WO2021125011A1 - Polymère, composition pour élément électroluminescent organique, composition pour former une couche de transport de trous ou une couche d'injection de trous, élément électroluminescent organique, dispositif d'affichage électroluminescent organique et illuminateur électroluminescent organique - Google Patents

Polymère, composition pour élément électroluminescent organique, composition pour former une couche de transport de trous ou une couche d'injection de trous, élément électroluminescent organique, dispositif d'affichage électroluminescent organique et illuminateur électroluminescent organique Download PDF

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WO2021125011A1
WO2021125011A1 PCT/JP2020/045835 JP2020045835W WO2021125011A1 WO 2021125011 A1 WO2021125011 A1 WO 2021125011A1 JP 2020045835 W JP2020045835 W JP 2020045835W WO 2021125011 A1 WO2021125011 A1 WO 2021125011A1
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group
substituent
ring
polymer
layer
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Japanese (ja)
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延軍 李
智宏 安部
良子 梶山
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三菱ケミカル株式会社
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Priority to KR1020227012362A priority Critical patent/KR20220117199A/ko
Priority to CN202080079850.9A priority patent/CN114729121A/zh
Priority to JP2021565515A priority patent/JPWO2021125011A1/ja
Publication of WO2021125011A1 publication Critical patent/WO2021125011A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers

Definitions

  • the present invention relates to a polymer. Specifically, the present invention relates to a polymer useful as a charge transport material for an organic electroluminescent device.
  • the present invention also includes a composition for an organic electroluminescent device containing the polymer, a composition for forming a hole transport layer or a hole injection layer, an organic electroluminescent device including a layer formed by using the composition, and an organic electroluminescent device.
  • the present invention relates to the manufacturing method, an organic EL display device having the organic electroluminescent element, and an organic EL illumination.
  • the vacuum vapor deposition method As a method for forming an organic layer in an organic electroluminescent device, there are a vacuum vapor deposition method and a wet film deposition method. Since the vacuum vapor deposition method is easy to stack, it has the advantages of improving charge injection from the anode and / or cathode and facilitating containment of excitons in the light emitting layer. On the other hand, the wet film forming method does not require a vacuum process, it is easy to increase the area, and by using a coating liquid in which a plurality of materials having various functions are mixed, a plurality of materials having various functions can be easily obtained. There are advantages such as being able to form a layer containing the above materials. However, since the wet film formation method is difficult to stack, the drive stability is inferior to that of the device by the vacuum vapor deposition method, and the current situation is that the drive stability has not reached the practical level except for a part.
  • Patent Documents 1 to 3 disclose an organic electroluminescent device containing a polymer having a specific repeating unit and laminated by a wet film forming method.
  • Patent Documents 4 and 5 disclose a hole injection transporting material having a structure in which a fluorene ring or a carbazole ring and a phenylene ring having no substituent are bonded to the main chain of the polymer.
  • Patent Document 6 the polymer having the repeating unit of quaternary carbon C4 and phenylene sp 3 hybridized, it is described that preferably includes a non-conjugated unit in the main chain.
  • Patent Document 6 discloses a side chain structure in which a triazine ring is connected to a main chain via an alkylene group.
  • Patent Document 7 discloses a polymer having a repeating unit containing a silicon atom and a carbazole ring in the main chain, in which a triazine group having a substituent is linked to the 9-position of the carbazole ring via an aryl group. There is.
  • Patent Document 8 discloses a polymer having a pyridine structure in the side chain of a polymer having an arylamine structure.
  • Patent Document 6 discloses a structure in which a triazine ring of a side chain and a main chain are connected via an alkylene group. However, this polymer has a structure in which the intermolecular charge transfer is blocked by the intermolecular charge transfer between the main chain and the triazine ring of the side chain via an alkylene group.
  • Patent Document 7 contains a silicon atom, so that the main chain of the polymer becomes unconjugated and is inferior in charge transportability.
  • Patent Document 8 discloses an arylamine polymer having a fluorenyl group having excellent charge transportability in the main chain.
  • the durability of the device is insufficient because the pyridine ring and the N atom in the main chain are directly bonded to each other to easily form an excimer.
  • the present inventor has found that the above problems can be solved by using a polymer having a specific structure in a side chain containing a specific 6-membered heteroaromatic ring having a nitrogen atom.
  • the gist of the present invention is as follows [1] to [16].
  • a polymer containing a repeating unit represented by the following formula (1) [1] A polymer containing a repeating unit represented by the following formula (1).
  • G represents an aromatic hydrocarbon group which may have a substituent or an N atom.
  • Ar 2 may have a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or a substituent.
  • a divalent group in which a plurality of two or more groups selected from a good divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group which may have a substituent are directly or via a linking group are linked.
  • A is a structure containing a specific 6-membered heteroaromatic ring having a nitrogen atom, and is represented by the formula (1) -2.
  • Ar 1 represents a divalent aromatic hydrocarbon group which may have a substituent.
  • Ar 3 and Ar 4 each independently have an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. It represents a monovalent group in which two or more groups selected from a good aromatic hydrocarbon group and an aromatic heterocyclic group which may have a substituent are directly or via a linking group.
  • X and Y independently represent C or N atoms, respectively. When X or Y is a C atom, it may have a substituent.
  • “ ⁇ *” Is a site that binds to G in the formula (1).
  • A is the same as A in the formula (1).
  • Q represents -C (R 5 ) (R 6 )-, -N (R 7 )-or -C (R 11 ) (R 12 ) -C (R 13 ) (R 14 )-.
  • R 1 to R 4 each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aralkyl group which may have a substituent.
  • R 5 to R 7 and R 11 to R 14 may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent.
  • a and b are independently integers of 0 to 4.
  • c1 to c5 are independently integers of 0 to 3. However, at least one of c3 and c5 is 1 or more.
  • d1 to d4 are independently integers of 1 to 4. When there are a plurality of R 1 , R 2 , R 3 , and R 4 in the repeating unit, R 1 , R 2 , R 3 , and R 4 may be the same or different.
  • Ar 7 excludes a group containing a specific 6-membered heteroaromatic ring having a nitrogen atom having a structure A represented by the formula (1) -2.
  • Q represents -C (R 5 ) (R 6 )-, -N (R 7 )-or -C (R 11 ) (R 12 ) -C (R 13 ) (R 14 )-.
  • R 1 to R 4 each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aralkyl group which may have a substituent.
  • R 5 to R 7 and R 11 to R 14 may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent.
  • a and b are independently integers of 0 to 4.
  • c1 to c5 are independently integers of 0 to 3. However, at least one of c3 and c5 is an integer of 1 or more.
  • d1 to d4 are independently integers of 1 to 4. When there are a plurality of R 1 , R 2 , R 3 , and R 4 in the repeating unit, R 1 , R 2 , R 3 , and R 4 may be the same or different.
  • Ar 1 in the formula (1) -2 is a group in which two or more divalent aromatic hydrocarbon groups which may have a substituent are linked.
  • the polymer according to any one.
  • a method for manufacturing an organic electroluminescent device which comprises a film forming step of forming by a wet film forming method using a composition for an organic electroluminescent device.
  • the hole injection layer, the hole transport layer, and the light emitting layer are included between the anode and the cathode, and the organic layer formed in the film forming step is the hole injection layer, the hole transport layer, and the light emitting layer.
  • An organic electroluminescent device including a layer containing the polymer according to any one of [1] to [8] or a polymer obtained by cross-linking the polymer.
  • the present invention it is possible to provide a polymer having high hole injection and transport ability and high durability, and a composition for an organic electroluminescent device containing the polymer. According to the present invention, it is also possible to provide an organic electroluminescent device having high brightness and a long drive life.
  • a positive having a specific structure in the side chain including a specific 6-membered heteroaromatic ring having a nitrogen atom which may have a substituent via an aromatic hydrocarbon group which may have a substituent.
  • the main chain and certain 6-membered heteroaromatic rings with nitrogen atoms form a conjugated structure.
  • HOMO is distributed in the vicinity of the amine of the main chain
  • LUMO is distributed around a specific 6-membered complex aromatic ring having a nitrogen atom. The longer the conjugate between the amine of the main chain and the specific 6-membered complex aromatic ring having a nitrogen atom, the easier it is for LUMO to be distributed in the specific 6-membered complex aromatic ring having a nitrogen atom.
  • HOMO and LUMO in the molecule are present due to the presence of Ar 1, which is a divalent aromatic hydrocarbon group, between the main chain and a specific 6-membered heteroaromatic ring having a nitrogen atom.
  • Ar 1 is a divalent aromatic hydrocarbon group
  • Ar 1 is a divalent aromatic hydrocarbon group
  • the portion of the LUMO having high electron durability receives electrons, it is considered that the durability against electrons is improved, the hole transportability of the main chain is not hindered, and the hole transportability is excellent.
  • the 6-membered heteroaromatic ring having a nitrogen atom refers to a 6-membered heteroaromatic ring containing X and Y contained in the structure A of the formula (1), and specifically, pyridine, pyrimidine, or triazine. It can take a structure.
  • the main chain of the polymer of the present embodiment preferably contains a fluorene ring or a carbazole ring.
  • a phenylene group is bonded to the 2,7-position of these fluorene ring or carbazole ring.
  • the phenylene group attached to the 2,7-position of the fluorene ring or the carbazole ring makes the fluorene ring or the carbazole ring electrically more stable. In particular, it is considered that the electronic durability is improved and the device drive life is extended.
  • the phenylene ring has a substituent at the ortho position
  • the plane of the phenylene group having the substituent is more twisted with respect to the plane of the adjacent fluorene ring or carbazole ring due to steric hindrance due to the substituent. It will be arranged.
  • the excited singlet energy level (S 1 ) and the excited triplet energy level (T 1 ) are high. It is excellent in light emission efficiency because quenching due to energy transfer from the light emission exciter is suppressed.
  • the main chain of the polymer of the present embodiment preferably contains a phenylene group having a substituent.
  • the surface of the phenylene group having the substituent is relative to the surface of the adjacent phenylene group, the divalent fluorene group, or the divalent carbazole group due to the steric disorder of the substituent.
  • crystallization is less likely to occur due to steric damage due to substituents, and the excited single-term energy level (S 1 ) and excited triple-term energy level (T 1 ) are high. Is preferable.
  • the main chain structure in which the spread of the ⁇ -conjugated system is inhibited is obtained. Therefore, the excited singlet energy level (S 1 ) and the excited triplet energy level (T 1 ) are high, and quenching due to energy transfer from the luminescence exciter is suppressed, so that the luminescence efficiency is excellent, which is preferable. ..
  • a charge transport material having an energy level higher than the energy level of the excitons of the light emitting material in the light emitting layer is preferable because it has a high effect of confining the excitons of the light emitting material. ..
  • the layer obtained by wet film formation using the composition for an organic electroluminescent device containing the polymer of the present embodiment is flat without cracks or the like.
  • the organic electroluminescent device according to another embodiment of the present invention having the layer has high brightness and a long drive life.
  • the element containing the layer formed by using the polymer is a light source that makes the best use of its characteristics as a flat panel display (for example, for an OA computer or a wall-mounted television), an in-vehicle display element, a mobile phone display, and a surface light emitter.
  • a light source of a copying machine, a backlight source of a liquid crystal display or an instrument), a display board, and an indicator light are conceivable, and their technical value is great.
  • FIG. 1 is a schematic cross-sectional view showing a structural example of the organic electroluminescent device of the present invention.
  • the following is a polymer according to one embodiment of the present invention, another embodiment of a composition for an organic electroluminescent device containing the polymer, and a composition for forming a hole transport layer or a hole injection layer.
  • An organic electroluminescent device including a layer formed by using the composition and a method for producing the same, and an organic EL display device having the organic electroluminescent device and an embodiment of organic EL lighting will be described in detail.
  • the following description is an example (representative example) of an embodiment of the present invention, and the present invention is not specified in these contents unless the gist thereof is exceeded.
  • the polymer according to one form of the present invention is a polymer containing a repeating unit represented by the following formula (1).
  • G represents an aromatic hydrocarbon group which may have a substituent or an N atom.
  • Ar 2 may have a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or a substituent.
  • a divalent group in which a plurality of two or more groups selected from a good divalent aromatic hydrocarbon group and a divalent aromatic heterocyclic group which may have a substituent are directly or via a linking group are linked.
  • A is a structure containing a specific 6-membered heteroaromatic ring having a nitrogen atom, and is represented by the formula (1) -2.
  • Ar 1 represents a divalent aromatic hydrocarbon group which may have a substituent.
  • Ar 3 and Ar 4 each independently have an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. It represents a monovalent group in which two or more groups selected from a good aromatic hydrocarbon group and an aromatic heterocyclic group which may have a substituent are directly or via a linking group.
  • X and Y independently represent C or N atoms, respectively. When X or Y is a C atom, it may have a substituent.
  • “ ⁇ *” Is a site that binds to G in the formula (1).
  • G represents an aromatic hydrocarbon group which may have a substituent or an N atom.
  • G has a substituent from the viewpoint of excellent charge transportability and the separation of LUMO distributed around a specific 6-membered heteroaromatic ring having a nitrogen atom and HOMO distributed in the main chain.
  • a benzene ring which may be present, a fluorene ring which may have a substituent, and a spirofluorene ring which may have a substituent are preferable, and the structure shown in the following scheme 1 is more preferable.
  • the following structure may have a substituent.
  • “-*” Represents the binding site with Ar 1.
  • the substituents that may be included include a substituent group Z described later, an aralkyl group having 7 to 40 carbon atoms, or a substituent having 4 to 4 carbon atoms. It is preferable to use any one of the 37 heterocyclic aralkyl groups or a combination thereof. Among them, in terms of durability, they are the same or different each time they appear, and they are an alkyl group having 1 to 24 carbon atoms, an aromatic group having 7 to 40 carbon atoms, and an aromatic group having a heterocycle having 3 to 37 carbon atoms.
  • the viewpoint of charge transportability it is the same or different each time it appears, and it is preferably an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic heterocyclic group having 3 to 24 carbon atoms, preferably phenyl. More preferably, it is a group, a naphthyl group, a fluorenyl group, a carbazolyl group, an indolocarbazolyl group, an indenocarbazolyl group, or an indenofluorenyl group.
  • G is preferably a fluorenyl group or an indenofluorenyl group.
  • G is preferably an N atom (nitrogen atom) from the viewpoint of excellent charge transportability, particularly excellent hole transportability.
  • Ar 1 represents a divalent aromatic hydrocarbon group which may have a substituent
  • Ar 2 may have a substituent.
