), a repeating unit represented by the following formula (55), a repeating unit represented by the following formula (56), and a repeating unit represented by the following formula (57). It is more preferable that the repeating unit contains a repeating unit represented by formula (55) or the following formula (57): It contains a structure similar to the repeating unit represented by the above formula (50) contained in polymer 1. As a result, a region where the HOMO and LUMO are close to each other is formed between the main chains of polymer 1 and polymer 2, and the charge transport property is improved. It is believed that this will result in superior performance and improved durability.

[0314] [ka]

[0315] (In formula (54), Ar 51 is Ar in the formula (50). 51 is the same as X is -C(R 207 )(R 208 )-, -N(R 209 )- or -C(R 211 ) (R 212 )-C(R 213 )(R214 )- and R 201 , R 202 , R 221 and R 222 Each of the groups independently has a substituent. is an alkyl group which may be R 207 ~R 209 and R 211 ~R 214 are each independently a hydrogen atom or a substituent. an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a an aromatic hydrocarbon group which may be a and b each independently represent an integer of 0 to 4, c is an integer from 0 to 3, d is an integer from 0 to 4, R 201 If there are multiple R 201 may be the same or different, R 202 If there are multiple R 202 may be the same or different, R 221 If there are multiple R 221 may be the same or different, R 222 If there are multiple R 222 may be the same or different, i and j are each independently an integer of 0 to 3.

[0316] [ka]

[0317] (In formula (55), Ar 51 is Ar in the formula (50). 51 is the same as R 303 and R 306 are each independently an alkyl group which may have a substituent. the law of nature, R 304 and R 305 each independently represents an alkyl group which may have a substituent; an optionally substituted alkoxy group or an optionally substituted aralkyl group; , l is 0 or 1; m is 1 or 2; n is 0 or 1 a5 is 0 or 1, b5 is 0 or 1.

[0318] [ka]

[0319] (In formula (57), Ar 51 is Ar in the formula (50). 51 is the same as R 517 ~R 519 each independently represents an alkyl group which may have a substituent; an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, f, g, and h each independently represent an integer of 0 to 4; e represents an integer of 0 to 3; However, if g is 1 or greater, e is 1 or greater.)

[0320] As described above, in the polymer 2, the above formula (54), the above formula (55), and the above formula (57) The repeating unit represented by the formula (54), the formula (55), or the formula (57) in the polymer 1 is The repeating units are the same as those shown in the above, and preferred embodiments are also the same.

[0321] [Bridging group] The polymer 2 may have a crosslinking group, but the organic thin film forming material of the present invention is preferably formed adjacent to the light emitting layer. When used in a layer where a crosslinking group is to be formed, it is preferred that the compound has no crosslinking group. As the crosslinking group of polymer 2, a group having the same structure as that described in [Crosslinking group] of polymer 1 can be used. This can be done.

[0322] <Crosslinking Group, Polymerizable Group, and Leavable Solubilizing Group of Polymer 1 and Polymer 2> The polymer 1 and the polymer 2 do not have a crosslinking group, a polymerizable group, or a leaving solubilizing group. is preferred. Polymer 1 and polymer 2 have crosslinking groups and polymerizable groups, and are capable of being crosslinked and polymerized by a crosslinking reaction and a polymerization reaction. When a thin film formed by an organic film-forming material becomes insoluble, a volume change occurs during the reaction. This can lead to distortion of the polymer chains even if no volume change occurs. In addition to the decrease in the efficiency of charge transport through the main chain, the resulting voids can trap the coating solvent. The characteristics of the organic electroluminescent device of the present invention are realized by the fact that the interface between the adjacent layers is in a mixed state. Therefore, polymer 1 and polymer 2 do not have crosslinking groups or polymerizable groups. It is preferable that

[0323] Furthermore, since the polymer 1 and the polymer 2 have a leaving solubilizing group, the polymer is dissolved in a solvent and a thin film is formed by elimination of the solubilizing group. It is believed that the stability of charge transport is hindered by the organic film-forming material of the present invention. When an adjacent layer is formed on the formed organic film by a coating method, the residual organic material in the organic film is It is believed that the detachable solubilizing group dissolves and mixes into the adjacent layer, deteriorating the properties. Therefore, it is preferable that polymer 1 and polymer 2 do not have a leaving solubilizing group.

[0324] <Molecular weight of polymer 1 and polymer 2> The molecular weights of Polymer 1 and Polymer 2 are described below.

[0325] Contains a repeating unit represented by formula (40), formula (50), formula (54) or formula (57) The weight average molecular weight (Mw) of the polymer is usually 3,000,000 or less, preferably 1,000 0,000 or less, more preferably 500,000 or less, and even more preferably 200,000 or less It is more preferably 100,000 or less, and particularly preferably 50,000 or less. The weight average molecular weight is usually 2,500 or more, preferably 5,000 or more. More preferably, it is 10,000 or more, even more preferably, it is 15,000 or more, and particularly preferably The number is over 17,000.

[0326] When the weight average molecular weight of the polymer is equal to or less than the upper limit, solubility in a solvent is obtained. In addition, when the weight average molecular weight of the polymer is equal to or greater than the above lower limit, the film-forming property tends to be excellent. This prevents the polymer's glass transition temperature, melting point, and vaporization temperature from decreasing, improving heat resistance. There are cases where this happens.

[0327] Furthermore, a repeating unit represented by formula (40), formula (50), formula (54) or formula (57) The number average molecular weight (Mn) of the polymer containing is 750,000 or less, more preferably 400,000 or less, and particularly preferably 100,0 The number average molecular weight is usually 2,000 or more, preferably 4,000 or less. It is 0 or more, more preferably 6,000 or more, and even more preferably 8,000 or more.

[0328] Furthermore, the repeating unit represented by formula (40), formula (50), formula (54) or formula (57) The dispersity (Mw / Mn) of the polymer containing the unit is preferably 3.5 or less, more preferably The dispersity is preferably 2.5 or less, and more preferably 2.0 or less. Therefore, the lower limit is ideally 1. If the dispersity of the polymer is equal to or less than the upper limit, precision is poor. It is easy to prepare, and has good solubility in solvents and charge transport properties.

[0329] The weight average molecular weight (Mw) of the polymer containing the repeating unit represented by formula (55) is preferably It is preferably 10,000 or more, more preferably 15,000 or more, and even more preferably The weight average molecular weight is 17,000 or more. 0 or less, more preferably 1,000,000 or less, and even more preferably 1 It is preferably 00,000 or less, and particularly preferably 50,000 or less.

[0330] By making the weight average molecular weight of the polymer equal to or less than the upper limit, the impurities are prevented from becoming high molecular weight. In addition, when the weight average molecular weight of the polymer is equal to or greater than the above lower limit, the polymer tends to be easily purified. This prevents the glass transition temperature, melting point, vaporization temperature, etc. from decreasing, improving heat resistance. This is a trend.

[0331] The number average molecular weight (Mn) of the polymer containing the repeating unit represented by formula (55) is preferably Preferably, it is 1,000,000 or less, more preferably 800,000 or less, and even more preferably More preferably, it is 500,000 or less. Also, it is preferably 4,000 or more, and even more preferably, it is 500,000 or less. It is more preferably 8,000 or more, and even more preferably 10,000 or more.

[0332] Furthermore, the dispersity (Mw / Mn) of a polymer containing a repeating unit represented by formula (55) is It is preferably 3.5 or less, more preferably 3.0 or less, and even more preferably 2. It is preferably 4 or less, particularly preferably 2.1 or less, and most preferably 2 or less. The dispersity of the polymer is preferably 1 or more, more preferably 1.1 or more, and It is more preferably 1.2 or more. When the dispersity of the polymer is equal to or less than the upper limit, It becomes easier to purify, and the decrease in solubility in solvents and the decrease in charge transport ability tend to be suppressed. It's in the direction.

[0333] The weight average molecular weight (Mw) of polymer 1 and polymer 2 is 15,000 or more and 50,000 or less. It is preferable that: The dispersity (Mw / Mn) of polymer 1 and polymer 2 is preferably 3.5 or less. stomach.

