WO2022230821A1 - 有機半導体素子の製造方法 - Google Patents

有機半導体素子の製造方法 Download PDF

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WO2022230821A1
WO2022230821A1 PCT/JP2022/018762 JP2022018762W WO2022230821A1 WO 2022230821 A1 WO2022230821 A1 WO 2022230821A1 JP 2022018762 W JP2022018762 W JP 2022018762W WO 2022230821 A1 WO2022230821 A1 WO 2022230821A1
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group
ring
solvent
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composition
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French (fr)
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誠 保科
優記 大嶋
延軍 李
君偉 沈
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三菱ケミカル株式会社
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Priority to CN202280031351.1A priority Critical patent/CN117296451A/zh
Priority to KR1020237036806A priority patent/KR20240004364A/ko
Priority to JP2023517515A priority patent/JPWO2022230821A1/ja
Publication of WO2022230821A1 publication Critical patent/WO2022230821A1/ja

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/12—Deposition of organic active material using liquid deposition, e.g. spin coating
    • 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
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G61/12—Macromolecular compounds containing atoms other than carbon in the main chain of the macromolecule
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/10—Apparatus or processes specially adapted to the manufacture of electroluminescent light sources
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/40—Thermal treatment, e.g. annealing in the presence of a solvent vapour
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/30—Monomer units or repeat units incorporating structural elements in the main chain
    • C08G2261/31—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain
    • C08G2261/316—Monomer units or repeat units incorporating structural elements in the main chain incorporating aromatic structural elements in the main chain bridged by heteroatoms, e.g. N, P, Si or B
    • C08G2261/3162—Arylamines
    • 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
    • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C08G2261/50—Physical properties
    • C08G2261/51—Charge transport
    • C08G2261/512—Hole transport

Definitions

  • the present invention relates to a method for manufacturing an organic semiconductor element capable of suitably forming a functional film, which is an organic film made of a functional material.
  • Organic semiconductor elements include organic electroluminescent elements and organic transistors.
  • a method for manufacturing an organic electroluminescence element a method of forming a film of an organic material by a vacuum deposition method and laminating the films is generally used.
  • a manufacturing method with more efficient use of materials there has been active research into a manufacturing method using a wet film-forming method in which organic materials in solution are deposited by an ink-jet method or the like and laminated.
  • the most stable method is to give the composition a cross-linking group or a polymerizable group, and then treat it after coating to form a bond to make it insoluble.
  • Patent Document 1 as an insolubilization method using a semiconductor material that does not contain a cross-linking group or a polymerizable group, it is partially insoluble by one or more of heat, vacuum, and drying in the open air, and the dissolved residue is washed away.
  • Patent Document 2 discloses a method of partially insolubilizing a polymer layered as a semiconductor material by heating it at a temperature higher than its glass transition temperature.
  • Patent Literature 3 discloses that the charge transport layer can be made insoluble by heating, electromagnetic wave irradiation, particularly UV irradiation, even in the absence of a crosslinkable group.
  • Patent Document 4 discloses a method in which thermally dissociable and soluble groups are dissociated and insolubilized by chemical change due to heat.
  • Patent Literature 2 is also based on the assumption that the residue after washing is used, and is similar in that the laminated material itself is not completely insolubilized.
  • Patent Document 3 also assumes the use of the residue after washing, but states that partial dissolution is more suitable for interfacial mixing with the upper layer. However, it impairs the use of optical interference, and in blue and phosphorescent green elements with shorter wavelengths, it may lead to deterioration in efficiency and lifetime.
  • the film thickness of the remainder is said to depend on the molecular weight, and in order to obtain a charge transport layer of 20 nm, it is necessary to use a charge transport material with a weight molecular weight of 300,000.
  • the charge transport layer preferably has a thickness of 50 to 150 nm. Forming a charge transport layer is difficult.
  • the method of insolubilizing the thermally dissociable soluble group by chemical change, as disclosed in Patent Document 4, may impede the efficiency of the device in terms of contamination of the upper layer with dissociated substances.
  • the functional material that constitutes the lower layer is a low-soluble material with a molecular weight of several hundred thousand, insolubilization is facilitated.
  • the use of a functional material with a large molecular weight increases the viscosity of the coating composition and adversely affects the coating properties, which in turn limits the thick film construction and high definition that require high-concentration ink.
  • Insolubilization treatment of the lower layer is required to be carried out in a short time and at a low temperature, and since the coating is applied to a panel having a larger area, it is required to withstand solvent infiltration for a long time required for coating.
  • the composition serving as the upper layer is as follows.
  • the first composition comprises a first functional material;
  • the first functional material comprises an arylamine polymer having a weight average molecular weight of 15,000 to 50,000 and having neither a crosslinkable group, a polymerizable group, nor a detachable solubilizing group,
  • the second composition contains a solvent and has a viscosity of 15 mPa s or less at 23 ° C., A method for producing an organic semiconductor device, wherein the solvent contains at least one first solvent component having a viscosity of 3 mPa ⁇ s or more at 23°C.
  • the solvent further comprises a second solvent component having a viscosity of less than 3 mPa s at 23°C,
  • the first composition comprises a first functional material;
  • the first functional material comprises an arylamine polymer having neither a cross-linking group, a polymerizing group, nor a leaving solubilizing group;
  • the second composition contains a solvent and has a viscosity of 15 mPa s or less at 23 ° C.,
  • the solvent contains at least one first solvent component having a flow activation energy of 17 kJ/mol or more, A method for producing an organic semiconductor device, wherein the solvent further contains a second solvent component having a viscosity of less than 3 mPa ⁇ s at 23°C.
  • Ar 51 is selected from at least one of an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group, wherein one group or a plurality of groups are linked
  • Each of the substituents is a group other than a cross-linking group, a polymerizing group, or a detachable solubilizing group.
  • Ar 52 is one group selected from at least one of an optionally substituted divalent aromatic hydrocarbon group and an optionally substituted divalent aromatic heterocyclic group, or Represents a divalent group in which a plurality of groups are linked, the linkage is made directly or via a linking group, and the substituents are all groups other than a cross-linking group, a polymerizing group, or a detachable solubilizing group. .
  • Ar 51 and Ar 52 may combine directly or via a linking group to form a ring. However, Ar 51 and Ar 52 have neither a cross-linking group, a polymerizing group nor a leaving solubilizing group. )
  • the arylamine polymer includes a structure in which a plurality of benzene ring structures are linked at the para position in the main chain, and at least one of the plurality of benzene ring structures is positioned next to the carbon atom that bonds to the adjacent benzene ring structure.
  • the method for producing an organic semiconductor device according to [6] or [7], wherein the repeating unit represented by the formula (50) is represented by the following formula (54).
  • a method for producing an organic semiconductor device according to [12] the second composition comprises a second functional material different from the first functional material; The method for producing an organic semiconductor device according to any one of [1] to [11], wherein the second functional material contains a low molecular weight aromatic compound having a molecular weight of less than 2000.
  • the heating in the step of providing the first functional film is performed at a temperature lower than the glass transition point of the arylamine polymer. .
  • a cross-linking group, a polymerizable group, and a detachable solubilizing group can be imparted to the functional film to make it insoluble by treatment after coating.
  • Another film can be formed on the functional film without using an organic substance.
  • the organic substance contained in the functional film can be widely selected, and the composition for forming the upper layer can be widely selected. It is possible to provide a method for manufacturing an organic electroluminescence device that enables lamination of functional materials with excellent luminous life and coating properties.
  • FIG. 1 is a schematic cross-sectional view showing a structural example of a general organic electroluminescence device.
  • the first composition comprises a first functional material
  • the first functional material has both a cross-linking group, a polymerizing group and a detachable solubilizing group.
  • the second composition contains a solvent, and has a viscosity of 15 mPa s or less at 23 ° C.
  • the solvent has a viscosity of 15 mPa s or less at 23 ° C.
  • a method for producing an organic semiconductor device comprising at least one first solvent component having a viscosity of 3 mPa ⁇ s or more.
  • the second composition contains a solvent and has a viscosity at 23 ° C. of 15 mPa s or less, and the solvent has a flow activation energy of 17 kJ / mol or more.
  • a method for producing an organic semiconductor device comprising at least one solvent component, the solvent further comprising a second solvent component having a viscosity of less than 3 mPa ⁇ s at 23°C.
  • the second composition contains a solvent and has a viscosity of 15 mPa s or less at 23 ° C., and the solvent has a viscosity of 3 mPa s or more at 23 ° C.
  • At least one solvent component is included, the solvent further includes a second solvent component having a viscosity of less than 3 mPa s at 23 ° C., and the flow activation energy of the first solvent component is 17 kJ / mol or more.
  • a method for producing an organic semiconductor device is included, the solvent further includes a second solvent component having a viscosity of less than 3 mPa s at 23 ° C., and the flow activation energy of the first solvent component is 17 kJ / mol or more.
  • the element can be produced. It is possible to realize an organic semiconductor device having a functional film with excellent luminous efficiency and luminous life by reducing adverse effects on the life and luminous efficiency when used as an organic electroluminescence device.