  • the aromatic hydrocarbon group preferably has 6 or more and 60 or less carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, and a chrysen ring.
  • a divalent group of a 6-membered monocyclic ring or a 2- to 5-fused ring such as a triphenylene ring, an anthracene ring, a fluorentene ring, a fluorene ring, or a divalent group in which a plurality of these are linked.
  • the aromatic heterocyclic group preferably has 3 or more carbon atoms and 60 or less carbon atoms, and specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, and an oxadiazole ring.
  • the group may be a group in which a plurality of the same groups are linked, or a group in which a plurality of different groups are linked.
  • Ar 1 has a substituent from the viewpoint of localizing LUMO distributed in a specific 6-membered heteroaromatic ring having a nitrogen atom and HOMO distributed in the main chain in the formula (1) -2. It may have one divalent aromatic hydrocarbon group or a substituent which may have a substituent. A group in which 2 to 10 divalent aromatic hydrocarbon groups are linked is preferable, and a substituent may be provided. It is more preferable that one divalent aromatic hydrocarbon group or a group in which 2 to 8 divalent aromatic hydrocarbon groups are linked, which may have a substituent, is more preferable, and among them, it may have a substituent. It is preferably a group in which two or more divalent aromatic hydrocarbon groups are linked.
  • a group in which 2 to 6 benzene rings which may have a substituent are linked is particularly preferable, and a quaterphenylene group in which 4 benzene rings which may have a substituent are linked are particularly preferable. Most preferred.
  • Ar 1 is a non-conjugated site 1,3. It preferably contains at least one benzene ring linked at the position, and more preferably contains two or more. In the case where Ar 1 is a group in which a plurality of divalent aromatic hydrocarbon groups which may have a substituent are linked, it is preferable that all of them are directly bonded and linked from the viewpoint of charge transportability or durability. ..
  • the present inventor has developed the following units DUL-413, DUL-414, DUL-415 and DUL-416 in which the specific 6-membered heteroaromatic ring having a nitrogen atom in the formula (1) -2 is a triazine ring.
  • the isoelectron density planes (0.02) of HOMO and LUMO are displayed on Gauss View (HPC Systems). Distribution analysis of HOMO and LUMO of the unit was performed. Furthermore, the overlap (square root of the inner product) between the frontier orbital (HOMO and LUMO) distributions defined in the Mulliken distribution flow was calculated, and the value was obtained as "HOMO-LUMO Overlap". The results are shown in Table 1.
  • the LUMO of the molecule is distributed around the triazine ring. Further, it is preferable that the phenylene group between the nitrogen atom of the amine and the triazine ring is linked at the meta position rather than at the para position because the overlapping value of HOMO and LUMO is smaller. Further, the larger the number of phenylene groups linked at the meta position between the nitrogen atom of the amine and the triazine ring, the smaller the overlap value of HOMO and LUMO.
  • the value of HOMO-LUMO Overlap is preferably 0.1 or less, more preferably 0.05 or less, and even more preferably less than 0.01. Since the overlap between HOMO and LUMO is smaller when the number of phenylene groups linked at the meta position is 4 than when it is 3, the value of HOMO-LUMO Overlap is particularly preferably less than 0.0024.
  • Ar 2 Since Ar 2 is excellent in charge transportability and durability, it may have a divalent aromatic hydrocarbon group which may have a substituent and a divalent aromatic complex which may have a substituent. It is preferable that one or more groups selected from the ring groups are divalent groups bonded directly or via a linking group.
  • the linking group is preferably an oxygen atom or a carbonyl group. Since the triplet level can be increased by forming a non-conjugated structure with the aromatic ring, a structure in which the rings are linked by an oxygen atom or a carbonyl group is preferable.
  • the ring contained in Ar 2 is preferably a benzene ring or a fluorene ring from the viewpoint that the charge transport property is improved by expanding the ⁇ -conjugated system and the stability is excellent.
  • the main chain structure is such that the spread of the ⁇ -conjugated system is inhibited, the excited singlet energy level (S 1 ) and the excited triplet energy level (T 1 ) are increased, and quenching due to energy transfer from the luminescent exciter is suppressed. Therefore, from the viewpoint of excellent quenching efficiency, a twisted structure in which a fluorene ring and a phenylene group having an alkyl group are bonded is particularly preferable. Among them, a structure containing a phenylene group having a methyl group is particularly preferable for Ar 2 from the viewpoint of difficulty in synthesizing and purifying a monomer intermediate.
  • an aromatic hydrocarbon group which may have a substituent is preferable, and the substituent is used.
  • a phenylene group which may have a substituent or a fluorenylene group which may have a substituent is more preferable, and a phenylene group which may have a substituent is particularly preferable. It is preferable that a fluorene ring or a carbazole ring is bonded to the benzene ring that is directly bonded to G, which is a nitrogen atom.
  • a structure in which one or more phenylene groups are further linked between the benzene ring directly bonded to the nitrogen atom of G and the fluorene ring or the carbazole ring is also preferable.
  • any one of the substituent group Z described later or a combination thereof can be used.
  • the preferred range of substituents that Ar 1 may have is the same as the substituents that Ar 1 may have when G is an aromatic hydrocarbon group.
  • the substituent that Ar 2 may have is the same as the substituent that may have when G is an aromatic hydrocarbon group.
  • X and Y independently represent a C (carbon) atom or an N (nitrogen) atom, respectively.
  • X or Y is a C atom, it may have a substituent. From the viewpoint of facilitating the localization of LUMO around a specific 6-membered heteroaromatic ring having a nitrogen atom, it is preferable that both X and Y are N atoms.
  • any one of the substituent group Z described later or a combination thereof can be used. From the viewpoint of charge transportability, it is more preferable to have no substituent.
  • Ar 3 and Ar 4 each independently have an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. It is a monovalent group in which a plurality of two or more groups selected from a good aromatic hydrocarbon group and an aromatic heterocyclic group which may have a substituent are directly or via a linking group are linked.
  • Ar 3 and Ar 4 are independently a-1 to a-4, b-1 to b-9, c-1 to c-5, and d shown in the following scheme 3. It is preferable to have a structure selected from -1 to d-17 and e-1 to e-4. Furthermore, from the viewpoint of promoting the spread of LUMO of the molecule by having an electron-attracting group, a-1 to a-4, b-1 to b-9, c-1 to c-5, d-1 to A structure selected from d-13 and e-1 to e-4 is preferable.
  • a-1 to a-4, d-1 to d-13, and e-1 to e-4 from the viewpoint of the effect of confining excitons formed in the light emitting layer, which has a higher triplet level.
  • the structure is preferred.
  • the structure of the benzene ring of -3 is particularly preferable. Further, these structures may have a substituent.
  • “-*” Represents a binding site with a specific 6-membered heteroaromatic ring having a nitrogen atom. When there are a plurality of "-*", one of them represents a site that binds to a specific 6-membered heteroaromatic ring having a nitrogen atom.
  • any one of the substituent group Z described later or a combination thereof can be used. From the viewpoint of durability and charge transportability, it is preferably the same as the above-mentioned Ar 2 substituent.
  • R 31 and R 32 of Scheme 3 are linear, branched or cyclic alkyl groups which may independently have substituents.
  • the number of carbon atoms of 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, more preferably 3 or less, and further preferably a methyl group or an ethyl group. ..
  • R 31 and R 32 may be the same or different and can be distributed around the homogeneously nitrogen atom charge, since the further synthesis is easy, all R 31 and R 32 Is preferably the same group.
  • the repeating unit represented by the formula (1) is preferably a repeating unit represented by any of the following formulas (2) -1 to (2) -3.
  • A is the same as A in the formula (1).
  • Q represents -C (R 5 ) (R 6 )-, -N (R 7 )-or -C (R 11 ) (R 12 ) -C (R 13 ) (R 14 )-.
  • R 1 to R 4 each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aralkyl group which may have a substituent.
  • R 5 to R 7 and R 11 to R 14 may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent.
  • a and b are independently integers of 0 to 4.
  • c1 to c5 are independently integers of 0 to 3. However, at least one of c3 and c5 is 1 or more.
  • d1 to d4 are independently integers of 1 to 4. When there are a plurality of R 1 , R 2 , R 3 , and R 4 in the repeating unit, R 1 , R 2 , R 3 , and R 4 may be the same or different.
  • R 1 and R 2 in the repeating unit represented by the formulas (2) -1 to (2) -3 each independently have an alkyl group and a substituent which may have a substituent. It is an alkoxy group which may be used, or an aralkyl group which may have a substituent. It is preferable that R 1 and R 2 are linear, branched or cyclic alkyl groups which may independently have a substituent.
  • the number of carbon atoms of 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, more preferably 3 or less, and further preferably a methyl group or an ethyl group. preferable.
  • R 1 and R 2 may be the same or different, but the charge can be uniformly distributed around the nitrogen atom. Further, since synthesis is easy, it is preferable that all R 1 and R 2 are the same group.
  • R 3 and R 4 in the repeating unit represented by the formulas (2) -1 to (2) -3 each independently have an alkyl group and a substituent which may have a substituent. It is an alkoxy group which may be used, or an aralkyl group which may have a substituent. It is preferable that R 3 and R 4 are linear, branched or cyclic alkyl groups each independently which may have a substituent.
  • the carbon number of the alkyl group is not particularly limited, but in order to maintain the solubility of the polymer, the carbon number is preferably 1 or more, more preferably 4 or more, preferably 12 or less, and further preferably. It is 8 or less, and is particularly preferably a hexyl group.
  • R 5 to R 7 and R 11 to R 14 may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. It is an aromatic hydrocarbon group which may have an aralkyl group or a substituent.
  • R 5 to R 7 and R 11 to R 14 may independently have an alkyl group which may have a substituent, an aromatic group which may have a substituent, or an aralkyl group which may have a substituent. It is preferably a good aromatic hydrocarbon group.
  • the alkyl group is not particularly limited, but a long one is preferable in order to easily improve the solubility of the polymer, and a short one is preferable in order to improve the stability of the film and the charge transportability.
  • the alkyl group preferably has 1 or more and 24 or less carbon atoms, more preferably 12 or less, further preferably 8 or less, particularly preferably 6 or less, more preferably 2 or more, still more preferably 3 or more, and particularly preferably 4 or more. preferable.
  • the alkyl group may have a linear, branched or cyclic structure.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group and n-hexyl.
  • examples include a group, an n-octyl group, a cyclohexyl group, a dodecyl group and the like.
  • the alkoxy group is not particularly limited, but since it is easy to improve the solubility of the polymer, the number of carbon atoms is preferably 1 or more and 24 or less, more preferably 12 or less, further preferably 8 or less, particularly preferably 6 or less, and 2 or more. Is more preferable, 3 or more is further preferable, and 4 or more is particularly preferable.
  • Specific examples of the alkoxy group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, an i-butoxy group, a tert-butoxy group, a hexyloxy group and the like.
  • the aralkyl group is not particularly limited, but since it is easy to improve the solubility of the polymer, the number of carbon atoms is preferably 7 or more and 60 or less, more preferably 40 or less, more preferably 8 or more, further preferably 10 or more, and 12 or more. Is particularly preferable.
  • Specific examples of the aralkyl group include 1,1-dimethyl-1-phenylmethyl group, 1,1-di (n-butyl) -1-phenylmethyl group, and 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-phenylethyl group, 5-phenyl-1-n-propyl group, 6-phenyl-1-n-hexyl group, 6-naphthyl-1-n-hexyl group, 7-phenyl-1 Examples thereof include -n-heptyl group, 8-phenyl-1-n-octyl group and 4-phenylcyclohexyl group.
  • the aromatic hydrocarbon group is not particularly limited, but the number of carbon atoms is preferably 6 or more and 60 or less, more preferably 30 or less, further preferably 24 or less, and 14 or less because it is easy to improve the solubility of the polymer. Especially preferable.
  • aromatic hydrocarbon group examples include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaphthene ring, and a fluorene ring.
  • examples thereof include a monovalent group of a 6-membered monocyclic ring or a 2 to 5 fused ring such as a fluorene ring, or a group in which 2 to 8 ring structures selected from these are linked. It is preferably a single ring or a group in which 2 to 4 are linked.
  • R 5 ⁇ R 7 is an alkyl group or an aromatic hydrocarbon group is preferred. More preferably, R 5 and R 6 are alkyl groups. More preferably, R 7 is an aromatic hydrocarbon group. The preferred carbon numbers of these groups are as described above. R 5 and R 6 are preferably an alkyl group having 3 or more and 8 or less carbon atoms or an aralkyl group having 9 or more and 40 or less carbon atoms in terms of improving solubility and excellent charge transportability.
  • R 5 ⁇ R 7 and R 11 ⁇ R 14 is further have a substituent You may. May further substituent of the alkyl group R 5 ⁇ R 7 and R 11 ⁇ R 14, alkoxy groups, groups exemplified as the preferable groups of the aralkyl group and an aromatic hydrocarbon group, or below described crosslinkable The group is mentioned.
  • Substituents that R 5 to R 7 and R 11 to R 14 may further have are insoluble in a solvent when the polymer of the present embodiment is formed into a film and then another layer is applied to form a film and laminated. From the viewpoint of improvement, it is preferable to use a crosslinkable group described later. Above all, since it does not hinder the charge transport property, it is preferable that any one of R 5 , R 6 , and R 11 to R 14 has a cross-linking group described later as a further substituent, and at least of R 5 and R 6. It is more preferable that one has a crosslinkable group described later as a further substituent.
  • a and b are independently integers of 0 to 4. It is preferable that a and b are 2 or less, respectively, and it is more preferable that both a and b are 0 or 1 at the same time.
  • c1 to c5 are independently integers of 0 to 3. However, at least one of c3 and c5 is 1 or more.
  • d1 to d4 are independently integers of 1 to 4. It is preferable that c1 to c5 and d1 to d4 are independently 2 or less. It is more preferable that both c1 and c2 are 0 or 1 at the same time. It is more preferable that c1 and c2 are 1 or more.
  • At least one of c3 or c4, or both c3 and c4 are preferably 1 or more. It is more preferable that both c3 and c4 are 1.
  • c5 is preferably 1 or more.
  • c1 and c2, c3 and c4, and d1 to d4 are equal to each other. It is even more preferable that all of c1 to c5 and d1 to d4 are 1 or 2. It is particularly preferable that all of c1 to c5 and d1 to d4 are 1.
  • Equation (2) both c1 and c2 in the repeating unit represented by -1 is 1 or 2 simultaneously, and, when both a and b is 2 or 1, R 1 and R 2 are each Most preferably, they are coupled at symmetrical positions.