[0334] Usually, the weight average molecular weight and number average molecular weight of a polymer are measured by SEC (size exclusion chromatography). In SEC measurements, the elution time is shorter for high molecular weight components, and The elution time is longer for the more abundant components, but it is the same as the elution time of polystyrene (standard sample) with known molecular weight. The weights were calculated by converting the elution time of the sample into molecular weight using a calibration curve calculated from the above. The weight average molecular weight and number average molecular weight are calculated.

[0335] The weight average molecular weights of polymer 1 and polymer 2 contained in the organic film-forming material of the present invention and The weight average molecular weight and number average molecular weight may be the same or different. The larger the viscosity of the film-forming liquid composition, the better the insolubility of the film formed. This causes difficulties in coating when manufacturing high-definition display devices. By mixing polymers, the viscosity can be reduced and adjusted to an appropriate range while maintaining insolubility. This is possible and is preferable.

[0336] <Polymer mixing ratio> The content of polymer 1 and polymer 2 contained in the organic film-forming material of the present invention is The content of polymer 1 is preferably 1% by mass or more, more preferably 1% by mass or more, based on the total content of polymer 2. or 5% by mass or more, more preferably 10% by mass or more, and most preferably 20% by mass or more The content of polymer 2 is preferably 1% by mass or more, more preferably 5% by mass or more. or more, more preferably 10% by mass or more, and most preferably 20% by mass or more, i.e. That is, the content of polymer 1 is preferably 99% by mass or less, more preferably 95% by mass or less, It is more preferably 90% by mass or less, and most preferably 80% by mass or less.

[0337] <Example> Specific examples of polymer 1 and polymer 2 are shown below.

[0338] Specific examples of the polymer containing the repeating unit represented by formula (40) are shown below. The polymers used are not limited to these. The numbers in the chemical formulas indicate the number of repeating units. The molar ratio is shown, and n is the number of repeats.

[0339] These polymers may be random copolymers, alternating copolymers, block copolymers, or graphene copolymers. The sequence of the monomers is not limited.

[0340] [ka]

[0341] [ka]

[0342] [ka]

[0343] [ka]

[0344] Specific examples of the polymer containing the repeating unit represented by formula (54) are shown below. The polymers used are not limited to these. The numbers in the chemical formulas indicate the number of repeating units. The molar ratio is shown, and n is the number of repeats.

[0345] These polymers may be random copolymers, alternating copolymers, block copolymers, or graphene copolymers. The sequence of the monomers is not limited.

[0346] [ka]

[0347] [ka]

[0348] A polymer containing a repeating unit represented by formula (55) and a repeating unit represented by formula (55) Units of Ar 51 Specific examples of polymers having a structure represented by formula (52) are shown below. The polymers used in the present invention are not limited to these. The molar ratio of repeat units is shown. n represents the number of repeat units.

[0349] These polymers may be random copolymers, alternating copolymers, block copolymers, or graphene copolymers. The sequence of the monomers is not limited.

[0350] [ka]

[0351] [ka]

[0352] [ka]

[0353] [ka]

[0354] [ka]

[0355] [ka]

[0356] [ka]

[0357] [ka]

[0358] A polymer containing a repeating unit represented by formula (40) and a repeating unit represented by formula (50) Specific examples of the polymers used in the present invention are shown below, but the polymers used in the present invention are not limited to these. The numbers in the chemical formula represent the molar ratio of repeating units, and n represents the number of repeats.

[0359] These polymers may be random copolymers, alternating copolymers, block copolymers, or graphene copolymers. The sequence of the monomers is not limited.

[0360] [ka]

[0361] [ka]

[0362] [ka]

[0363] [ka]

[0364] [ka]

[0365] <Composition for organic film formation> The organic film-forming composition of the present invention (referred to as the first composition) will be described below. The composition of the present invention contains the above-mentioned polymer 1, polymer 2, and a solvent. It is used to form organic layers and organic films by ordinary wet film formation methods, and is particularly used for organic electroluminescent devices. It is preferable that the organic layer is used to form a hole transport layer. The first composition preferably contains one kind of the first polymer and one kind of the polymer 2. It may contain two or more of either one or both of them. They may be contained in any combination and in any ratio.

[0366] (Content) The content of the polymer in the first composition is usually 0.01% by mass or more and 70% by mass or less, Preferably, the content is 0.1% by mass or more and 60% by mass or less, and more preferably, 0.5% by mass or more and 50% by mass or less. The amount is less than %. When the content is within the above range, defects are unlikely to occur in the formed organic layer, and film thickness unevenness is also unlikely to occur. This is preferable because it is unlikely to occur.

[0367] (solvent) The first composition usually contains a solvent. This solvent is one that dissolves the above polymer. Specifically, the above polymer is preferably added to the first composition at room temperature in an amount of usually 0.05% by mass or more. A solvent that dissolves the above-mentioned compound in an amount of preferably 0.5% by mass or more, and more preferably 1% by mass or more is suitable. is.

[0368] Specific examples of the solvent include toluene, xylene, mesitylene, cyclohexylbenzene, Aromatic solvents such as methylnaphthalene; 1,2-dichloroethane, chlorobenzene, o-dichloroethane Halogen-containing solvents such as chlorobenzene; ethylene glycol dimethyl ether, ethylene glycol Licorice diethyl ether, propylene glycol-1-monomethyl ether acetate Aliphatic ethers such as (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxy Benzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole, etc. Ether solvents such as aromatic ethers; ethyl acetate, n-butyl acetate, ethyl lactate, n-lactic acid -butyl and other aliphatic ester solvents; phenyl acetate, phenyl propionate, methyl benzoate ethyl, ethyl benzoate, isopropyl benzoate, propyl benzoate, n-butyl benzoate Ester-based solvents such as aromatic esters; organic solvents such as those for forming the hole injection layer described below. Examples of the organic solvents include those used in the composition for forming the hole transport layer and the composition for forming the hole transport layer.

[0369] The solvent may be used alone or in any combination of two or more solvents in any ratio. may be used in combination.

[0370] The surface tension of the solvent at 20°C is usually less than 40 dyn / cm, preferably less than 36 dyn / cm or less, more preferably 33 dyn / cm or less.

[0371] On the other hand, the vapor pressure of the solvent at 25°C is usually 10 mmHg or less, and preferably The pressure is 5mmHg or less, and usually 0.1mmHg or more. As a result, the polymer is suitable for a process for producing an organic electroluminescent device by a wet film-forming method. Compositions can be prepared to suit the body's characteristics.

[0372] Specific examples of such solvents include the above-mentioned toluene, xylene, mesitylene, cyclohexane, and the like. Examples of the solvent include aromatic solvents such as hexylbenzene, ether solvents, and ester solvents.

[0373] However, moisture can cause performance degradation of organic electroluminescent devices, especially This may accelerate the decrease in brightness during continuous operation. In order to reduce the amount of water as much as possible, the solubility of water in the solvent at 25°C is preferably 1% by mass or less. , and more preferably 0.1 mass % or less.

[0374] The content of the solvent in the first composition is usually 10% by mass or more, preferably 30% by mass or more, The content of the solvent is more preferably 50% by mass or more, and particularly preferably 80% by mass or more. By ensuring that the content is equal to or greater than the lower limit, the flatness and uniformity of the layer to be formed can be improved. Cut.

[0375] [Electron-accepting compounds] The first composition preferably further contains an electron-accepting compound in order to reduce the resistance. In particular, when the first composition is used to form a hole injection layer, the first composition Preferably, the photosensitive layer contains an electron-accepting compound.

[0376] The electron-accepting compound has an oxidizing power and is capable of accepting one electron from the polymer contained in the first organic layer. Compounds having an electron affinity of 4 eV or more are preferred. Compounds having an electron affinity of 5 eV or more are preferred.

[0377] The first composition may contain only one of the above electron-accepting compounds, or Any combination and ratio of two or more of these may be included.

[0378] When the first composition contains an electron-accepting compound, the content of the electron-accepting compound in the first composition The content is usually 0.0005% by mass or more, preferably 0.001% by mass or more, and usually 2 It is 0% by mass or less, preferably 10% by mass or less.

[0379] The ratio of the electron-accepting compound to the polymer in the first composition is usually 0.5% by mass. or more, preferably 1% by mass or more, more preferably 3% by mass or more, and usually 80% by mass or more The content is preferably 60% by mass or less, and more preferably 40% by mass or less.