  • the arylamine polymer has neither a cross-linking group, a polymerizing group, nor a detachable solubilizing group, a polymer with a small molecular weight that can suppress the increase in viscosity due to concentration is used as a functional material, and is applied and heated. A first functional membrane can be obtained.
  • the second composition constituting the second functional film has a viscosity of 15 mPa ⁇ s or less at 23°C and a first solvent component satisfying the viscosity of 3 mPa ⁇ s or more at 23°C, or , contains a first solvent component that satisfies a flow activation energy of 17 kJ / mol or more and a second solvent component that satisfies a viscosity of less than 3 mPa s at 23 ° C., so that the first functional film as a lower layer is crosslinked Even if it does not have a group, a polymerizable group, or a detachable solubilizing group, the dissolution of the first functional film and the dissolution of the dissolved component of the second It is possible to prevent performance deterioration due to contamination of the functional film.
  • the first functional material that does not contain a structure that deteriorates the characteristics is used for the first functional film, and the same Prevents elution of the first functional material and mixing into the second functional film when the second composition is applied to the film to form the second functional film, thereby improving the characteristics can do.
  • the structures that degrade the properties are cross-linking groups, polymerizing groups, and detachable solubilizing groups.
  • the organic semiconductor device is an organic electroluminescence device, such properties mean luminescence properties.
  • the long-term insoluble durability property of the first functional material is realized, so that the coating on a large-sized substrate is facilitated.
  • the first functional film is a film obtained by applying and heating the first composition, and the second functional film is formed on this film.
  • the first functional film in the case of the organic electroluminescence device shown in FIG. 1, for example, the hole injection layer 3 formed on the anode 2 or the hole injection layer 3 A hole transport layer 4 may be mentioned.
  • the second functional film is a functional film obtained by applying the second composition on the surface of the first functional film.
  • the hole transport layer 4 formed on the hole injection layer 3 or the light emitting layer 5 formed on the hole transport layer 4 can be cited. be done.
  • the first composition comprises a first functional material, the first functional material containing an arylamine polymer without cross-linking groups, polymerizing groups and leaving solubilizing groups. It also usually contains a solvent (organic solvent).
  • the first composition may contain one type of the above arylamine polymer as the first functional material, or may contain two or more types in any combination and in any ratio. .
  • the first composition may contain functional materials other than the first functional material, such as electron-accepting compounds and charge-transporting materials described later.
  • the first functional material is an arylamine polymer having neither a crosslinkable group, a polymerizable group, nor a detachable solubilizing group, and is, for example, a polymer having a repeating unit represented by the following formula (50). .
  • Ar 51 is selected from at least one of an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group, wherein one group or a plurality of groups are linked
  • Each of the substituents is a group other than a cross-linking group, a polymerizing group, or a detachable solubilizing group.
  • Ar 52 is one group selected from at least one of an optionally substituted divalent aromatic hydrocarbon group and an optionally substituted divalent aromatic heterocyclic group, or Represents a divalent group in which a plurality of groups are linked, the linkage is made directly or via a linking group, and the substituents are all groups other than a cross-linking group, a polymerizing group, or a detachable solubilizing group. .
  • Ar 51 and Ar 52 may combine directly or via a linking group to form a ring. However, Ar 51 and Ar 52 have neither a cross-linking group, a polymerizing group nor a leaving solubilizing group. )
  • crosslinking group The arylamine polymer used for the first functional material has neither a crosslinkable group, a polymerizable group, nor a removable solubilizing group.
  • the cross-linking group means a group that reacts with other cross-linking groups located in the vicinity of the cross-linking group by irradiation with heat and/or active energy rays to form a new chemical bond.
  • the reactive group may be the same group as the bridging group or a different group.
  • cross-linking groups include, but are not limited to, alkenyl group-containing groups, conjugated diene structure-containing groups, alkynyl group-containing groups, oxirane structure-containing groups, oxetane structure-containing groups, aziridine structure-containing groups, azide groups, anhydrous Examples thereof include a group containing a maleic acid structure, a group containing an alkenyl group bonded to an aromatic ring, and a cyclobutene ring condensed to an aromatic ring.
  • Specific examples of the cross-linking group include groups selected from the following cross-linking group T.
  • R 3 represents an alkyl group having 1 to 4 carbon atoms. From the viewpoint of easy formation of an oxetane ring, R 3 is particularly preferably a methyl group or an ethyl group.
  • R XL represents a methylene group, an oxygen atom or a sulfur atom, and n XL represents an integer of 0-5. When multiple R XL are present, they may be the same or different, and when multiple n XL are present, they may be the same or different.
  • * and *1 represent binding positions. These cross-linking groups may have substituents.
  • the polymerizable group not possessed by the arylamine polymer used in the first functional material refers to a functional group that undergoes a polymerization reaction in the usual reaction of polymerizing a monomer to obtain a polymer.
  • the detachable solubilizing group that the arylamine polymer used for the first functional material does not have is a group that exhibits solubility in a solvent, and a specific It represents a group that thermally dissociates at a temperature or higher (for example, 70° C. or higher). Dissociation of such a leaving soluble group reduces the solubility of the polymer in a solvent.
  • the detachable solubilizing group includes, for example, the “thermally dissociable solubilizing group” described in Japanese Patent Application Laid-Open No. 2010-059417.
  • Ar 52 is an optionally substituted divalent aromatic hydrocarbon group and an optionally substituted divalent aromatic represents a group in which one or more groups selected from at least one heterocyclic group are linked. When multiple selected groups are linked, they may be linked directly or via a linking group.
  • the substituents that the aromatic hydrocarbon group and the aromatic heterocyclic group may have are substituents other than a bridging group, a polymerizing group, or a detachable solubilizing group, and the substituent group Z described later. Groups similar to are preferred.
  • the cross-linking group, the polymerizable group and the detachable solubilizing group may be collectively referred to as "cross-linking group, etc.”.
  • the aromatic hydrocarbon group preferably has 6 or more and 60 or less carbon atoms, and specifically includes a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, and chrysene ring. , triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like.
  • a divalent group with 2 to 10 linked groups can be mentioned, and a divalent group with 2 to 5 linked groups is preferred.
  • a divalent group of a benzene ring means "a benzene ring having a divalent free atom valence", that is, a phenylene group.
  • the aromatic heterocyclic group preferably has 3 or more and 60 or less carbon atoms, and specifically includes a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and an oxadiazole ring.
  • indole ring carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine 5- to 6-membered rings such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring or a divalent group of 2 to 4 condensed rings, or a group in which
  • the divalent groups in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group are the same group.
  • the group having a plurality of linked groups is preferably a divalent group in which 2 to 10 groups are linked, more preferably a divalent group in which 2 to 5 groups are linked.
  • Ar 51 is at least one of an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group represents a group in which one group or a plurality of groups are linked together, selected from
  • the substituents that the aromatic hydrocarbon group and the aromatic heterocyclic group may have are substituents other than a bridging group, a polymerizing group, or a detachable solubilizing group, and the substituent group Z described later. Groups similar to are preferred.
  • the aromatic hydrocarbon group preferably has 6 or more and 60 or less carbon atoms, and specifically includes a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, and chrysene ring. , a triphenylene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring and the like, a monovalent 6-membered ring or a 2 to 5 condensed ring monovalent group, or a group in which a plurality of these are linked.
  • a monovalent group in which 2 to 10 groups are linked is exemplified, and a monovalent group in which 2 to 5 groups are linked is preferable.
  • a monovalent group of a benzene ring means "a benzene ring having a monovalent free atom valence", that is, a phenyl group.
  • the aromatic heterocyclic group preferably has 3 or more and 60 or less carbon atoms, and specifically includes a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and an oxadiazole ring.
  • indole ring carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine 5- to 6-membered rings such as ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring or a monovalent group of 2 to 4 condensed rings, or a group in which
  • the monovalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked may be a group in which a plurality of the same groups are linked. , may be a group in which a plurality of different groups are linked.
  • the group having a plurality of linked groups is preferably a monovalent group in which 2 to 10 groups are linked, more preferably a monovalent group in which 2 to 5 groups are linked.
  • Ar 51 is preferably an aromatic hydrocarbon group which may have a substituent other than a cross-linking group, etc., from the viewpoint of excellent charge transportability and durability.
  • Benzene ring or fluorene ring monovalent group that may be A fluorenyl group which may have a substituent is more preferred, and a 2-fluorenyl group which may have a substituent other than a cross-linking group is particularly preferred.
  • Substituents other than the cross-linking group that the aromatic hydrocarbon group and aromatic heterocyclic group of Ar 51 may have are not particularly limited as long as they do not significantly reduce the properties of the present polymer.
  • the substituent is preferably a group selected from the group Z of substituents described below, more preferably an alkyl group, an alkoxy group, an aromatic hydrocarbon group, or an aromatic heterocyclic group, and still more preferably an alkyl group.
  • Ar 51 is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms, particularly a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms. preferable. Furthermore, a 9-alkyl-2-fluorenyl group in which the 9-position of the 2-fluorenyl group is substituted with an alkyl group is preferred, and a 9,9′-dialkyl-2-fluorenyl group in which the 9-position is substituted with an alkyl group is particularly preferred.
