WO2022059725A1 - 重合体 - Google Patents

重合体 Download PDF

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WO2022059725A1
WO2022059725A1 PCT/JP2021/034013 JP2021034013W WO2022059725A1 WO 2022059725 A1 WO2022059725 A1 WO 2022059725A1 JP 2021034013 W JP2021034013 W JP 2021034013W WO 2022059725 A1 WO2022059725 A1 WO 2022059725A1
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Prior art keywords
group
substituent
ring
polymer
aromatic hydrocarbon
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PCT/JP2021/034013
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English (en)
French (fr)
Japanese (ja)
Inventor
延軍 李
麻未 山下
淑 杉山
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三菱ケミカル株式会社
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Priority to JP2022550595A priority Critical patent/JPWO2022059725A1/ja
Priority to CN202180063359.1A priority patent/CN116194981A/zh
Priority to KR1020237008695A priority patent/KR20230069114A/ko
Publication of WO2022059725A1 publication Critical patent/WO2022059725A1/ja

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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
    • C08G73/02—Polyamines
    • G—PHYSICS
    • G09—EDUCATION; CRYPTOGRAPHY; DISPLAY; ADVERTISING; SEALS
    • G09F—DISPLAYING; ADVERTISING; SIGNS; LABELS OR NAME-PLATES; SEALS
    • G09F9/00—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements
    • G09F9/30—Indicating arrangements for variable information in which the information is built-up on a support by selection or combination of individual elements in which the desired character or characters are formed by combining individual elements
    • 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
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices

Definitions

  • the present invention relates to a polymer, and more particularly to a polymer useful as a charge transporting material for an organic electroluminescent device. Further, the present invention comprises a composition for an organic electroluminescent device containing the polymer, an organic electroluminescent device including a layer formed by using the composition, and an organic EL display device having the organic electroluminescent device. And organic EL lighting.
  • Examples of the method for forming the organic layer in the organic electroluminescent device include 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.
  • Patent Documents 1 and 2 disclose a hole injection transporting material having a structure in which a fluorene ring or a carbazole ring and a phenylene ring are bonded to the main chain of a polymer.
  • Patent Document 3 discloses a polymer having a triarylamine repeating unit and a polymer containing a fluorene ring in the main chain. It is also described that the polymer backbone contains a phenylene group having a substituent to generate a twist and increase the triplet energy of the polymer.
  • Patent Document 4 discloses a polymer having a triarylamine and fluorene in its main chain, in which a twist is generated by providing a substituent on a phenylene group adjacent to a nitrogen atom.
  • the polymers described in Patent Documents 1 and 2 have low excited singlet energy levels (S 1 ) and excited triplet energy levels (T 1 ) due to the spread of the ⁇ -conjugated system in the main chain, and are light-emitting materials. There is a problem that quenching occurs due to energy transfer from the luminescence exciter and the luminescence efficiency is lowered. Therefore, a charge-transporting material having a high S1 level and a high T1 level is required.
  • Patent Document 3 discloses that the triplet energy of a polymer is increased by generating a twist by containing a phenylene group having a substituent, and the general formula (III) is disclosed as an example. However, Patent Document 3 does not disclose a polymer that can solve the above problem. The same applies to Patent Document 4.
  • the present invention has a high excitation singlet energy level (S 1 ) and an excited triplet energy level (T 1 ), suppresses quenching due to energy transfer from a light emitting material and a light emitting exciter, and has high light emission efficiency.
  • An object of the present invention is to provide a composition for an organic electroluminescent element containing the polymer.
  • the gist of the present invention lies in the following ⁇ 1> to ⁇ 17>.
  • ⁇ 1> A polymer containing a repeating unit represented by the following formula (1).
  • Ar 1 may have a monovalent aromatic hydrocarbon group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent, or a substituent.
  • Ar 2 and Ar 3 are independently or independently linked with a divalent aromatic hydrocarbon group which may have a substituent or a plurality of aromatic hydrocarbon groups which may have a substituent.
  • R 1 to R 8 independently has a hydrogen atom, 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 1 , R 2 , R 5 , and R 6 may have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent.
  • R 9 to R 13 are independent hydrogen atoms, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aralkyl group which may have a substituent. Alternatively, it represents an aromatic hydrocarbon group which may have a substituent. n represents an integer of 1 to 3. However, the two structures constituting the main chain of the polymer and directly bonded to the nitrogen atom of the main chain amine of the formula (1) are both phenylene groups which may have a substituent. ..
  • ⁇ 3> The two structures in the main chain of the polymer bonded to the nitrogen atom of the main chain amine in the above formula (1) are phenylene groups having no substituent, ⁇ 1> or ⁇ 2>.
  • the polymer according to. ⁇ 4> The polymer according to any one of ⁇ 1> to ⁇ 3>, wherein the formula (1) is represented by the following formula (2) -1 or the following formula (2) -2.
  • Ar 4 is a monovalent aromatic hydrocarbon group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent, or a substituent independently in each repeating unit.
  • a monovalent group in which a plurality of groups selected from an aromatic hydrocarbon group which may have a group and an aromatic heterocyclic group which may have a substituent are linked directly or via a linking group.
  • X 30 represents -C (R 37 ) (R 38 )-, -N (R 39 )-, or -C (R 40 ) (R 41 ) -C (R 42 ) (R 43 )-.
  • R 33 , R 34 , R 37 , R 38 , and R 120 to R 123 are each independently a hydrogen atom, an alkyl group which may have a substituent, and an alkoxy group which may have a substituent.
  • Each of R 39 to R 43 independently has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aralkyl group which may have a substituent.
  • it represents an aromatic hydrocarbon group which may have a substituent.
  • g 3 , h 3 , and i 3 each independently represent an integer of 1 to 3.
  • j 3 and k 3 each independently represent an integer of 1 to 2.
  • Ar 6 and Ar 7 each independently have a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or a substituent.
  • Ar 8 may have a monovalent aromatic hydrocarbon group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent, or a substituent.
  • Ar 36 and Ar 37 each independently have a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent.
  • Ar 38 may have a monovalent aromatic hydrocarbon group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent, or a substituent.
  • Ar 39 represents a hydrogen atom or a substituent and represents -* Represents the bond position with the nitrogen atom in the formula (3) -1 or the formula (3) -2.
  • R 1 and R 2 each independently have 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.
  • ⁇ 9> The polymer according to any one of ⁇ 1> to ⁇ 8>, wherein the polymer has a crosslinkable group as a substituent.
  • ⁇ 10> The weight according to any one of ⁇ 1> to ⁇ 9>, wherein the weight average molecular weight (Mw) is 10,000 or more and the dispersity (Mw / Mn) is 3.5 or less.
  • Mw weight average molecular weight
  • Mn dispersity
  • ⁇ 11> A composition for an organic electroluminescent device containing the polymer according to any one of ⁇ 1> to ⁇ 10>.
  • ⁇ 12> A method for manufacturing an organic electroluminescent device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode.
  • a method for manufacturing an organic electroluminescent device comprising a step of forming the organic layer by a wet film forming method using the composition for an organic electroluminescent device according to ⁇ 11>.
  • ⁇ 13> The method for manufacturing an organic electroluminescent device according to ⁇ 12>, wherein the organic layer has at least one of a hole injection layer and a hole transport layer.
  • the hole injection layer, the hole transport layer, and the light emitting layer are included between the anode and the cathode.
  • ⁇ 15> An organic electroluminescent device including a layer containing the polymer according to any one of ⁇ 1> to ⁇ 10>, or a polymer obtained by cross-linking the polymer.
  • ⁇ 17> An organic EL lighting provided with the organic electroluminescent device according to ⁇ 15>.
  • the excited singlet energy level (S 1 ) and the excited triplet energy level (T 1 ) are high, quenching due to energy transfer from a light emitting material and a light emitting exciter is suppressed, and light emission efficiency is high.
  • a polymer and a composition for an organic electroluminescent element containing the polymer can be provided.
  • FIG. 1 is a schematic cross-sectional view showing a structural example of the organic electroluminescent device of the present invention.
  • the polymer of the present invention is a polymer containing a structure represented by the following formula (1).
  • Ar 1 may have a monovalent aromatic hydrocarbon group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent, or a substituent.
  • Ar 2 and Ar 3 are independently or independently linked with a divalent aromatic hydrocarbon group which may have a substituent or a plurality of aromatic hydrocarbon groups which may have a substituent.
  • R 1 to R 8 independently has a hydrogen atom, 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 1 , R 2 , R 5 , and R 6 may have an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent.
  • R 9 to R 13 are independent hydrogen atoms, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aralkyl group which may have a substituent. Alternatively, it represents an aromatic hydrocarbon group which may have a substituent. n represents an integer of 1 to 3.
  • the two structures constituting the main chain of the polymer and directly bonded to the nitrogen atom of the main chain amine of the formula (1) are both phenylene groups which may have a substituent. It is preferable to have.
  • the ring bonded to the nitrogen atom of the main chain amine in Ar 2 has a substituent.
  • the ring bonded to the nitrogen atom of the main chain amine in Ar 2 has no substituent. It is preferable that at least one of the fact that the ring bonded to the nitrogen atom of the main chain amine in Ar 3 has no substituent is satisfied.
  • the atom bonded to Ar 3 in the repeating unit bonded adjacent to Ar 3 is not the nitrogen atom of the main chain amine, it is bonded to the nitrogen atom of the main chain amine in the structure represented by Ar 2 .
  • the structure is a phenylene group without a substituent,
  • the atom bonded to Ar 3 in the repeating unit bonded adjacent to Ar 3 is the nitrogen atom of the main chain amine, it is bonded to the nitrogen atom of the main chain amine in the structure represented by Ar 2 .
  • the structure is a phenylene group having no substituent, and in the structure represented by Ar 3 , the structure bonded to the nitrogen atom of the main chain amine in the repeating unit bonded adjacent to Ar 3 is It is preferable that at least one of the phenylene groups having no substituent is satisfied.
  • Ar 2 is a phenylene group having no substituent, and is a structure in which R 62 described later is all hydrogen in the following formula (1) -4 representing Ar 2 .
  • Ar 2 in which the structure bonded to the nitrogen atom of the main chain amine is a phenylene group having no substituent is referred to in the following formula (1) -4 representing Ar 2 .
  • the structure is such that R 62 , which will be described later, is all hydrogen.
  • Ar 3 is a phenylene group in which the structure bonded to the nitrogen atom of the main chain amine in the repeating unit bonded adjacent to Ar 3 does not have a substituent is Ar.
  • the structure is such that R 63 described later is all hydrogen.
  • the main chain of the polymer of the present invention contains a fluorene ring having a substituent at a specific position, a carbazole ring having a substituent at a specific position, or a specific ring. It contains a 9,10 dihydrophenanthrene derivative structure with a substituent at the position. It is preferable that a phenylene group is bonded to the 2,7-position of these fluorene ring, carbazole ring or 9,10 dihydrophenanthrene derivative structure.
  • the specific position is a replacement position of R 1 , R 2 , R 5 , or R 6 .
  • the fluorene ring By having a substituent at the substitution position of R1 , R2 , R5 , or R6 of these fluorene ring, carbazole ring, or 9,10 dihydrophenanthrene derivative structure, the fluorene ring, due to the steric damage caused by the substituent, The faces of the carbazole ring or 9,10 dihydrophenanthrene derivative structures are more twisted with respect to the faces of the rings attached to the 2- or 7-positions of those structures.
  • the polymer of the present invention has a main chain structure in which the spread of the ⁇ -conjugated system is hindered by the steric hindrance of the substituent. Therefore, the excited singlet energy level (S 1 ) and the excited triplet energy level (T 1 ) has a high property, and since quenching due to energy transfer from the emission exciter is suppressed, the emission efficiency is excellent.