[0380] When the content of the electron-accepting compound in the first composition is equal to or greater than the lower limit, electrons are released from the polymer. The acceptor accepts electrons, and the resistance of the formed organic layer is reduced, which is preferable. When the content of the electron-accepting compound is equal to or less than the upper limit, defects are unlikely to occur in the formed organic layer, In addition, it is preferable because unevenness in the film thickness is unlikely to occur.

[0381] [Cation radical compounds] The first composition may further contain a cation radical compound. The cation radical compound is a chemical species obtained by removing one electron from a hole transport compound. Ionic compounds consisting of a cation radical and a counter anion are preferred. When the radical is derived from a hole-transporting polymer compound, the cation radical is The structure is one in which one electron is removed from the repeating unit.

[0382] In addition, the cation radical is a chemical compound obtained by removing one electron from a hole transport compound described later. It is preferable that the compound is a species obtained by removing one electron from a compound preferable as a hole transporting compound. The chemical species are preferable in terms of amorphousness, visible light transmittance, heat resistance, solubility, etc. be.

[0383] Here, the cation radical compound is a compound containing a hole transporting compound described later and an electron accepting compound described above. It can be produced by mixing a hole transporting compound and an electron accepting compound. By mixing the compound, electrons are transferred from the hole transporting compound to the electron accepting compound. This occurs when the cation radical of the hole transport compound and the counter anion are ionized. A compound is produced.

[0384] When the first composition contains a cation radical compound, the cation radical of the composition for organic electroluminescent devices The content of the on-radical compound is usually 0.0005 mass % or more, preferably 0.001 mass % or more. The content is usually 40% by mass or less, preferably 20% by mass or less. When the content of the calcium compound is equal to or more than the lower limit, the resistance of the formed organic layer is reduced, which is preferable. When the content is equal to or less than the upper limit, defects are unlikely to occur in the formed organic layer, and thickness unevenness is unlikely to occur. preferable.

[0385] In addition to the above components, the first composition may contain a composition for forming a hole injection layer and a hole transport layer, which will be described later. The components contained in the layer-forming composition may be contained in the amounts described below.

[0386] [Polymer manufacturing method] The method for producing polymer 1 and polymer 2 in the present invention is not particularly limited and may be any method. For example, polymerization methods using the Suzuki reaction, polymerization methods using the Grignard reaction, and polymerization methods using the Yam Polymerization by Amoto reaction, polymerization by Ullmann reaction, Buchwald reaction -Hartwig reaction polymerization method, etc.

[0387] Polymerization by Ullmann reaction and Buchwald-Hartwig reaction In the case of the polymerization method, for example, an aryl dihalide represented by the following formula (2a) (Z is I, B represents a halogen atom such as r, Cl, or F, and a primary aminoaryl group represented by the following formula (2b): By reacting the compound with the repeating unit represented by formula (2), a polymer containing the repeating unit represented by formula (2) is synthesized. do.

[0388] [ka]

[0389] (In the above reaction scheme, Ar 1 , R 1 , R 2 , X and a to d are the same as in the formula (2). .)

[0390] Also, polymerization methods using the Ullmann reaction and the Buchwald-Hartwig reaction In the case of the polymerization method according to the formula (3a), for example, an aryl dihalide represented by the formula (3a) (Z is I, represents a halogen atom such as Br, Cl, or F.) and a primary aminoaryl represented by formula (2b) By reacting with the above, a polymer containing a repeating unit represented by formula (3) is synthesized. .

[0391] [ka]

[0392] (In the above reaction scheme, Ar 2 , R 3 ~R 6 , l to n, p, and q are the same as in the formula (3). be.)

[0393] Also, polymerization methods using the Ullmann reaction and the Buchwald-Hartwig reaction In the case of the polymerization method according to the formula (3a), for example, an aryl dihalide represented by the formula (3a) (Z is I, represents a halogen atom such as Br, Cl, or F.) and a primary aminoaryl represented by formula (2b) By reacting with the above, a polymer containing a repeating unit represented by formula (3) is synthesized. .

[0394] [ka]

[0395] [ka]

[0396] (In the above reaction scheme, Ar 2 , R 3 ~R 6 , l to n, p, and q are the same as in the formula (3). be.)

[0397] In the above polymerization method, the reaction for forming an N-aryl bond is usually carried out by, for example, This is carried out in the presence of a base such as potassium tert-butoxide, sodium tert-butoxide, or triethylamine. . It can also be carried out in the presence of a transition metal catalyst such as a copper or palladium complex.

[0398] The organic semiconductor device of the present invention has an organic layer containing the organic film-forming material of the present invention. Specific examples include organic electroluminescent devices, organic solar cell devices, and power generation devices for sensor equipment. Examples of such devices include integrated circuits for electronic tags.

[0399] <Structure of organic electroluminescent device> The organic electroluminescent device of the present invention comprises an anode, a cathode, and an organic layer disposed between the anode and the cathode on a substrate. An organic electroluminescent device having a layer, the organic layer comprising a hole transport layer and a and an adjacent light-emitting layer, wherein the hole transport layer contains the organic thin film-forming material of the present invention. do. As an example of the structure of the organic electroluminescent device of the present invention, an example of the structure of the organic electroluminescent device 8 is shown in FIG. In Fig. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, and 4 is a hole 5 represents a light-emitting layer, 6 represents an electron-transporting layer, and 7 represents a cathode.

[0400] [substrate] The substrate 1 serves as a support for the organic electroluminescent device, and is usually made of a quartz or glass plate, a gold plate, or a metal plate. Metal plates, metal foils, plastic films and sheets, etc. are used. Among these, glass plates and transparent composites such as polyester, polymethacrylate, polycarbonate, and polysulfone. A resin plate is preferable. The substrate is less likely to cause deterioration of the organic electroluminescent element due to the outside air. Therefore, it is preferable to use a material with high gas barrier properties. When using a material with low gas barrier properties, such as It is preferable to provide a protective film or the like to improve the gas barrier properties.

[0401] [anode] The anode 2 has the function of injecting holes into the layer on the light-emitting layer 5 side.

[0402] The anode 2 is usually made of a metal such as aluminum, gold, silver, nickel, palladium, or platinum; Metal oxides such as zinc and / or tin oxide; metal halides such as copper iodide; carbon Black and highly conductive materials such as poly(3-methylthiophene), polypyrrole, and polyaniline It is composed of molecules, etc.

[0403] The anode 2 is usually formed by a dry method such as sputtering or vacuum deposition. In addition, there are many metal particles such as silver, copper iodide particles, carbon black, conductive gold When forming the anode using metal oxide fine particles, conductive polymer fine powder, etc., a suitable binder is required. Alternatively, the layer can be formed by dispersing the layer in a dye resin solution and applying it onto a substrate. In the case of conductive polymers, a thin film can be formed directly on the substrate by electrolytic polymerization, or a conductive film can be formed on the substrate. Anodes can also be formed by coating polymers (Appl. Phys. Lett., 60 Vol., pp. 2711, 1992).

[0404] The anode 2 usually has a single-layer structure, but may have a laminated structure as appropriate. In this case, a different conductive material may be laminated on the first anode layer.

[0405] The thickness of the anode 2 may be determined depending on the required transparency and material. When this is required, the thickness is preferably such that the transmittance of visible light is 60% or more. The thickness of the anode 2 is preferably 5 nm or more, more preferably 80% or more. It is usually 10 nm or more, and is usually 1000 nm or less, preferably 500 nm or less. On the other hand, when transparency is not required, the thickness of the anode 2 can be arbitrarily determined depending on the required strength, etc. In this case, the anode 2 may have the same thickness as the substrate.

[0406] When forming another layer on the surface of the anode 2, ultraviolet light / ozone, oxygen plasma, By applying argon plasma treatment or the like, impurities on the anode 2 are removed and the It is preferable to adjust the ionization potential to improve the hole injection property.