  • Equation (2) both c3 and c4 in the repeating unit represented by -2 1 or 2 simultaneously, and, when both a and b is 2 or 1, R 1 and R 2 are each Most preferably, they are coupled at symmetrical positions.
  • Specific examples of a preferable repeating unit structure include the following structures.
  • substituent group Z examples include the following substituents. For example, 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, cyclohexyl group, dodecyl group and the like.
  • an alkenyl group such as a vinyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less
  • an alkoxy group such as a methoxy group or an ethoxy group having a carbon number of usually 1 or more, usually 24 or less, preferably 12 or less
  • an alkoxycarbonyl group such as a methoxy
  • Aromatic hydrocarbon groups of 24 or less For example, a monovalent group in which a plurality of aromatic heterocycles of the same or different monocyclic or condensed rings are linked, such as a thienyl group, usually has 3 or more carbon atoms, preferably 5 or more carbon atoms, and usually 36 or less, preferably 36 or less carbon atoms.
  • aromatic heterocyclic groups A monovalent aromatic group in which an aromatic hydrocarbon ring and an aromatic heterocyclic group are linked, and when there are a plurality of aromatic hydrocarbon rings or aromatic heterocyclic groups, they may be the same or different.
  • an aromatic heterocyclic group other than the above-mentioned alkyl group, alkoxy group, aromatic hydrocarbon group, group containing a specific 6-membered heteroaromatic ring having a nitrogen atom, or aromatic group is a monovalent aromatic group in which a group hydrocarbon ring and an aromatic heterocyclic group are linked. From the viewpoint of charge transportability, it has no substituent or has a monovalent aromatic group in which an aromatic hydrocarbon group, an aromatic heterocyclic group, an aromatic hydrocarbon ring and an aromatic heterocyclic group are linked. Is even more preferable.
  • Each substituent of the substituent group Z may further have a substituent.
  • substituents include the same substituents as the above-mentioned substituents (substituent group Z) or crosslinkable groups described later.
  • it does not have a further substituent, or has an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, a phenyl group, or a crosslinkable group described later as a further substituent. From the viewpoint of charge transportability, it is more preferable to have no additional substituent.
  • the terminal group refers to the structure of the terminal portion of the polymer formed by the end cap agent used at the end of the polymerization of the polymer.
  • the terminal group of the polymer of this embodiment is usually a hydrocarbon group. From the viewpoint of charge transportability, the hydrocarbon group preferably has 1 or more and 60 or less carbon atoms, more preferably 1 or more and 40 or less, and further preferably 1 or more and 30 or less.
  • the terminal group preferably includes the following. For example, 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, cyclohexyl group, dodecyl group and the like.
  • an alkenyl group such as a vinyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less.
  • an alkynyl group such as an ethynyl group having a carbon number of usually 2 or more, usually 24 or less, preferably 12 or less.
  • hydrocarbon groups may further have a substituent.
  • the substituent which may be possessed is preferably an alkyl group or an aromatic hydrocarbon group, and when there are a plurality of substituents which may be further possessed, they may be bonded to each other to form a ring.
  • the substituent that the hydrocarbon group of the terminal group may further have is preferably an alkyl group or an aromatic hydrocarbon group from the viewpoint of charge transportability and durability, and more preferably an aromatic hydrocarbon. It is a group.
  • the polymer of the present embodiment preferably has a soluble group for soluble expression in a solvent.
  • the soluble group in the present embodiment is a group having a linear or branched alkyl group or alkylene group having 3 or more and 24 or less carbon atoms, preferably 12 or less carbon atoms.
  • an alkyl group, an alkoxy group, or an aralkyl group is preferable, and for example, an n-propyl group, a 2-propyl group, an n-butyl group, an isobutyl group, an n-hexyl group, an n-octyl group and the like. .. More preferably, it is an n-hexyl group or an n-octyl group.
  • the soluble group may have a substituent.
  • the number of soluble groups contained in the polymer of the present embodiment can be expressed by the number of moles per gram of the polymer.
  • the number of soluble groups contained in the polymer of the present embodiment is represented by the number of moles per 1 g of the polymer, it is usually 4.0 mmol or less, preferably 3.0 mmol or less, more preferably 3.0 mmol or less per 1 g of the polymer. It is 2.0 mmol or less, and usually 0.1 mmol or more, preferably 0.5 mmol or more.
  • the number of soluble groups is within the above range, the polymer is easily dissolved in a solvent, and a composition containing a polymer suitable for a wet film forming method can be easily obtained. Further, since the soluble group density is appropriate and the solubility in the organic solvent after drying with a heating solvent is sufficient, a multi-layer laminated structure can be formed by a wet film forming method.
  • the number of soluble groups per gram of the polymer can be calculated from the molar ratio of the charged monomer at the time of synthesis and the structural formula, excluding the terminal groups thereof from the polymer.
  • the case of the polymer 1 synthesized in Example 1 described later will be described as follows.
  • the molecular weight of the repeating unit excluding the terminal group is 748.4 on average.
  • the average number of hexyl groups, which are soluble groups, is 1.3 per repeating unit.
  • the number of soluble groups per 1 g of molecular weight is calculated to be 1.74 mmol.
  • the polymer of this embodiment may have a crosslinkable group.
  • the crosslinkable group in the polymer of the present embodiment may be present in the repeating unit represented by the formula (1), and may be present in a repeating unit different from the repeating unit represented by the formula (1). It may exist.
  • By having a crosslinkable group it is possible to make a large difference in solubility in an organic solvent before and after a reaction (poor solubility reaction) caused by irradiation with heat and / or active energy rays.
  • a crosslinkable group is a group that forms a new chemical bond by reacting with a group constituting another molecule located in the vicinity of the crosslinkable group by irradiation with heat and / or active energy rays.
  • the reacting group may be the same group as the crosslinkable group or a different group.
  • crosslinkable group a cyclobutene ring fused to the aromatic ring and a group containing an alkenyl group bonded to the aromatic ring are preferable, and a group selected from the following crosslinkable group group K is more preferable. It is preferable that the crosslinkable group is contained in the polymer in a form further substituted with the substituent having each structure.
  • the crosslinkable group K has the structure shown below.
  • R 21 to R 23 each independently represent a hydrogen atom or an alkyl group.
  • R 24 to R 26 each independently represent an alkyl group or an alkoxy group.
  • p represents an integer of 1 to 4
  • q represents an integer of 1 to 4
  • r represents an integer of 1 to 4.
  • the plurality of R 24s may be the same or different, and adjacent R 24s may be bonded to each other to form a ring.
  • the plurality of R 25s may be the same or different, and adjacent R 25s may be bonded to each other to form a ring.
  • the plurality of R 26s may be the same or different, and adjacent R 26s may be bonded to each other to form a ring.
  • Ar 21 and Ar 22 each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent. "-*" Is a binding site.
  • Examples of the alkyl group of R 21 to R 26 include a linear or branched chain alkyl group having 6 or less carbon atoms.
  • Examples of the alkoxy group of R 24 to R 26 include a linear or branched chain alkoxy group having 6 or less carbon atoms.
  • the number of carbon atoms of R 24 to R 26 is 6 or less, it is considered that the film formed by the polymer of the present embodiment is likely to be insolubilized without sterically inhibiting the cross-linking reaction.
  • Examples of the aromatic hydrocarbon group which may have a substituent of Ar 21 and Ar 22 include a single ring of a 6-membered ring such as a benzene ring and a naphthalene ring having one free valence, or 2 to 2 to. Examples include a 5-fused ring. In particular, a benzene ring having one free valence is preferable.
  • Ar 22 may be a group in which two or more aromatic hydrocarbon groups which may have a substituent are bonded. Examples of such a group include a biphenylene group and a terphenylene group, and a 4,4'-biphenylene group is preferable.
  • Examples of the aromatic heterocyclic group which may have a substituent of Ar 21 and Ar 22 include a single ring of a 6-membered ring having one free valence, such as a pyridine ring and a triazine ring, or 2 to 2 to Examples include a 5-fused ring. In particular, a triazine ring having one free valence is preferable.
  • crosslinkable group cyclization of an arylvinylcarbonyl group such as a cinnamoyle group, a benzocyclobutene ring having a monovalent free valence, and a 1,2-dihydrocyclobuta [a] naphthalene ring having a monovalent free valence.
  • Additive reacting groups are preferred in that they further improve the electrochemical stability of the device.
  • a cyclobutene ring fused to an aromatic ring having a monovalent free valence and a 1,2-dihydrocyclobutane having a monovalent free valence are particularly stable in the structure after cross-linking.
  • a group containing a naphthalene ring is preferable, and among them, a benzocyclobutene ring or a 1,2-dihydrocyclobuta [a] naphthalene ring having a monovalent free valence is more preferable.
  • a 1,2-dihydrocyclobuta [a] naphthalene ring having a monovalent free valence in terms of low cross-linking reaction temperature is particularly preferred.
  • the crosslinkable group of the polymer of the present embodiment is preferably sufficiently insolubilized by crosslinking, and it becomes easy to form another layer on the crosslinkable group by a wet film forming method.
  • the number of crosslinkable groups is small in that cracks are unlikely to occur in the formed layer, unreacted crosslinkable groups are unlikely to remain, and the organic electroluminescent device tends to have a long life.
  • the number of crosslinkable groups present in one polymer chain is preferably 1 or more, more preferably 2 or more, preferably 200 or less, and more preferably 100 or less.
  • the number of crosslinkable groups contained in the polymer of the present embodiment can be represented by the number per 1000 molecular weight of the polymer.
  • the number of crosslinkable groups contained in the polymer of the present embodiment is expressed by the number per 1000 molecular weight of the polymer, it is usually 3.0 or less, preferably 2.0 or less, more preferably 2.0 or less per 1000 molecular weight.
  • the number is 1.0 or less, usually 0.01 or more, preferably 0.05 or more.
  • the number of crosslinkable groups is within the above range, cracks and the like are unlikely to occur, and a flat film can be easily obtained from the polymer of the present embodiment. Further, since the cross-linking density is appropriate, there are few unreacted cross-linking groups remaining in the layer after the cross-linking reaction, which does not easily affect the life of the obtained device. Further, since the poor solubility in the organic solvent after the crosslinking reaction is sufficient, it is easy to form a multilayer laminated structure by the wet film forming method.
  • the number of crosslinkable groups per 1000 molecular weight of the polymer can be calculated from the molar ratio of the charged monomer at the time of synthesis and the structural formula, excluding the terminal groups thereof from the polymer.
  • the case of the polymer 1 synthesized in the examples described later will be described as follows.
  • the molecular weight of the repeating unit excluding the terminal group is 748.4 on average.
  • the number of crosslinkable groups is 0.15 per repeating unit. When this is calculated by simple proportion, the number of crosslinkable groups per 1000 molecular weight is calculated to be 0.20.
  • the content of the repeating unit represented by the formula (1) is not particularly limited, but it is usually contained in the polymer in an amount of 5 mol% or more, preferably 10 mol% or more, and 15 It is more preferably contained in an amount of mol% or more, and particularly preferably contained in an amount of 20 mol% or more.
  • the repeating unit may be composed of only the repeating unit represented by the formula (1), but for the purpose of balancing various performances when the organic electroluminescent device is used, the formula (1) It may have a repeating unit different from that of 1).
  • the content of the repeating unit represented by the formula (1) in the polymer is usually 99 mol% or less, preferably 95 mol% or less.
  • the polymer of the present embodiment further preferably contains a repeating unit represented by any of the following (3) -1, formula (3) -2 or formula (3) -3.
  • Ar 7 excludes a group containing a specific 6-membered heteroaromatic ring having a nitrogen atom having a structure A represented by the formula (1) -2.
  • Q represents -C (R 5 ) (R 6 )-, -N (R 7 )-or -C (R 11 ) (R 12 ) -C (R 13 ) (R 14 )-.
  • R 1 to R 4 each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aralkyl group which may have a substituent.
  • R 5 to R 7 and R 11 to R 14 may independently have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent.
  • a and b are independently integers of 0 to 4.
  • c1 to c5 are independently integers of 0 to 3. However, at least one of c3 and c5 is an integer of 1 or more.
  • d1 to d4 are independently integers of 1 to 4. When there are a plurality of R 1 , R 2 , R 3 , and R 4 in the repeating unit, R 1 , R 2 , R 3 , and R 4 may be the same or different.
  • Ar 7 independently contains a group containing a specific 6-membered heteroaromatic ring having a nitrogen atom in the present invention. It represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, excluding the structure A represented by the formula (1) -2.
  • the aromatic hydrocarbon group preferably has 6 or more and 60 or less carbon atoms, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, and a chrysen.
  • Examples thereof include a 6-membered monocyclic ring or a 2- to 5-fused ring such as a ring, a triphenylene ring, an anthracene ring, a fluorene ring, and a fluorene ring, or a monovalent group in which a plurality of these are linked.
  • the aromatic heterocyclic group preferably has 3 or more carbon atoms and 60 or less carbon atoms, and specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, a pyrazole ring, an imidazole ring, or an oxadiazole.
  • a 5- to 6-membered monocyclic ring such as a pyrazine ring, a pyridazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring. Examples thereof include 2 to 4
  • Ar 7 is preferably an aromatic hydrocarbon group which may have a substituent from the viewpoint of excellent charge transportability and durability.
  • a monovalent group of a benzene ring or a fluorene ring which may have a substituent that is, a phenyl group or a fluorenyl group which may have a substituent is more preferable, and a substituent may be provided.
  • a fluorenyl group is more preferred, and a 2-fluorenyl group, which may have a substituent, is particularly preferred.
  • the substituent that the aromatic hydrocarbon group of Ar 7 may have is not particularly limited as long as it does not significantly reduce the characteristics of the polymer of the present embodiment.
  • a group selected from the substituent group Z or the crosslinkable group is mentioned, and an aromatic heterocycle other than a specific 6-membered heteroaromatic ring having an alkyl group, an alkoxy group, an aromatic hydrocarbon group and a nitrogen atom can be mentioned.
  • a group or the crosslinkable group is preferable, and an alkyl group is more preferable.
  • Ar 7 is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms, and particularly a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms. preferable. Further, a 9-alkyl-2-fluorenyl group in which the alkyl group is substituted at the 9-position of the 2-fluorenyl group is preferable, and a 9,9'-dialkyl-2-fluorenyl group in which the alkyl group is 2-substituted is particularly preferable.