  • the two structures in the main chain of the polymer which are directly bonded to the nitrogen atom of the main chain amine in the formula (1), are monocyclic phenylene groups, so that the T 1 level and the S 1 level are used.
  • the rank is high, which is preferable.
  • a substituent is provided on a ring such as a phenylene group bonded to a nitrogen atom, and a structure such as fluorene bonded next to the substituent is twisted.
  • a substituent was introduced into the ring bonded to the nitrogen atom of the main chain amine in this way, it is considered that the presence of the substituent hindered the spread of HOMO around the nitrogen atom and weakened the electron durability.
  • the ring bonded adjacent to the nitrogen atom of the main chain amine does not have a substituent, the spread of HOMO around the nitrogen atom is not hindered, and the HOMO spreads to the ring adjacent to the nitrogen atom.
  • High electronic durability is realized. As a result, it is considered that an organic electroluminescent device having a long drive life can be obtained while maintaining high luminous efficiency.
  • the spread of HOMO around the nitrogen atom is not hindered, and the HOMO spreads to the ring adjacent to the nitrogen atom.
  • High electronic durability is realized.
  • an organic electroluminescent device having a long drive life can be obtained while maintaining high luminous efficiency.
  • the aromatic ring is bonded at the 2,7-position. It is considered that this makes it more electrically stable and can obtain high durability.
  • LUMO is completely from the 9-position of the fluorene ring, carbazole ring, or 9,10 dihydrophenanthrene derivative structure. It is distributed in extended conjugate groups.
  • HOMO is distributed in the main chain near the amine, HOMO and LUMO in the molecule are localized apart from each other, and it is considered that the durability against electrons and excitons tends to be improved.
  • an organic electroluminescent device if the energy level difference between each organic layer is not appropriate, it becomes difficult to inject carriers into the light emitting layer, and the drive voltage rises. Alternatively, it is considered that carrier leakage from the light emitting layer to the adjacent layer is likely to occur, and the device efficiency is lowered.
  • 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 as in the present invention 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 invention is flat without cracks or the like.
  • the organic electroluminescent device of the present invention having the layer has high brightness and a long drive life.
  • the organic electric field light source element including a layer formed by using the polymer of the present invention is a flat panel display (for example, for an OA computer or a wall-mounted television).
  • a flat panel display for example, for an OA computer or a wall-mounted television.
  • In-vehicle display elements mobile phone displays, light sources that take advantage of their characteristics as surface emitters (for example, light sources for copying machines, backlight sources for liquid crystal displays and instruments), display boards, and indicator lights. , Its technical value is great.
  • Ar 1 may have a monovalent aromatic hydrocarbon group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent, or a substituent.
  • the plurality of Ar 1s may be the same or different.
  • an aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms is preferable, and specifically, a benzene ring, an azulene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, and the like.
  • Examples thereof include a monovalent group of a 6-membered monocyclic ring or a 2- to 5-fused fused ring such as a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaften ring, a fluorene ring, and a fluorene ring.
  • a monovalent group of a 6-membered monocyclic ring or a 2- to 5-fused fused ring such as a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaften ring, a fluorene ring, and a fluorene ring.
  • the monovalent aromatic heterocyclic group is preferably an aromatic heterocyclic group having 3 or more and 60 or less carbon atoms, and specifically, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrazole ring, or a pyrazole ring.
  • Examples include monovalent groups of 5- or 6-membered monocycles or 2-4 fused rings.
  • linking group examples include 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 phenylene rings are linked by an oxygen atom or a carbonyl group can also be used. A structure that directly links without a linking group is preferable. The same applies to the linking groups in Ar 2 , Ar 3 , Ar 4 , Ar 6 , Ar 7 , Ar 8 , Ar 11 , Ar 12 , Ar 36 , Ar 37 , and Ar 38 .
  • a monovalent aromatic hydrocarbon group is preferable, a monovalent group of a benzene ring or a fluorene ring is more preferable, and a phenyl group or a fluorenyl group is further preferable, from the viewpoints of excellent charge transportability and durability.
  • a fluorenyl group is particularly preferred, and a 2-fluorenyl group is most preferred.
  • Ar 1 is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms, and a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms is preferable from the viewpoint of solubility in a coating solvent. Especially preferable.
  • Ar 1 is preferably a 9-alkyl-2-fluorenyl group in which an alkyl group is substituted at the 9-position of the 2-fluorenyl group, and particularly a 9,9-dialkyl-2-fluorenyl group in which the alkyl group is 2-substituted. preferable. Since Ar 1 is a fluorenyl group substituted with an alkyl group, its solubility in a solvent is improved, which is preferable.
  • a monovalent group in which a plurality of groups selected from an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent are linked directly or via a linking group As, a monovalent group in which a plurality of groups selected from the aromatic hydrocarbon group and the aromatic heterocyclic group are directly or via a linking group can be used.
  • an electron-attracting group lowers the LUMO of the molecule, making it more susceptible to electrons, and in a polymer having an arylamine, the electron durability of the molecule increases due to the localization of LUMO and HOMO.
  • those represented by the formula (A1) described later such as a monovalent group having a benzene ring and a carbazole ring and a monovalent group having a triazine ring, are preferable.
  • Examples of the substituent that Ar 1 may have include a group selected from the substituent group Z described later or a crosslinkable group described later.
  • Ar 1 is preferably represented by the following formula (A1).
  • Ar 6 and Ar 7 each independently have a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent.
  • Ar 8 may have a monovalent aromatic hydrocarbon group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent, or a substituent.
  • Ar 9 represents a hydrogen atom or a substituent and represents -* Represents the bond position with the nitrogen atom in the formula (1), the formula (2) -1 or the formula (2) -2.
  • an aromatic hydrocarbon group having 6 or more carbon atoms and 60 or less carbon atoms is preferable, and specifically, a benzene ring, an azulene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, and a tetracene ring.
  • a benzene ring an aromatic hydrocarbon group having 6 or more carbon atoms and 60 or less carbon atoms
  • a benzene ring an azulene ring
  • a naphthalene ring an anthracene ring
  • a phenanthrene ring a perylene ring
  • tetracene ring tetracene ring
  • the aromatic heterocyclic group preferably has an aromatic heterocyclic group having 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, or an imidazole.
  • Examples thereof include a bivalent group of a 6-membered monocyclic ring or a 2- to 4-
  • a divalent group in which a plurality of groups selected from an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent are linked directly or via a linking group.
  • the group may be a group in which the same group is linked in plurality, or a group in which a plurality of different groups are linked.
  • a divalent group in which a plurality of groups selected from an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent are linked directly or via a linking group.
  • a monovalent group in which a plurality of the aromatic hydrocarbon groups or the aromatic heterocyclic groups are directly linked or linked via a linking group can be used.
  • Ar 6 and Ar 7 are selected from a divalent aromatic hydrocarbon group having no substituent and a divalent aromatic heterocyclic group having no substituent because of their excellent charge transportability and durability.
  • a divalent group in which one group or a plurality of groups are bonded directly or via a linking group is preferable, and since hole transportability is improved, a substituent is used as the group directly bonded to the nitrogen atom.
  • An aromatic hydrocarbon group having no substituent is preferable, a phenylene group having no substituent or a divalent fluorene group having no substituent is more preferable, and a phenylene group having no substituent is particularly preferable.
  • a fluorene ring, a carbazole ring, or a 9,10 dihydrophenanthrene derivative structure is bonded to the phenylene ring directly bonded to the nitrogen atom, and the phenylene ring directly bonded to the nitrogen atom and the fluorene ring, the carbazole ring, or 9 , 10
  • a structure in which one or more phenylene groups are further linked between the dihydrophenanthrene derivative structures is also preferable.
  • Ar 7 has 1 to 6 divalent aromatic hydrocarbon groups which may have a substituent from the viewpoint of localization with LUMO distributed at the 9-position of the carbazole ring and HOMO distributed in the main chain.
  • a linked group is preferable, a group in which 2 to 4 divalent aromatic hydrocarbon groups which may have a substituent are linked are more preferable, and a phenylene ring which may have a substituent is 1 to 1 to.
  • a group in which four are linked is more preferable, and biphenylene in which two phenylene rings which may have a substituent are linked are particularly preferable.
  • Ar 8 is preferably a group in which one or a plurality of monovalent aromatic hydrocarbon groups which may be the same or different are linked, from the viewpoint of excellent charge transportability and durability, and the monovalent aromatic group is preferable.
  • the group hydrocarbon group may have a substituent.
  • it is preferable that the number of linkages is large from the viewpoint of distribution of LUMO in the structure represented by -Ar 7 -Ar 8 , but it is preferable that the number of linkages is small from the viewpoint of charge transportability and film stability. preferable. In the case of ligation, 2 or more and 10 or less are preferable, 6 or less is more preferable, and 3 or less is particularly preferable from the viewpoint of film stability.
  • Preferred aromatic hydrocarbon structures are a benzene ring, a naphthalene ring, an anthracene ring, and a fluorene ring, and more preferably a benzene ring and a fluorene ring.
  • Preferred aromatic complex structures are benzothiophene ring, indole ring, carbazole ring, triazine ring and quinazoline ring.
  • a group 2 to 4 phenylene rings which may have a substituent are linked, or a phenylene ring which may have a substituent and a fluorene ring which may have a substituent are linked.
  • LUMO biphenylene in which two phenylene rings which may have a substituent are linked is particularly preferable.
  • the substituent that Ar 8 may have, any one of the substituent group Z described later or a combination thereof can be used. From the viewpoint of inhibiting the spread of LUMO, the substituent that Ar 8 may have is preferably other than the N-carbazolyl group, the indolocarbazolyl group, and the indenocarbazolyl group, which is more preferable.
  • the substituent is a phenyl group, a naphthyl group, or a fluorenyl group.
  • R 30 and R 31 each independently have a hydrogen atom or an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and a substituent. Represents a optionally Aralkyl group.
  • alkyl group, alkoxy group, and aralkyl group the same groups as those of R 1 to R 8 can be used, and the substituents that R 30 and R 31 may have are also the same as those of R 1 to R 8 . Can be used.
  • Ar 9 represents a hydrogen atom or a substituent.
  • Ar 9 is a substituent, it is not particularly limited, but is preferably an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • the preferred structure is the same as the group mentioned in Ar 4 .
  • Ar 9 is a substituent
  • Ar 9 is bonded to the 3-position of carbazole from the viewpoint of improving durability.
  • Ar 9 is preferably a hydrogen atom from the viewpoint of ease of synthesis and charge transportability.
  • Ar 9 is preferably an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. , It is more preferable that it is an aromatic hydrocarbon group which may have a substituent.
  • the polymer of the present invention has a structure represented by the formula (1) in which Ar 1 is a monovalent group of a benzene ring which may have a substituent or a fluorene ring which may have a substituent. It is preferable to include both a certain structure and a structure represented by the formula (A1), and the structure which is a monovalent group of a fluorene ring which may have a substituent and the structure represented by the formula (A1) are represented by the formula (A1). It is more preferable to include both structures of the structures to be made.
  • Ar 2 and Ar 3 are independently or independently linked with a divalent aromatic hydrocarbon group which may have a substituent or a plurality of aromatic hydrocarbon groups which may have a substituent. Represents a divalent group linked in the main chain direction via a group.
  • the structure is a phenylene group without a substituent
  • the atom bonded to Ar 3 in the repeating unit bonded adjacent to Ar 3 is the nitrogen atom of the main chain amine, it is bonded to the nitrogen atom of the main chain amine in the structure represented by Ar 2 .