  • At least one of the 9- and 9'-positions is a fluorenyl group substituted with an alkyl group, which tends to improve the solubility in solvents and the durability of the fluorene ring. Furthermore, since both the 9- and 9'-positions are alkyl-substituted fluorenyl groups, the solubility in solvents and the durability of the fluorene ring tend to be further improved.
  • Ar 51 is also preferably a spirobifluorenyl group from the viewpoint of solubility in a coating solvent.
  • Ar 51 may bond with Ar 52 directly or via a linking group to form a ring.
  • the content of the repeating unit represented by formula (50) is not particularly limited, but the repeating unit represented by formula (50) is usually 10 mol in the polymer. % or more, preferably 30 mol % or more, more preferably 40 mol % or more, even more preferably 50 mol % or more.
  • the repeating unit may be composed only of repeating units represented by formula (50), that is, 100 mol %, but the organic electroluminescent device and For the purpose of balancing various performances in the case of formula (50), it may have a repeating unit other than the formula (50).
  • the content of the repeating unit represented by formula (50) in the polymer is usually 99 mol % or less, preferably 95 mol % or less.
  • terminal group refers to the terminal structure of a polymer formed by an endcapping agent used to terminate polymerization of the polymer.
  • the terminal group of the polymer containing the repeating unit represented by formula (50) is preferably a hydrocarbon group.
  • the hydrocarbon group is preferably a hydrocarbon group having 1 to 60 carbon atoms, more preferably a hydrocarbon group having 1 to 40 carbon atoms, and a hydrocarbon group having 1 to 30 carbon atoms. is more preferred.
  • hydrocarbon groups include the following. carbon, such as 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
  • a linear, branched or cyclic alkyl group whose number is usually 1 or more, preferably 4 or more, usually 24 or less, preferably 12 or less
  • An aromatic hydrocarbon group having usually 6 or more and 36 or less carbon atoms, preferably 24 or less, such as a
  • hydrocarbon groups may further have a substituent, and the substituent that may further have is preferably an alkyl group or an aromatic hydrocarbon group. When there are a plurality of these substituents which may be additionally contained, they may be combined with each other to form a ring.
  • the terminal group is preferably an alkyl group or an aromatic hydrocarbon group, more preferably an aromatic hydrocarbon group.
  • Substituent group Z includes an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, a heteroaryloxy group, an alkoxycarbonyl group, a dialkylamino group, a diarylamino group, an arylalkylamino group, an acyl group, a halogen atom, A group consisting of haloalkyl groups, alkylthio groups, arylthio groups, silyl groups, siloxy groups, cyano groups, aromatic hydrocarbon groups and aromatic heterocyclic groups. These substituents may contain any structure of linear, branched and cyclic.
  • substituent group Z include the following structures. linear, branched, or cyclic alkyl having 1 or more carbon atoms, preferably 4 or more carbon atoms, 24 or less, preferably 12 or less, more preferably 8 or less, and more preferably 6 or less Base. Specific examples include 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 and dodecyl group. etc.
  • Specific examples include a dimethylamino group and a diethylamino group.
  • Specific examples include a diphenylamino group, a ditolylamino group, an N-carbazolyl group and the like.
  • a specific example is a phenylmethylamino group.
  • Specific examples include an acetyl group and a benzoyl group.
  • halogen atoms such as fluorine atoms and chlorine atoms
  • Specific examples include a trifluoromethyl group and the like.
  • Specific examples include a methylthio group, an ethylthio group, and the like.
  • an arylthio group having 4 or more, preferably 5 or more carbon atoms and 36 or less, preferably 24 or less;
  • Specific examples include a phenylthio group, a naphthylthio group, a pyridylthio group, and the like.
  • an aromatic heterocyclic group having 3 or more, preferably 4 or more, and 36 or less, preferably 24 or less carbon atoms; Specific examples include a thienyl group and a pyridyl group.
  • the above substituents may have any structure of linear, branched or cyclic.
  • substituent groups Z described above alkyl groups, alkoxy groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups are preferred. From the viewpoint of charge transportability, it is more preferable not to have a substituent. Further, each substituent in the substituent group Z may further have a substituent. Examples of these substituents include the same substituents as in the substituent group Z described above. Substituents which may further be present are preferably not present, or alkyl groups having 8 or less carbon atoms, alkoxy groups having 8 or less carbon atoms, or phenyl groups, more preferably alkyl groups having 6 or less carbon atoms. group, an alkoxy group having 6 or less carbon atoms, or a phenyl group. From the viewpoint of charge transport properties, it is more preferable not to have additional substituents.
  • Ar 51 is a group represented by the following formula (51), the following formula (52), or the following formula (53). Preferably.
  • Ar 53 and Ar 54 are each independently selected from at least one of an optionally substituted divalent aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group It represents a divalent group in which one group or a plurality of groups are linked, and the linkage is made directly or via a linking group.
  • Ar 55 is 1 selected from at least one of an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group or 1 in which a plurality of groups are linked represents a valence group, the link being made directly or via a linking group.
  • Ar 56 represents a hydrogen atom or a substituent.
  • each aromatic hydrocarbon group and each aromatic heterocyclic group may have, and Ar 56 in the case of being a substituent, are substituents other than a bridging group and the like.
  • Ar 53 and Ar 54 are each independently a divalent aromatic hydrocarbon group optionally having a substituent and optionally having a substituent It represents a divalent group in which one group or a plurality of groups selected from at least one of divalent aromatic heterocyclic groups are linked, and the linkage is made directly or via a linking group.
  • it is an optionally substituted divalent aromatic hydrocarbon group or a group in which a plurality of optionally substituted divalent aromatic hydrocarbon groups are linked.
  • the substituents which the aromatic hydrocarbon group and the aromatic heterocyclic group may have are substituents other than a bridging group and the like, and the same groups as in the substituent group Z are preferable.
  • the aromatic hydrocarbon group and aromatic heterocyclic group for Ar 53 and Ar 54 the same aromatic hydrocarbon group and aromatic heterocyclic group as for Ar 52 can be used.
  • the valent group may be a group in which a plurality of the same groups are linked, or may be a group in which a plurality of different groups are linked.
  • a divalent group in which 2 to 10 groups are linked is preferable, and a divalent group in which 2 to 5 groups are linked is preferable.
  • Ar 53 is preferably one divalent aromatic hydrocarbon group optionally having substituent(s) or a group in which 2 to 6 are linked, and is preferably a divalent aromatic hydrocarbon group optionally having substituent(s).
  • a group having one aromatic hydrocarbon group or a group having 2 to 4 linked aromatic hydrocarbon groups is more preferable. More preferred is biphenylene in which two optionally substituted phenylene rings are linked.
  • the groups are preferably groups in which the multiple linked divalent aromatic hydrocarbon groups are bonded so as not to be conjugated. Specifically, it preferably contains a 1,3-phenylene group or a group having a substituent and having a twisted structure due to the steric effect of the substituent.
  • the substituent that Ar 53 may have is a substituent other than a cross-linking group and the like, and the same groups as those in the substituent group Z are preferable.
  • Ar 53 has no substituents.
  • Ar 54 has one divalent aromatic hydrocarbon group or divalent aromatic hydrocarbon groups which may be the same or different from the viewpoint of excellent charge transportability and excellent durability. is preferably a group in which a plurality of is linked, and the divalent aromatic hydrocarbon group may have a substituent. When a plurality of divalent aromatic hydrocarbon groups are linked, the number of divalent aromatic hydrocarbon groups is preferably 2 or more and 10 or less, more preferably 6 or less, and particularly preferably 3 or less from the viewpoint of film stability.
  • Preferred aromatic hydrocarbon structures are benzene ring, naphthalene ring, anthracene ring and fluorene ring, and more preferred are benzene ring and fluorene ring.
  • a group in which a plurality of groups are linked a group in which 2 to 4 phenylene rings which may have a substituent are linked, or a phenylene ring which may have a substituent and a substituent may be used.
  • a group in which fluorene rings are linked is preferred. It is also preferable that the number of phenylene rings which may have a substituent is one.
  • Biphenylene in which two optionally substituted phenylene rings are linked is particularly preferable from the viewpoint of expanding LUMO.
  • any one of the substituent group Z or a combination thereof can be used.
  • the above substituent is preferably other than N-carbazolyl group, indolocarbazolyl group and indenocarbazolyl group, and more preferable substituent groups are phenyl group, naphthyl group and fluorenyl group. Moreover, it is also preferable not to have a substituent.
  • Ar 55 is selected from at least one of an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group or a plurality of groups linked together represents a monovalent group, and the link is made directly or via a linking group.
  • it is an optionally substituted monovalent aromatic hydrocarbon group or a group in which a plurality of optionally substituted monovalent aromatic hydrocarbon groups are linked.
  • the substituents which the aromatic hydrocarbon group and the aromatic heterocyclic group may have are substituents other than a bridging group and the like, and the same groups as in the substituent group Z are preferable.