  • Ar 7 is a fluorenyl group in which at least one of the 9-position and the 9'-position is substituted with an alkyl group, the solubility in a solvent and the durability of the fluorene ring are likely to be improved. Further, since both the 9-position and the 9'-position are substituted with an alkyl group, the solubility in a solvent and the durability of the fluorene ring are likely to be further improved. It is preferable that Ar 7 contains the crosslinkable group because the insolubility in the solvent is improved when the film is laminated and coated after the film formation.
  • the polymer of the present embodiment contains a repeating unit represented by the formulas (3) -1 to (3) -3 containing at least one of the above-mentioned crosslinkable groups as a further substituent. It is preferable that the crosslinkable group is further substituted with a substituent which the aromatic hydrocarbon group represented by Ar 7 may have.
  • Specific examples of the repeating unit structure represented by the formulas (3) -1 to (3) -3 include the following structures.
  • the polymer of the present embodiment may further contain a repeating unit represented by the following formula (4) or the following formula (5) in terms of charge transportability and durability.
  • R 8 and R 9 are each independently a hydrogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or a substituent. Represents an aromatic heterocyclic group which may have a group.
  • Ar 10 has a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent. Two or more groups selected from a divalent aromatic hydrocarbon group which may be present and a divalent aromatic heterocyclic group which may have a substituent are linked directly or via a linking group. Represents a valence group.
  • R 8 and R 9 examples of the alkyl group, aromatic hydrocarbon group and aromatic heterocyclic group of R 8 and R 9 include the alkyl group exemplified as the substituent group Z, the aromatic hydrocarbon group and the aromatic heterocyclic group.
  • the substituents that these groups may have are preferably a group similar to the substituent group Z or the crosslinkable group.
  • Ar 10 As a specific structure of Ar 10, a divalent group similar to Ar 2 in the above formula (1) can be mentioned.
  • the substituents that these groups may have are preferably a group similar to the substituent group Z or the crosslinkable group.
  • the weight average molecular weight (Mw) of the polymer of the present embodiment is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 200,000 or less, particularly preferably. Is less than 100,000.
  • the weight average molecular weight (Mw) of the polymer of the present embodiment is usually 10,000 or more, preferably 15,000 or more.
  • the weight average molecular weight of the polymer When the weight average molecular weight of the polymer is not more than the above upper limit value, solubility in a solvent is obtained, and the film forming property tends to be excellent. When the weight average molecular weight of the polymer is at least the above lower limit value, the decrease in the glass transition temperature, the melting point and the vaporization temperature of the polymer may be suppressed, and the heat resistance may be improved. In addition, the coating film after the cross-linking reaction may be sufficiently insoluble in the organic solvent.
  • the number average molecular weight (Mn) of the polymer of the present embodiment is usually 2.5 million or less, preferably 750,000 or less, more preferably 400,000 or less, and particularly preferably 100,000 or less.
  • the number average molecular weight (Mn) of the polymer of the present embodiment is usually 2,000 or more, preferably 4,000 or more, more preferably 8,000 or more, and further preferably 20,000 or more.
  • the dispersity (Mw / Mn) in the polymer of the present embodiment is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less.
  • the dispersity of the polymer is not more than the above upper limit value, purification is easy, and solubility in a solvent and charge transporting ability are good.
  • the weight average molecular weight and the number average molecular weight of the polymer are determined by SEC (size exclusion chromatography) measurement.
  • SEC size exclusion chromatography
  • the weight average molecular weight and the number average molecular weight are calculated.
  • the polymer of the present embodiment is most preferably represented by any of the following formulas (6a) to (6o).
  • A, Q, R 1 , R 2 , R 3 , and R 4 are the same as those in the formulas (2) -1 to (2) -3.
  • Ar 7 is the same as in the above equations (3) -1 to (3) -3.
  • At least one A or Ar 7 in each polymer preferably has the above-mentioned crosslinkable group.
  • n and m represent the number of repetitions.
  • the method for producing the polymer of the present embodiment is not particularly limited.
  • it can be produced by a polymerization method by Suzuki reaction, a polymerization method by Grignard reaction, a polymerization method by Yamamoto reaction, a polymerization method by Ullmann reaction, a polymerization method by Buchwald-Hartwig reaction, or the like.
  • the aryl dihalide represented by the following formula (1a) (E represents a halogen atom such as I, Br, Cl, F) and the formula.
  • the polymer of the present embodiment is synthesized by reacting with the primary aminoaryl represented by (1b) and further reacting with the dial halide represented by the formula (2a).
  • A, R 1 ⁇ R 2 , Q, a, b, c1, d1 has the same meaning as the formula (2) -1 to (2) -3.
  • n and m represent the number of repetitions.
  • the reaction for forming an N-aryl bond is usually carried out in the presence of a base such as potassium carbonate, tert-butoxysodium or triethylamine. It can also be carried out in the presence of a transition metal catalyst such as a copper or palladium complex.
  • a base such as potassium carbonate, tert-butoxysodium or triethylamine. It can also be carried out in the presence of a transition metal catalyst such as a copper or palladium complex.
  • the polymer of the present embodiment can be particularly preferably used as an organic electroluminescent device material. That is, the polymer of the present embodiment is preferably an organic electroluminescent device material.
  • the polymer of the present embodiment is usually suitably used for forming a layer contained between an anode and a light emitting layer in an organic electric field generating element. That is, the polymer of the present embodiment is preferably used as a material that forms at least one of the hole injection layer and the hole transport layer, that is, a charge transport material.
  • a layer having high charge transportability to the light emitting layer and high durability against electrons leaked from the light emitting layer is used as an anode and a light emitting layer. It can be provided between and.
  • a charge transporting material one type of the polymer of the present embodiment may be used, or two or more types may be used in any combination and in any ratio.
  • the inclusion of the polymer of the present embodiment in the hole injection layer or the hole transport layer is usually 1 to 100% by weight, preferably 5 to 100% by weight, and more preferably 10 to 100% by weight.
  • the above range is preferable because the charge transportability of the hole injection layer or the hole transport layer is improved, the drive voltage is reduced, and the drive stability is improved.
  • the other components constituting the hole injection layer or the hole transport layer include hole transport described later. Examples include sex compounds.
  • the polymer of the present embodiment is preferably used for the organic layer formed by the wet film forming method.
  • composition for organic electroluminescent device contains the polymer of the present embodiment.
  • the composition for an organic electroluminescent device of the present embodiment may contain one kind of the above polymer, or may contain two or more kinds in any combination and any ratio.
  • the content of the polymer in the composition for an organic electroluminescent device of the present embodiment is usually 0.01 to 70% by weight, preferably 0.1 to 60% by weight, and more preferably 0.5 to 50% by weight. %. When it is within the above range, defects are unlikely to occur in the formed organic layer and uneven film thickness is unlikely to occur, which is preferable.
  • the composition for an organic electroluminescent device of the present embodiment may contain a solvent or the like in addition to the above polymer.
  • the composition for an organic electroluminescent device of the present embodiment usually contains a solvent.
  • the solvent is preferably one that dissolves the above polymer.
  • a solvent that dissolves the polymer in an amount of usually 0.05% by weight or more, preferably 0.5% by weight or more, and more preferably 1% by weight or more at room temperature is preferable.
  • the solvent include aromatic solvents such as toluene, xylene, mesityrene and cyclohexylbenzene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether and propylene.
  • Aliper ethers such as glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, Ether-based solvents such as aromatic ethers such as 2,3-dimethylanisole and 2,4-dimethylanisole; aliphatic ester-based solvents such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate; phenyl acetate, Ester-based solvents such as phenyl propionate, methyl benzoate, ethyl benzoate, isopropyl benzoate, propyl benzoate, n-butyl benzoate and other aromatic esters; Examples thereof include organic solvents used in the composition for forming a hole transport layer and the
  • One type of solvent may be used, or two or more types may be used in any combination and in any ratio.
  • the surface tension at 20 ° C. is usually less than 40 dyn / cm, preferably 36 dyn / cm or less, more preferably 33 dyn / cm or less. Solvents are preferred.
  • the solvent and the substrate have a high affinity. .. This is because the uniformity of the film quality greatly affects the uniformity and stability of the light emission of the organic electroluminescent device. Therefore, the composition for an organic electroluminescent device used in the wet film forming method is required to have a low surface tension so that a more levelable and uniform coating film can be formed. Therefore, by using a solvent having a low surface tension as described above, a uniform layer containing the polymer can be formed, and a uniform crosslinked layer can be formed, which is preferable.
  • the low surface tension solvent examples include the above-mentioned aromatic solvents such as toluene, xylene, mesityrene and cyclohexylbenzene, ester solvents such as ethyl benzoate, ether solvents such as anisole, trifluoromethoxyanisole and penta. Fluoromethoxybenzene, 3- (trifluoromethyl) anisole, ethyl (pentafluorobenzoate) and the like can be mentioned.
  • aromatic solvents such as toluene, xylene, mesityrene and cyclohexylbenzene
  • ester solvents such as ethyl benzoate
  • ether solvents such as anisole, trifluoromethoxyanisole and penta. Fluoromethoxybenzene, 3- (trifluoromethyl) anisole, ethyl (pentafluorobenzoate) and the like can be mentioned.
  • the solvent contained in the composition for an organic electroluminescent device of the present embodiment preferably has a vapor pressure at 25 ° C. of usually 10 mmHg or less, preferably 5 mmHg or less, and usually 0.1 mmHg or more.
  • a solvent By using such a solvent, it is possible to prepare a composition for an organic electroluminescent device, which is suitable for a process of manufacturing an organic electroluminescent device by a wet film forming method and suitable for the properties of the polymer of the present embodiment. it can.
  • Specific examples of such a solvent include the above-mentioned aromatic solvents such as toluene, xylene and mesitylene, ether solvents and ester solvents.
  • Moisture may cause performance deterioration of the organic electroluminescent element, and in particular, it may promote a decrease in brightness during continuous driving.
  • those having a water solubility at 25 ° C. of 1% by weight or less are preferable, and those having a solubility of 0.1% by weight or less are more preferable. preferable.
  • the content of the solvent contained in the composition for an organic electroluminescent device of the present embodiment is usually 10% by weight or more, preferably 30% by weight or more, and particularly preferably 50% by weight or more.
  • the content of the solvent is at least the above lower limit, the flatness and uniformity of the formed layer can be improved.
  • the composition for an organic electroluminescent device of the present embodiment preferably further contains an electron-accepting compound from the viewpoint of reducing resistance.
  • the composition for an organic electroluminescent device of the present embodiment when used for forming a hole injection layer, it preferably contains an electron-accepting compound.
  • the electron-accepting compound a compound having an oxidizing power and an ability to accept one electron from the above polymer is preferable. Specifically, a compound having an electron affinity of 4 eV or more is preferable, and a compound having an electron affinity of 5 eV or more is more preferable.
  • Examples of such an electron-accepting compound include a triarylboron compound, a metal halide, a Lewis acid, an organic acid, an onium salt, a salt of an arylamine and a metal halide, and a salt of an arylamine and a Lewis acid.
  • Examples thereof include one kind or two or more kinds of compounds selected from the group consisting of two or more kinds.
  • onium salts substituted with organic groups such as 4-isopropyl-4'-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrafluoroborate (International Publication No. 2005/089024), ( International Publication No. 2017/164268); High valence inorganic compounds such as iron chloride (III) (Japanese Patent Laid-Open No. 11-251067), ammonium peroxodisulfate; cyano compounds such as tetracyanoethylene; tris (pentafluorophenyl) Aromatic boron compounds such as borane (Japanese Patent Laid-Open No. 2003-31365); fullerene derivatives, iodine and the like can be mentioned.
  • organic groups such as 4-isopropyl-4'-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate,
  • composition for an organic electroluminescent device of the present embodiment may contain one kind of the above-mentioned electron-accepting compound alone, or may contain two or more kinds in any combination and ratio.
  • the content of the electron-accepting compound is usually 0.0005% by weight or more, preferably 0.001% by weight or more, and is usually 20. By weight or less, preferably 10% by weight or less.
  • the ratio of the electron-accepting compound to the polymer in the composition for an organic electroluminescent element is usually 0.5% by weight or more, preferably 1% by weight or more, more preferably 3% by weight or more, and usually 80% by weight. Hereinafter, it is preferably 60% by weight or less, more preferably 40% by weight or less.
  • the electron acceptor receives electrons from the polymer and the formed organic layer has low resistance, which is preferable.
  • the content of the electron-accepting compound in the composition for an organic electroluminescent device is not more than the above upper limit, defects are less likely to occur in the formed organic layer and uneven film thickness is less likely to occur, which is preferable.
  • composition for an organic electroluminescent device of the present embodiment may further contain a cationic radical compound.
  • the cation radical compound an ionic compound composed of a cation radical, which is a chemical species obtained by removing one electron from a hole transporting compound, and a counter anion is preferable.
  • the cation radical is derived from a hole-transporting polymer compound, the cation radical has a structure in which one electron is removed from the repeating unit of the polymer compound.
  • the cation radical is preferably a chemical species obtained by removing one electron from the hole transporting compound described later.
  • a chemical species obtained by removing one electron from a preferable compound as a hole transporting compound is preferable from the viewpoints of amorphousness, visible light transmittance, heat resistance, solubility and the like.
  • the cationic radical compound can be produced by mixing the hole transporting compound described later and the electron accepting compound described above. That is, by mixing the hole-transporting compound and the electron-accepting compound, electron transfer occurs from the hole-transporting compound to the electron-accepting compound, which consists of the cation radical of the hole-transporting compound and the counter anion. A cationic ion compound is produced.
  • the content of the cation radical compound in the composition for an organic electroluminescent device is usually 0.0005% by weight or more, preferably 0.001% by weight. % Or more, usually 40% by weight or less, preferably 20% by weight or less.
  • the content of the cationic radical compound is at least the above lower limit, the resistance of the formed organic layer is lowered, which is preferable.
  • the content of the cationic radical compound is not more than the above upper limit, defects are less likely to occur in the formed organic layer and uneven film thickness is less likely to occur, which is preferable.
  • the components contained in the hole injection layer forming composition and the hole transport layer forming composition described later are contained in the contents described below. It may be contained.
  • the light emitting layer material includes a light emitting material and a host material. ..
  • the light emitting material a phosphorescent light emitting material or a fluorescent light emitting material can be used.
  • [Phosphorescent layer] In an organic electroluminescent device in which the polymer according to the embodiment of the present invention is used as a charge transporting material for forming at least one of a hole injection layer and a hole transport layer, when the light emitting layer is a phosphorescent light emitting layer, phosphorescence is achieved.
  • the following materials are preferable as the light emitting material.
  • the phosphorescent material refers to a material that emits light from an excited triplet state.