  • the structure is a phenylene group having no substituent, and in the structure represented by Ar 3 , the structure directly bonded to the nitrogen atom of the main chain amine in the repeating unit bonded adjacent to Ar 3 . Is a phenylene group having no substituent, and it is preferable that at least one of them is satisfied.
  • an aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms is preferable, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, and the like.
  • Examples thereof include a 6-membered monocyclic ring or a divalent group of a 2 to 5 fused ring such as a pyrene ring, a benzpyrene ring, a chrysen ring, a triphenylene ring, an acenaften ring, a fluorene ring, and a fluorene ring.
  • one group or a plurality of groups selected from divalent aromatic hydrocarbon groups having no substituent are bonded directly or via a linking group because of their excellent charge transportability and durability.
  • Divalent groups are preferred.
  • an aromatic hydrocarbon group having no substituent is preferable, and a phenylene group having no substituent or a divalent fluorene group having no substituent is more preferable as Ar 2 because the hole transport property is improved.
  • a phenylene group having no substituent is particularly preferable.
  • a fluorene ring, a carbazole ring, or a 9,10 dihydrophenanthrene derivative structure is bonded to the phenylene ring directly bonded to the nitrogen atom, and the phenylene ring directly bonded to the nitrogen atom and the fluorene ring, the carbazole ring, or 9 , 10
  • a structure in which one or more phenylene groups are further linked between the dihydrophenanthrene derivative structures is also preferable.
  • the divalent group in which aromatic hydrocarbon groups may have a plurality of substituents are directly linked or linked via a linking group may be a group in which the same group is linked in plurality, or a group in which a plurality of different groups are linked. But it doesn't matter.
  • Examples of the divalent group in which an aromatic hydrocarbon group which may have a plurality of substituents is directly or via a linking group include a biphenyl group and a terphenyl group.
  • the aromatic hydrocarbon group which may have a plurality of substituents is directly bonded and linked without having a linking group.
  • any one of the substituent group Z described later can be used.
  • the substituents that Ar 2 and Ar 3 may have are particularly preferably linear, branched or cyclic alkyl groups that may 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, more preferably 4 or more, preferably 12 or less, more preferably 8 or less, and an alkyl group. Is particularly preferably a hexyl group.
  • a combination thereof can be used.
  • the substituent that the linear, branched or cyclic alkyl group may have can be similarly selected from the substituent group Z described later, but a hydrogen atom is particularly preferable from the viewpoint of stability.
  • Ar 2 and Ar 3 have a ring adjacent to the nitrogen atom, at least one of the rings does not have a substituent, so that the HOMO of the molecule is lowered and the charge can be easily injected into the light emitting layer. be.
  • Ar 2 and Ar 3 have rings adjacent to the nitrogen atom, it is particularly preferred that all of the rings have no substituents.
  • X represents -C (R 7 ) (R 8 )-, -N (R 9 )-, or -C (R 10 ) (R 11 ) -C (R 12 ) (R 13 )-.
  • X is preferably -C (R 7 ) (R 8 )-or-C (R 10 ) (R 11 ) -C (R 12 ) (R 13 )-, and most preferably -C (R 7 ). ) (R 8 )-.
  • R 1 to R 8 each independently contain hydrogen, 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. show.
  • Each of R 1 to R 8 is an independent hydrogen atom, 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. Therefore, a twist can be formed in the main chain.
  • alkyl group examples include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a tert-butyl group and an n-hexyl group.
  • N-octyl group, cyclohexyl group, dodecyl group and the like which have 1 or more carbon atoms and 24 or less carbon atoms, and examples thereof include linear, branched, or cyclic alkyl groups.
  • an alkoxy group having 1 or more and 24 or less carbon atoms is preferable because it tends to improve the solubility of the polymer, and specifically, a methoxy group, an ethoxy group, an n-propoxy group, and an i-propoxy. Examples thereof include a 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 tends to improve the solubility of the polymer, an aralkyl group having 5 or more and 60 or less carbon atoms is preferable, an aralkyl group having 40 or less carbon atoms is more preferable, and an aralkyl group having 7 or more carbon atoms is preferable.
  • the group is more preferable, the aralkyl group having 10 or more carbon atoms is further preferable, and the aralkyl group having 12 or more carbon atoms is particularly preferable.
  • 1,1-dimethyl-1-phenylmethyl group 1,1-di (n-butyl) -1-phenylmethyl group, 1,1-di (n-hexyl) -1-phenylmethyl group.
  • 1,1-di (n-octyl) -1-phenylmethyl group phenylmethyl group, phenylethyl group, 3-phenyl-1-propyl group, 4-phenyl-1-n-butyl group, 1-methyl- 1-Phenylethyl group, 5-Phenyl-1-n-propyl group, 6-Phenyl-1-n-hexyl group, 6-naphthyl-1-n-hexyl group, 7-Phenyl-1-n-heptyl group, Examples thereof include 8-phenyl-1-n-octyl group and 4-phenylcyclohexyl group.
  • R 1 to R 8 are preferably linear, branched or cyclic alkyl groups which may 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 1 to R 8 other than hydrogen atoms When a plurality of R 1 to R 8 other than hydrogen atoms are present, the electric charge can be uniformly distributed around the nitrogen atom and the synthesis is easy, so that R 1 to R 8 other than hydrogen atoms are present. When there are a plurality of them, it is preferable that they are the same group.
  • R 1 , R 2 , R 5 and R 6 has an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. It is an aralkyl group that may be used.
  • R 1 and R 2 may both have a substituent, or R 5 and R 6 may both have a substituent, an alkyl group may have a substituent, and an alkoxy group may have a substituent.
  • R 1 and R 2 are independently each of an alkyl group and a substituent which may have a substituent. It is particularly preferable that it is an alkoxy group which may have a substituent or an aralkyl group which may have a substituent.
  • R 1 and R 2 are independently alkyl groups from the viewpoint of being considered to have the highest durability.
  • the number of carbon atoms of the alkyl group is preferably 8 or less, and more preferably 6 or less, because the main chain is twisted, the distance between the polymers in the film is not separated, and the charge transportability is considered to be excellent.
  • the number of carbon atoms of the alkyl group is 4 or less, the distance between the polymers in the membrane is sufficiently close to each other, and it is considered that the charge transportability is further improved. Therefore, a methyl group having 1 carbon atom is further preferable.
  • R 1 to R 8 may have include any of the substituent group Z described later, an aralkyl group having 7 to 40 carbon atoms, or an aralkyl group having a heterocycle having 4 to 37 carbon atoms, which will be described later. It is preferable to use a combination of these.
  • R 1 to R 8 may have include an alkyl group having 1 to 24 carbon atoms, an aralkyl group having 7 to 40 carbon atoms, and a heterocycle having 3 to 37 carbon atoms from the viewpoint of durability.
  • Aralkyl group, arylamino group having 10 to 24 carbon atoms, aromatic hydrocarbon group having 6 to 36 carbon atoms, or aromatic heterocyclic group having 3 to 36 carbon atoms is preferable.
  • Aromatic heterocyclic groups are more preferred
  • Aryl groups having 6 to 24 carbon atoms are more preferable.
  • R 1 to R 8 may have is an aromatic hydrocarbon group having 6 to 24 carbon atoms or an aromatic heterocyclic group having 3 to 24 carbon atoms from the viewpoint of charge transportability. It is preferably a phenyl group, a naphthyl group, a fluorenyl group, a carbazolyl group, an indolocarbazolyl group, an indenocarbazolyl group, or an indenofluorenyl group.
  • R 1 to R 8 are preferably hydrogen, an alkyl group having no substituent, an alkoxy group having no substituent, or an aralkyl group having no substituent. ..
  • R 9 to R 13 are independent hydrogen atoms, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aralkyl group which may have a substituent. Alternatively, it represents an aromatic hydrocarbon group which may have a substituent.
  • alkyl group alkoxy group, and aralkyl group
  • the same groups as those of R 1 to R 8 can be used, and the substituents that R 9 to R 13 may have are also the same as those of R 1 to R 8 .
  • an aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms is preferable, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, and the like.
  • examples thereof include monovalent groups of 6-membered monocyclic rings or 2 to 5 fused rings such as benzpyrene ring, chrysen ring, triphenylene ring, acenaften ring, fluorantene ring, and fluorene ring. From the viewpoint of durability, monovalent groups of a benzene ring and a fluorene ring are particularly preferable.
  • the substituents R 7 to R 13 of X may further have from the viewpoint of improving insolubility in a solvent when the polymer of the present invention is formed into a film and then another layer is applied to form a film and laminated. , It is preferable that it is a crosslinkable group described later. Among them, any one of R 7 , R 8 , and R 10 to R 13 preferably has a crosslinkable group described later as a further substituent because it does not hinder the charge transport property, and at least one of R 7 and R 8 is preferable. However, it is more preferable to have a crosslinkable group described later as a further substituent.
  • R 7 and R 5 , R 7 and R 6 do not combine to form a ring.
  • the two structures in the main chain of the polymer bonded to the nitrogen atom of the main chain amine in the formula (1) are phenylene groups which may have a substituent.
  • the repeating unit represented by the above formula (1) is more preferably represented by the following formula (2) -1 or the following formula (2) -2.
  • Ar 1 , R 1 to R 6 , and X are the same as the definitions in the above equation (1).
  • R 20 to R 23 are independent of each other and are the same as R 1 .
  • g, h, and i independently represent integers of 1 to 3, respectively.
  • j and k each independently represent an integer of 1 to 2.
  • the structure in the main chain of the polymer, which is directly bonded to the nitrogen atom of the main chain amine in the formula (2) -1 or the formula (2) -2 may be a phenylene group having no substituent. preferable.
  • g and i are each independently an integer of 1 to 3. Further, g + i is preferably 2 or more. Further, it is preferable that g and i are independently 2 or less, and it is more preferable that both g and i are 1 because it does not hinder the charge transport property.
  • H is an integer of 1 to 3. Further, h is preferably 2 or less, and h is more preferably 1 because it does not hinder the charge transport property.
  • j and k are each independently an integer of 1 to 2. Further, it is preferable that j + k is 2 or more. Further, it is preferable that j and k are independently 2 or less, and it is more preferable that both j and k are 1 because it does not hinder the charge transport property.
  • ⁇ Preferable repeating unit structure and partial structure> The structure constituting the main chain of the polymer of the present invention, in which the two structures directly bonded to the nitrogen atom of the main chain amine in the formula (1) are both phenylene groups which may have a substituent. It is more preferable to have.
  • the two structures directly bonded to the nitrogen atom of the main chain amine in the formula (1) are both phenylene groups which may have a substituent. Is the following two cases (a) and (b).
  • B When a structure other than the above formula (1) is bonded next to N of the repeating unit represented by the above formula (1).
  • the polymer of the present invention has a repeating unit represented by the following formula (1) -2.
  • the polymer of the present invention has a partial structure represented by the following formula (1) -3.
  • Ar 1 , Ar 2 , Ar 3 , R 1 to R 6 , X, n represent Ar 1 , Ar 2 , Ar 3 , R 1 to R 6 , X, n in the equation (1).
  • n62 and n63 are 4, Each of the plurality of R 62s is independently the same as that of R 1 in the formula (1), that is, hydrogen, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and the like.
  • Ar 2 is a phenylene group which may have a substituent
  • it represents a direct bond and represents a direct bond
  • equation (1) -5 * Represents the bond of the main chain Ar 33 may have a substituent from Ar 3 of the above formula (1), which is directly bonded to the repeating unit next to the repeating unit represented by the formula (1) contained in Ar 3 . It is the remaining structure excluding However, when Ar 3 is a phenylene group which may have a substituent, it represents a direct bond and represents a direct bond.