[0407] [Hole injection layer] The layer that transports holes from the anode 2 side to the light-emitting layer 5 side is usually a hole injection transport layer or This layer is called a hole transport layer. It transports holes from the anode 2 side to the light-emitting layer 5 side. When there are two or more layers, the layer closer to the anode side is sometimes called the hole injection layer 3. The injection layer 3 is formed to enhance the function of transporting holes from the anode 2 to the light-emitting layer 5. When the hole injection layer 3 is formed, the hole injection layer 3 is usually formed on the anode 2. It is preferable to have a hole injection layer 3 between the anode 2 and a hole transport layer 4 described later. Preferably, the hole injection layer comprises tetraarylborate ions.

[0408] The thickness of the hole injection layer 3 is usually 1 nm or more, preferably 5 nm or more, and is usually 1000 nm or less, preferably 500 nm or less.

[0409] The hole injection layer may be formed by a vacuum deposition method or a wet film formation method. is preferably formed by a wet film forming method.

[0410] A general method for forming a hole injection layer will be described below. In the device, the hole injection layer is formed by a wet film formation method using the composition for organic electroluminescent elements. It is preferred that a .alpha.- ...beta.

[0411] [Hole transport compounds] The composition for forming a hole injection layer usually contains a hole transporting compound that will become the hole injection layer 3 . In addition, in the case of a wet film formation method, the composition for forming a hole injection layer usually further contains a solvent. The hole injection layer-forming composition has high hole transport properties and can efficiently transport injected holes. Therefore, the hole mobility is large, and impurities that become traps are easily removed during manufacturing and use. It is preferable that the generation of the ionized gas is difficult. It is preferable that the transparency to light is high. In particular, when the hole injection layer is in contact with the light emitting layer, it is preferable that the light emitting layer is transparent. The luminescence efficiency is improved by forming an exciplex with the luminescent layer, which does not quench the luminescence from the luminescent layer. In this case, it is particularly preferable that the organic film-forming material of the present invention is contained. I wish.

[0412] As the hole transporting compound, from the viewpoint of the charge injection barrier from the anode to the hole injection layer, 4.5 A compound having an ionization potential of 6.0 eV to 6.0 eV is preferred. Examples of the compounds include aromatic amine compounds, phthalocyanine compounds, and porphyrin compounds. , oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, Compounds in which tertiary amines are linked via fluorene groups, hydrazone compounds, silazane compounds, Examples thereof include nacridone compounds.

[0413] Among the above-mentioned exemplary compounds, aromatic amine compounds are preferred in terms of amorphousness and visible light transmittance. An aromatic tertiary amine compound is particularly preferred. is a compound having an aromatic tertiary amine structure, and having a group derived from an aromatic tertiary amine Also includes compounds.

[0414] The type of aromatic tertiary amine compound is not particularly limited, but it is preferable to use a compound having a uniform surface smoothing effect. Polymerization with a weight average molecular weight of 1,000 or more and 1,000,000 or less is preferred because it is easy to obtain light emission. It is preferable to use a polymer compound (a polymer compound having a series of repeating units).

[0415] [Formation of hole injection layer by wet film formation method] When the hole injection layer 3 is formed by a wet film formation method, the material for the hole injection layer is usually a soluble material. Mix with a solvent (solvent for hole injection layer) to prepare a film-forming composition (composition for forming hole injection layer) Then, this hole injection layer-forming composition is applied to a layer corresponding to the layer below the hole injection layer (usually, The hole injection layer 3 is formed by applying the solution onto the anode (electrode) to form a film and drying it.

[0416] The concentration of the hole transporting compound in the composition for forming the hole injection layer significantly improves the effect of the present invention. However, in terms of uniformity of the film thickness, a lower value is preferable. A higher content is preferable in that defects are less likely to occur in the hole injection layer. It is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. It is particularly preferable that the content is 70% by mass or less, and more preferably 60% by mass or less. It is more preferable that the content is less than 50% by mass, and particularly preferable that the content is 50% by mass or less.

[0417] Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, and Examples include mide-based solvents.

[0418] Examples of ether solvents include ethylene glycol dimethyl ether, ethylene glycol Licorice diethyl ether, propylene glycol-1-monomethyl ether acetate Aliphatic ethers such as (PGMEA) and 1,2-dimethoxybenzene, 1,3-dimethoxybenzene Dibenzoylbenzene, Anisole, Phenetole, 2-Methoxytoluene, 3-Methoxytoluene , 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole, etc. Examples of aromatic ethers include the following.

[0419] Examples of ester solvents include phenyl acetate, phenyl propionate, and methyl benzoate. aromatic esters such as benzoic acid ethyl, benzoic acid ethyl, benzoic acid propyl, benzoic acid n-butyl, etc. Examples include:

[0420] Examples of aromatic hydrocarbon solvents include toluene, xylene, and cyclohexylbenzene. benzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diphenyl Examples include isopropylbenzene, cyclohexylbenzene, and methylnaphthalene.

[0421] Examples of amide solvents include N,N-dimethylformamide and N,N-dimethylazoline. cetoamide and the like.

[0422] In addition to these, dimethyl sulfoxide and the like can also be used.

[0423] The formation of the hole injection layer 3 by a wet film formation method is usually carried out by preparing a composition for forming the hole injection layer, followed by: This is applied to the layer below the hole injection layer 3 (usually the anode 2) to form a film, and then dried. This is done by:

[0424] After the hole injection layer 3 is formed, the coated film is usually dried by heating, drying under reduced pressure, or the like.

[0425] [Formation of hole injection layer by vacuum deposition method] When the hole injection layer 3 is formed by vacuum deposition, the material of the hole injection layer 3 is usually One or more types of materials are placed in a crucible installed in a vacuum chamber (using two or more types of materials) In this case, each is usually placed in a separate crucible), and the vacuum chamber is evacuated by a vacuum pump for 10 -4 Pa level Then, the crucible is heated (when two or more materials are used, usually each crucible is The material in the crucible is evaporated while controlling the amount of evaporation (when two or more materials are used, When using a crucible, the evaporation rate is usually controlled independently, and the melts are placed facing each other. A hole injection layer is formed on the anode on the substrate. When two or more materials are used, The mixture can also be placed in a crucible, heated, and evaporated to form the hole injection layer.

[0426] The degree of vacuum during deposition is not limited as long as it does not significantly impair the effects of the present invention. x10 -6 Torr (0.13 × 10 -4 Pa) or more, 9.0×10 -6 Torr(12 .0×10 -4 The deposition rate is not more than 100 Pa. The deposition rate is not limited as long as it does not significantly impair the effects of the present invention. The deposition rate is not fixed, but is usually between 0.1 Å / sec and 5.0 Å / sec. There are no particular limitations as long as the effect of the present invention is not significantly impaired, but the temperature is preferably 10°C or higher, 50°C or higher. It is done below.

[0427] The hole injection layer 3 may be crosslinked in the same manner as the hole transport layer 4 described below.

[0428] [Hole transport layer] The hole transport layer 4 is a layer that transports holes from the anode 2 side to the light-emitting layer 5 side. The transport layer 4 is not an essential layer in the organic electroluminescent device of the present invention, but it is a layer that transports light from the anode 2 to the light-emitting layer 5. It is preferable to form this layer in order to enhance the function of transporting holes to the hole transport layer. When forming the hole transport layer 4, the hole transport layer 4 is usually formed between the anode 2 and the light emitting layer 5. When the hole injection layer 3 is present, it is formed between the hole injection layer 3 and the light emitting layer 5 .

[0429] The thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more. , usually 300 nm or less, preferably 100 nm or less.

[0430] The hole transport layer 4 may be formed by vacuum deposition or wet film formation. In this case, it is preferable to form the film by a wet film forming method.

[0431] A general method for forming a hole transport layer will be described below. In the method, the hole transport layer is formed by a wet film formation method using the first composition. preferable.

[0432] The hole transport layer 4 usually contains a hole transporting compound. The conductive compound preferably contains the organic film-forming material of the present invention.

[0433] In addition to the organic film-forming material of the present invention, the hole transport compound, 4,4'-bis[ Two or more tertiary Aromatic diamines containing amines and having two or more condensed aromatic rings substituted on the nitrogen atom (Patent Publication No. 5- 234681), 4,4',4''-tris(1-naphthylphenylamino)tri Aromatic amine compounds with starburst structures such as phenylamine (J. Lumin. , vol. 72-74, p. 985, 1997), an aromatic compound consisting of a tetramer of triphenylamine Amine compounds (Chem. Commun., p. 2175, 1996), 2,2',7, Spiration of 7'-tetrakis-(diphenylamino)-9,9'-spirobifluorene etc. Compound (Synth.Metals, vol. 91, p. 209, 1997), 4,4'-N,N Carbazole derivatives such as '-dicarbazole biphenyl are preferred. In addition, for example, polyvinylcarbazole, polyvinyltriphenylamine (JP-A-7-2002) 53953), polyarylene ether salts containing tetraphenylbenzidine Hong (Polym. Adv. Tech., Vol. 7, p. 33, 1996) and the like. .