  • a monovalent group in which 2 to 10 groups are linked is preferable, and 2 to 5 groups are linked. More preferably, it is a linked monovalent group.
  • the aromatic hydrocarbon group and aromatic heterocyclic group the same aromatic hydrocarbon group and aromatic heterocyclic group as those for Ar 51 can be used.
  • Ar 55 preferably has a structure represented by any of schemes 2 below. Furthermore, from the viewpoint of distributing the LUMO of the molecule, a-1 to a-4, b-1 to b-9, c-1 to c-4, d-1 to d-16, and e shown in Scheme 2 below Structures selected from -1 to e-4 are preferred. Furthermore, from the viewpoint of promoting the spread of the LUMO of the molecule by having an electron-withdrawing group, a-1 to a-4, b-1 to b-9, d-1 to d-12, and e-1 Structures selected from ⁇ e-4 are preferred.
  • the triplet level is high, a-1 to a-4, d-1 to Structures selected from d-12, and e-1 through e-4 are preferred. Further, from the viewpoint of easy synthesis and excellent stability, d-1 and d-10 are more preferable, and the benzene ring structure of d-1 is particularly preferable.
  • R 31 and R 32 in Scheme 2 are each independently an optionally substituted linear, branched or cyclic alkyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited, 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 more preferably a methyl group or an ethyl group. .
  • R 31 and R 32 may be the same or different, and when a plurality of R 31 and R 32 are present, they may be the same or different, but All R 31 and R 32 are preferably the same group because they can be distributed around the nitrogen atom and are easy to synthesize.
  • any one of the substituent group Z or a combination thereof can be used. From the viewpoint of durability and charge transport properties, it is preferably selected from the same substituents as the substituents that Ar 54 may have.
  • Ar 56 represents a hydrogen atom or a substituent.
  • Ar 56 is a substituent, it is not particularly limited, but is preferably an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group.
  • Preferred structures are monovalent structures similar to the aromatic hydrocarbon structures and aromatic heterocyclic structures exemplified for Ar 53 and Ar 54 .
  • Ar 56 is a substituent, it is not a bridging group or the like.
  • Ar 56 is a substituent, it is preferably bonded to the 3-position of carbazole from the viewpoint of improving durability.
  • an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group is preferable. It is more preferably an aromatic hydrocarbon group which may have a group.
  • Ar 56 is preferably a hydrogen atom from the viewpoint of ease of synthesis and charge transport properties.
  • Ar 56 is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group
  • substituents listed in the above substituent group Z groups, preferred substituents are the same, and substituents which these substituents may further have are also the same.
  • Ar 51 in the repeating unit represented by formula (50) above is also preferably a group represented by formula (52) below.
  • formula (52) a group represented by formula (52) below.
  • LUMO is distributed in the aromatic hydrocarbon group or aromatic heterocyclic group between the nitrogen atoms of each other, and the main chain amine in formula (50) This is thought to be due to the fact that the influence on the amine is suppressed and the durability of the main chain amine to electrons and excitons is improved.
  • Ar 61 and Ar 62 are each independently from at least one of an optionally substituted divalent aromatic hydrocarbon group and an optionally substituted divalent aromatic heterocyclic group It represents a divalent group to which one or more selected groups are linked, and the linkage is made directly or via a linking group.
  • Ar 63 to Ar 65 are each independently a hydrogen atom or a substituent. * represents the bonding position to the nitrogen atom in formula (50).
  • each aromatic hydrocarbon group and each aromatic heterocyclic group may have, and Ar 63 to Ar 65 when they are substituents, are substituents other than bridging groups and the like.
  • Ar 63 to Ar 65 are each independently the same as Ar 56 in formula (51).
  • Ar 62 is one group selected from at least one of an optionally substituted divalent aromatic hydrocarbon group and an optionally substituted divalent aromatic heterocyclic group, or It represents a divalent group in which a plurality of groups are linked, and the linkage is made directly or via a linking group. Preferably, it is an optionally substituted divalent aromatic hydrocarbon group or a group in which a plurality of optionally substituted divalent aromatic hydrocarbon groups are linked.
  • a specific structure of Ar 62 is the same as Ar 54 in formula (51).
  • a specific preferred group for Ar 62 is a divalent group of a benzene ring, a naphthalene ring, an anthracene ring, or a fluorene ring, or a group in which a plurality of these are linked, more preferably a divalent group of a benzene ring or a fluorene ring.
  • the phenylene group preferably has no substituents other than the linking position so that Ar 62 is not twisted due to the steric effect of the substituents.
  • the fluorenylene group preferably has substituents at the 9 and 9′ positions from the viewpoint of improving solubility and durability of the fluorene structure.
  • Ar61 is the same group as Ar 53 in formula (52), and the preferred structure is also the same.
  • Ar 51 (Preferred Ar 51 : Formula (53)) At least one Ar 51 in the repeating unit represented by formula (50) above is also preferably a group represented by formula (53) below.
  • Ar 71 represents a divalent aromatic hydrocarbon group which may have a substituent
  • Ar 72 and Ar 73 are each independently one group selected from at least one of an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group Alternatively, it represents a divalent group in which a plurality of groups are linked, and the linkage is made directly or via a linking group.
  • Ring HA is an aromatic heterocyclic ring containing a nitrogen atom
  • X 2 and Y 2 each independently represent a C atom or an N atom, and when X 2 or Y 2 is a C atom, it has a substituent may be )
  • Ar 71 is the same group as Ar 53 in formula (51).
  • Ar 71 is one optionally substituted divalent aromatic hydrocarbon group or a group in which 2 to 10 optionally substituted divalent aromatic hydrocarbon groups are linked. is preferable, and a group in which one divalent aromatic hydrocarbon group which may have a substituent or 2 to 8 divalent aromatic hydrocarbon groups which may have a substituent are linked is further Among them, a group in which 2 to 6 optionally substituted divalent aromatic hydrocarbon groups are linked is more preferable.
  • Ar 71 is particularly preferably a group in which 2 to 6 optionally substituted benzene rings are linked, and a quaterphenylene group in which 4 optionally substituted benzene rings are linked. Most preferred.
  • Ar 71 preferably contains at least one, more preferably two or more, benzene rings linked at the 1 and 3 positions, which are non-conjugated sites.
  • Ar 71 is a group in which a plurality of optionally substituted divalent aromatic hydrocarbon groups are linked, from the viewpoint of charge transport property or durability, it is preferable that all of them are directly linked and linked. . Therefore, as Ar 71 , a preferred structure connecting N of the main chain of the polymer and ring HA in formula (53) is as shown in the following structural formula.
  • the two "-*" represent a site where one is bonded to the N of the main chain of the polymer and the other is bonded to the ring HA of the formula (53). Either of the two "-*" may be bonded to the N of the main chain of the polymer or may be bonded to the ring HA.
  • any one of the substituent group Z or a combination thereof can be used.
  • a preferred range of the substituent that Ar 71 may have is the same group as Ar 53 in formula (51) above, and a more preferred structure is the same as the preferred group for Ar 53 .
  • X2 and Y2 each independently represent a C (carbon) atom or an N (nitrogen) atom.
  • X 2 or Y 2 is a C atom, it may have a substituent.
  • Both X 2 and Y 2 are preferably N atoms from the viewpoint of facilitating localization of LUMO around ring HA.
  • any one of the above-mentioned substituent group Z or a combination thereof can be used as the substituent which may be possessed. From the viewpoint of charge transportability, it is more preferable not to have a substituent.
  • Ar 72 and Ar73 are each independently selected from at least one of an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group. represents a divalent group in which a group or a plurality of groups are linked, and the linkage is made directly or via a linking group;
  • Ar 72 and Ar 73 are each independently represented by a-1 to a-4, b-1 to b- 9, c-1 to c-4, d-1 to d-16, and e-1 to e-4. Furthermore, from the viewpoint of promoting the spread of the LUMO of the molecule by having an electron-withdrawing group, a-1 to a-4, b-1 to b-9, c-1 to c-5, d-1 to Structures selected from d-12, and e-1 through e-4 are preferred.
  • a-1 to a-4, d-1 to Structures selected from d-12, and e-1 through e-4 are preferred.
  • a structure selected from d-1 to d-12 and e-1 to e-4 is more preferable.
  • Ar 72 and Ar 73 have the same structure, and d-1 or d-10 is preferable, and d-1 is particularly preferably a benzene ring structure.
  • Ar 72 and Ar 73 may have, any one of those shown as the above (substituent group Z) or a combination thereof can be used. From the viewpoint of durability and charge-transporting properties, it is a substituent other than the cross-linking group and the like, and is preferably the same group as the substituent group Z described above.
  • the arylamine polymer having a repeating unit represented by the above formula (50) includes a structure in which a plurality of benzene ring structures are linked to the main chain at the para position, and at least one of the plurality of benzene ring structures is adjacent to each other. At least one of the two carbon atoms adjacent to the carbon atom bonded to the benzene ring structure preferably has a substituent. Either one or both of the two adjacent benzene ring structures may be part of a condensed ring. This is because the glass transition temperature of the arylamine polymer is lowered, making it easier for the layer to harden.