  • the phenylene group which may have R 62 represented by Q is a part or all of the structure directly bonded to N of the repeating unit represented by the formula (1).
  • Ar 1 , Ar 2 , Ar 32 , R 1 to R 6 , R 62 , X, n, n 62 are Ar 1 , Ar 2 , Ar 32 , R 1 to R 6 , R 62 , in equation (1) -2. Similar to X, n, n62, Ar 3 is the same as Ar 3 in the equation (1).
  • n61 is 4, Each of the plurality of R 61s is independently the same as that of R 1 in the formula (1), that is, hydrogen, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and the like. Or represents an aralkyl group which may have a substituent and represents However, Ar 2 is given by Eq. (1) -4. )
  • Ar 3 in the formula (1) -3 preferably has a structure represented by the formula (1) -5.
  • the repeating unit represented by the formula (1) -2 is preferably the following formula (1)-. It is 2-2, and more preferably the following formula (1) 2-3.
  • Equations (1) and -2-2 represent that in the above equation (1) -2, two of the four R 62s are hydrogen and two of the four R 63s are hydrogen. At least one of the two R 62s attached to the phenylene group is not hydrogen, and at least one of the two R 63s attached to the phenylene group is not hydrogen.
  • Equations (1) and 2-3 represent that in the above equation (1) -2, the four existing R 62 and the four existing R 63 are all hydrogen.
  • the partial structure represented by the formula (1) -3 is preferably the following formula (1) -3-2. , More preferably, the following formula (1) -3-3.
  • Equation (1) -3-2 represents that in the above equation (1) -3, two of the four R 61s are hydrogen and two of the four R 62s are hydrogen. At least one of the two R 61s attached to the phenylene group is not hydrogen, and at least one of the two R 62s attached to the phenylene group is not hydrogen.
  • Ar 3 in the formula (1) -3-2 is preferably a structure represented by the formula (1) -5.
  • Formula (1) -3-3 represents that in the above formula (1) -3, the four existing R 61 and the four existing R 62 are all hydrogen.
  • Ar 3 in the formula (1) -3-3 preferably has a structure represented by the formula (1) -5. Further, the Ar 2 represented by the formula (1) -4 is preferably a structure represented by the formula (1) 4-2 or the formula (1) -4-3.
  • R 20 and R 22 are independently the same as R 20 and R 22 in the above equation (2) -2.
  • g is the same as g in the above formula (2) -1, and represents an integer of 1 to 3, and the preferable value and the reason are also the same as g in the above formula (2) -1.
  • j is the same as j in the above formula (2) -2, represents an integer of 1 to 2, and has the same preferable value and reason as j in the above formula (2) -2.
  • the Ar 3 represented by the formula (1) -5 is preferably a structure represented by the formula (1) -5-2 or the formula (1) -5-3.
  • R 23 and R 24 are independently the same as R 23 and R 24 in the above equation (2) -2.
  • i is the same as i in the above formula (2) -1, and represents an integer of 1 to 3, and the preferable value and the reason are the same as i in the above formula (2) -1.
  • k is the same as k in the above formula (2) -2, represents an integer of 1 to 2, and has the same preferable value and reason as k in the above formula (2) -2.
  • each partial structure constituting the structure represented by (1) -5-2 and the formula (1) -5-3 may have a substituent, select from the substituent group Z described later. Can be done. Preferably, it is a structure having no substituent which may be possessed.
  • substituent group Z examples include the following structures. 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.
  • a linear, branched, or cyclic alkyl group usually having 1 or more carbon atoms, preferably 4 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 usually having 1 or more carbon atoms
  • the above-mentioned substituent group Z the above-mentioned alkyl group, alkoxy group, aromatic hydrocarbon group and aromatic heterocyclic group are preferable. From the viewpoint of charge transportability or ease of synthesis, it is more preferable that Ar 1 to Ar 3 , R 1 to R 13 , and R 20 to R 23 do not have a substituent.
  • each substituent of the above-mentioned 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.
  • Each of the substituents of the above-mentioned substituent group Z preferably has no 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. .. From the viewpoint of charge transportability, it is more preferable that each of the substituents of the substituent group Z does not have a further 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 the present invention is usually a hydrocarbon group.
  • the number of carbon atoms of the hydrocarbon group is preferably 1 or more and 60 or less, more preferably 1 or more and 40 or less, and further preferably 1 or more and 30 or less, from the viewpoint of charge transportability.
  • a linear, branched, or cyclic alkyl group usually having 1 or more carbon atoms, preferably 4 or more, usually 24 or less, preferably 12 or less;
  • an aromatic hydrocarbon ring group having a carbon number of usually 6 or more, usually 36 or less, preferably 24 or less, such as a phenyl group and a naphthyl group; can be mentioned.
  • hydrocarbon groups may further have a substituent, and the substituent which may further have is preferably an alkyl group or an aromatic hydrocarbon group, and there are a plurality of these substituents which may further have. In some cases, they may be bonded to each other to form a ring.
  • the substituent which may be further possessed is preferably an alkyl group or an aromatic hydrocarbon group, and more preferably an aromatic hydrocarbon group from the viewpoint of charge transportability and durability.
  • the polymer of the present invention preferably has a soluble group for soluble expression in a solvent.
  • the soluble group in the present invention 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, and the like. More preferably, it is an n-hexyl group or an n-octyl group.
  • the soluble group may have a substituent.
  • the amount of the soluble group contained in the polymer of the present invention is large in that it is easy to obtain a polymer solution that can be used in the wet film forming method.
  • a small amount is preferable in that the film thickness decrease due to the layer being dissolved in the solvent when another layer is formed on the formed layer by the wet film forming method is small.
  • the number of soluble groups contained in the polymer of the present invention 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 invention is expressed in terms of the number of moles per 1 g of the polymer, it is usually 4.0 mmol or less, preferably 3.0 mmol or less, and more preferably 2 per 1 g of the polymer. It is 0.0 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 the solvent, and a composition containing the polymer suitable for the wet film forming method is easily obtained.
  • the solubility in an organic solvent after drying with a heated solvent is sufficient. Therefore, it is possible to form a multi-layer laminated structure by the wet film forming method.
  • the number of soluble groups per 1 g 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 from the polymer.
  • the molecular weight of the repeating unit excluding the terminal group in the polymer 1 is 682 on average, and the hexyl group which is a soluble group is a soluble group.
  • the average is 0.9 per repeating unit.
  • the polymer of the present invention may have a crosslinkable group.
  • the crosslinkable group in the polymer of the present invention may be present in the repeating unit represented by the formula (1), or is present in a repeating unit different from the repeating unit represented by the formula (1). May be.
  • the polymer of the present invention has a crosslinkable group, it is possible to make a large difference in solubility in an organic solvent before and after the 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 T is more preferable.
  • the crosslinkable group is preferably further substituted with the substituent group Z.
  • Crosslinkable group T The crosslinkable group T has the structure shown below.
  • R 24 to R 26 each independently represent a hydrogen atom or an alkyl group.
  • R 27 to R 29 each independently represent an alkyl group or an alkoxy group.
  • Ar 21 and Ar 22 represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.
  • p is an integer of 1 to 4
  • q is an integer of 1 to 5
  • r is an integer of 1 to 7.
  • the plurality of R 27s may be the same or different, and adjacent R 27s may be bonded to each other to form a ring.
  • the plurality of R 28s may be the same or different, and may be substituted with an aromatic ring and the adjacent R 28s may be bonded to each other to form a ring.
  • the plurality of R 29s may be the same or different.
  • Examples of the alkyl group of R 24 to R 29 include a linear or branched chain alkyl group having 6 or less carbon atoms.
  • Examples of the alkoxy group of R 27 to R 29 include a linear or branched chain alkoxy group having 6 or less carbon atoms, for example, a methoxy group, an ethoxy group, an n-propoxy group, a 2-propoxy group, and the like. It is an n-butoxy group or the like. More preferably, it is a methoxy group or an ethoxy group.
  • the number of carbon atoms of the alkoxy groups of R 27 to R 29 is 6 or less, the cross-linking reaction is not sterically inhibited, and the insolubilization of the film tends to occur easily.
  • the aromatic hydrocarbon group which may have a substituent includes a single ring of a 6-membered ring such as a benzene ring and a naphthalene ring having one free atomic value, or 2 to 5 Examples include the group of the fused ring. In particular, a benzene ring having one free valence is preferable.
  • an aromatic heterocyclic group having one free atomic value and having 3 or more carbon atoms and 60 or less carbon atoms is used.
  • a furan ring a benzofuran ring, a thiophene ring, a benzothiophene ring, an imidazole ring, an indole ring, a carbazole ring, a benzoimidazole ring, a pyridine ring, a pyrimidine ring, a triazine ring, an isoquinoline ring, a quinoxalin ring, and a phenant.
  • Examples thereof include a monovalent group of a 5- to 6-membered monocyclic ring or a 2- to 4-fused ring such as a lysine ring and a quinazoline ring, or a monovalent group in which a plurality of structures selected from these are linked.
  • a benzofuran ring, a benzothiophene ring, a carbazole ring, and a triazine ring are 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.
  • the substituents that Ar 21 and Ar 22 may have are the same as those of the above-mentioned substituent group Z.
  • Cyclization of arylvinylcarbonyl groups such as cinnamoyl groups, benzocyclobutene rings having a monovalent free valence, and 1,2-dihydrocyclobuta [a] naphthalene rings having a monovalent free valence as crosslinkable groups.
  • Additive reacting groups are preferred in that they further improve the electrochemical stability of the device.
  • the cyclobutene ring condensed into an aromatic ring having a monovalent free valence and 1,2-dihydro having a monovalent free valence are particularly stable in the structure after cross-linking.
  • a group containing a cyclobutane [a] naphthalene ring is preferable, and a group of a benzocyclobutene ring or a 1,2-dihydrocyclobutane [a] naphthalene ring having a monovalent free valence is more preferable, and the cross-linking reaction temperature is low.
  • a group of 1,2-dihydrocyclobutane [a] naphthalene rings having a monovalent free valence in terms of points is particularly preferred.
  • the crosslinkable group of the polymer of the present invention is preferably sufficiently insolubilized by crosslinking, and it is 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, and preferably 200 or less, more preferably 100 or less.
  • the number of crosslinkable groups possessed by the polymer of the present invention can be expressed by the number per 1000 molecular weight of the polymer.
  • the number of crosslinkable groups of the polymer of the present invention 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 1 per 1000 molecular weight. It is 0.0 or less, and usually 0.01 or more, preferably 0.05 or more.
  • the content of the repeating unit represented by the formula (1) is not particularly limited, but is usually contained in the polymer in an amount of 5 mol% or more, preferably 10 mol% or more, preferably 20 mol. It is more preferably contained in an amount of% or more, and particularly preferably contained in an amount of 30 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 electric field light emitting element is used, the formula (1) is used. ) May have a repeating unit different from that of), in which case the content of the repeating unit represented by the formula (1) in the polymer is usually 50 mol% or more, preferably 60 mol% or more. Is.
  • the polymer of the present invention preferably further contains at least one of the repeating unit represented by the following formula (3) -1 and the repeating unit represented by the following formula (3) -2.
  • Ar 4 is a monovalent aromatic hydrocarbon group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent, or a substituent independently in each repeating unit.
  • a monovalent group in which a plurality of groups selected from an aromatic hydrocarbon group which may have a group and an aromatic heterocyclic group which may have a substituent are linked directly or via a linking group.
  • X 30 represents -C (R 37 ) (R 38 )-, -N (R 39 )-, or -C (R 40 ) (R 41 ) -C (R 42 ) (R 43 )-.