[0434] [Formation of hole transport layer by wet film formation method] When forming a hole transport layer by a wet film formation method, the hole injection layer is usually formed by a wet film formation method. In the same manner as in the case of forming a hole transport layer, the hole transport layer forming composition is used instead of the hole injection layer forming composition. It is formed using.

[0435] When the hole transport layer is formed by a wet film formation method, the composition for forming the hole transport layer is usually further dissolved. The solvent used in the composition for forming a hole transport layer is the same as that used in the composition for forming a hole injection layer. The same solvent as used in the step 1 can be used.

[0436] The concentration of the hole transport compound in the composition for forming the hole transport layer is The concentration of the hole transporting compound in the material can be in the same range as that of the hole transporting compound in the material.

[0437] The hole transport layer can be formed by a wet film formation method in the same manner as the hole injection layer formation method described above. Cut.

[0438] [Formation of hole transport layer by vacuum deposition method] When forming a hole transport layer by vacuum deposition, the hole injection layer is usually formed by vacuum deposition. In the same manner as in the case of forming the hole injection layer by the deposition method, a hole transport layer forming composition is used instead of the hole injection layer forming composition. The film can be formed using a composition. The film formation conditions, such as the degree of vacuum during deposition, deposition rate, and temperature, can be adjusted. The film can be formed under the same conditions as those for the vacuum deposition of the hole injection layer.

[0439] [Emitting layer] When an electric field is applied between the pair of electrodes, the light-emitting layer 5 converts holes injected from the anode 2 and electrons injected from the cathode This layer is excited by the recombination of electrons injected from 7 and emits light. The light-emitting layer 5 is a layer formed between the anode 2 and the cathode 7, and the light-emitting layer is formed on the anode by a hole-injecting If there is a layer, it is formed between the hole injection layer and the cathode, and if there is a hole transport layer on the anode, , formed between the hole transport layer and the cathode.

[0440] The thickness of the light-emitting layer 5 is arbitrary as long as it does not significantly impair the effects of the present invention. On the other hand, a thinner film is preferable because it is easier to achieve a low driving voltage. Therefore, it is preferable that the thickness is 3 nm or more, and more preferably 5 nm or more. On the other hand, it is usually preferably 200 nm or less, more preferably 100 nm or less. It's nice.

[0441] The light-emitting layer 5 contains at least a material having light-emitting properties (light-emitting material), and Preferably, it contains a charge transporting material (host material).

[0442] [Formation of light-emitting layer by wet film formation method] The light-emitting layer may be formed by vacuum deposition or wet film formation. From these viewpoints, wet film-forming methods are preferred, and spin coating and ink-jet methods are more preferred. The above composition for organic electroluminescent devices is used to form a hole injection layer or a hole transport layer which is a layer below the light emitting layer. When a transfer layer is formed, lamination by a wet film forming method is easy, so the wet film forming method is adopted. When the light-emitting layer is formed by a wet film-forming method, the hole-injecting layer is usually formed by a wet film-forming method. In the same manner as in the case of forming the layer by the film-forming method, a layer to be used as the light-emitting layer is used instead of the hole-injection layer-forming composition. The light-emitting layer is formed using a composition for forming a light-emitting layer prepared by mixing the material to be formed with a soluble solvent (solvent for the light-emitting layer). Complete.

[0443] Examples of the solvent include the ether-based solvents and ester-based solvents mentioned for forming the hole injection layer. Solvents, aromatic hydrocarbon solvents, amide solvents, alkane solvents, halogenated aromatic carbon Hydrogen hydride solvents, aliphatic alcohol solvents, alicyclic alcohol solvents, aliphatic ketone solvents Specific examples of solvents are listed below, but the effects of the present invention can be achieved by The present invention is not limited to these examples, provided that they do not impair the rights of the applicant.

[0444] For example, ethylene glycol dimethyl ether, ethylene glycol diethyl ether , aliphatic alcohols such as propylene glycol-1-monomethyl ether acetate (PGMEA) Ether solvents; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene 2,3-dimethylanisole, 2,4-dimethylanisole, diphenyl ether, etc. Aromatic ether solvents; phenyl acetate, phenyl propionate, methyl benzoate, benzoic acid Aromatic ester solvents such as ethyl benzoate, propyl benzoate, and n-butyl benzoate; toluene benzene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3-isopropylbenzene Phenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, Aromatic hydrocarbon solvents such as cyclohexylbenzene and methylnaphthalene; N,N-dimethyl Amide solvents such as methylformamide and N,N-dimethylacetamide; n-decane, cyclohexane Alkane solvents such as hexane, ethylcyclohexane, decalin, and bicyclohexane; Halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene Solvents: Aliphatic alcohol solvents such as butanol, hexanol, etc.; cyclohexanol, cyclohexanol, etc. Alicyclic alcohol solvents such as cyclooctanol; methyl ethyl ketone, dibutyl ketone, etc. Aliphatic ketone solvents such as cyclohexanone, cyclooctanone, and fenchone; Among these, alkane solvents and aromatic hydrocarbon solvents are Particularly preferred.

[0445] [Hole blocking layer] A hole-blocking layer may be provided between the light-emitting layer 5 and the electron-injecting layer described below. This layer is laminated on the optical layer 5 so as to be in contact with the interface of the light-emitting layer 5 on the cathode 7 side.

[0446] This hole blocking layer has the role of preventing holes migrating from the anode 2 from reaching the cathode 7. and efficiently transports electrons injected from the cathode 7 toward the light-emitting layer 5. The properties required for the material that constitutes the hole blocking layer are high electron mobility and low hole mobility. The energy gap (difference between HOMO and LUMO) is large, and the excited triplet level ( T1) is high.

[0447] Examples of materials for the hole blocking layer that satisfy these conditions include bis(2-methyl-8- Quinolinolato) (phenolato) aluminum, bis(2-methyl-8-quinolinolato) ( Mixed ligand complexes such as triphenylsilanolate)aluminum, bis(2-methyl-8-oxo) (2-methyl-8-quinolinolato)aluminum-μ-oxo-bis-(2-methyl-8-quinolinolato)aluminum metal complexes such as dinuclear metal complexes, styryl compounds such as distyrylbiphenyl derivatives (see Japanese Patent Laid-Open No. 2003-200644); 11-242996), 3-(4-biphenylyl)-4-phenyl-5-(4- tert-butylphenyl)-1,2,4-triazole and other triazole derivatives (Patent Publication No. 7-41759), phenanthroline derivatives such as bathocuproine (JP-A-10- 79297) and the like. Furthermore, the method described in International Publication No. 2005 / 022962 Compounds having at least one pyridine ring substituted at the 2-, 4-, and 6-positions of the formula (I) are also useful for forming hole-blocking layers. It is a preferred material.

[0448] There is no limitation on the method for forming the hole blocking layer. Therefore, the hole blocking layer may be formed by a wet film forming method, a vapor deposition method, or other methods. It can be formed.

[0449] The thickness of the hole blocking layer is arbitrary as long as it does not significantly impair the effect of the present invention. nm or more, preferably 0.5 nm or more, and is usually 100 nm or less, preferably 5 0nm or less.

[0450] [Electron transport layer] The electron transport layer 6 is formed between the light-emitting layer 5 and the cathode in order to further improve the current efficiency of the device. It is located between 7.

[0451] The electron transport layer 6 efficiently transports electrons injected from the cathode 7 between the electrodes to which an electric field is applied. The electron transport layer 6 is made of a compound that can transport electrons in the direction of the light-emitting layer 5. The electron transporting compound to be used is one having high electron injection efficiency from the cathode 7 and high electron mobility. It is necessary that the compound has a high conductivity and can efficiently transport injected electrons. do.