  • a metal complex compound having Ir, Pt, Eu, etc. is a typical example, and a material containing a metal complex is preferable as the structure of the material.
  • a phosphorescent organometallic complex that emits light via the triplet state it is a long-periodic periodic table (hereinafter, unless otherwise specified, the term "periodic table” refers to the long-periodic table.
  • a Werner-type complex or an organometallic complex compound containing a metal selected from Groups 7 to 11 as a central metal can be mentioned.
  • a compound represented by the following formula (201) or a compound represented by the following formula (205) is preferable, and a compound represented by the following formula (201) is more preferable. is there.
  • the ring A1 represents an aromatic hydrocarbon ring structure which may have a substituent or an aromatic heterocyclic structure which may have a substituent.
  • Ring A2 represents an aromatic heterocyclic structure which may have a substituent.
  • R 201 and R 202 are structures independently represented by the equation (202). “*” Represents a binding site with ring A1 or ring A2.
  • R 201 and R 202 may be the same or different, and when a plurality of R 201 and R 202 are present, they may be the same or different.
  • Ar 201 and Ar 203 each independently represent an aromatic hydrocarbon structure which may have a substituent or an aromatic heterocyclic structure which may have a substituent.
  • Ar 202 has an aromatic hydrocarbon structure which may have a substituent, an aromatic heterocyclic structure which may have a substituent, or an aliphatic hydrocarbon structure which may have a substituent. Represent. Substituents bonded to ring A1, substituents bonded to ring A2, or substituents bonded to ring A1 and substituents bonded to ring A2 may be bonded to each other to form a ring.
  • B 201- L 200- B 202 represents an anionic bidentate ligand.
  • B 201 and B 202 each independently represent a carbon atom, an oxygen atom, or a nitrogen atom, and these atoms may be atoms constituting a ring.
  • L 200 represents a single bond, or represents an atomic group together with B 201 and B 202 constituting the bidentate ligand. When there are a plurality of B 201- L 200- B 202 , they may be the same or different.
  • i1 and i2 independently represent integers of 0 or more and 12 or less.
  • i3 is an integer of 0 or more up to a number substitutable for Ar 202.
  • j1 is an integer of 0 or more up to a number substitutable for Ar 201.
  • k1 and k2 are independently integers of 0 or more, up to a number substitutable for rings A1 and A2, respectively.
  • m1 is an integer of 1 to 3.
  • Aryl group An alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, further preferably an alkyl group having 1 to 8 carbon atoms, and particularly preferably an alkyl group having 1 to 6 carbon atoms.
  • -Aalkoxy group An alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, further preferably an alkoxy group having 1 to 6 carbon atoms, and an aryloxy group: preferably 6 to 20 carbon atoms.
  • Aryloxy group more preferably an aryloxy group having 6 to 14 carbon atoms, further preferably an aryloxy group having 6 to 12 carbon atoms, particularly preferably an aryloxy group having 6 carbon atoms or a heteroaryloxy group: preferably carbon.
  • Amino group / arylamino group preferably an arylamino group having 6 to 36 carbon atoms, more preferably an arylamino group / aralkyl group having 6 to 24 carbon atoms: preferably an aralkyl group having 7 to 40 carbon atoms, more preferably carbon.
  • An aryl group having 6 to 18 carbon atoms particularly preferably an aryl group having 6 to 14 carbon atoms and a heteroaryl group: preferably a heteroaryl group having 3 to 30 carbon atoms, more preferably having 3 to 24 carbon atoms.
  • an alkylsilyl group / arylsilyl group having an alkyl group having 1 to 12 carbon atoms preferably an arylcy having an aryl group having 6 to 20 carbon atoms.
  • Substituents having a carbonyl group or more may have one or more hydrogen atoms replaced with fluorine atoms, or one or more hydrogen atoms may have been replaced with heavy hydrogen atoms.
  • the aryl group is an aromatic hydrocarbon group and the heteroaryl group is an aromatic heterocyclic group.
  • an alkyl group, an alkoxy group, an aryloxy group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkylsilyl group, an arylsilyl group, and one or more hydrogen atoms of these groups are present.
  • an alkyl group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, or a heteroaryl group is particularly preferably, an alkyl group, an arylamino group, an aralkyl group, an aryl group, or a heteroaryl group.
  • substituent group Z' may further have a substituent selected from the substituent group Z'as a substituent.
  • Preferred groups, more preferable groups, further preferable groups, particularly preferable groups, and most preferable groups of the substituents which may be possessed are the same as the preferable groups in the substituent group Z'.
  • Ring A1 represents an aromatic hydrocarbon ring structure which may have a substituent or an aromatic heterocyclic structure which may have a substituent.
  • the aromatic hydrocarbon ring of ring A1 is preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms. Specifically, a benzene ring, a naphthalene ring, an anthracene ring, a triphenylyl ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring are preferable.
  • an aromatic heterocycle of ring A1 an aromatic heterocycle having 3 to 30 carbon atoms containing any of a nitrogen atom, an oxygen atom, and a sulfur atom as a heteroatom is preferable, and a furan ring and a benzofuran ring are more preferable.
  • the ring A1 is more preferably a benzene ring, a naphthalene ring, or a fluorene ring, particularly preferably a benzene ring or a fluorene ring, and most preferably a benzene ring.
  • Ring A2 represents an aromatic heterocyclic structure which may have a substituent.
  • the aromatic heterocycle of ring A2 is preferably an aromatic heterocycle having 3 to 30 carbon atoms, which contains any of a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom.
  • a pyridine ring More preferably, it is a pyridine ring, a pyrazine ring, a pyrimidine ring, an imidazole ring, a benzothiazole ring, a benzoxazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, or a quinazoline ring. More preferably, it is a pyridine ring, an imidazole ring, a benzothiazole ring, a quinoline ring, an isoquinoline ring, a quinoxaline ring, or a quinazoline ring. Most preferably, it is a pyridine ring, an imidazole ring, a benzothiazole ring, a quinoline ring, a quinoxaline ring, or a quinazoline ring.
  • ring A1 and ring A2 when expressed as (ring A1-ring A2), (benzene ring-pyridine ring), (benzene ring-quinoline ring), (benzene ring-quinoxaline ring), (benzene ring- Quinazoline ring), (benzene ring-imidazole ring), (benzene ring-benzothiazole ring).
  • Ar 201 and Ar 203 each independently represent an aromatic hydrocarbon ring structure which may have a substituent or an aromatic heterocyclic structure which may have a substituent.
  • Ar 202 has an aromatic hydrocarbon ring structure which may have a substituent, an aromatic heterocyclic structure which may have a substituent, or an aliphatic hydrocarbon structure which may have a substituent. Represents.
  • Ar 201 , Ar 202 , and Ar 203 are aromatic hydrocarbon structures which may have a substituent, the aromatic hydrocarbon structure is preferably an aromatic hydrocarbon having 6 to 30 carbon atoms. It is a ring.
  • benzene ring examples include a benzene ring, a naphthalene ring, an anthracene ring, a triphenylyl ring, an acenaphthene ring, a fluoranthene ring and a fluorene ring, more preferably a benzene ring, a naphthalene ring and a fluorene ring, and most preferably a benzene ring. ..
  • Ar 201 or Ar 202 is a benzene ring which may have a substituent
  • at least one benzene ring is preferably bonded to an adjacent structure at the ortho-position or the meta-position, and at least one. It is more preferable that one benzene ring is bonded to an adjacent structure at the meta position.
  • Ar 201 , Ar 202 , and Ar 203 are aromatic heterocyclic structures which may have a substituent
  • the aromatic heterocyclic structure is preferably a nitrogen atom, an oxygen atom, or a heteroatom as a heteroatom. It is an aromatic heterocycle containing any of the sulfur atoms and having 3 to 30 carbon atoms.
  • Ar 202 is an aliphatic hydrocarbon structure which may have a substituent, it is an aliphatic hydrocarbon structure having a straight chain, a branched chain, or a cyclic structure, and the number of carbon atoms thereof is preferably 1 or more and 24. It is less than or equal to, more preferably 1 or more and 12 or less, and further preferably 1 or more and 8 or less.
  • i1 represents an integer of 0 to 12, preferably an integer of 1 to 12, more preferably 1 to 8, and even more preferably an integer of 1 to 6. Within this range, the solubility and charge transportability are expected to be improved.
  • ⁇ Preferable range of i3> i3 preferably represents an integer of 0 to 5, more preferably 0 to 2, and even more preferably 0 or 1.
  • j1 preferably represents an integer of 0 to 2, more preferably 0 or 1.
  • k1 and k2 preferably represent an integer of 0 to 3, more preferably 1 to 3, still more preferably 1 or 2, and particularly preferably 1.
  • the substituents that Ar 201 , Ar 202 , and Ar 203 may have can be arbitrarily selected, but preferably one or a plurality of substituents selected from the substituent group Z'.
  • the preferred group is also the same as that of the substituent group Z', but more preferably a hydrogen atom, an alkyl group or an aryl group, particularly preferably a hydrogen atom or an alkyl group, and most preferably an unsubstituted (hydrogen atom). is there.
  • Ar 201 is an aromatic hydrocarbon structure or an aromatic heterocyclic structure, i1 is 1 to 6, Ar 202 is an aliphatic hydrocarbon structure, i2 is 1 to 12, preferably 3 to 8, and Ar 203 is a benzene ring. Structure, i3 is 0 or 1.
  • Ar 201 has the aromatic hydrocarbon structure, more preferably a structure in which 1 to 5 benzene rings are linked, and more preferably one benzene ring. With this structure, it is expected that the solubility is improved and the charge transportability is improved.
  • ⁇ Dendron> A structure in which dendron is bound to ring A1 or ring A2.
  • Ar and Ar 202 have a benzene ring structure
  • Ar 203 has a biphenyl or terphenyl structure
  • i1 and i2 have 1 to 6
  • i3 has 2
  • j has 2.
  • B 201- L 200- B 202 > B 201- L 200- B 202 represents an anionic bidentate ligand.
  • B 201 and B 202 each independently represent a carbon atom, an oxygen atom, or a nitrogen atom, and these atoms may be atoms constituting a ring.
  • L 200 represents a single bond, or represents an atomic group together with B 201 and B 202 constituting the bidentate ligand. When there are a plurality of B 201- L 200- B 202 , they may be the same or different.
  • the structure represented by B 201- L 200- B 202 is preferably a structure represented by the following formula (203) or (204).
  • R 211 , R 212 , and R 213 represent substituents.
  • ring B3 represents an aromatic heterocyclic structure containing a nitrogen atom, which may have a substituent.
  • Ring B3 is preferably a pyridine ring.
  • the phosphorescent material represented by the formula (201) is not particularly limited, and specific examples thereof include the following structures. In the following, “Ph” represents a “phenyl group” and “Me” represents a "methyl group”.
  • M 2 represents a metal.
  • T represents a carbon atom or a nitrogen atom.
  • R 92 to R 95 each independently represent a substituent. If T is a nitrogen atom, then R 94 and R 95 are absent.
  • M 2 represents a metal.
  • Specific examples include metals selected from Groups 7 to 11 of the Periodic Table. Of these, ruthenium, rhodium, palladium, silver, renium, osmium, iridium, platinum or gold are preferable, and divalent metals such as platinum and palladium are particularly preferable.
  • R 92 and R 93 are independently hydrogen atom, halogen atom, alkyl group, aralkyl group, alkenyl group, cyano group, amino group, acyl group, alkoxycarbonyl group, carboxyl group and alkoxy group, respectively. , Alkylamino group, aralkylamino group, haloalkyl group, hydroxyl group, aryloxy group, aromatic hydrocarbon group or aromatic heterocyclic group.
  • R 94 and R 95 independently represent substituents represented by the same examples as R 92 and R 93, respectively.
  • T is a nitrogen atom, there is no R 94 or R 95 that directly binds to the T.
  • R 92 to R 95 may further have a substituent.
  • the substituent can be the above-mentioned substituent. Any two or more groups of R 92 to R 95 may be connected to each other to form a ring.
  • the molecular weight of the phosphorescent material is preferably 5000 or less, more preferably 4000 or less, and particularly preferably 3000 or less.
  • the molecular weight of the phosphorescent material is usually 800 or more, preferably 1000 or more, and more preferably 1200 or more. Within this molecular weight range, it is considered that the phosphorescent materials do not aggregate and are uniformly mixed with the charge transport material, so that a light emitting layer having high luminous efficiency can be obtained.
  • the molecular weight of the phosphorescent material is high in Tg, melting point, decomposition temperature, etc., excellent heat resistance of the phosphorescent material and the formed light emitting layer, and film quality due to gas generation, recrystallization, molecular migration, etc. It is preferable that it is large in that it is unlikely that a decrease in the concentration of impurities or an increase in the concentration of impurities due to thermal decomposition of the material will occur. On the other hand, the molecular weight of the phosphorescent material is preferably small in that the organic compound can be easily purified.
  • the host material preferably contains the following materials.
  • the host material of the light emitting layer is a material having a skeleton excellent in charge transportability, and is preferably selected from an electron transporting material, a hole transporting material, and a bipolar material capable of transporting both electrons and holes.
  • skeleton with excellent charge transport Specific examples include an aromatic structure, an aromatic amine structure, a triarylamine structure, a dibenzofuran structure, a naphthalene structure, a phenanthrene structure, a phthalocyanine structure, a porphyrin structure, a thiophene structure, and a benzylphenyl structure.
  • Examples thereof include a fluorene structure, a quinacridone structure, a triphenylene structure, a carbazole structure, a pyrene structure, an anthracene structure, a phenanthrene structure, a quinoline structure, a pyridine structure, a pyrimidine structure, a triazine structure, an oxadiazole structure or an imidazole structure.
  • Electrode transporting material a compound having a pyridine structure, a pyrimidine structure, and a triazine structure is more preferable, and a compound having a pyrimidine structure and a triazine structure is preferable from the viewpoint of being a material having excellent electron transportability and a relatively stable structure. Is more preferable.
  • the hole transporting material is a compound having a structure excellent in hole transporting property.
  • a carbazole structure, a dibenzofuran structure, a triarylamine structure, a naphthalene structure, a phenanthrene structure or a pyrene structure is preferable as a structure having excellent hole transport properties
  • a carbazole structure, a dibenzofuran structure or a tria structure is preferable.
  • a reelamine structure is more preferred.
  • the host material of the light emitting layer preferably has a condensed ring structure of 3 or more rings, and is further preferably a compound having 2 or more condensed ring structures of 3 or more rings or a compound having at least one condensed ring structure of 5 or more rings. preferable.