  • Each of R 33 , R 34 , R 37 , R 38 , and R 120 to R 123 is independently hydrogen, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an alkoxy group.
  • Each of R 39 to R 43 is independently hydrogen, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aralkyl group which may have a substituent, or an aralkyl group which may have a substituent.
  • Represents an aromatic hydrocarbon group that may have a substituent, g 3 , h 3 , and i 3 each independently represent an integer of 1 to 3.
  • j 3 and k 3 each independently represent an integer of 1 to 2.
  • alkyl group, alkoxy group, and aralkyl group in R 33 , R 34 , R 37 , R 38 , and R 120 to R 123 the same ones as those in R 1 to R 8 can be used.
  • alkyl group alkoxy group, aralkyl group, and aromatic hydrocarbon group in R 39 to R 43 , the same groups as those in R 9 to R 13 can be used.
  • Ar 4 is a monovalent aromatic hydrocarbon group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent, or a substituent independently in each repeating unit.
  • the plurality of Ar 4s may be the same or different.
  • an aromatic hydrocarbon group having 6 or more carbon atoms and 60 or less carbon atoms is preferable, and specifically, a benzene ring, an azulene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, and a tetracene ring.
  • a benzene ring an aromatic hydrocarbon group having 6 or more carbon atoms and 60 or less carbon atoms
  • a benzene ring an azulene ring
  • a naphthalene ring an anthracene ring
  • a phenanthrene ring a perylene ring
  • tetracene ring tetracene ring
  • the aromatic heterocyclic group preferably has an aromatic heterocyclic group having 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, or an imidazole.
  • Examples thereof include a monovalent group of a 6-membered monocyclic ring or a 2- to 4-
  • Ar 4 is preferably an aromatic hydrocarbon group which may have a substituent, and above all, a benzene ring or a fluorene ring which may have a substituent from the viewpoints of excellent charge transportability and durability.
  • a monovalent group that is, a phenyl group or a fluorenyl group which may have a substituent is more preferable, a fluorenyl group which may have a substituent is further preferable, and a fluorenyl group which may have a substituent may be possessed.
  • a 2-fluorenyl group is particularly preferred.
  • the substituent that the aromatic hydrocarbon group or aromatic heterocyclic group of Ar 4 may have is not particularly limited as long as it does not significantly reduce the characteristics of the polymer of the present invention.
  • Preferred are the substituent group Z or a group selected from the crosslinkable groups, preferably an alkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group or the crosslinkable group, with the alkyl group being more preferred. preferable.
  • Ar 4 is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms from the viewpoint of solubility in a coating solvent, 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 4 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 tend to be improved. Furthermore, since Ar 4 is a fluorenyl group in which 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 tend to be further improved.
  • Ar 4 contains the crosslinkable group because the insolubility in a solvent is improved when the film is laminated and coated after the film formation.
  • the polymer of the present invention contains, as a further substituent, a repeating unit represented by the formulas (3) -1 and the formula (3) -2 containing at least one of the above-mentioned crosslinkable groups. It is preferable that the crosslinkable group is further substituted with a substituent which may be possessed by an aromatic hydrocarbon group represented by Ar 4 or an aromatic heterocyclic group.
  • the polymer of the present invention preferably further contains a repeating unit represented by the formula (3) -1.
  • Ar 4 is preferably represented by the following formula (A2).
  • Ar 36 and Ar 37 each independently have a divalent aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a substituent.
  • Ar 38 may have a monovalent aromatic hydrocarbon group which may have a substituent, a monovalent aromatic heterocyclic group which may have a substituent, or a substituent.
  • Ar 39 represents a hydrogen atom or a substituent and represents -* Represents the bond position with the nitrogen atom in the formula (3) -1 or the formula (3) -2.
  • Ar 36 to Ar 39 Specific examples and preferable ranges of Ar 36 to Ar 39 are the same as those of Ar 6 to Ar 9 .
  • the weight average molecular weight (Mw) of the polymer of the present invention 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, and particularly preferably 200,000 or less. It is 100,000 or less. Further, it is usually 10,000 or more, preferably 15,000 or more, and more preferably 20,000 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. Further, 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) in the polymer of the present invention is usually 2,500,000 or less, preferably 750,000 or less, more preferably 400,000 or less, and particularly preferably 100,000 or less. Further, it is usually 2,000 or more, preferably 4,000 or more, more preferably 8,000 or more, still more preferably 20,000 or more.
  • the dispersity (Mw / Mn) in the polymer of the present invention is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. Since the smaller the value of the dispersion, the better, the lower limit is ideally 1. When the dispersity of the polymer of the present invention is not more than the above upper limit, 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 invention may further contain a repeating unit represented by the formula (5) or the formula (6) in terms of charge transportability and durability.
  • the repeating unit represented by the following formula (5) is represented by the above formula (1), formula (2) -1, formula (2) -2, formula (3) -1 or formula (3) -2.
  • a structure that matches a part of the structural part in the repeating unit is also included, but it is a structure of another repeating unit.
  • Ar 10 represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
  • Ar 11 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.
  • Ar 12 has 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 groups selected from an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent are directly linked or linked in the main chain direction via a linking group. Represents.
  • Ar 10 Ar 10 is a group similar to Ar 1 in the formula (1)
  • Ar 11 and Ar 12 are Ar in the formula (A1).
  • the substituents that Ar 10 , Ar 11 and Ar 12 may have are preferably the substituent group Z or a group similar to the crosslinkable group.
  • the plurality of Ar 10s may be the same or different.
  • the polymer of the present invention most preferably contains a repeating unit represented by any of the following formula group (7).
  • Ar 13 represents the above Ar 1 and Ar 4 , and a plurality of Ar 13s in each polymer may be the same or different, and Ar in each polymer. At least one of 13 is the above Ar 1 , and X, R 1 , R 2 , R 20 , R 21 , R 22 , and R 23 are the same as those of the above equations (2) -1 and (2) -2. .. n 1 and m 1 represent the molar ratio of repeating units in the polymer.
  • polymers of the present invention are shown below, but the present invention is not limited thereto.
  • the numbers in the chemical formula represent the molar ratio of the repeating unit.
  • These polymers may be random copolymers, alternate copolymers, block copolymers, graft copolymers, or the like, and the order of arrangement of the monomers is not limited.
  • the method for producing the polymer of the present invention is not particularly limited.
  • the polymer of the present invention can be produced, for example, 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 dial halide represented by the formula (1a) (Y represents a halogen atom such as I, Br, Cl, F) and the formula (
  • the polymer of the present invention is synthesized by reacting with the primary aminoaryl represented by 1b) and further reacting with the compound represented by the formula (2a).
  • Ar 1 , R 1 to R 2 , X, g, and i are synonymous with the above formulas (2) -1 to (2) -2.
  • the numbers in the chemical formula represent the molar ratio of the repeating unit.
  • 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 copper or palladium complex.
  • the polymer of the present invention can be particularly preferably used as an organic electroluminescent device material. That is, the polymer of the present invention is preferably an organic electroluminescent device material. Since the polymer of the present invention is a polymer having excellent hole transporting properties, it is preferable to use it as a hole transporting material.
  • the polymer of the present invention is usually contained between the anode and the light emitting layer in the organic electric field generation device. That is, it is preferable to use it as a material that forms at least one of the hole injection layer and the hole transport layer, that is, a charge transport material. Further, the polymer of the present invention may be contained in a light emitting layer in an organic electroluminescent device. That is, it can be used as a charge transport material contained in the light emitting layer. When used as a charge transporting material, it may contain one kind of polymer of the present invention, or may contain two or more kinds in any combination and any ratio.
  • the content of the polymer of the present invention in the hole injection layer or the hole transport layer is , Usually 1 to 100% by mass, preferably 5 to 100% by mass, and more preferably 10 to 100% by mass.
  • 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 components constituting the hole injection layer or the hole transport layer include the hole transport property described later. Examples include compounds. Further, since the organic electroluminescent device can be easily manufactured, the polymer of the present invention is preferably used for the organic layer formed by the wet film forming method.
  • composition for an organic electroluminescent device of the present invention contains the polymer of the present invention.
  • the composition for an organic electroluminescent device of the present invention may contain one kind of polymer of the present invention, or may contain two or more kinds in any combination and any ratio. good.
  • the content of the polymer in the composition for an organic electroluminescent device of the present invention is usually 0.01 to 70% by mass, preferably 0.1 to 60% by mass, and more preferably 0.5 to 50% by mass. 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 invention may contain a solvent or the like in addition to the above polymer.
  • the composition for an organic electroluminescent device of the present invention usually contains a solvent.
  • the solvent is preferably one that dissolves the above polymer.
  • a solvent that dissolves the polymer at room temperature in an amount of usually 0.05% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more 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; organic solvents such as, and other hole injection layer formation described later. Examples thereof include organic solvent
  • a solvent having a surface tension at 20 ° C. of usually less than 40 dyn / cm, preferably 36 dyn / cm or less, more preferably 33 dyn / cm or less. Is preferable.
  • 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 uniform coating film having higher leveling property 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, mesitylene 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, mesitylene 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.
  • a solvent having a vapor pressure at 25 ° C. of usually 10 mmHg or less, preferably 5 mmHg or less, and usually 0.1 mmHg or more is preferable. ..
  • a composition for an organic electroluminescent device suitable for the process of manufacturing an organic electroluminescent device by a wet film forming method and suitable for the properties of the polymer of the present invention can be prepared.
  • 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. Therefore, in order to reduce the water content remaining during the wet film formation as much as possible, among the above-mentioned solvents, those having a water solubility at 25 ° C. of 1% by mass or less are preferable, and those having a solubility of 0.1% by mass or less are preferable. Is more preferable.
  • the content of the solvent contained in the composition for an organic electroluminescent device of the present invention is usually 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 80% by mass 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 invention preferably further contains an electron-accepting compound in terms of lowering the resistance.
  • an electron accepting compound when the composition for an organic electroluminescent device of the present invention is used for forming a hole injection layer, it is preferable to contain 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.
  • an onium salt substituted with an organic group such as 4-isopropyl-4'-methyldiphenyliodonium tetrakis (pentafluorophenyl) boronate and triphenylsulfonium tetrafluoroborate (International Publication No. 2005/089024, International Publication No. 2005/089024) No. 2017/164268); High atomic value inorganic compounds such as iron chloride (III) (Japanese Patent Laid-Open No.
  • ammonium peroxodisulfate ammonium peroxodisulfate
  • cyano compounds such as tetracyanoethylene
  • tris (pentafluorophenyl) borane Purge boron compounds
  • fullerene derivatives iodine and the like can be mentioned.
  • composition for an organic electroluminescent device of the present invention 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 mass or more, preferably 0.001% by mass or more, and usually 20% by mass. % Or less, preferably 10% by mass or less.
  • the content of the electron-accepting compound with respect to the polymer in the composition for an organic electric field light emitting element is usually 0.5% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and is usually used. It is 80% by mass or less, preferably 60% by mass or less, and more preferably 40% by mass or less.
  • the electron acceptor receives electrons from the polymer and the formed organic layer has a low resistance, which is preferable. This is preferable because defects are less likely to occur in the formed organic layer and uneven film thickness is less likely to occur.
  • the composition for an organic electroluminescent device of the present invention may further contain a cationic radical compound.
  • a cationic 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 in terms 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, and the hole transporting compound is composed of a cation radical and a counter anion. A cationic ion compound is produced.
  • the content of the cation radical compound in the composition for an organic electroluminescent element is usually 0.0005% by mass or more, preferably 0.001% by mass. It is usually 40% by mass or less, preferably 20% by mass or less.
  • the content of the cationic radical compound is not less than the lower limit, the formed organic layer has a low resistance, which is preferable, and when it is not more than the upper limit, the formed organic layer is less likely to have defects and uneven film thickness is less likely to occur.