[0452] Specific examples of the electron transporting compound used in the electron transport layer include 8-hydroxybenzophenone-1, ...2, 8-hydroxybenzophenone-3, 8-hydroxybenzophenone-4, 8-hydroxybenzophenone-5, 8-hydroxybenzophenone-6, 8-hydroxybenzophenone-7, 8-hydroxybenzophenone-8, 8-hydroxybenzophenone-9, 8-hydroxybenzophenone-10, Metal complexes such as aluminum complexes of quinoline (JP-A-59-194393), 10- Metal complexes of hydroxybenzo[h]quinoline, oxadiazole derivatives, distyrylbifuric acid Phenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone Benzoxazole metal complexes, benzothiazole metal complexes, trisbenz imidazolylbenzene (U.S. Pat. No. 5,645,948), quinoxaline compounds (Patent JP-A No. 6-207169), phenanthroline derivatives (JP-A No. 5-331459) Report), 2-tert-butyl-9,10-N,N'-dicyanoanthraquinone diimine, Examples include n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, and n-type zinc selenide.

[0453] The thickness of the electron transport layer 6 is usually 1 nm or more, preferably 5 nm or more. 00 nm or less, preferably 100 nm or less.

[0454] The electron transport layer 6 is formed on the hole blocking layer by the wet film forming method or the vacuum deposition method in the same manner as described above. The film is usually formed by laminating a layer of a metal such as a silicon dioxide powder onto a substrate.

[0455] [Electron injection layer] The electron injection layer efficiently injects electrons injected from the cathode 7 into the electron transport layer 6 or the light-emitting layer 5. It may also be provided for inputting

[0456] To efficiently inject electrons, the material forming the electron injection layer is preferably a metal with a low work function. Examples include alkali metals such as sodium and cesium, and barium and calcium. The thickness of the film is preferably 0.1 nm or more and 5 nm or less. It's nice.

[0457] Furthermore, nitrogen-containing heterocyclic compounds such as bathophenanthroline and 8-hydroxyquinoline Organic electron transport materials, such as metal complexes, are often used in combination with sodium, potassium, and cerium. Doping with alkali metals such as sodium, lithium, rubidium, etc. (Patent Publication No. 10-27017 1, JP 2002-100478 A, JP 2002-100482 A, etc. (described above) also improves electron injection and transport properties, making it possible to achieve both excellent film quality. preferable.

[0458] The thickness of the electron injection layer is usually 5 nm or more, preferably 10 nm or more, and is usually 20 The thickness is in the range of 0 nm or less, preferably 100 nm or less.

[0459] The electron injection layer is formed by a wet film formation method or a vacuum deposition method on the light-emitting layer 5 or the hole-blocking layer thereon. The insulating layer 10 is formed by laminating it on the electron transport layer 6 . The details of the wet film formation method are the same as those of the light-emitting layer described above.

[0460] The hole blocking layer, electron transport layer, and electron injection layer are formed by co-doping the electron transport material with a lithium complex. It may also be made into one layer.

[0461] [cathode] The cathode 7 serves to inject electrons into the layer (electron injection layer or light-emitting layer, etc.) on the light-emitting layer 5 side. vinegar.

[0462] The cathode 7 may be made of the same material as the anode 2. For efficient electron injection, it is preferable to use a metal with a low work function, for example, , tin, magnesium, indium, calcium, aluminum, silver, or other metals or Specific examples include magnesium-silver alloys, magnesium -Indium alloy, aluminum-lithium alloy, and other low work function alloy electrodes. do.

[0463] In terms of the stability of the organic electroluminescent device, a material with a high work function and stability against the atmosphere is placed on the cathode. It is preferable to laminate a metal layer having a low work function to protect the cathode. Examples of metals that can be used include aluminum, silver, copper, nickel, chromium, gold, and platinum. Examples include:

[0464] The thickness of the cathode is usually the same as that of the anode.

[0465] [Other layers] The organic electroluminescent device of the present invention may further comprise other layers as long as the effects of the present invention are not significantly impaired. That is, any of the other layers described above may be present between the anode and the cathode. stomach.

[0466] [Other element configurations] The organic electroluminescent device of the present invention has a structure opposite to that described above, i.e., a cathode on a substrate. , electron injection layer, electron transport layer, hole blocking layer, light emitting layer, hole transport layer, hole injection layer, and anode in this order. Stacking is also possible.

[0467] The organic film-forming material of the present invention is an organic electroluminescent element having an emission peak wavelength of 500 nm or less. Suitable for children. The organic film-forming material of the present invention has a wide band gap and a high triplet energy level. This suppresses exciton deactivation even for light-emitting materials that exhibit high-energy emission wavelengths. The light-emitting layer that emits high energy light can be contained The HOMO level of the material tends to be deep, and the hole injection barrier tends to be large. The film-forming material reduces the injection barrier and improves charge transport within the hole transport layer, enabling highly efficient driving. It is believed that a light emitting device with a long dynamic life can be obtained.

[0468] When the organic electroluminescent element of the present invention is applied to an organic electroluminescent device, a single organic electroluminescent element When used as an element, a plurality of organic electroluminescent elements are arranged in an array. Alternatively, the anodes and cathodes may be arranged in an XY matrix.

[0469] <Organic EL display device> The organic EL display device (organic electroluminescent device display device) of the present invention is There are no particular limitations on the type or structure of the organic EL display device of the present invention. The organic electroluminescent device can be assembled in accordance with a conventional method.

[0470] For example, "Organic EL Display" (Ohmsha, August 20, 2004, Shizuo Tokito) The organic EL display device of the present invention can be manufactured by a method such as that described in the publications by Adachi Chihaya and Murata Hideyuki. can be formed.

[0471] <Organic EL lighting> The organic EL lighting (organic electroluminescent element lighting) of the present invention is provided with the organic electroluminescent element of the present invention. There is no particular limitation on the type or structure of the organic electroluminescence lighting device of the present invention. It can be assembled using optical elements in accordance with conventional methods. [Example]

[0472] The present invention will be described in more detail below with reference to examples. The present invention is not limited to the examples, and can be implemented by any modifications without departing from the gist of the present invention. It can be implemented.

[0473] [Example 1] An organic electroluminescent device was fabricated in the following manner. Deposit a 50nm thick indium tin oxide (ITO) transparent conductive film on a glass substrate. (Geomatec Co., Ltd., sputtered film) was processed by ordinary photolithography. The anode was formed by patterning into 2 mm wide stripes using acid etching. The substrate on which the ITO pattern was formed was then ultrasonically cleaned with a surfactant solution and washed with ultrapure water. After washing in the order of water washing with ultrapure water, ultrasonic cleaning with ultrapure water, and water washing with ultrapure water, it was dried with compressed air. Finally, UV ozone cleaning was performed.

[0474] A solution containing an arylamine polymer compound and tetraarylborate ions is applied to a substrate. The solution was spin-coated onto a substrate and dried on a hot plate to form a uniform thin film with a thickness of 55 nm. This was used as a hole injection layer.

[0475] Next, 75 parts by mass of a charge transporting polymer compound having the following structural formula (HT-1), 25 parts by mass of a charge-transporting polymer compound having the formula (HT-2) was dissolved in mesitylene, A 3.3 wt % solution was prepared.

[0476] [ka]

[0477] [ka]

[0478] This solution was spin-coated on the substrate on which the hole injection layer had been formed in a nitrogen glove box. The coated film was dried at 240°C for 30 minutes on a hot plate in a nitrogen glove box. A uniform thin film with a thickness of 100 nm was formed as a hole transport layer.

[0479] Next, as a material for the light-emitting layer, 97 parts by mass of a compound represented by the following structural formula (H-1) was added. 3 parts by mass of a compound represented by the following structural formula (D-1) was weighed, and cyclohexylbenzene A 4.2% by mass solution was prepared by dissolving the compound in

[0480] [ka]

[0481] This solution was spin-coated on the substrate on which the hole transport layer had been formed in a nitrogen glove box. The coated film was dried on a hot plate in a nitrogen glove box at 130°C for 20 minutes. A uniform thin film with a thickness of 40 nm was formed as the light-emitting layer.