  • the rigidity of the molecule is increased, and the effect of suppressing the degree of molecular motion in response to heat can be easily obtained.
  • the condensed ring having 3 or more rings and the condensed ring having 5 or more rings have an aromatic hydrocarbon ring or an aromatic heterocycle in terms of charge transportability and material durability.
  • fused ring structure having three or more rings include anthracene structure, phenanthrene structure, pyrene structure, chrysene structure, naphthacene structure, triphenylene structure, fluorene structure, benzofluorene structure, indenofluorene structure, and indolofluorene structure.
  • fused ring structure having three or more rings include anthracene structure, phenanthrene structure, pyrene structure, chrysene structure, naphthacene structure, triphenylene structure, fluorene structure, benzofluorene structure, indenofluorene structure, and indolofluorene structure.
  • examples thereof include a carbazole structure, an indenocarbazole structure, an indolocarbazole structure, a dibenzofuran structure, and a dibenzothiophene structure.
  • At least one selected from the group consisting of phenanthrene structure, fluorene structure, indenofluorene structure, carbazole structure, indenocarbazole structure, indolocarbazole structure, dibenzofuran structure and dibenzothiophene structure is selected.
  • a carbazole structure or an indolocarbazole structure is more preferable from the viewpoint of durability against charge.
  • At least one of the host materials of the light emitting layer is a material having a pyrimidine skeleton or a triazine skeleton.
  • the host material of the light emitting layer is preferably a polymer material from the viewpoint of excellent flexibility.
  • a light emitting layer formed by using a material having excellent flexibility is preferable as a light emitting layer of an organic electroluminescent element formed on a flexible substrate.
  • the molecular weight thereof is preferably 5,000 or more and 1,000,000 or less, more preferably 10,000 or more and 500,000 or less, and further preferably 10,000. It is 100,000 or less.
  • the host material of the light emitting layer is a small molecule from the viewpoints of ease of synthesis and purification, ease of designing electron transport performance and hole transport performance, and ease of viscosity adjustment when dissolved in a solvent. Is preferable.
  • the host material contained in the light emitting layer is a low molecular weight material, the molecular weight thereof is preferably 5,000 or less, more preferably 4,000 or less, particularly preferably 3,000 or less, and most preferably 2. It is 000 or less, usually 300 or more, preferably 350 or more, and more preferably 400 or more.
  • the polymer according to the embodiment of the present invention is used as a charge transporting material for forming at least one of a hole injection layer and a hole transport layer, when the light emitting layer is a fluorescent light emitting material, the following It is preferably a blue fluorescence emitting material.
  • the light emitting material for the blue fluorescent light emitting layer is not particularly limited, but a compound represented by the following formula (211) is preferable.
  • Ar 241 represents an aromatic hydrocarbon condensed ring structure which may have a substituent.
  • Ar 242 and Ar 243 represent an alkyl group which may independently have a substituent, an aromatic hydrocarbon group, or a group to which these are bonded.
  • n41 is an integer of 1 to 4.
  • Ar 241 preferably represents an aromatic hydrocarbon condensed ring structure having 10 to 30 carbon atoms.
  • Specific structures include naphthalene ring, acenaphthene ring, fluorene ring, anthracene ring, phenatren ring, fluoranthene ring, pyrene ring, tetracene ring, chrysene ring, perylene ring and the like. More preferably, it has an aromatic hydrocarbon condensed ring structure having 12 to 20 carbon atoms.
  • Specific structures include an acenaphthene ring, a fluorene ring, an anthracene ring, a phenatren ring, a fluoranthene ring, a pyrene ring, a tetracene ring, a chrysene ring, and a perylene ring. More preferably, it has an aromatic hydrocarbon condensed ring structure having 16 to 18 carbon atoms, and specific structures include a fluoranthene ring, a pyrene ring, and a chrysene ring.
  • N41 is an integer of 1 to 4, preferably 1 to 3, more preferably 1 to 2, and most preferably 2.
  • the substituents that Ar 241 , Ar 242 , and Ar 243 may have are preferably a group selected from the substituent group Z', more preferably a hydrocarbon group contained in the substituent group Z', and further. It is preferably a hydrocarbon group among the groups preferred as the substituent group Z'.
  • the host material for the blue fluorescent light emitting layer is not particularly limited, but a compound represented by the following formula (212) is preferable.
  • R 241 and R 242 have structures independently represented by the following formula (213).
  • R243 represents a substituent. When there are a plurality of R 243s , they may be the same or different.
  • n43 is an integer from 0 to 8.
  • Ar 244 and Ar 245 each independently represent an aromatic hydrocarbon structure which may have a substituent or a heteroaromatic ring structure which may have a substituent. When a plurality of Ar 244 and Ar 245 exist, they may be the same or different. n44 is an integer of 1 to 5, and n45 is an integer of 0 to 5.
  • Ar 244 is preferably an aromatic hydrocarbon structure which is a monocyclic or fused ring having 6 to 30 carbon atoms, which may have a substituent, and more preferably it may have a substituent.
  • An aromatic hydrocarbon structure which is a monocyclic or fused ring having 6 to 12 carbon atoms.
  • Ar 245 preferably has an aromatic hydrocarbon structure which is a monocyclic or fused ring having 6 to 30 carbon atoms, which may have a substituent, or may have a substituent, which has 6 carbon atoms. It has an aromatic heterocyclic structure which is a fused ring of to 30 and more preferably an aromatic hydrocarbon structure which is a monocyclic ring or a fused ring having 6 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon structure. It is an aromatic heterocyclic structure which is a fused ring having 12 carbon atoms which may have a substituent.
  • n44 is preferably an integer of 1 to 3, more preferably 1 or 2.
  • n45 is preferably 0 to 3, more preferably 0 to 2.
  • the substituents R 243 and Ar 244 and Ar 245 may have a substituent preferably selected from the substituent group Z', and more preferably a hydrocarbon contained in the substituent group Z'. It is a group, more preferably a hydrocarbon group among the groups preferred as the substituent group Z'.
  • the molecular weight of the light emitting material for the blue fluorescent light emitting layer and its host material is preferably 5,000 or less, more preferably 4,000 or less, particularly preferably 3,000 or less, and most preferably 2,000 or less. , Usually 300 or more, preferably 350 or more, more preferably 400 or more.
  • the organic electroluminescent device of the present embodiment is an organic electroluminescent device having an anode and a cathode and an organic layer between the anode and the cathode on a substrate, in which the organic layer contains the polymer. It is characterized by including a layer formed by a wet film forming method using a composition for an element.
  • the layer formed by the wet film formation method using the composition for an organic electroluminescent device containing the polymer is at least one of a hole injection layer and a hole transport layer.
  • the organic layer of the organic electroluminescent device includes a hole injection layer, a hole transport layer, and a light emitting layer, and all of the hole injection layer, the hole transport layer, and the light emitting layer are organic electroluminescent devices containing the polymer. It is preferable that the layer is formed by a wet film forming method using the composition for use.
  • the wet film forming method is a film forming method, that is, as a coating method, for example, a spin coating method, a dip coating method, a die coating method, a bar coating method, a blade coating method, a roll coating method, a spray coating method, and the like.
  • a method of forming a film by adopting a wet film forming method such as a capillary coating method, an inkjet method, a nozzle printing method, a screen printing method, a gravure printing method, or a flexographic printing method, and drying the coating film.
  • a spin coating method, a spray coating method, an inkjet method, a nozzle printing method and the like are preferable.
  • FIG. 1 shows a schematic view (cross section) of a structural example of the organic electroluminescent device 10.
  • 1 is a substrate
  • 2 is an anode
  • 3 is a hole injection layer
  • 4 is a hole transport layer
  • 5 is a light emitting layer
  • 6 is a hole blocking layer
  • 7 is an electron transport layer
  • 8 is an electron injection layer.
  • 9 represents each cathode.
  • the substrate 1 serves as a support for the organic electroluminescent element.
  • a quartz or glass plate, a metal plate, a metal foil, a plastic film, a sheet, or the like is usually used for the substrate 1.
  • a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable.
  • the substrate is preferably made of a material having a high gas barrier property because the organic electroluminescent element is unlikely to be deteriorated by the outside air. Therefore, particularly when a material having a low gas barrier property such as a synthetic resin substrate is used, it is preferable to provide a dense silicon oxide film or the like on at least one surface of the substrate to improve the gas barrier property.
  • the anode 2 has a function of injecting holes into the layer on the light emitting layer 5 side.
  • the anode 2 is usually a metal such as aluminum, gold, silver, nickel, palladium, platinum; a metal oxide such as an oxide of indium and / or tin; a metal halide such as copper iodide; carbon black and poly (3). -Methylthiophene), polypyrrole, polyaniline and other conductive polymers.
  • the anode 2 is usually formed by a dry method such as a sputtering method or a vacuum vapor deposition method.
  • a dry method such as a sputtering method or a vacuum vapor deposition method.
  • metal fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc.
  • disperse them in an appropriate binder resin solution it can also be formed by applying it on a substrate.
  • a conductive polymer a thin film can be formed directly on the substrate by electrolytic polymerization, or an anode can be formed by applying the conductive polymer on the substrate (Appl. Phys. Lett., 60 volumes, 2711 p., 1992).
  • the anode 2 usually has a single-layer structure, but may have a laminated structure as appropriate. When the anode 2 has a laminated structure, different conductive materials may be laminated on the first-layer anode.
  • the thickness of the anode 2 may be determined according to the required transparency, material, and the like. When particularly high transparency is required, a thickness having a visible light transmittance of 60% or more is preferable, and a thickness having a visible light transmittance of 80% or more is more preferable.
  • the thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
  • the thickness of the anode 2 may be arbitrarily set according to the required strength and the like. In this case, the anode 2 may have the same thickness as the substrate.
  • impurities on the anode 2 are removed and the ionization potential thereof is formed by treating the surface of the anode 2 with ultraviolet rays / ozone, oxygen plasma, argon plasma, or the like. It is preferable to improve the hole injection property.
  • the layer having a function of transporting holes from the anode 2 side to the light emitting layer 5 side is usually called a hole injection transport layer or a hole transport layer.
  • the layer closer to the anode side may be referred to as the hole injection layer 3.
  • the hole injection layer 3 is preferably formed in terms of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5.
  • the hole injection layer 3 is usually formed on the anode 2.
  • the film thickness of the hole injection layer 3 is usually 1 nm or more, preferably 5 nm or more, usually 1000 nm or less, preferably 500 nm or less.
  • the hole injection layer may be formed by either a vacuum vapor deposition method or a wet film deposition method. In terms of excellent film forming property, it is preferably formed by a wet film forming method.
  • the hole injection layer 3 preferably contains a hole transporting compound, and more preferably contains a hole transporting compound and an electron accepting compound. Further, it is preferable to contain a cationic radical compound in the hole injection layer, and it is particularly preferable to contain a cationic radical compound and a hole transporting compound.
  • the hole injection layer is preferably formed by a wet film forming method using the composition for an organic electroluminescent device.
  • the composition for forming a hole injection layer usually contains a hole transporting compound that becomes the hole injection layer 3.
  • a solvent is usually further contained. It is preferable that the composition for forming a hole injection layer has high hole transportability and can efficiently transport the injected holes. Therefore, it is preferable that the hole mobility is high and impurities that serve as traps are unlikely to be generated during production or use. Further, it is preferable that the stability is excellent, the ionization potential is small, and the transparency to visible light is high.
  • the hole injection layer 3 when the hole injection layer 3 is in contact with the light emitting layer 5, those that do not quench the light emitted from the light emitting layer 5 or those that form an exciplex with the light emitting layer 5 and do not reduce the luminous efficiency are preferable.
  • hole transporting compound a compound having an ionization potential of 4.5 eV to 6.0 eV is preferable from the viewpoint of a charge injection barrier from the anode 2 to the hole injection layer 3.
  • hole-transporting compounds include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, compounds in which a tertiary amine is linked with a fluorene group, and hydrazone. Examples thereof include system compounds, silazane compounds, and quinacridone compounds.
  • aromatic amine compounds are preferable, and aromatic tertiary amine compounds are particularly preferable, from the viewpoint of amorphousness and visible light transmission.
  • the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and also includes a compound having a group derived from the aromatic tertiary amine.
  • the type of the aromatic tertiary amine compound is not particularly limited, but a polymer compound having a weight average molecular weight of 1000 or more and 1000,000 or less (polymerized compound in which repeating units are continuous) is easy to obtain uniform light emission due to the surface smoothing effect. ) Is preferably used.
  • the hole injecting layer 3 can improve the conductivity of the hole injecting layer by oxidizing the hole transporting compound, the hole injecting layer 3 contains the above-mentioned electron accepting compound and the above-mentioned cationic radical compound. Is preferable.
  • Cationic radical compounds derived from polymer compounds such as PEDOT / PSS (Adv. Mater., 2000, Vol. 12, p. 481) and emeraldine hydrochloride (J. Phys. Chem., 1990, Vol. 94, p. 7716) It is also produced by oxidative polymerization (dehydrogenation polymerization).
  • the oxidative polymerization referred to here is to chemically or electrochemically oxidize a monomer in an acidic solution using peroxodisulfate or the like.
  • a cation radical obtained by removing one electron from a repeating unit of a polymer, which is polymerized by oxidizing a monomer and has an anion derived from an acidic solution as a counter anion, is generated. Generate.
  • the material to be the hole injection layer 3 is usually mixed with a soluble solvent (solvent for the hole injection layer) to form a composition for film formation (positive).
  • a composition for forming a hole injection layer is prepared, and this composition for forming a hole injection layer is applied onto a layer (usually an anode 2) corresponding to the lower layer of the hole injection layer 3, formed into a film, and dried. It is formed by letting it.
  • the concentration of the hole-transporting compound in the composition for forming a hole injection layer is arbitrary as long as the effect of the present invention is not significantly impaired, but it is preferably low in terms of film thickness uniformity, and hole injection Higher is preferable in that defects are less likely to occur in the layer.
  • it is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, particularly preferably 0.5% by weight or more, and 70% by weight or less. Is more preferable, and it is more preferably 60% by weight or less, and particularly preferably 50% by weight or less.
  • solvent examples include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents and the like.
  • ether-based solvent examples include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and anisole. , Fenetol, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and other aromatic ethers.
  • aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and anisole.
  • PMEA propylene glycol-1-monomethyl ether acetate
  • Fenetol 2-methoxytoluen
  • ester-based solvent examples include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.
  • aromatic hydrocarbon solvent examples include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, methylnaphthalene and the like. Be done.