  • the composition for an organic electroluminescent device of the present invention contains components contained in the hole injection layer forming composition and the hole transport layer forming composition described later. It may be contained in.
  • the light emitting layer includes a light emitting material and a host material.
  • a phosphorescent light emitting material or a fluorescent light emitting material can be used as the light emitting material.
  • the phosphorescent light emitting material is used.
  • the following materials are preferred.
  • the phosphorescent material is 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 organic metal complex that emits light via a triplet state it is a long-periodic periodic table (hereinafter, unless otherwise specified, the term "periodic table” refers to a long-periodic table.
  • a Werner-type complex or an organic metal complex compound containing a metal selected from Groups 7 to 11 as a central metal can be mentioned.
  • a compound represented by the formula (201) or a compound represented by the formula (202) is preferable, and a compound represented by the formula (201) is more preferable.
  • M is a metal selected from Groups 7 to 11 of the periodic table, and examples thereof include ruthenium, rhodium, palladium, silver, renium, osmium, iridium, platinum, gold, and europium.
  • 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 above formula (202), and “*” indicates that they are bonded to rings A1 and / 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. show.
  • 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.
  • L200 represents a single bond or an atomic group constituting a bidentate ligand together with B 201 and B 202 .
  • B 201 -L 200 -B 202 When there are a plurality of B 201 -L 200 -B 202 , they may be the same or different.
  • i1 and i2 each independently represent an integer 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 integers of 0 or more, each independently up to a number substitutable for rings A1 and A2.
  • m1 is an integer of 1 to 3.
  • ⁇ Substituent group Z'> -Alkyl group preferably 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. ..
  • An alkoxy group preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and further preferably an alkoxy group having 1 to 6 carbon atoms.
  • An aryloxy group preferably an aryloxy group having 6 to 20 carbon atoms, more preferably an aryloxy group having 6 to 14 carbon atoms, still more preferably an aryloxy group having 6 to 12 carbon atoms, particularly preferably 6 carbon atoms.
  • a heteroaryloxy group preferably a heteroaryloxy group having 3 to 20 carbon atoms, more preferably a heteroaryloxy group having 3 to 12 carbon atoms.
  • An alkylamino group preferably an alkylamino group having 1 to 20 carbon atoms, and more preferably an alkylamino group having 1 to 12 carbon atoms.
  • An arylamino group preferably an arylamino group having 6 to 36 carbon atoms, and more preferably an arylamino group having 6 to 24 carbon atoms.
  • An aralkyl group preferably an aralkyl group having 7 to 40 carbon atoms, more preferably an aralkyl group having 7 to 18 carbon atoms, and further preferably an aralkyl group having 7 to 12 carbon atoms.
  • -Heteroaralkyl group preferably a heteroaralkyl group having 7 to 40 carbon atoms, more preferably a heteroaralkyl group having 7 to 18 carbon atoms.
  • An alkenyl group preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, further preferably an alkenyl group having 2 to 8 carbon atoms, and particularly preferably an alkenyl group having 2 to 6 carbon atoms. ..
  • An alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms, and more preferably an alkynyl group having 2 to 12 carbon atoms.
  • An aryl group preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, further preferably an aryl group having 6 to 18 carbon atoms, and particularly preferably an aryl group having 6 to 14 carbon atoms. ..
  • a heteroaryl group preferably a heteroaryl group having 3 to 30 carbon atoms, more preferably a heteroaryl group having 3 to 24 carbon atoms, still more preferably a heteroaryl group having 3 to 18 carbon atoms, and particularly preferably 3 to 18 carbon atoms. 14 heteroaryl groups.
  • alkylsilyl group preferably an alkylsilyl group having 1 to 20 carbon atoms, more preferably an alkylsilyl group having 1 to 12 carbon atoms.
  • An arylsilyl group preferably an arylsilyl group having 6 to 20 carbon atoms, more preferably an arylsilyl group having 6 to 14 carbon atoms.
  • -Alkylcarbonyl group preferably an alkylcarbonyl group having 2 to 20 carbon atoms.
  • -Arylcarbonyl group preferably an arylcarbonyl group having 7 to 20 carbon atoms.
  • one or more hydrogen atoms may be replaced with a fluorine atom, or one or more hydrogen atoms may be replaced with a deuterium atom.
  • substituent group Z' Preferable group in substituent group Z', Preferable group in substituent group Z', Preferable group in substituent group Z', Preferably, 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.
  • Group or -SF 5 More preferably, it is 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 or an arylsilyl group. Particularly preferred are an alkyl group, an arylamino group, an aralkyl group, an alkenyl group, an aryl group, and a heteroaryl group. Most preferably, it is an alkyl group, an arylamino group, an aralkyl group, an aryl group, or a heteroaryl group.
  • substituents Z' may further have a substituent selected from the substituent group Z as a substituent.
  • Preferred groups, more preferred groups, more preferred groups, particularly preferred groups, and most preferred groups of the substituents which may be possessed are the same as the preferred 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, and specifically, a benzene ring, a naphthalene ring, an anthracene ring, a triphenylyl ring, an acenaphthene ring, a fluoranthene ring, and the like.
  • a fluorene ring is preferred.
  • aromatic heterocycle of ring A1 an aromatic heterocycle having 3 to 30 carbon atoms containing any of a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom is preferable, and a furan ring or a benzofuran ring is more preferable.
  • Thiophene ring, benzothiophene ring is 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 and containing any of a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom, and specifically, a pyridine ring.
  • a pyridine ring preferably 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 quinoxalin ring, and a quinazoline ring, and more preferably a pyridine ring and an imidazole 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).
  • the substituents that the rings A1 and A2 may have can be arbitrarily selected, but are preferably one or a plurality of substituents selected from the substituent group Z'.
  • 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.
  • a benzene ring, a naphthalene ring, an anthracene ring, a triphenylyl ring, an acenaften ring, a fluorantene ring, and a fluorene ring are preferable, more preferably a benzene ring, a naphthalene ring, and a fluorene ring are preferable, and most preferable. It is a benzene ring.
  • Ar 201 or Ar 202 is a benzene ring which may have a substituent
  • at least one benzene ring is 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 sulfur atoms and having 3 to 30 carbon atoms. Specifically, it is a pyridine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an imidazole ring, an oxazole ring, a thiazole ring, or a benzothiazole ring.
  • Benzoxazole ring benzoimidazole ring, quinoline ring, isoquinoline ring, quinoxalin ring, quinazoline ring, naphthylidine ring, phenanthridine ring, carbazole ring, dibenzofuran ring, dibenzothiophene ring, and more preferably pyridine ring and pyrimidine. It is a ring, a triazine ring, a carbazole ring, a dibenzofuran ring, and a dibenzothiophene ring.
  • N position of carbazole If any of Ar 201 , Ar 202 , and Ar 203 is a carbazole ring that may have a substituent, the N-position of the carbazole ring may have a substituent or be attached to an adjacent structure. preferable.
  • Ar 202 is an aliphatic hydrocarbon structure which may have a substituent, it is an aliphatic hydrocarbon structure having a linear, branched or cyclic structure, preferably having 1 or more and 24 or less carbon atoms. Yes, more preferably the number of carbon atoms is 1 or more and 12 or less, and further preferably the number of carbon atoms is 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, improvement in solubility and charge transportability is expected.
  • i3 preferably represents an integer of 0 to 5, more preferably 0 to 2, and more preferably 0 or 1.
  • j1 preferably represents an integer of 0 to 2, and more preferably 0 or 1.
  • k1 and k2 preferably represent an integer of 0 to 3, more preferably 1 to 3, 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 are preferably one or more substituents selected from the substituent group Z', and the preferred group is also the above-mentioned.
  • the substituent group Z' it is 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).
  • 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 201 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 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.
  • L200 represents a single bond or an atomic group constituting a bidentate ligand together with B 201 and B 202 .
  • B 201 -L 200 -B 202 When there are a plurality of B 201 -L 200 -B 202 , they may be the same or different.
  • the structure represented by the following formula (203) or (204) is preferable.
  • R 211 , R 212 , and R 213 represent substituents.
  • the substituent can be arbitrarily selected, but is preferably one or a plurality of substituents selected from the substituent group Z'.
  • ring B3 represents an aromatic heterocyclic structure containing a nitrogen atom, which may have a substituent.
  • Ring B3 is preferably a pyridine ring.
  • the substituent that the ring B3 may have is not particularly limited, but is preferably one or a plurality of substituents selected from the substituent group Z'.
  • the phosphorescent material represented by the formula (201) is not particularly limited, and specific examples thereof include the following structures.
  • M 2 represents a metal and T represents a carbon atom or a nitrogen atom.
  • R 92 to R 95 each independently represent a substituent. However, when T is a nitrogen atom, there are no R 94 and R 95 .
  • M 2 represents a metal.
  • the above-mentioned metal can be mentioned as a metal selected from the 7th to 11th groups of the periodic table.
  • ruthenium, rhodium, palladium, silver, renium, osmium, iridium, platinum or gold are preferred, and divalent metals such as platinum and palladium are particularly preferred.
  • R 92 and R 93 are independently each of a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, an amino group, an acyl group, an alkoxycarbonyl group and a carboxyl group.
  • R 94 and R 95 independently represent substituents represented by the same examples as R 92 and R 93 , respectively. Further, when T is a nitrogen atom, there is no R 94 or R 95 directly bonded to the T.
  • R 92 to R 95 may further have a substituent.
  • the substituent the above-mentioned substituent can be used.
  • 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. It is considered that within this molecular weight range, the phosphorescent luminescent materials do not aggregate and are uniformly mixed with the charge transporting 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., and the phosphorescent material and the formed light emitting layer are excellent in heat resistance, and the film quality due to gas generation, recrystallization, molecular migration, etc. It is preferable that the amount is large in that the decrease in the amount of impurities and the increase in the concentration of impurities due to the thermal decomposition of the material are unlikely to occur. On the other hand, the molecular weight of the phosphorescent light emitting material is preferably small in that the organic compound can be easily purified.
  • a polymer according to an 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 material.
  • the following materials are preferable as the host material.
  • 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 transportability Specific examples of the skeleton having excellent charge transport properties 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 transportable material As the electron 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 transporting property and a relatively stable structure. Is even more preferable.
  • the hole transporting material is a compound having a structure excellent in hole transporting property, and among the central skeletons having excellent hole transporting property, a carbazole structure, a dibenzofuran structure, a triarylamine structure, a naphthalene structure, a phenanthrene structure or
  • the pyrene structure is preferable as a structure having excellent hole transportability, and a carbazole structure, a dibenzofuran structure or a triarylamine structure is more preferable.
  • the polymer of the present invention can also be used as a hole transport material contained in the light emitting layer.
  • the host material of the light emitting layer is preferably a compound having three or more fused ring structures, and is a compound having two or more fused ring structures or a compound having at least one fused ring structure of five or more rings. Is even more 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 durability of the material.
  • fused ring structure having three or more rings include anthracene structure, phenanthrene structure, pyrene structure, chrysen structure, naphthacene structure, triphenylene structure, fluorene structure, benzofluorene structure, indenofluorene structure, and indolofluorene structure.
  • examples thereof include a carbazole structure, an indenocarbazole structure, an indrocarbazole 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 preferably 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 device formed on a flexible substrate.
  • the molecular weight is preferably 5,000 or more and 1,000,000 or less, more preferably 10,000 or more and 500,000 or less, and more 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 molecular weight 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.
  • Fluorescent light emitting layer material In an organic electroluminescent device using the polymer of the present invention as a charge transporting material forming at least one of a hole injection layer and a hole transport layer, when the light emitting layer is a fluorescent light emitting layer material, the following blue fluorescence It is preferably a light emitting layer material.