[0482] The substrate on which the light-emitting layer had been formed was placed in a vacuum deposition device, and the inside of the device was heated to 2 × 10 -4 Pa or less It was vented until Next, the compound represented by the following structural formula (HB-1) and 8-hydroxyquinolinolatrile were A 30 nm thick hole blocking layer was formed on the light emitting layer by vacuum evaporation. A stop layer was formed.

[0483] [ka]

[0484] Next, a 2mm wide striped shadow mask was used as a mask for cathode evaporation, and the anode The aluminum is attached to the substrate perpendicular to the ITO stripe, and the molybdenum The cathode was formed by heating the substrate with a heater to form an aluminum layer with a thickness of 80 nm. Thus, an organic electroluminescent device having a light-emitting area measuring 2 mm x 2 mm was obtained.

[0485] [Example 2] The solution used to apply the hole transport layer is a highly charge-transporting polymer having the structural formula (HT-1). 50 parts by mass of a molecular compound, and a charge transporting polymer compound having the structural formula (HT-2) An organic electroluminescent device was fabricated in the same manner as in Example 1, except that 50 parts by mass of the solution was dissolved. did.

[0486] [Example 3] The solution used to apply the hole transport layer is a highly charge-transporting polymer having the structural formula (HT-1). 25 parts by mass of a molecular compound, and a charge transport polymer compound having the structural formula (HT-2) An organic electroluminescent device was fabricated in the same manner as in Example 1, except that 75 parts by mass of the solution was dissolved. did.

[0487] [Example 4] The solution used to apply the hole transport layer is a highly charge-transporting polymer having the structural formula (HT-1). 75 parts by mass of a molecular compound, and a charge-transporting polymer compound having the following structural formula (HT-3): An organic electroluminescent device was fabricated in the same manner as in Example 1, except that 25 parts by mass of the solution was dissolved. did.

[0488] [ka]

[0489] [Example 5] The solution used to apply the hole transport layer is a highly charge-transporting polymer having the structural formula (HT-1). 50 parts by mass of a molecular compound, and a charge transport polymer compound having the following structural formula (HT-3): An organic electroluminescent device was fabricated in the same manner as in Example 1, except that 50 parts by mass of the solution was dissolved. did.

[0490] [Comparative Example 1] The solution used to apply the hole transport layer is a highly charge-transporting polymer having the structural formula (HT-1). The organic electroluminescence was produced in the same manner as in Example 1, except that 100 parts by mass of the molecular compound was dissolved. The device was fabricated.

[0491] Comparative Example 2 The solution used to apply the hole transport layer is a highly charge-transporting polymer having the structural formula (HT-2). The organic electroluminescence was produced in the same manner as in Example 1, except that 100 parts by mass of the molecular compound was dissolved. The device was fabricated.

[0492] Comparative Example 3 The solution used to apply the hole transport layer is a highly charge-transporting polymer having the structural formula (HT-3). The organic electroluminescence was prepared in the same manner as in Example 1, except that 100 parts by mass of the molecular compound was dissolved. The device was fabricated.

[0493] [Evaluation of organic electroluminescent devices] When a current was applied to the organic electroluminescent devices obtained in Examples 1 to 5 and Comparative Examples 1 to 3, In the organic electroluminescent device, blue light emission with a peak wavelength of 462 nm was confirmed. The organic electroluminescent device has a brightness of 1000 cd / m 2 Voltage (V) and current efficiency when emitting light (cd / A) was measured. In addition, these organic electroluminescent devices were exposed to a current of 20 mA / cm 2 When current continues to flow at a current density of The time required for the luminance of the device to decrease to 95% of the initial luminance (LT95) was measured.

[0494] Voltage differences (referred to as relative voltages) between Examples 1 to 3 and Comparative Examples 1 and 2 relative to the voltage of Comparative Example 1 , The current efficiency of Comparative Example 1 and the current efficiency of Examples 1 to 3 and Comparative Examples 1 and 2 when LT95 is set to 1 The relative values ​​(referred to as relative current efficiency and relative life span, respectively) are shown in Table 1.

[0495] [Table 1]

[0496] Voltage differences (referred to as relative voltages) between Examples 4 and 5 and Comparative Examples 2 and 3 relative to the voltage of Comparative Example 3 , the current efficiency of Comparative Example 3, and the phase efficiency of Examples 4 to 5 and Comparative Examples 2 to 3 when LT95 is set to 1. The paired values ​​(referred to as relative current efficiency and relative life span, respectively) are shown in Table 2.

[0497] [Table 2]

[0498] From the results of Tables 1 and 2, it can be seen that the organic electroluminescent device of the present invention has a low driving voltage and a high current efficiency. It was found that the operating life was long. [Industrial Applicability]

[0499] The present invention relates to various fields in which organic electroluminescent devices are used, such as flat panel displays. Spray (for example, for OA computers or wall-mounted TVs) and taking advantage of the characteristics of surface light emitters light sources (e.g., light sources in copiers, backlight sources for LCD displays and meters), It can be suitably used in fields such as signboards and marker lights. The organic semiconductor element of the present invention can be applied to organic solar cells, electronic tags, and sensor devices. This has resulted in great technological value. [Explanation of symbols]

[0500] 1 board 2 Anode 3. Hole injection layer 4. Hole transport layer 5. Light-emitting layer 6 Electron transport layer 7 Cathode 8. Organic electroluminescent device

Claims

1. Polymer 1 containing a repeating unit represented by the following formula (50) and polymer 2 containing a repeating unit represented by the following formula (40) and a polymer 2 containing a repeating unit, The polymer 1 is an organic film-forming material that does not contain a repeating unit represented by the following formula (40): Fee. 【Chemical 1】 (In formula (50), Ar ５１ is an aromatic hydrocarbon group which may have a substituent and a substituted a group to which one or more groups selected from the group consisting of aromatic heterocyclic groups are linked, Ar ５２ is a divalent aromatic hydrocarbon group which may have a substituent and and a divalent aromatic heterocyclic group, The linkage is made directly or via a linking group. Ar ５１ and Ar ５２ may be bonded directly or via a linking group to form a ring. 【Chemistry 2】 (In formula (40), Ar １ and Ar ２ each independently represents a divalent aromatic hydrocarbon which may have a substituent. a divalent aromatic heterocyclic group optionally having a substituent, and a divalent aromatic heterocyclic group optionally having a substituent; represents a divalent group to which a group or a plurality of groups are linked, and the linkage is made directly or via a linking group. There are. R １ ~R １８ each independently represents a direct bond, a hydrogen atom, a deuterium atom, a halogen atom, or a substituted and a group formed by linking 2 to 8 of the aromatic rings. p and q each independently represent an integer of 0 to 1, and p+q is 1 or more. Ar ３ is Ar in the formula (50). ５１ is the same as: r represents an integer of 0 to 1. G is a direct bond, a divalent aromatic ring group which may have a substituent, or the aromatic ring is a divalent aromatic ring group which may have a substituent. represents a divalent group formed by linking four groups. s and t each independently represent an integer of 0 to 1. However, the case where s is 0, t is 1, p is 0, and r is 1 is excluded. R １ ~R ８ and R ９ are respectively Ar １ , N-Ar ３ Nitrogen atom of , G.R. １０ ~R １８ Any one of Ar ２ or directly bonded to the main chain of polymer 2 、 R １０ ~R １７ and R １８ One of them is G or R １ ~R ９ of One of them is directly bonded to Ar, and the other is ２ or directly bonded to the main chain of polymer 2 (I'm doing it.)

2. Ar in the formula (50) ５２ may have a divalent aromatic hydrocarbon group and a substituent. a divalent group formed by linking together multiple groups selected from the group consisting of divalent aromatic heterocyclic groups, The Ar ５２ The compound contains a structure in which a plurality of benzene ring structures are linked at para positions, At least one of the benzene ring structures is positioned next to the carbon atom bonding to the adjacent benzene ring structure.

2. The organic film according to claim 1, wherein at least one of the two adjacent carbon atoms has a substituent. Forming materials.