  • the repeating unit represented by the formula (50) is a repeating unit represented by the following formula (54), a repeating unit represented by the following formula (55), a repeating unit represented by the following formula (56), or a repeating unit represented by the following formula (56).
  • a repeating unit represented by the formula (57) is preferable, and a repeating unit represented by the following formula (54) is more preferable.
  • Ar 51 is the same as Ar 51 in formula (50) above, X is -C(R 7 )(R 8 )-, -N(R 9 )- or -C(R 11 )(R 12 )-C(R 13 )(R 14 )-; R 1 and R 2 are each independently an alkyl group optionally having a substituent other than a cross-linking group, R 7 to R 9 and R 11 to R 14 are each independently a hydrogen atom, an alkyl group which may have a substituent other than a bridging group, or a substituent other than a bridging group.
  • a and b are each independently an integer of 0 to 4; c is an integer from 1 to 3, d is an integer from 0 to 4,
  • R 1s When there are multiple R 1s , the multiple R 1s may be the same or different, When there are multiple R 2 s, the multiple R 2s may be the same or different.
  • R 1 , R 2 ) R 1 and R 2 in the repeating unit represented by formula (54) are each independently an alkyl group optionally having a substituent other than a bridging group or the like.
  • the alkyl group is a linear, branched or cyclic alkyl group. Although the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1 or more, preferably 8 or less, more preferably 6 or less, and even more preferably 3 or less, in order to maintain the solubility of the polymer. More preferably, the alkyl group is a methyl group or an ethyl group.
  • the plurality of R 1 When there is a plurality of R 1 , the plurality of R 1 may be the same or different, and when there is a plurality of R 2 , the plurality of R 2 may be the same or different.
  • the case where R 1 is plural includes the case where a is an integer of 2 or more, the case where c is an integer of 2 or more, or the case where both are R 1 may be the same or different.
  • R 2 and the case where R 2 is plural includes the case where b is an integer of 2 or more, the case where d is an integer of 2 or more, or both.
  • multiple R 2 may be the same or different. All R 1 and R 2 are preferably the same group because the charge can be uniformly distributed around the nitrogen atom and the synthesis is easy.
  • the alkyl groups of R 1 and R 2 may have substituents other than a cross-linking group. Substituents other than the bridging group and the like include groups mentioned as preferred groups of alkyl groups, aralkyl groups and aromatic hydrocarbon groups for R 7 to R 9 and R 11 to R 14 described later.
  • the alkyl groups of R 1 and R 2 most preferably have no substituent from the viewpoint of low voltage.
  • R 7 to R 9 and R 11 to R 14 are each independently a hydrogen atom, an alkyl group which may have a substituent other than a bridging group, or a substituent other than a bridging group. aralkyl group, or an aromatic hydrocarbon group which may have a substituent other than a bridging group or the like.
  • the alkyl group is not particularly limited, the number of carbon atoms is preferably 1 or more, preferably 24 or less, more preferably 8 or less, and even more preferably 6 or less, because it tends to improve the solubility of the polymer. Also, the alkyl group may have a linear, branched or cyclic structure.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group and n-hexyl group. , n-octyl group, cyclohexyl group, dodecyl group and the like.
  • the aralkyl group is not particularly limited, the number of carbon atoms is preferably 5 or more, preferably 60 or less, and more preferably 40 or less, because it tends to improve the solubility of the polymer.
  • aralkyl group examples include 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, 8-phenyl-1-n-octyl group, 4-phenylcyclohexyl group and the like.
  • the aromatic hydrocarbon group is not particularly limited, the number of carbon atoms is preferably 6 or more, preferably 60 or less, and more preferably 30 or less, because it tends to improve the solubility of the polymer.
  • aromatic hydrocarbon group examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, and fluorene.
  • a 6-membered monocyclic or 2-5 condensed monovalent group such as a ring, or a group in which a plurality of these are linked, and the like can be mentioned.
  • R 7 to R 9 are preferably methyl groups or aromatic hydrocarbon groups, R 7 and R 8 are more preferably methyl groups, and R 9 is a phenyl group. is more preferable.
  • alkyl groups, aralkyl groups and aromatic hydrocarbon groups of R 7 to R 9 and R 11 to R 14 may have substituents other than bridging groups.
  • Substituents other than the bridging group include the groups exemplified as preferred alkyl groups, aralkyl groups and aromatic hydrocarbon groups for R 7 to R 9 and R 11 to R 14 above.
  • the alkyl groups, aralkyl groups and aromatic hydrocarbon groups of R 7 to R 9 and R 11 to R 14 most preferably have no substituents from the viewpoint of low voltage.
  • a and b are each independently an integer of 0-4.
  • the value represented by a+b is preferably 1 or more, more preferably each of a and b is 2 or less, and more preferably both a and b are 1.
  • the structure in which a is 1 or more is defined independently by c phenylene groups when c is 1 or more, and the structure in which b is 1 or more includes d phenylene groups when d is 1 or more. are independently defined in groups.
  • the value represented by a + b is 1 or more, the aromatic ring of the main chain is twisted due to steric hindrance, and the solubility of the polymer in a solvent is excellent, and the coating film formed by a wet film formation method and heat-treated. tend to have excellent insolubility in solvents. Therefore, when the value represented by a+b is 1 or more, when another organic layer, that is, the second functional film is formed on the first functional film by a wet film-forming method, an organic solvent is used. The elution of the polymer, such as the arylamine polymer, contained in the first composition into the containing second composition is suppressed. As a result, the formed second functional film is less affected, and the operating life of the organic semiconductor element is considered to be further extended.
  • c is an integer of 1-3 and d is an integer of 0-4.
  • Each of c and d is preferably 2 or less, more preferably c and d are equal, and it is particularly preferable that both c and d are 1 or both c and d are 2.
  • both c and d in the repeating unit represented by the above formula (54) are 1 or both c and d are 2 and both a and b are 2 or 1, R 1 and R 2 are most preferably bonded at symmetrical positions.
  • the binding of R 1 and R 2 at positions symmetrical to each other means the binding position of R 1 and R 2 with respect to the fluorene ring, carbazole ring or 9,10-dihydrophenanthrene derivative structure in formula (54). is symmetrical. At this time, 180° rotation around the main chain is regarded as the same structure.
  • (X) X in the above formula (54) is preferably -C(R 7 )(R 8 )- or -N(R 9 )- because of its high stability during charge transport, and -C(R 7 )(R 8 )— is more preferred.
  • the repeating unit represented by the above formula (54) is particularly preferably a repeating unit represented by any one of the following formulas (54-1) to (54-4).
  • Ar 51 , R 1 , R 2 and X are the same as Ar 51 , R 1 , R 2 and X in formula (54), respectively, but R 1 and R 2 are the same, and R 1 and R 2 are preferably bonded at symmetrical positions.
  • main chain of repeating unit represented by formula (54) Although the main chain structure excluding the nitrogen atom in the above formula (54) is not particularly limited, examples thereof include the following structures.
  • Ar 51 is the same as Ar 51 in the formula (50), R 3 and R 6 are each independently an alkyl group optionally having a substituent other than a cross-linking group, R 4 and R 5 are each independently an alkyl group optionally having a substituent other than a bridging group, etc., an alkoxy group optionally having a substituent other than a bridging group etc., or a group other than a bridging group etc. is an aralkyl group optionally having a substituent of l is 0 or 1, m is 1 or 2, n is 0 or 1, p is 0 or 1, q is 0 or 1; )
  • R 3 , R 6 ) R 3 and R 6 in the repeating unit represented by formula (55) are each independently an alkyl group optionally having a substituent other than a bridging group or the like.
  • alkyl group include the same as those for R 1 and R 2 in the formula (54), and the same substituents and preferred structures as those for R 1 and R 2 may be included.
  • R4 , R5) R 4 and R 5 in the repeating unit represented by the above formula (55) are each independently an alkyl group optionally having a substituent other than a bridging group or the like, or a substituent other than a bridging group or the like. It is an alkoxy group which may have or an aralkyl group which may have a substituent other than a bridging group or the like.
  • the alkyl group is a linear, branched or cyclic alkyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited, it is preferably 1 or more, preferably 24 or less, more preferably 8 or less, and even more preferably 6 or less, because it tends to improve the solubility of the polymer.
  • alkyl group examples include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group and n-hexyl. group, n-octyl group, cyclohexyl group, dodecyl group and the like.
  • the alkoxy group is not particularly limited, and the alkyl group represented by R 10 of the alkoxy group (-OR 10 ) may have any structure of linear, branched or cyclic, and improves the solubility of the polymer. Therefore, the number of carbon atoms is preferably 1 or more, preferably 24 or less, and more preferably 12 or less.
  • alkoxy group examples include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, hexyloxy group, 1-methylpentyloxy group, cyclohexyloxy group and the like.
  • the aralkyl group is not particularly limited, the number of carbon atoms is preferably 5 or more, preferably 60 or less, and more preferably 40 or less, because it tends to improve the solubility of the polymer.
  • aralkyl group examples include 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, 8-phenyl-1-n-octyl group, 4-phenylcyclohexyl group and the like.