  • the blue fluorescent light emitting layer material is not particularly limited, but a compound represented by the following formula (211) is preferable.
  • Ar 241 represents an aromatic hydrocarbon fused ring structure which may have a substituent
  • Ar 242 and Ar 243 are alkyl groups which may independently have a substituent.
  • n41 is an integer of 1 to 4.
  • Ar 241 preferably represents an aromatic hydrocarbon condensed ring structure having 10 to 30 carbon atoms, and specific structures include naphthalene, acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, tetracene, chrysene, perylene and the like. Be done. More preferably, it is an aromatic hydrocarbon fused ring structure having 12 to 20 carbon atoms, and specific structures include acenaphthene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, tetracene, chrysene, and perylene. More preferably, it is an aromatic hydrocarbon fused ring structure having 16 to 18 carbon atoms, and specific structures include fluoranthene, pyrene, and chrysene.
  • the alkyl group in Ar 242 and Ar 243 is preferably a linear, branched or cyclic alkyl group which may have a substituent.
  • the number of carbon atoms of the alkyl group is not particularly limited, but the number of carbon atoms is preferably 1 or more and 6 or less, and more preferably 3 or less, in order to maintain the solubility of the blue fluorescent light emitting layer material.
  • the alkyl group is more preferably a methyl group, an ethyl group or a tert-butyl group.
  • Ar 242 and Ar 243 may be the same or different.
  • Ar 242 and Ar 243 preferably represent an aromatic hydrocarbon ring structure having 6 to 18 carbon atoms or a group in which these are bonded or condensed, and specific structures include a benzene ring, a biphenyl ring, and a tarphenyl ring. Examples thereof include a naphthalene ring, a fluorene ring, a dibenzothiophene ring, a dibenzofuran ring, a carbazole ring, a triphenylene ring, and a perylene ring.
  • it is an aromatic hydrocarbon ring structure having 6 to 12 carbon atoms or a group in which these are bonded or condensed, and preferably, a benzene ring, a biphenyl ring, a tarphenyl ring, a naphthalene ring, a fluorene ring, a dibenzothiophene ring, etc. Examples thereof include a dibenzofuran ring and a carbazole ring.
  • it is an aromatic hydrocarbon ring structure having 12 carbon atoms or a group obtained by condensing them, and specific structures include a fluorene ring, a dibenzothiophene ring, a dibenzofuran ring, and a carbazole ring.
  • N41 is an integer of 1 to 4, preferably 1 to 3, more preferably 1 to 2, and most preferably 2.
  • the substituent that Ar 241 , Ar 242 , and Ar 243 may have is preferably a group selected from the above-mentioned substituent group Z', and more preferably a hydrocarbon group contained in the substituent group Z'. More preferably, it is a hydrocarbon group among the groups preferred as the substituent group Z'.
  • the host material is as follows. Material is preferred.
  • 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 are each independently represented by the following formula (213), R 243 represents a substituent, and R 243 is different even if they are the same when there are a plurality of them.
  • N43 may be an integer of 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, and Ar 244 and Ar 245 respectively. When there are a plurality of them, they may be the same or different, and 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 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 may have 6 carbon atoms. It is an aromatic heterocyclic structure which is a fused ring of to 30 and more preferably an aromatic hydrocarbon structure which is a monocycle or a fused ring having 6 to 12 carbon atoms or which may have a substituent. It is an aromatic heterocyclic structure which is a fused ring having 12 carbon atoms which may have a substituent.
  • N44 is preferably 1 to 3, more preferably 1 or 2, and 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 a group selected from the above-mentioned substituent group Z', and more preferably a hydrocarbon contained in the substituent group Z'. It is a hydrogen group, and 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 the 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. It is usually 300 or more, preferably 350 or more, and more preferably 400 or more.
  • the organic electroluminescent device of the present invention is an organic electroluminescent device having an anode and a cathode and an organic layer between the anode and the cathode on a substrate, wherein the organic layer contains the polymer. It is characterized by including a layer formed by a wet film forming method using a composition for a light emitting device.
  • the layer formed by the wet film forming method is preferably at least one of a hole injection layer and a hole transport layer, and in particular, this organic layer is a hole injection layer and positive. It is preferable that the hole transport layer and the light emitting layer are provided, and all of the hole injection layer, the hole transport layer and the light emitting layer are formed by a wet film forming method.
  • 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 a capillary. It refers to a method of forming a film by adopting a wet film forming method such as a coating method, an inkjet method, a nozzle printing method, a screen printing method, a gravure printing method, and a flexographic printing method, and drying the obtained 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 an organic electric field light emitting element, and usually a quartz or glass plate, a metal plate, a metal foil, a plastic film, a sheet, or the like is used. Of these, 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 device is unlikely to be deteriorated by the outside air. Therefore, particularly when a material having a low gas barrier property such as a substrate made of synthetic resin is used, it is preferable to provide a dense silicon oxide film or the like on at least one side 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 halide metal 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.
  • an appropriate binder resin solution it can also be formed by dispersing and 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). Volume, p. 2711, 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, and 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 that it enhances the function of transporting holes from the anode 2 to the light emitting layer 5 side.
  • 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, and 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. From the viewpoint of excellent film forming property, it is preferable to form a hole injection layer 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 that the hole injection layer contains a cationic radical compound, and it is particularly preferable that the cationic radical compound and the hole transporting compound are contained.
  • the hole injection layer is formed by a wet film forming method using the composition for an organic electroluminescent device. It is preferable to be done.
  • the composition for forming a hole injection layer usually contains a hole transporting compound that becomes the hole injection layer 3. Further, in the case of the wet film forming method, 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 manufacturing or use. Further, it is preferable that the stability is excellent, the ionization potential is small, and the transparency to visible light is high. In particular, when the hole injection layer is in contact with the light emitting layer, those that do not quench the light emitted from the light emitting layer or those that form an exciplex with the light emitting layer 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 to the hole injection layer.
  • 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, quinacridone compounds and the like.
  • 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 1,000,000 or less (a 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 injection layer 3 can improve the conductivity of the hole injection layer by oxidizing the hole transporting compound, the hole injection 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 (dehydropolymerization).
  • the oxidative polymerization referred to here is to chemically or electrochemically oxidize the 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 used. Generate.
  • the material to be the hole injection layer is usually mixed with a soluble solvent (solvent for the hole injection layer) to form a composition for film formation (holes).
  • a composition for forming an injection layer is prepared, and this composition for forming a hole injection layer is applied onto a layer (usually an anode) corresponding to the lower layer of the hole injection layer to form a film, which is then dried.
  • 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 preferable that the concentration is low in terms of film thickness uniformity. , Higher is preferable in that defects are less likely to occur in the hole injection layer.
  • the concentration is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and on the other hand.
  • the concentration is preferably 70% by mass or less, more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
  • solvent examples include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents and the like.
  • ether solvent examples include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and propylene glycol-1-monomethyl ether acetate (PGMEA), and 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), and 1,2-dimethoxybenzene, 1,3-dimethoxybenzene and anisole.
  • PMEA propylene glycol-1-monomethyl ether acetate
  • Fenetol 2-methoxytoluene
  • 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, methylnaphthalene and the like.
  • 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.
  • Evaporate while controlling the amount of evaporation) to form a hole injection layer on the anode on the substrate placed facing the crucible Evaporate while controlling the amount of evaporation) to form a hole injection layer on the anode on the substrate placed facing the crucible.
  • a mixture thereof can be placed in a crucible and heated and evaporated to form a hole injection layer.
  • the degree of vacuum at the time of 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 ( 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 having a function of transporting holes from the anode 2 side to the light emitting layer 5 side.
  • the hole transport layer 4 is not an essential layer in the organic electroluminescent device of the present invention, but it is preferable to form this layer in terms of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5. ..
  • the hole transport layer 4 is usually formed between the anode 2 and the light emitting layer 5. Further, when the hole injection layer 3 described above is present, it 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 on the other hand, 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. From the viewpoint of excellent film forming property, it is preferable to form the hole transport layer 4 by a wet film forming method.
  • the hole transport layer is formed by a wet film forming method using the above composition for an organic electroluminescent device. Is preferable.
  • the hole transport layer 4 usually contains a hole transport compound.
  • the hole-transporting compound contained in the hole-transporting layer 4 the above-mentioned polymer or a polymer obtained by cross-linking the above-mentioned polymer is preferable.
  • two or more tertiary amines represented by the hole transporting compound, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl can be added. Fragrant 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'-tetrakis- (diphenylamino) -9,9'-spirobifluorene and other spiro compounds (Synth. Metalls, Vol. 91, p.
  • the hole transport layer 4 is a polyarylene ether sulfone containing, for example, polyvinylcarbazole, polyvinyltriphenylamine (Japanese Patent Laid-Open No. 7-53953), and tetraphenylbenzidine (Polym. Adv. Tech., Vol. 7, Vol. 33). Page, 1996) and the like may be included.
  • hole transport layer is formed by the wet film forming method
  • holes are usually formed instead of the hole injection layer forming composition in the same manner as in the case where the hole injection layer is formed by the wet film forming method. It is formed using a composition for forming a transport layer.
  • the composition for forming the hole transport layer usually further contains a solvent.
  • a solvent used in the composition for forming a hole transport layer
  • the same solvent as the solvent used in the composition for forming a hole injection layer 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 can be formed by the wet film formation method in the same manner as the hole injection layer film formation method described above.
  • the hole transport is usually performed instead of the composition for forming the hole injection layer in the same manner as in the case of forming the hole injection layer by the vacuum vapor deposition method. It can be formed using a layer-forming composition.
  • the film formation conditions such as the degree of vacuum, the vapor deposition rate, and the temperature at the time of vapor deposition can be the same as those at the time of vacuum deposition of the hole injection layer.
  • 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, and the light emitting layer is formed between the hole injection layer and the cathode when there is a hole injection layer on the anode, and the anode. If there is a hole transport layer on top of it, it is formed between the hole transport layer and the cathode.
  • the film thickness of the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired. .. Therefore, the film thickness of the light emitting layer 5 is preferably 3 nm or more, more preferably 5 nm or more, and more preferably 200 nm or less, further preferably 100 nm or less.
  • the light emitting layer 5 contains at least a material having a light emitting property (light emitting material) and preferably a material having a charge transporting property (charge transporting material). Above all, the material mentioned as the light emitting layer material is preferable. In addition, the following materials are also preferably used.
  • 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.
  • Examples of the fluorescent light emitting material (blue fluorescent light emitting material) that gives blue light emission include naphthalene, perylene, pyrene, anthracene, coumarin, chrysene, p-bis (2-phenylethenyl) benzene, and derivatives thereof.
  • Examples of the fluorescent light emitting material (green fluorescent light emitting material) that gives green light emission include a quinacridone derivative, a coumarin derivative, an aluminum complex such as Al (C 9H 6 NO ) 3 , and the like.
  • Examples of the fluorescent light emitting material that gives yellow light emission include rubrene, a perimidone derivative, and the like.
  • Examples of the fluorescent light emitting material (red fluorescent light emitting material) that gives red light emission include a DCM (4- (dimethyraminostylyl) -4H-pyran) compound, a benzopyran derivative, and a rhodamine derivative. , Benzothioxanthene derivatives, azabenzothioxanthene and the like.
  • examples of the phosphorescent light emitting material include an organic metal complex containing a metal selected from Groups 7 to 11 of the long periodic table.
  • Preferred metals selected from Groups 7 to 11 of the Periodic Table include ruthenium, rhodium, palladium, silver, renium, osmium, iridium, platinum, gold and the like.