3. The repeating unit represented by the formula (50) is represented by the following formula (54), the following formula (55), or the following formula (56):

2. The organic film-forming material according to claim 1, which is a repeating unit represented by the formula (57): 【Chemistry 3】 (In formula (54), Ar ５1 is Ar in the formula (50). ５１ is the same as X is -C(R ２０７ ) (R ２０８ ) -, -N(R ２０９ ) - or -C(R ２１１ ) ( R ２１２ )-C(R ２１３ ) (R ２１４ ) - and R ２０１ , R ２０２ , R ２２１ and R ２２２ may each independently have a substituent. It is a good alkyl group, R ２０７ ~R ２０９ and R ２１１ ~R ２１４ are each independently a hydrogen atom, a group having a substituent, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted an aromatic hydrocarbon group which may be optionally substituted, a and b are each independently an integer from 0 to 4; c is an integer from 0 to 3; d is an integer from 0 to 4, R ２０１ If there are multiple R ２０１ may be the same or different, R ２０２ If there are multiple R ２０２ may be the same or different, R ２２１ If there are multiple R ２２１ may be the same or different, R ２２２ If there are multiple R ２２２ may be the same or different, i and j are each independently an integer of 0 to 3. 【Chemistry 4】 (In formula (55), Ar ５1 is Ar in the formula (50). ５１ is the same as R ３０３ and R ３０６ are each independently an alkyl group which may have a substituent, 、 R ３０４ and R ３０５ each independently represents an alkyl group which may have a substituent, a substituted an alkoxy group which may have one or more groups or an aralkyl group which may have one or more groups, l is 0 or 1; m is 1 or 2; n is 0 or 1 a5 is 0 or 1; b5 is 0 or 1. 【Chemistry 5】 (In formula (57), Ar ５１ is Ar in the formula (50). ５１ is the same as R ５１７ ~R ５１９ each independently represents an alkyl group which may have a substituent; an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, f, g, and h each independently represent an integer of 0 to 4; e represents an integer of 0 to 3; However, when g is 1 or more, e is 1 or more.)

4. The polymer 2 is a repeating unit represented by the following formula (54), the following formula (55), or the following formula (57): The organic film-forming material according to claim 1 , which comprises a repeating unit. 【Chemistry 6】 (In formula (54), Ar ５1 is Ar in the formula (50). ５１ is the same as X is -C(R ２０７ ) (R ２０８ ) -, -N(R ２０９ ) - or -C(R ２１１ ) ( R ２１２ )-C(R ２１３ ) (R ２１４ ) - and R ２０１ , R ２０２ , R ２２１ and R ２２２ may each independently have a substituent. It is a good alkyl group, R ２０７ ~R ２０９ and R ２１１ ~R ２１４ are each independently a hydrogen atom, a group having a substituent, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted an aromatic hydrocarbon group which may be optionally substituted, a and b are each independently an integer from 0 to 4; c is an integer from 0 to 3; d is an integer from 0 to 4, R ２０１ If there are multiple R ２０１ may be the same or different, R ２０２ If there are multiple R ２０２ may be the same or different, R ２２１ If there are multiple R ２２１ may be the same or different, R ２２２ If there are multiple R ２２２ may be the same or different, i and j are each independently an integer of 0 to 3. 【Chemistry 7】 (In formula (55), Ar ５1 is Ar in the formula (50). ５１ is the same as R ３０３ and R ３０６ are each independently an alkyl group which may have a substituent, 、 R ３０４ and R ３０５ each independently represents an alkyl group which may have a substituent, a substituted an alkoxy group which may have one or more groups or an aralkyl group which may have one or more groups, l is 0 or 1; m is 1 or 2; n is 0 or 1 a5 is 0 or 1; b5 is 0 or 1. 【Chemistry 8】 (In formula (57), Ar ５１ is Ar in the formula (50). ５１ is the same as R ５１７ ~R ５１９ each independently represents an alkyl group which may have a substituent; an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, f, g, and h each independently represent an integer of 0 to 4; e represents an integer of 0 to 3; However, when g is 1 or more, e is 1 or more.)

5. Ar in the formula (40) １ and Ar ２ At least one of the following formula (41) or The organic film-forming material according to claim 1, which is represented by the formula (42): 【Chemistry 9】 (In formula (41), R ２０１ , R ２０２ , a to d, and X are the same as in formula (54), and are independent of polymer 1. m4 represents an integer of 1 or 2.) 【Chemistry 10】 (In formula (42), R ２３ and R ２５ each independently represents an alkyl group which may have a substituent, R ２４ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent. represents a group or an aralkyl group which may have a substituent, u and w each independently represent an integer of 0 to 2; v represents an integer of 1 or 2; x, y, and z each independently represent an integer of 0 to 2, and x+z is 1 or more.

6. The repeating unit represented by the formula (40) is a repeating unit represented by the following formula (43): The organic film-forming material according to claim 1 . 【Chemistry 11】 (In formula (43), R １ ~R ６ , R ８ , R １０ , R １２ ~R １７ are each independently a hydrogen atom, a deuterium atom, A halogen atom, an aromatic ring group which may have a substituent, and a group in which 2 to 8 of the aromatic rings are linked together represents a group represented by the formula: Ar １ ~Ar ３ , G, p, q, r, s, and t are the same as in equation (40).

7. 2. The organic film-forming material according to claim 1, wherein t is 1 in the formula (40).

8. 2. The organic film-forming material according to claim 1, wherein r is 1 in the formula (40).

9. The content ratio of the polymer 1 to the total content of the polymer 1 and the polymer 2 is 10 The organic film-forming material according to claim 1, wherein the content is from 100 to 90% by mass.

10. Ar in the formula (40) ３ and Ar in the formula (50). ５１ At least one of The organic film-forming material according to claim 1 , wherein the organic film-forming material comprises a structure represented by the following formula (51): 【Chemistry 12】 (In formula (51), * represents a bond to the nitrogen atom of the main chain of formula (50), Ar ５３ and Ar ５４ are each independently a divalent aromatic hydrocarbon group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, Heterocyclic group, or aromatic hydrocarbon group which may have a substituent or represents a divalent group in which a plurality of aromatic heterocyclic groups are linked together directly or via a linking group, and Ar ５５ is an aromatic hydrocarbon group which may have a substituent and an aromatic hydrocarbon group which may have a substituent. a monovalent group having one or more groups linked together selected from at least one of aromatic heterocyclic groups; The linkage is direct or via a linking group. Ar ５６ represents a hydrogen atom or a substituent.

11. Ar in the formula (40) ３ and Ar in the formula (50). ５１ At least one of The organic film-forming material according to claim 1 , wherein the organic film-forming material comprises a structure represented by the following formula (52): 【Chemistry 13】 (In formula (52), Ar ６１ and Ar ６２ are each independently an optionally substituted divalent aromatic hydrocarbon group or an optionally substituted divalent is an aromatic heterocyclic group, Ar ６３ ~Ar ６５ are each independently a hydrogen atom or a substituent. * indicates the bond position.)

12. The weight average molecular weight (Mw) of the polymer 1 and the polymer 2 is 15,000 or more and 50,000 or less.

2. The organic film-forming material according to claim 1, wherein the molecular weight of the organic film is 0.00 or less.

13. 2. The polydispersity (Mw / Mn) of the polymer 1 and the polymer 2 is 3.5 or less. The organic film-forming material described above.

14. The polymer 1 and the polymer 2 do not have a crosslinking group, a polymerizable group, or a leaving solubilizing group.

2. The organic film-forming material according to claim 1.

15. An organic film-forming composition comprising the organic film-forming material according to any one of claims 1 to 14 and a solvent. composition.

16. A method for producing an organic film by forming the organic film-forming composition according to claim 15 by a wet film-forming method. Law.

17. An organic film having an organic layer containing the organic film-forming material according to any one of claims 1 to 14. Semiconductor element.

18. An organic electroluminescent device having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate. the organic layer has a hole transport layer and a light emitting layer adjacent to the hole transport layer, The hole transport layer contains the material for forming an organic film according to any one of claims 1 to 14. Organic electroluminescent device.

19. 19. The organic electroluminescent device according to claim 18, having an emission peak wavelength of 500 nm or less.

20. A hole injection layer is provided between the anode and the hole transport layer, and the hole injection layer is a tetraaryl group 19. The organic electroluminescent device of claim 18, comprising a fluoroborate ion.

21. An organic EL display device comprising the organic electroluminescent device according to claim 18.

22. An organic electroluminescent lighting device comprising the organic electroluminescent device according to claim 18.

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