  • amide-based solvent examples include N, N-dimethylformamide, N, N-dimethylacetamide and the like. In addition to these, dimethyl sulfoxide and the like can also be used.
  • the formation of the hole injection layer 3 by the wet film formation method is usually performed on the layer corresponding to the lower layer of the hole injection layer 3 (usually, the anode 2) after preparing the composition for forming the hole injection layer. It is carried out by applying a film to the film and drying it. In the hole injection layer 3, the coating film is usually dried by heating, vacuum drying, or the like after the film formation.
  • the hole injection layer 3 is formed by the vacuum vapor deposition method
  • the constituent materials of the hole injection layer 3 the above-mentioned hole transporting compound, electron accepting compound, etc.
  • Place in a crucible installed inside the container when using two or more materials, usually put each in a separate crucible
  • exhaust the inside of the vacuum container to about 10-4 Pa with a vacuum pump, and then heat the crucible.
  • each crucible is usually heated
  • the material in the crucible is evaporated while controlling the amount of evaporation (when two or more types of materials are used, each is usually independent).
  • a mixture thereof can be placed in a crucible and heated and evaporated to form a hole injection layer.
  • the degree of vacuum during vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 ⁇ 10 -6 Torr (0.13 ⁇ 10 -4 Pa) or more, 9.0 ⁇ 10 -6 Torr ( It is 12.0 ⁇ 10 -4 Pa) or less.
  • the vapor deposition rate is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 ⁇ / sec or more and 5.0 ⁇ / sec or less.
  • the film formation temperature at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is preferably 10 ° C. or higher and 50 ° C. or lower.
  • the hole injection layer 3 may be crosslinked in the same manner as the hole transport layer 4 described later.
  • the hole transport layer 4 is a layer that has a function of transporting holes from the anode 2 side to the light emitting layer 5.
  • the hole transport layer 4 is not an essential layer in the organic electroluminescent device of the present embodiment, but it is possible to form this layer in terms of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5. preferable.
  • the hole transport layer 4 is usually formed between the anode 2 and the light emitting layer 5.
  • the hole transport layer 4 is formed between the hole injection layer 3 and the light emitting layer 5.
  • the film thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and usually 300 nm or less, preferably 100 nm or less.
  • the hole transport layer 4 may be formed by either a vacuum vapor deposition method or a wet film deposition method. In terms of excellent film forming property, it is preferably formed by a wet film forming method.
  • the hole transport layer is preferably formed by a wet film forming method using the above composition for an organic electroluminescent device.
  • the hole transport layer 4 usually contains a hole transport compound.
  • the hole-transporting compound contained in the hole-transporting layer 4 the polymer of the present embodiment or, when the polymer has a crosslinkable group, a polymer in which the polymer is crosslinked is preferable.
  • two or more tertiary amines represented by the hole transporting compound 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, can be used.
  • Aromatic diamine Japanese Patent Laid-Open No.
  • Aromatic amine compounds with a starburst structure J. Lumin., 72-74, pp. 985, 1997), aromatic amine compounds consisting of triphenylamine tetramers (Chem. Commun., 2175, 1996). Year), 2,2', 7,7'-tetrax- (diphenylamino) -9,9'-spirobifluorene and other spiro compounds (Synth. Metals, Vol. 91, p.
  • polyvinylcarbazole polyvinyltriphenylamine
  • polyarylene ether sulfone containing tetraphenylbenzidine Polym. Adv. Tech., Vol. 7, p. 33, 1996) and the like can be used. It may be included.
  • the hole transport layer 4 is formed by the wet film forming method, usually, in the same manner as when the hole injection layer 3 is formed by the wet film forming method, instead of the hole injection layer forming composition. It is formed using a composition for forming a hole transport layer.
  • the hole transport layer forming composition usually further contains a solvent.
  • the solvent used in the hole transport layer forming composition the same solvent as the solvent used in the hole injection layer forming composition described above can be used.
  • the concentration of the hole-transporting compound in the composition for forming the hole-transporting layer can be in the same range as the concentration of the hole-transporting compound in the composition for forming the hole-injecting layer.
  • the hole transport layer 4 can be formed by the wet film formation method in the same manner as the hole injection layer 3 film formation method described above.
  • the light emitting layer 5 is a layer having a function of emitting light by being excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 when an electric field is applied between the pair of electrodes. ..
  • the light emitting layer 5 is a layer formed between the anode 2 and the cathode 9.
  • the light emitting layer 5 is formed between the hole injection layer 3 and the cathode 9 when the hole injection layer 3 is above the anode 2.
  • the hole transport layer 4 is above the anode 2
  • the light emitting layer 5 is formed between the hole transport layer 4 and the cathode 9.
  • the film thickness of the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but a thicker one is preferable in that defects are less likely to occur in the film, and a thinner film is preferable in that a low driving voltage is likely to be obtained. Therefore, the film thickness of the light emitting layer 5 is preferably 3 nm or more, more preferably 5 nm or more, usually 200 nm or less, and further preferably 100 nm or less.
  • the light emitting layer 5 contains at least a material having light emitting properties (light emitting material), and preferably contains a material having charge transporting property (charge transporting material).
  • the light emitting layer is preferably formed by a wet film forming method using the above composition for an organic electroluminescent device, particularly the above-mentioned light emitting layer material and host material.
  • the light emitting material is not particularly limited as long as it emits light at a desired light emitting wavelength and the effect of the present invention is not impaired, and a known light emitting material can be applied.
  • the light emitting material may be either a fluorescent light emitting material or a phosphorescent light emitting material, but a material having good luminous efficiency is preferable, and a phosphorescent light emitting material is preferable from the viewpoint of internal quantum efficiency.
  • Examples of the fluorescent light emitting material include the following materials.
  • fluorescent light emitting material blue fluorescent light emitting material
  • examples of the fluorescent light emitting material that gives blue light emission include naphthalene, perylene, pyrene, anthracene, coumarin, chrysene, p-bis (2-phenylethenyl) benzene, and derivatives thereof.
  • the fluorescent light-emitting material giving green luminescence for example, quinacridone derivatives, coumarin derivatives, Al (C 9 H 6 NO ) aluminum complex such as 3.
  • Examples of the fluorescent light emitting material that gives yellow light emission include rubrene, a perimidone derivative, and the like.
  • red fluorescent light emitting material examples include DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostylyl) -4H-pyran) -based compounds, benzopyran derivatives, and rhodamine derivatives. , Benzothioxanthene derivatives, azabenzothioxanthene and the like.
  • Examples of the phosphorescent material include an organometallic complex containing a metal selected from Groups 7 to 11 of the periodic table.
  • Examples of the metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, renium, osmium, iridium, platinum, and gold.
  • a ligand in which a (hetero) aryl group such as a (hetero) arylpyridine ligand or a (hetero) arylpyrazole ligand is linked to a pyridine, pyrazole, phenanthroline or the like is preferable.
  • a phenylpyridine ligand and a phenylpyrazole ligand are preferable.
  • the (hetero) aryl represents an aryl group or a heteroaryl group.
  • Preferred phosphorescent materials include, for example, tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, tris (2-phenylpyridine).
  • Phenylpyridine complexes such as osmium and tris (2-phenylpyridine) renium
  • porphyrin complexes such as octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethyl palladium porphyrin, and octaphenyl palladium porphyrin can be mentioned.
  • Polymer-based luminescent materials include poly (9,9-dioctylfluorene-2,7-diyl) and poly [(9,9-dioctylfluorene-2,7-diyl) -co- (4,4'-).
  • the charge transporting material is a material having a positive charge (hole) or negative charge (electron) transporting property, and is not particularly limited as long as the effect of the present invention is not impaired, and a known light emitting material can be applied.
  • the charge transporting material a compound or the like conventionally used for the light emitting layer of the organic electroluminescent device can be used, and a compound used as a host material for the light emitting layer is particularly preferable.
  • the charge transporting material include aromatic amine compounds containing the polymer of the present invention, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, and fluorene groups.
  • Examples thereof include compounds exemplified as hole transporting compounds in the hole injection layer such as compounds in which a tertiary amine is linked, hydrazone compounds, silazane compounds, silanamin compounds, phosphamine compounds, and quinacridone compounds.
  • electron-transporting compounds such as anthracene-based compounds, pyrene-based compounds, carbazole-based compounds, pyridine-based compounds, phenanthroline-based compounds, oxadiazole-based compounds, and silol-based compounds can be mentioned.
  • Aromatic amine compounds having a starburst structure such as aromatic diamine (Japanese Patent Laid-Open No. 5-234681), 4,4', 4''-tris (1-naphthylphenylamino) triphenylamine (J. Lumin. , 72-74, pp. 985, 1997), Aromatic amine compounds consisting of triphenylamine tetramers (Chem. Commun., pp.
  • 2- (4-biphenylyl) -5- (p-tershalbutylphenyl) -1,3,4-oxadiazole tBu-PBD
  • 2,5-bis (1-naphthyl) -1, Oxadiazole compounds such as 3,4-oxadiazole (BND)
  • silol compounds such as silol (PyPySPyPy) and phenanthroline compounds such as vasophenanthroline (BPhen) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP, vasocproin).
  • the light emitting layer 2 may be formed by either a vacuum vapor deposition method or a wet film forming method, but the wet film forming method is preferable, and the spin coating method and the inkjet method are more preferable because of the excellent film forming property.
  • the hole injection layer 3 or the hole transport layer 4 to be the lower layer of the light emitting layer 2 is formed by using the composition for the organic electroluminescent device, the lamination by the wet film forming method is easy, so that the wet layer is easy. It is preferable to adopt a film forming method.
  • the light emitting layer 5 is formed by the wet film forming method, usually, in the same manner as when the hole injection layer is formed by the wet film forming method, the light emitting layer is replaced with the composition for forming the hole injection layer. It is formed by using a composition for forming a light emitting layer prepared by mixing the material to be No. 5 with a soluble solvent (solvent for a light emitting layer).
  • the solvent examples include ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, amide-based solvents, alcan-based solvents, halogenated aromatic hydrocarbon-based solvents, etc., which were mentioned for the formation of the hole injection layer 3.
  • examples thereof include an aliphatic alcohol solvent, an alicyclic alcohol solvent, an aliphatic ketone solvent and an alicyclic ketone solvent. Specific examples of the solvent are given below, but the present invention is not limited thereto as long as the effect of the present invention is not impaired.
  • aliphatic ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetol, 2 -Aromatic ether solvents such as methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole, diphenyl ether; phenyl acetate, phenyl propionate, methyl benzoate, benzoic acid Aromatic ester solvents such as ethyl, propyl benzoate, n-butyl benzoate; toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3-iropropylbiphenyl, 1,2,3,4
  • the solvent evaporates at an appropriate rate from the liquid film immediately after the film formation. Therefore, as described above, the boiling point of the solvent used is usually 80 ° C. or higher, preferably 100 ° C. or higher, more preferably 120 ° C. or higher, usually 270 ° C. or lower, preferably 250 ° C. or lower, and more preferably 230 ° C. or lower. Is.
  • the amount of the solvent used is arbitrary as long as the effect of the present invention is not significantly impaired, but the content in the composition for forming a light emitting layer is preferably 1% by mass or more, more preferably 10% by mass or more, and particularly preferably 50. It is 9% by mass or more, preferably 99.99% by mass or less, more preferably 99.9% by mass or less, and particularly preferably 99% by mass or less.
  • heating or depressurization can be used as a method for removing the solvent after the wet film formation.
  • heating or depressurization can be used as the heating means used in the heating method.
  • a clean oven and a hot plate are preferable because heat is evenly applied to the entire film.
  • the heating temperature in the heating step is arbitrary as long as the effect of the present invention is not significantly impaired, but a high temperature is preferable in terms of shortening the drying time, and a low temperature is preferable in terms of less damage to the material.
  • the upper limit of the heating temperature is usually 250 ° C. or lower, preferably 200 ° C. or lower, and more preferably 150 ° C. or lower.
  • the lower limit of the heating temperature is usually 30 ° C. or higher, preferably 50 ° C. or higher, and more preferably 80 ° C. or higher.
  • a temperature at which the heating temperature exceeds the above upper limit is higher than the heat resistance of a commonly used charge transporting material or phosphorescent material, and these may be decomposed or crystallized, which is not preferable.
  • the heating time in the heating step is appropriately determined by the boiling point and vapor pressure of the solvent in the composition for forming the light emitting layer, the heat resistance of the material, and the heating conditions.
  • each crucible When materials are used, each crucible is usually heated), and the material in the crucible is evaporated while controlling the amount of evaporation (when two or more kinds of materials are used, the amount of evaporation is usually controlled independently). Evaporate) to form a light emitting layer 5 on the hole injection layer 3 or the hole transport layer 4 placed facing the crucible. When two or more kinds of materials are used, a mixture thereof can be put in a crucible and heated and evaporated to form a light emitting layer 5.
  • the degree of vacuum during vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 ⁇ 10 -6 Torr (0.13 ⁇ 10 -4 Pa) or more, 9.0 ⁇ 10 -6 Torr ( It is 12.0 ⁇ 10 -4 Pa) or less.
  • the vapor deposition rate is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 ⁇ / sec or more and 5.0 ⁇ / sec or less.
  • the film formation temperature at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is preferably 10 ° C. or higher and 50 ° C. or lower.
  • a hole blocking layer 6 may be provided between the light emitting layer 5 and the electron injection layer 8 described later.
  • the hole blocking layer 6 is a layer laminated on the light emitting layer 5 so as to be in contact with the interface of the light emitting layer 5 on the cathode 9 side.
  • the hole blocking layer 6 has a role of blocking holes moving from the anode 2 from reaching the cathode 9 and a role of efficiently transporting electrons injected from the cathode 9 toward the light emitting layer 5.
  • the physical properties required for the material constituting the hole blocking layer 6 are high electron mobility and low hole mobility, a large energy gap (difference between HOMO and LUMO), and an excited triplet level (T1). Is high.
  • Examples of the material of the hole blocking layer 6 satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolato) aluminum and bis (2-methyl-8-quinolinolato) (triphenylsilanorat) aluminum.
  • Mixed ligand complexes such as, bis (2-methyl-8-quinolato) aluminum- ⁇ -oxo-bis- (2-methyl-8-quinolilato) aluminum dinuclear metal complexes and other metal complexes, distyrylbiphenyl derivatives, etc.
  • Triazole derivatives such as styryl compounds (Japanese Patent Laid-Open No.
  • the hole blocking layer 6 There are no restrictions on the method of forming the hole blocking layer 6. Therefore, it can be formed by a wet film forming method, a thin film deposition method, or another method.
  • the film thickness of the hole blocking layer 6 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less. is there.