  • 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.
  • the preferred phosphorescent material include tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, and tris.
  • examples thereof include phenylpyridine complexes such as (2-phenylpyridine) osmium and tris (2-phenylpyridine) renium, and porphyrin complexes such as octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethyl palladium porphyrin, and octaphenyl palladium porphyrin.
  • 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 positive charge (hole) or negative charge (electron) transportability, and is not particularly limited as long as the effect of the present invention is not impaired, and known light emitting materials can be applied.
  • a compound or the like conventionally used for a light emitting layer of an organic electroluminescent device can be used, and a compound used as a host material for the light emitting layer is particularly preferable.
  • the polymer of the present invention can also be used as a host material for the light emitting layer.
  • 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, and anthracene.
  • electron transporting compounds such as system compounds, pyrene compounds, carbazole compounds, pyridine compounds, phenanthroline compounds, oxadiazole compounds, and silol compounds.
  • Aromatic amine compounds having a starburst structure such as substituted aromatic diamines (Japanese Patent Laid-Open No. 5-234681), 4,4', 4''-tris (1-naphthylphenylamino) triphenylamine (J. Lumin., Vol. 72-74, pp. 985, 1997), Aromatic amine compounds consisting of triphenylamine tetramers (Chem. Commun., P.
  • BPhen vasophenanthroline
  • BCP bathocuproine
  • the light emitting layer 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 or the hole transport layer to be the lower layer of the light emitting layer is formed by using the above composition for an organic electroluminescent device, laminating by the wet film forming method is easy, so that the wet film forming method is performed. It is preferable to adopt.
  • the hole injection layer is formed with the light emitting layer instead of the composition for forming the hole injection layer in the same manner as in the case of forming the hole injection layer by the wet film forming method.
  • the material is formed by using a composition for forming a light emitting layer prepared by mixing 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, and fats mentioned for the formation of the hole injection layer.
  • examples thereof include a group alcohol solvent, an alicyclic alcohol solvent, an aliphatic ketone solvent, an alicyclic ketone solvent and the like. 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, mesitylen, cyclohexylbenzene, tetralin, 3-isopropylbiphenyl, 1,2,3,
  • Halogenized aromatic hydrocarbon solvent such as chlorobenzene, dichlorobenzene, trichlorobenzene
  • aliphatic alcohol solvent such as butanol, hexanol
  • alicyclic alcohol solvent such as cyclohexanol, cyclooctanol
  • an alicyclic ketone solvent such as cyclohexanone, cyclooctanone, fencon and the like.
  • alkane-based solvents and aromatic hydrocarbon-based solvents are particularly preferable.
  • 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 on the cathode 9 side of the light emitting layer 5.
  • 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 (T 1 ). ) Is high.
  • Examples of the material of the hole blocking layer satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanorat) aluminum and the like.
  • Mixed ligand complex bis (2-methyl-8-quinolinolat) aluminum- ⁇ -oxo-bis- (2-methyl-8-quinolinolato) aluminum dinuclear metal complex and other metal complexes, distyrylbiphenyl derivative and the like.
  • Triazole derivatives such as styryl compounds (Japanese Patent Laid-Open No.
  • the hole blocking layer 6 There is no limitation 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. be.
  • 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 between electrodes to which an electric field is applied in the direction of the light emitting layer 5.
  • 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 capable compound.
  • 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), 10-hydroxybenzo [h].
  • 2-t-butyl-9,10-N, N'-dicyano examples thereof include anthraquinone diimine, n-type hydrided amorphous 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, a vacuum deposition method is used.
  • the electron injection layer 8 serves to efficiently inject 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 is preferably 0.1 nm or more and 5 nm or less.
  • an organic electron transport material represented by a nitrogen-containing heterocyclic compound such as basophenanthroline or a metal complex such as an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium and rubidium ().
  • an alkali metal such as sodium, potassium, cesium, lithium and rubidium ().
  • 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 of the wet film forming method are the same as those of the above-mentioned light emitting layer.
  • the cathode 9 serves to inject electrons into a layer on the light emitting layer 5 side (electron injection layer, light emitting layer, 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, for example, tin and magnesium.
  • a metal having a low work function for example, tin and magnesium.
  • Indium, calcium, aluminum, metals such as silver or alloys thereof are used.
  • Specific examples of the alloy 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 to the atmosphere on the cathode 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 is usually the same as the film thickness of the anode.
  • the organic electroluminescent device of the present invention may further have another layer as long as the effect of the present invention is not significantly impaired. That is, any of the above-mentioned other layers may be provided between the anode and the cathode.
  • the organic electroluminescent device of the present invention has a structure opposite to that described above, that is, a cathode, an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, a hole transport layer, and a hole injection layer on a substrate. It is also possible to have a structure in which the anodes are laminated in order.
  • the organic electroluminescent device of the present invention When the organic electroluminescent device of the present invention 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 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 invention are not particularly limited, and can be assembled according to a conventional method using the above-mentioned organic electroluminescent device.
  • the organic EL display device of the present invention can be obtained by a method as described in "Organic EL Display” (Ohmsha, published on August 20, 2004, by Shizushi Tokito, Chihaya Adachi, Hideyuki Murata). Can be formed.
  • the organic EL lighting (organic electroluminescent element lighting) of the present invention uses the above-mentioned organic electroluminescent element.
  • the type and structure of the organic EL lighting of the present invention are not particularly limited, and can be assembled according to a conventional method using the above-mentioned organic electroluminescent element.
  • Compound 7 was synthesized by the method described in International Publication No. 2019/177175.
  • Solution B1 was added to solution A1 in a nitrogen stream, and a heated reflux reaction was carried out for 1.0 hour. After confirming that compound 7 had disappeared, compound 10 (2.50 g, 5.08 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 2 hours. The reaction mixture was allowed to cool, 101 ml of toluene was added, and the mixture was added dropwise to an ethanol / water (550 ml / 100 ml) solution to obtain an end-capped crude polymer.
  • Example 1 a calibration curve was prepared using polystyrene having each molecular weight, and the molecular weight of the polymer was measured under the following conditions.
  • Device SHIMADZU GPC system
  • System Control CBM-20Alite
  • Oven CTO-20APump: LC-20ATDetector: SPD-20AVSolvent: THFColumns (manufacturer, model no .: TSKgel Supermultipore HZ-M (4.6mm ID x 150mm)) x4 ⁇ m
  • Temperature 40 °C Flow rate: 0.35mL / min
  • Injection volume and concentration of sample 10 ⁇ L, 1% conc.
  • Solution B2 was added to solution A2 in a nitrogen stream, and a heated reflux reaction was carried out for 1.0 hour. After confirming that compound 7 had disappeared, compound 6 (0.26 g, 0.49 mmol) was added. After 1 hour, compound 10 (0.804 g, 1.63 mmol) was added. After heating under reflux for 1 hour, bromobenzene (0.5 g, 3.18 mmol) was added, and the mixture was heated under reflux for 2 hours. The reaction solution was allowed to cool and dropped into an ethanol / water (270 ml / 50 ml) solution to obtain an end-capped crude polymer.
  • Examples 1 and 2 (polymers 1 and 2) have higher S 1 and T 1 energy levels than Comparative Examples 1 and 2 (polymers 7 and 11), respectively, in the organic electroluminescent element. It was shown that quenching due to energy transfer from the electroluminescence exciter to the polymer is unlikely to occur.
  • Solution B3 was added to solution A3 in a nitrogen stream, and a heated reflux reaction was carried out for 1.0 hour. After confirming that compound 6 had disappeared, compound 6 (1.34 g, 2.51 mmol) was added. After heating under reflux for 2 hours, bromobenzene (0.49 g, 3.12 mmol) was added, and the mixture was heated under reflux for 1 hour. The reaction solution was allowed to cool and dropped into an ethanol / water (270 ml / 50 ml) solution to obtain an end-capped crude polymer.
  • An organic electroluminescent device was manufactured by the following method.
  • 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 solution of a surfactant, 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.
  • composition for forming the hole injection layer 3.0% by mass of the hole transporting polymer compound having a repeating structure of the following formula (P-1) and 0.6% by mass of the electron accepting compound (HI-1). And was dissolved in ethyl benzoate to prepare a composition.
  • This solution was 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 to form a hole injection layer.
  • polymer 3 having the following structural formula was dissolved in 1,3,5-trimethylbenzene to prepare a 2.0% by mass solution.
  • This solution is 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 to form a uniform thin film having a thickness of 40 nm. It was formed and used as a hole transport layer.
  • the compound having the following structure (H-1) was 1.2% by mass
  • the compound having the following structure (H-2) was 1.2% by mass
  • (H-3) was dissolved in cyclohexylbenzene at a concentration of 0.8% by mass and the compound (D-1) having the following structure was dissolved in cyclohexylbenzene at a concentration of 1.0% by mass to prepare a composition for forming a light emitting layer.
  • This solution was 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 form a uniform thin film having a film thickness of 40 nm. It 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.
  • 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. Formed to form a cathode.
  • an organic electroluminescent device having a light emitting area portion having a size of 2 mm ⁇ 2 mm was obtained.
  • the hole transport layer is formed from a composition in which a polymer compound having the following structural formula (HT-2) is dissolved in 1,3,5-trimethylbenzene, and the organic electroluminescence is the same as in Example 3. A light emitting element was manufactured.
  • Solution B4 was added to solution A4 in a nitrogen stream, and a heated reflux reaction was carried out for 1.0 hour. After confirming that compound 11 had disappeared, compound 11 (2.15 g, 4.26 mmol) was added. After heating under reflux for 2 hours, bromobenzene (0.55 g, 3.50 mmol) was added, and the mixture was heated under reflux for 1 hour. The reaction mixture was allowed to cool, 88 g of toluene was added to dilute the reaction solution, and the mixture was added dropwise to an ethanol / water (300 ml / 50 ml) solution to obtain an end-capped crude polymer.
  • the organic electroluminescent device of the present invention can provide a high-performance device.
  • fluorene has no substituents at the 1-position, 3-position, 6-position, and 8-position, and the phenylene next to the fluorene is methylated to the carbon atom next to the carbon atom bonded to the fluorene.
  • the units 1 and 2 which are the structures of the present invention, have a higher S1 level than the unit 3 and are better. Do you get it.
  • the unit 2 had a higher T1 level than the unit 1 and the unit 3 and was good.
  • the main chain of the polymer of the present invention is preferably a monocycle, that is, phenylene next to the nitrogen atom of the amine. In this case, it is more preferable that the phenylene is unsubstituted.
  • the S1 level and the T1 level are higher when the monocycle is next to the nitrogen atom of the amine than when it is a condensed ring. Therefore, it is considered that the organic electroluminescent device in which the light emitting layer is formed in contact with the hole transport layer containing the polymer of the present invention has high luminous efficiency.
  • the T 1 and S 1 levels were calculated for the structures of units 5-9.
  • the unit structure (1) in the formula (A) is a structure included in the repeating structure represented by the formula (1).
  • the T 1 and S 1 level results of this calculation are shown in Table 4.
  • the divalent group of fluorene whose structure bonded to the nitrogen atom of the main chain is a fused ring is more than that of the divalent group. It was found that the divalent group and phenylene group of biphenyl having a monocyclic structure bonded to the nitrogen atom have higher T 1 and S 1 levels and are better.
  • R 1 and R 2 of fluorene which is a partial structure of the unit structure (1)
  • R 51 and R 52 are hydrogen
  • the structure in which R 1 and R 2 of fluorene, which is a partial structure of the unit structure (1) is hydrogen and the main chain phenylene is R 51 and R 52 . It was found that the S1 level was higher and better than the structure of unit 8 which is a methyl group.

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