  • l and n are each independent, and the value represented by l+n is preferably 1 or more, more preferably 1 or 2, and still more preferably 2.
  • the value represented by l+n is within the above range, the solubility of the polymer contained in the first functional film is increased, and precipitation from the first composition containing the polymer tends to be suppressed. It is in.
  • n 1 or 2
  • the organic semiconductor device is an organic electroluminescent device, it can be driven at a low voltage, and the hole injection ability, transport ability, and durability tend to be improved, so it should be 1. is preferred.
  • main chain of repeating unit represented by formula (55) Although the main chain structure excluding the nitrogen atom in formula (55) is not particularly limited, examples thereof include the following structures.
  • Ar 51 is the same as Ar 51 in the formula (50), Ar 41 is a divalent aromatic hydrocarbon group which may have a substituent other than a bridging group or the like and a divalent aromatic heterocyclic group which may have a substituent other than a bridging group or the like. represents a divalent group in which one group or a plurality of groups selected from at least one are linked, and the linkage is made directly or via a linking group; R 41 and R 42 are each independently an alkyl group optionally having a substituent other than a bridging group, t is 1 or 2; u is 0 or 1, r and s are each independently an integer of 0-4. )
  • R41 , R42 ) R 41 and R 42 in the repeating unit represented by formula (56) are each independently an alkyl group optionally having a substituent other than a bridging group or the like.
  • the alkyl group is a linear, branched or cyclic alkyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited, but in order to maintain the solubility of the polymer, the number of carbon atoms is preferably 1 or more, preferably 10 or less, more preferably 8 or less, and more preferably 6 or less. More preferably, the alkyl group is a methyl group or a hexyl group.
  • R 41 and R 42 When a plurality of R 41 and R 42 are present in the repeating unit represented by formula (56) above, the plurality of R 41 and R 42 may be the same or different.
  • the case where R 41 is plural includes the case where r is 2 or more, the case where t is 2 or more, or both.
  • the case where R 42 is plural means the case where s is 2 or more.
  • r and s are each independently an integer of 0-4.
  • the value represented by r+s is preferably 1 or more, and r and s are each preferably 2 or less.
  • the drive life of the organic semiconductor device is considered to be further extended for the same reason as a and b in the formula (54).
  • t is 1 or 2, and u is 0 or 1.
  • t is preferably 1 and u is preferably 1.
  • Ar 41 is a divalent aromatic hydrocarbon group which may have a substituent other than a bridging group or the like and a divalent aromatic heterocyclic group which may have a substituent other than a bridging group or the like. represents a divalent group in which one group or a plurality of groups selected from at least one are linked, and the linkage is made directly or via a linking group;
  • aromatic hydrocarbon group and aromatic hydrocarbon group for Ar 41 include the same groups as for Ar 52 in the formula (50).
  • aromatic hydrocarbon group and the substituent that the aromatic hydrocarbon group may have are preferably the same groups as in the above substituent group Z, and the substituent that may be further included in the above substituent group Z is preferably the same as
  • repeating unit represented by formula (56) Although the repeating unit represented by formula (56) is not particularly limited, examples thereof include the following structures.
  • Ar 51 is the same as Ar 51 in the formula (50), R 17 to R 19 each independently represent an alkyl group optionally having a substituent other than a bridging group, etc., an alkoxy group optionally having a substituent other than a bridging group etc., a group other than a bridging group etc.
  • An aralkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent other than a bridging group, or an aromatic heterocyclic ring which may have a substituent other than a bridging group represents the group, f, g, and h each independently represent an integer of 0 to 4, the value represented by f + g + h is 1 or more, e represents an integer of 0 to 3; )
  • the aromatic hydrocarbon group and aromatic heterocyclic group in R 17 to R 19 are each independently the same aromatic hydrocarbon group and aromatic heterocyclic group as those mentioned for Ar 51 above, and Substituents other than the cross-linking group that these groups may have are preferably the same groups as in the above-described substituent group Z or.
  • the alkyl group and aralkyl group in R 17 to R 19 are preferably the same groups as the alkyl group and aralkyl group mentioned above for R 7 , respectively . Groups similar to are preferred.
  • the alkoxy groups in R 17 to R 19 are preferably the alkoxy groups listed in the above substituent group Z, and the substituents other than the cross-linking group that may be contained are also the same as those in the above substituent group Z.
  • (f, g, h) f, g, and h each independently represent an integer of 0 to 4, and the value represented by f+g+h is 1 or more.
  • g is independently defined by e phenylene groups when e is 2 or more.
  • the value represented by f + h is preferably 1 or more, More preferably, the value represented by f + h is 1 or more, and f, g, and h are all 2 or less, More preferably, the value represented by f + h is 1 or more, and both f and h are 1 or less, Most preferably, both f and h are 1.
  • R 17 and R 19 are preferably bonded at symmetrical positions.
  • R 17 and R 19 are preferably the same, and g is more preferably 2.
  • the two R 18 are most preferably attached to each other in the para position, and when g is 2, the two R 18 are most preferably the same.
  • the binding positions where R 17 and R 19 are symmetrical to each other refer to the following binding positions. However, for notation, 180° rotation about the main chain is regarded as the same structure.
  • repeating unit represented by formula (57) above is preferably a repeating unit represented by formula (58) below.
  • the binding positions are preferably 2- and 5-positions.
  • g 0, i.e., when there is no steric hindrance by R 18 ;
  • R 17 and R 19 can be bonded at positions symmetrical to each other.
  • the binding positions are preferably 2- and 5-positions.
  • R 17 and R 19 can be combined at symmetrical positions.
  • the weight-average molecular weight (Mw) of the arylamine polymer is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 1,000,000 or less. is 500,000 or less, more preferably 200,000 or less, particularly preferably 100,000 or less, most preferably 50,000 or less.
  • the weight average molecular weight is usually 2,500 or more, preferably 5,000 or more, more preferably 10,000 or more, still more preferably 15,000 or more, and particularly preferably 17,000 or more.
  • the weight-average molecular weight of the arylamine polymer When the weight-average molecular weight of the arylamine polymer is equal to or less than the above upper limit, solubility in a solvent is obtained, and the film-forming property tends to be excellent. Further, when the weight average molecular weight of the arylamine polymer is at least the above lower limit, the glass transition temperature, melting point, and vaporization temperature of the arylamine polymer are suppressed from being lowered, and heat resistance may be improved. Conventionally, it was believed that an arylamine polymer having a weight-average molecular weight of 15,000 to 50,000 and having no cross-linking group or the like could not achieve industrially practical insolubility. By using the composition of the present invention, it is possible to achieve industrially required durability to the upper layer solvent for 2 minutes or more, preferably 15 minutes or more, even with relatively low-temperature and short-time firing.
  • the number average molecular weight (Mn) of the arylamine polymer is usually 2,500,000 or less, preferably 750,000 or less, more preferably 400,000 or less, particularly preferably 100,000 or less, and most preferably 40000 or less.
  • the number average molecular weight is usually 2,000 or more, preferably 4,000 or more, more preferably 6,000 or more, and still more preferably 8,000 or more.
  • the dispersity (Mw/Mn) in the arylamine polymer is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less.
  • the lower limit value is ideally 1 because the smaller the value of the degree of dispersion, the better.
  • the weight average molecular weight and number average molecular weight of a polymer are usually determined by SEC (size exclusion chromatography) measurement. In SEC measurement, the higher the molecular weight, the shorter the elution time, and the lower the molecular weight, the longer the elution time. By conversion, the weight average molecular weight and number average molecular weight are calculated.
  • arylamine polymer (Concrete example) Specific examples of the arylamine polymer are shown below, but the arylamine polymer in the present embodiment is not limited to these.
  • the numbers in the chemical formulas represent the molar ratio of repeating units. n represents the number of repetitions.
  • arylamine polymers may be random copolymers, alternating copolymers, block copolymers, graft copolymers, or the like, and the sequence of the monomers is not limited.
  • arylamine polymer containing the repeating unit represented by formula (56) are shown below, but the arylamine polymer in the present embodiment is not limited to these.
  • the numbers in the chemical formulas represent the molar ratio of repeating units. n represents the number of repetitions.
  • arylamine polymers may be random copolymers, alternating copolymers, block copolymers, graft copolymers, or the like, and the sequence of the monomers is not limited.
  • the method for producing the arylamine polymer contained in the first functional material is not particularly limited and is arbitrary. Examples thereof include 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, and the like.
  • Z represents a halogen atom such as I, Br, Cl, F.
  • Ar 1 , R 1 , R 2 , X, a to d represent Ar 1 , R 1 in the above formula (54). , R 2 , X, a to d are synonymous.
  • Z represents a halogen atom such as I, Br, Cl, F.
  • Ar 2 , R 3 to R 6 , l to n, p, and q represent Ar 2 , are synonymous with R 3 to R 6 , l to n, p, and q.
  • the reaction for forming an N-aryl bond is usually carried out in the presence of a base such as potassium carbonate, sodium tert-butoxy, or triethylamine. It can also be carried out in the presence of a transition metal catalyst such as copper or a palladium complex.