  • the electron transport layer 7 is provided between the light emitting layer 5 and the electron injection layer 8 for the purpose of further improving the current efficiency of the device.
  • the electron transport layer 7 is formed of a compound capable of efficiently transporting electrons injected from the cathode 9 in the direction of the light emitting layer 5 between the electrodes to which an electric field is applied.
  • the electron-transporting compound used in the electron-transporting layer 7 has high electron-injection efficiency from the cathode 9 or the electron-injection layer 8 and high electron mobility, and efficiently transports the injected electrons. It needs to be a compound that can.
  • Examples of the electron-transporting compound used in the electron-transporting layer include a metal complex such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), a metal complex of 10-hydroxybenzo [h] quinoline, and oxadi.
  • phenanthroline derivative Japanese Patent Laid-Open No. 5-331459
  • 2-t-butyl-9,10-N, N'-dicyanoanthraquinone diimine n-type hydride amorphous Examples thereof include silicon carbide, n-type zinc sulfide, and n-type zinc selenium.
  • the film thickness of the electron transport layer 7 is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.
  • the electron transport layer 7 is formed by laminating on the hole blocking layer 6 by a wet film forming method or a vacuum vapor deposition method in the same manner as described above. Usually, the vacuum deposition method is used.
  • the electron injection layer 8 plays a role of efficiently injecting the electrons injected from the cathode 9 into the electron transport layer 7 or the light emitting layer 5.
  • the material forming the electron injection layer 8 is preferably a metal having a low work function.
  • alkali metals such as sodium and cesium, alkaline earth metals such as barium and calcium, and the like are used.
  • the film thickness of the electron injection layer 8 is usually preferably 0.1 nm or more and 5 nm or less.
  • Materials for forming the electron injection layer 8 include organic electron transport materials typified by a nitrogen-containing heterocyclic compound such as vasophenanthroline and a metal complex such as an aluminum complex of 8-hydroxyquinoline, and sodium, potassium, cesium, and the like.
  • a nitrogen-containing heterocyclic compound such as vasophenanthroline
  • a metal complex such as an aluminum complex of 8-hydroxyquinoline, and sodium, potassium, cesium, and the like.
  • Dope with an alkali metal such as lithium or rubidium (described in JP-A No. 10-270171, JP-A-2002-100478, JP-A-2002-1000482, etc.) also improves electron injection and transportability and is excellent. It is preferable because it makes it possible to achieve both film quality and film quality.
  • the film thickness of the electron injection layer 8 is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.
  • the electron injection layer 8 is formed by laminating on the light emitting layer 5 or the hole blocking layer 6 or the electron transport layer 7 on the light emitting layer 5 by a wet film forming method or a vacuum vapor deposition method.
  • the details in the case of the wet film forming method are the same as in the case of the light emitting layer described above.
  • the cathode 9 plays a role of injecting electrons into a layer on the light emitting layer 5 side (electron injection layer 8 or light emitting layer 5 or the like).
  • the material used for the anode 2 can be used, but in order to efficiently inject electrons, it is preferable to use a metal having a low work function.
  • a metal having a low work function for example, metals such as tin, magnesium, indium, calcium, aluminum, and silver, or alloys thereof and the like are used. Specific examples include alloy electrodes having a low work function such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.
  • a metal layer having a high work function and stable with respect to the atmosphere on the cathode 9 to protect the cathode made of a metal having a low work function.
  • the metal to be laminated include metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum.
  • the film thickness of the cathode 9 is usually the same as that of the anode 2.
  • the organic electroluminescent device of the present embodiment may further have another layer as long as the effect of the present invention is not significantly impaired. That is, an arbitrary layer other than the above-mentioned layer may be provided between the anode 2 and the cathode 9.
  • the organic electroluminescent device of the present embodiment has a structure opposite to that described above, that is, the cathode 9, the electron injection layer 8, the electron transport layer 7, the hole blocking layer 6, the light emitting layer 5, and the holes on the substrate 1. It is also possible to stack the transport layer 4, the hole injection layer 3, and the anode 2 in this order. It is also possible to provide the organic electroluminescent device of the present invention between two substrates having at least one highly transparent substrate.
  • the organic electroluminescent device of the present embodiment When the organic electroluminescent device of the present embodiment is applied to an organic electroluminescent device, it may be used as a single organic electroluminescent device or may be used in a configuration in which a plurality of organic electroluminescent devices are arranged in an array. , The anode and the cathode may be arranged in an XY matrix.
  • Organic EL display device uses the above-mentioned organic electroluminescent element.
  • the model and structure of the organic EL display device of the present embodiment are not particularly limited, and can be assembled according to a conventional method using the above-mentioned organic electroluminescent element.
  • the organic EL display device of the present invention can be used by the method described in "Organic EL Display” (Ohmsha, published on August 20, 2004, by Shizushi Tokito, Chihaya Adachi, Hideyuki Murata). Can be formed.
  • Organic EL lighting uses the above-mentioned organic electroluminescent element.
  • the type and structure of the organic EL illumination of the present embodiment are not particularly limited, and can be assembled according to a conventional method using the above-mentioned organic electroluminescent element.
  • Compound 14 was synthesized by the same method as that for compound 12 except that 1-bromo-4-iodobenzene was used instead of 5-bromo-2-iodotoluene.
  • Solution B1 was added to solution A1 in a nitrogen stream, and a heating reflux reaction was carried out for 1.0 hour. After confirming that compounds 7, 10 and 13 had disappeared, compound 14 (1.78 g, 3.5 mmol) was added. After heating under reflux for 2 hours, bromobenzene (1.84 g, 11.7 mmol) was added, and the mixture was heated under reflux for 1 hour. The reaction mixture was allowed to cool and added dropwise to an ethanol / water (370 ml / 70 ml) solution to obtain an end-capped crude polymer. The end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered off.
  • the obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol.
  • the polymer collected by filtration was purified by column chromatography to obtain the target polymer 1 (2.5 g).
  • the molecular weight and the like of the obtained polymer 1 were as follows.
  • Solution B2 was added to solution A2 in a nitrogen stream, and a heating reflux reaction was carried out for 1.0 hour. After confirming that the commercially available 2-amino-9,9'-dimethylfluorene, compound 7 and compound 13 had disappeared, compound 14 (2.08 g, 4.13 mmol) was added. After heating under reflux for 2 hours, bromobenzene (0.89 g, 5.67 mmol) was added, and the mixture was heated under reflux for 1 hour. The reaction mixture was allowed to cool and added dropwise to an ethanol / water (370 ml / 70 ml) solution to obtain an end-capped crude polymer.
  • the end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was filtered off.
  • the obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol.
  • the polymer collected by filtration was purified by column chromatography to obtain the target polymer 2 (2.8 g).
  • the molecular weight and the like of the obtained polymer 2 were as follows.
  • Example II-1 An organic electroluminescent device was manufactured by the following method. A 2 mm wide stripe of indium tin oxide (ITO) transparent conductive film deposited on a glass substrate to a thickness of 50 nm (a sputtered film product manufactured by Geomatec) using ordinary photolithography technology and hydrochloric acid etching. The anode was formed by patterning. The substrate on which the ITO pattern is formed is washed in the order of ultrasonic cleaning with an aqueous surfactant solution, water washing with ultrapure water, ultrasonic cleaning with ultrapure water, and water washing with ultrapure water, and then dried with compressed air. Finally, UV ozone cleaning was performed.
  • ITO indium tin oxide
  • the hole-transporting polymer compound 3.0% by weight which is the polymer of the present invention represented by the following formula (P-1) (polymer 2 synthesized in Example I-2), and the structure are shown below. 0.6% by weight of the oxidizing agent (PD-1) was dissolved in ethyl benzoate to prepare a composition for forming a hole injection layer.
  • This composition for forming a hole injection layer is spin-coated on the substrate in the atmosphere and dried on an atmospheric hot plate at 240 ° C. for 30 minutes to form a uniform thin film having a film thickness of 60 nm, and hole injection is performed. Layered.
  • a composition for forming a hole transport layer was prepared by dissolving 2.0% by weight of the charge-transporting polymer compound represented by the following formula (HT-1) in cyclohexylbenzene.
  • This composition for forming a hole transport layer was spin-coated in a nitrogen glove box on a substrate coated with the hole injection layer and dried at 230 ° C. for 30 minutes on a hot plate in the nitrogen glove box. A uniform thin film having a film thickness of 25 nm was formed to form a hole transport layer.
  • a composition for forming a light emitting layer was prepared by dissolving it in cyclohexylbenzene.
  • This composition for forming a light emitting layer is spin-coated in a nitrogen glove box on a substrate coated with the hole transport layer and dried at 120 ° C. for 20 minutes on a hot plate in the nitrogen glove box to obtain a film thickness.
  • a uniform thin film of 80 nm was formed and used as a light emitting layer.
  • the substrate on which the film was formed up to the light emitting layer was installed in a vacuum vapor deposition apparatus, and the inside of the apparatus was exhausted until it became 2 ⁇ 10 -4 Pa or less.
  • the compound represented by the following structural formula (HB-1) and 8-hydroxyquinolinolatritium were co-deposited on the light emitting layer at a weight ratio of 2: 3 by a vacuum deposition method, and the film thickness was 30 nm. Formed a hole blocking layer.
  • a 2 mm wide striped shadow mask as a mask for cathode vapor deposition is brought into close contact with the substrate so as to be orthogonal to the ITO stripe of the anode, and aluminum is heated by a molybdenum boat to form an aluminum layer having a thickness of 80 nm.
  • a cathode was formed by vacuum deposition.
  • an organic electroluminescent device having a light emitting area portion having a size of 2 mm ⁇ 2 mm was obtained.
  • the element was manufactured in the same manner as in 1.
  • Example II-1 the voltage difference between Example II-1 and Comparative Example II-1 (voltage of Example II-1-voltage of Comparative Example II-1) is used as the voltage difference
  • Comparative Example II-1 is used as the relative current efficiency.
  • Example II-2 3.0% by weight of the hole-transporting polymer compound, which is the polymer of the present invention represented by the following formula (P-3) (polymer 1 synthesized in Example I-1), and an oxidizing agent (PD-). 1) 0.6% by weight was dissolved in ethyl benzoate to prepare a composition for forming a hole injection layer.
  • P-3 polymer 1 synthesized in Example I-1
  • PD- oxidizing agent
  • This composition for forming a hole injection layer is spin-coated on the substrate in the atmosphere and dried on an atmospheric hot plate at 240 ° C. for 30 minutes to form a uniform thin film having a film thickness of 60 nm, and hole injection is performed. Layered.
  • Example II-1 After forming the light emitting layer, an element was manufactured in the same manner as in Example II-1.
  • the element was manufactured in the same manner as in 2.
  • Example II-3 After forming the hole injection layer and the hole transport layer in the same manner as in Example II-2, as the material of the light emitting layer, 4.0% by weight of the light emitting layer material (H-3) shown below and (D- 2) A composition for forming a light emitting layer was prepared by dissolving 0.2% by weight in cyclohexylbenzene.
  • This composition for forming a light emitting layer is spin-coated in a nitrogen glove box on a substrate coated with the hole transport layer and dried at 120 ° C. for 20 minutes on a hot plate in the nitrogen glove box to obtain a film thickness.
  • a uniform thin film having a diameter of 40 nm was formed to form a light emitting layer.
  • Example II-1 After forming the light emitting layer, an element was manufactured in the same manner as in Example II-1.
  • the element was manufactured in the same manner as in 3.
  • Example II-4 After cleaning the substrate in the same manner as in Example II-1, the composition for forming the hole injection layer was prepared with 3.0% by weight of the hole-transporting polymer compound represented by the following formula (P-4). 0.6% by weight of the oxidizing agent (PD-1) was dissolved in ethyl benzoate to prepare a composition for forming a hole injection layer.
  • This composition for forming a hole injection layer is spin-coated on the substrate in the atmosphere and dried on an atmospheric hot plate at 240 ° C. for 30 minutes to form a uniform thin film having a film thickness of 40 nm, and hole injection is performed. Layered.
  • the material of the light emitting layer 5.0% by weight of the light emitting layer material (H-4) shown below and 0.75% by weight of the above (D-1) are dissolved in cyclohexylbenzene to form a light emitting layer composition.
  • the thing was prepared.
  • This composition for forming a light emitting layer is spin-coated in a nitrogen glove box on a substrate coated with the hole transport layer and dried at 120 ° C. for 20 minutes on a hot plate in the nitrogen glove box to obtain a film thickness.
  • a uniform thin film of 60 nm was formed and used as a light emitting layer.
  • Example II-1 After forming the light emitting layer, an element was manufactured in the same manner as in Example II-1.

Abstract

L'invention concerne un polymère ayant une capacité élevée d'injection / de transport de trous et une durabilité élevée, une composition pour des éléments électroluminescents organiques qui contient le polymère, et un élément électroluminescent organique ayant une luminance élevée et une longue durée de vie. Le polymère comprend des motifs répétitifs représentés par la formule (1). G représente un groupe hydrocarboné aromatique éventuellement substitué ou un atome d'azote. Ar1 est un groupe hydrocarboné aromatique éventuellement substitué. Ar2, Ar3 et Ar4 représentent chacun un groupe hydrocarboné aromatique éventuellement substitué ou un groupe hétérocyclique aromatique éventuellement substitué ou un groupe formé par liaison, soit directement soit par un groupe de liaison, d'au moins deux groupes choisis parmi des groupes hydrocarbonés aromatiques éventuellement substitués et des groupes hétérocycliques aromatiques éventuellement substitués. X et Y représentent chacun un atome de carbone ou un atome d'azote. L'atome de carbone a éventuellement été substitué. Le symbole « -* » est le site de combinaison avec G.
PCT/JP2020/045835 2019-12-16 2020-12-09 Polymère, composition pour élément électroluminescent organique, composition pour former une couche de transport de trous ou une couche d'injection de trous, élément électroluminescent organique, dispositif d'affichage électroluminescent organique et illuminateur électroluminescent organique WO2021125011A1 (fr)

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KR1020227012362A KR20220117199A (ko) 2019-12-16 2020-12-09 중합체, 유기 전계 발광 소자용 조성물, 정공 수송층 또는 정공 주입층 형성용 조성물, 유기 전계 발광 소자, 유기 el 표시 장치 및 유기 el 조명
CN202080079850.9A CN114729121A (zh) 2019-12-16 2020-12-09 聚合物、有机电致发光元件用组合物、空穴传输层或空穴注入层形成用组合物、有机电致发光元件、有机el显示装置和有机el照明
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