  • a base such as potassium carbonate, sodium tert-butoxy, or triethylamine. It can also be carried out in the presence of a transition metal catalyst such as copper or a palladium complex.
  • the content of the arylamine polymer in the first composition is usually 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and It is usually 70% by mass or less, preferably 60% by mass or less, more preferably 50% by mass or less, and particularly preferably 20% by mass or less.
  • the content of the arylamine polymer is within the above range, the formed first functional film is less likely to have defects and less likely to have uneven film thickness, which is preferable.
  • the first composition usually contains a solvent.
  • the solvent is preferably one that dissolves the arylamine polymer.
  • a solvent that dissolves the arylamine polymer in the first composition at room temperature in an amount of usually 0.05% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more, is suitable. .
  • solvents include aromatic solvents such as toluene, xylene, mesitylene, cyclohexylbenzene and methylnaphthalene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene and o-dichlorobenzene; ethylene glycol dimethyl ether and ethylene glycol diethyl.
  • Ethers aliphatic ethers such as propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4- Ether solvents such as aromatic ethers such as methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole; Aliphatic ester solvents such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate; Ester-based solvents such as aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, isopropyl benzoate, propyl benzoate, and n-butyl benzoate; Organic solvents used in the composition for forming the injection layer and the composition
  • solvent may be used, or two or more types may be used in any combination and in any ratio.
  • the surface tension of the solvent at 20°C is usually less than 40 dyn/cm, preferably 36 dyn/cm or less, more preferably 33 dyn/cm or less.
  • the lower limit of the surface tension is not particularly limited, it is usually 20 dyn/cm or more.
  • the vapor pressure of the solvent at 25°C is usually 10 mmHg or less, preferably 5 mmHg or less, and usually 0.1 mmHg or more.
  • solvents include aromatic solvents such as toluene, xylene, mesitylene, and cyclohexylbenzene, ether solvents, and ester solvents.
  • the solubility of the solvent in water at 25° C. is preferably 1% by mass or less, more preferably 0.1% by mass or less, and the smaller the better.
  • the content of the solvent in the first composition 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 upper limit of the solvent content is not particularly limited, it is usually 99.95% by mass or less.
  • the second composition is a composition that is applied onto the first functional film to form a second functional film.
  • the second composition contains a solvent and has a viscosity of 15 mPa ⁇ s or less at 23°C.
  • the solvent contains at least one first solvent component that satisfies a viscosity of 3 mPa ⁇ s or more at 23°C, or at least one first solvent component that satisfies a flow activation energy of 17 kJ/mol or more and 23°C. and at least one second solvent component that satisfies a viscosity of less than 3 mPa ⁇ s.
  • the second composition may contain a second functional material different from the first functional material contained in the first composition.
  • a functional material such as a light-emitting material is usually the second functional material.
  • the viscosity of the first solvent component at 23°C is 3 mPa ⁇ s or more, but this does not dissolve the first functional film.
  • the viscosity is preferably 4 mPa ⁇ s or more, more preferably 5 mPa ⁇ s or more.
  • the viscosity of the first solvent component is desirably 20 mPa ⁇ s or less.
  • the solvent may contain only the first solvent component, or may contain other solvent components.
  • the upper limit of the viscosity of the second composition changes depending on the application method.
  • the viscosity of the second composition at 23° C. is preferably 15 mPa ⁇ s or less, more preferably 12 mPa ⁇ s or less, and 10 mPa ⁇ s or less from the viewpoint of facilitating ejection from an inkjet head when applied by an inkjet device. is more preferred.
  • the viscosity of the second composition at 23° C. is preferably 1 mPa ⁇ s or more, more preferably 2 mPa ⁇ s or more.
  • the viscosity in the present embodiment is a value measured using an E-type viscometer RE85L (manufactured by Toki Sangyo Co., Ltd.) under a 23° C. environment with a cone plate rotation speed of 20 rpm to 100 rpm.
  • the immersion time is long.
  • the temperature of the second composition decreases and the viscosity increases.
  • a solvent with a high viscosity temperature dependence flow activation energy
  • a solvent with a lower initial viscosity is used as the first solvent component
  • the first solvent in the second composition is It is possible to lower the composition ratio.
  • another aspect of the present invention includes a first solvent component having a flow activation energy of 17 kJ/mol or more and a second solvent component having a viscosity of less than 3 mPa ⁇ s.
  • the flow activation energy of the first solvent component is 17 kJ/mol or more, more preferably 19 kJ/mol or more, and still more preferably 21 kJ/mol or more.
  • the upper limit is not particularly limited, it is preferably 40 kJ/mol or less, more preferably 35 kJ/mol or less, still more preferably 32 kJ/mol or less, and particularly preferably 30 kJ/mol or less.
  • the larger the flow activation energy the larger the increase in viscosity due to the decrease in temperature when the latent heat is taken away by volatilization of the solvent, which is preferable.
  • the solvent includes a first solvent component having a viscosity at 23° C. of 3 mPa ⁇ s or more and a flow activation energy of 17 kJ/mol or more; A second solvent component having a viscosity at °C of less than 3 mPa ⁇ s is included.
  • Preferred ranges for the viscosity at 23° C. and flow activation energy of the first solvent component are as described above.
  • the viscosity at 23 ° C. is 3 mPa s or more
  • the flow activation energy is 17 kJ / mol or more can be used.
  • the numbers in parentheses after the solvents indicate flow activation energy (unit: kJ/mol).
  • Flow activation energy is E in the following formula (I). Flow activation energy is determined from the slope of the logarithm of viscosity plotted against the reciprocal of temperature by measuring the viscosity of the solvent at different temperatures.
  • the second composition contains at least one first solvent component that satisfies a viscosity of 3 mPa s or more at 23 ° C. and / or a flow activation energy of 17 kJ / mol or more, so that the first function Even if the arylamine polymer of the functional film is not insolubilized by a cross-linking group or the like, and the thin film contains the first functional material with a small molecular weight that is baked at a relatively low temperature for a short time, the reaction time is 2 minutes or more.
  • An industrially required insolubilization durability of preferably 5 minutes or more, more preferably 15 minutes or more can be achieved.
  • the heat treatment causes rearrangement on the surface and interface of the first functional membrane prior to the bulk, forming a relatively insoluble cover and preventing solvent permeation and elution into the interior of the first functional membrane. This is considered to be because it can be suppressed.
  • the easiness of penetration into the inside varies depending on the volume and shape of the solvent molecules contained in the second composition, and the internal degree of freedom.
  • the greater the intermolecular force between the solvent molecules the greater the impediment to permeation and dispersion. More accurately, the plurality of factors described above are determined by the relational expression (A) described later, but for simplicity, one or more first solvent components having a viscosity of 3 mPa s or more at 23 ° C. are used. can be achieved with
  • the first solvent component preferably has an aromatic hydrocarbon structure. Specifically, benzoic acid, biphenyl, naphthalene, etc. A solvent component having a structure is included.
  • the Hansen solubility parameter ⁇ P of the first solvent component preferably satisfies ⁇ P ⁇ 10, and more preferably satisfies ⁇ P ⁇ 7. Due to the insolubilization property of the first functional film, the durability time tends to be shortened by a highly polar solvent.
  • the theoretical surface area ( ⁇ 2 ), volume ( ⁇ 3 ), and boiling point (° C.) calculated by the COSMO-RS solvation model of the first solvent component, and the viscosity at 23° C. (mPa s ) satisfies the following relational expression (A).
  • the first solvent component satisfies the following relational expression (A)
  • insolubilization can be achieved for a longer period of time.
  • Viscosity in the above relational expression (A) is the viscosity (mPa ⁇ s) of the first solvent component at 23°C.
  • Boiling point is the boiling point at atmospheric pressure of the first solvent component.
  • the "theoretical surface area” and “volume” of the first solvent component are described in A. Klamt, “COSMO-RS: From Quantum Chemistry to Fluid Phase Thermodynamics and Drug Design", Elsevier Science, 1st edition (September 29, 2005). To put it simply, it is a value obtained by multiplying the volume obtained by superimposing VDW spheres on the atoms of the structure-optimized molecule and its surface area (cavity volume used for COSMO calculation).
  • Each coefficient in the above relational expression (A) is a numerical value obtained experimentally.
  • Viscosity indicates the force that holds the solvent molecules together, and correlates with the difficulty of penetrating and dispersing into the first functional film.
  • the larger the volume of the solvent molecules the more difficult it is to permeate the first functional membrane, but the larger the surface area for the same volume, the less spherical, and the smaller the cross-sectional area, that is, the more easily permeable direction. Therefore, a smaller surface area is preferable.
  • a solvent with a lower boiling point evaporates more easily, and lowers the temperature of the second composition by the heat of vaporization, resulting in an effect of increasing the viscosity of the solvent.
  • the effect of the solvent on the underlying functional material film is suppressed.
  • the value represented by the left side of the above relational expression (A) is more preferably 160 or more, and even more preferably 180 or more.
  • the first solvent component that satisfies the above relational expression (A) include isoamyl benzoate (3.45), fenchone (3.47), decylbenzene (3.5), and hexyl benzoate (4.08).
  • the second composition may contain other solvents than the first solvent component.
  • a solvent other than the first solvent component may include a second solvent component having a lower viscosity than the first solvent component. That is, the second solvent component is a solvent having a viscosity of less than 3 mPa ⁇ s at 23°C. Specifically, among the solvents exemplified as the solvents contained in the first composition, those having a viscosity of less than 3 mPa ⁇ s at 23° C. can be mentioned.
  • the second solvent component is preferably included when the flow activation energy of the first solvent component satisfies 17 kJ/mol or more.
  • the flow activation energy of the second solvent component is preferably 10 kJ/mol or more, more preferably 12 kJ/mol or more, still more preferably 14 kJ/mol or more.
  • the upper limit is not particularly limited, it is preferably 18 kJ/mol or less, more preferably 17 kJ/mol or less, even more preferably 16 kJ/mol or less, and even more preferably 15 kJ/mol or less.
  • the viscosity of the second composition When applied by an inkjet device, it is desirable to reduce the viscosity of the second composition as a whole by including a low-viscosity second solvent component from the viewpoint of proper ejection from an inkjet head.
  • the boiling point of the second solvent component is preferably 180° C. or higher from the viewpoint of avoiding drying in the process of applying the second composition and providing the second functional film.
  • Such second solvent components include, for example, ethyl benzoate, tetralin, 2-ethylnaphthalene, ethyl toluate, cyclohexylbenzene, and butyl benzoate.
  • the first solvent component is preferably contained in the second composition in a total amount of 15% by mass or more, more preferably 20% by mass or more, and still more preferably 25% by mass or more.
  • the upper limit of the total content of the first solvent component is not particularly limited, it is usually 99% by mass or less.
  • the total content of the first solvent component is preferably 95% by mass or less, and when the second solvent component is contained, the total content of the first solvent component The amount is preferably 90% by mass or less.
  • the total content of the first solvent component is preferably 70% by mass or less, more preferably 50% by mass or less.
  • the ratio of the first solvent component to the total of the first solvent component and the second solvent component is preferably 10% or more, more preferably 15% or more, by mass. The reason for this is that when considering the order of evaporation of the mixed solvent, it is desirable that a certain amount of the first solvent component remains until the second solvent component, which does not correspond to the first solvent component, evaporates.
  • the ratio of the second solvent component to the total of the first solvent component and the second solvent component is preferably 30% by mass or more. When it is 30% by mass or more, the temperature of the first solvent can be appropriately lowered by evaporation of the second solvent component, and the viscosity of the first solvent component can be increased.
  • the ratio of the second solvent component is more preferably 50% by mass or more, most preferably 70% by mass or more. From the viewpoint of flatness of the functional film, the ratio of the second solvent component is preferably 90% by mass or less, and from the viewpoint of leaving a certain amount of the first solvent component until the second solvent component evaporates. , the ratio of the second solvent component is more preferably 85% by mass or less.
  • the boiling point of the second solvent component is preferably lower than the boiling point of the first solvent component, preferably 280° C. or lower, and preferably 250° C., from the viewpoint of evaporating earlier than the first solvent component. More preferably: On the other hand, the boiling point of the second solvent component is preferably 180° C. or higher, more preferably 200° C. or higher, from the viewpoint of drying control in large-area coating.
  • the second composition contains a first solvent component having a viscosity of 3 mPa ⁇ s or more at 23°C.
  • the viscosity of the composition is preferably low (viscosity of 15 mPa ⁇ s or less at 23° C.) from the viewpoint of ejection properties in inkjet coating.
  • the second composition has a second solvent component with a viscosity of less than 3 mPa ⁇ s at 23°C.
  • the second solvent component is preferably included when the flow activation energy of the first solvent component satisfies 17 kJ/mol or more.
  • the second solvent component is a low-viscosity solvent (viscosity less than 3 mPa ⁇ s at 23° C.) and tends to volatilize before the first solvent component. At that time, the heat of vaporization is removed and the temperature of the second composition is lowered. Since the flow activation energy of the first solvent component is high, the viscosity of the remaining second composition is high, so that it is difficult to permeate the first functional layer, which is the lower layer, which is preferable from the viewpoint of insolubilization.
  • the second composition may contain a second functional material different from the first functional material.
  • the organic semiconductor device is an organic electroluminescent device and the second functional film is a hole transport layer
  • examples of the second functional material include a hole transport material.
  • it may contain the same arylamine polymer as the arylamine polymer of formula (50) that the first functional film has, and a hole-transporting material described later can also be used.
  • the second functional material may be a light-emitting material such as a phosphorescent light-emitting material, or a charge transport material, which will be described later. can be done. It is also preferable that the second functional material contains a low-molecular-weight aromatic compound. When the second functional material is low molecular weight, the viscosity of the second composition can be made lower than when it is high molecular weight.
  • the viscosity of the second composition as a whole tends to increase, but the second functional material is Low molecular weights are easily tolerated.
  • the molecular weight of the low molecular weight aromatic compound is preferably less than 5,000, more preferably 4,000 or less, even more preferably 3,000 or less, and particularly preferably less than 2,000.
  • the second composition in the present embodiment may contain only one type of the second functional material, or may contain two or more types.
  • the contents of the first functional material and the second functional material in the first composition and the second composition in the present embodiment are not particularly limited, but each is preferably 0.1% by weight. Above, it is more preferably 0.5% by weight or more, more preferably 1.0% by weight or more, preferably 20% by weight or less, still more preferably 15% by weight or less, and more preferably 10% by weight or less.
  • a method for manufacturing an organic semiconductor device includes steps of applying and heating a first composition to provide a first functional film, and applying a second composition on the first functional film. and providing a second functional film by applying.
  • the organic semiconductor device is an organic electroluminescent device
  • the first functional film is a hole injection layer and the second functional film is a hole transport layer
  • examples i) or ii) below, in which the first functional film is the hole-transporting layer and the second functional film is the emitting layer include, but are not limited to.
  • a substrate provided with an electrode usually has a minute region in which light emitting pixels are partitioned by partition walls called a bank.
  • the first functional film is formed by applying the first composition of the present embodiment by, for example, ejecting it into the minute regions partitioned by the banks, drying it, and heating it as appropriate.
  • the ejection method is a method of ejecting a droplet smaller than the minute area partitioned by the bank from a minute nozzle, and by ejecting a plurality of droplets, the minute area partitioned by the bank is filled with the first composition. preferably fulfilled.
  • An ink jet method is preferable as the ejection method.
  • the first composition is filled into minute areas defined by banks, and then vacuum-dried. Vacuum drying is volatilizing the solvent by reducing the pressure.
  • the solvent can be volatilized by vacuum drying, but it is preferable to then heat dry to ensure sufficient drying.
  • the heating temperature is preferably a temperature and time at which the first functional film does not crystallize or aggregate.
  • the heating temperature is usually 50°C or higher, preferably 80°C or higher, more preferably 100°C or higher, more preferably 120°C or higher, and usually 200°C or higher. °C or lower, preferably 180 °C or lower, more preferably 150 °C or lower.
  • the heating time is usually 1 minute or more, preferably 3 minutes or more, more preferably 5 minutes or more, and usually 120 minutes or less, preferably 90 minutes or less, more preferably 60 minutes or less.
  • the heating temperature is usually 80° C. or higher, preferably 100° C. or higher, more preferably 150° C. or higher, more preferably 200° C. or higher, It is usually 300° C. or lower, preferably 270° C. or lower, more preferably 240° C. or lower.
  • the heating time is usually 1 minute or more, preferably 3 minutes or more, more preferably 5 minutes or more, and usually 120 minutes or less, preferably 90 minutes or less, more preferably 60 minutes or less.
  • the heating temperature in the step of providing the first functional film is preferably lower as long as the solvent is removed and the required insolubilization durability time is achieved. good.
  • the heating method can be carried out by hot plate, oven, infrared irradiation, etc.
  • infrared irradiation that directly gives molecular vibration
  • a heating time close to the above lower limit is sufficient. requires a long time.
  • oven heating that is, in the case of heating with a gas in the oven, usually air or an inert gas such as nitrogen or argon, it takes time to raise the temperature, so a heating time close to the upper limit of the above heating time is preferable.
  • the heating time is appropriately adjusted depending on the heating method.
  • a second functional film is formed by applying a second composition onto the first functional film formed in the bank by application and heating.
  • the method of application is preferably an inkjet method.
  • the second composition to be applied contains at least one first solvent component that satisfies a viscosity of 3 mPa s or more at 23° C. and/or a flow activation energy of 17 kJ/mol or more,
  • the first functional film does not dissolve for a time longer than the industrially required time.
  • industrially the process of forming a film on a large substrate by a coating method, particularly an inkjet method, is applied to the first functional film, and then the second composition is included in the second composition. It takes at least 2 minutes or more for the solvent to evaporate.
  • immersion means that the second composition exists in contact with the first functional film entirely or partially in a liquid state.
  • the first functional film does not dissolve when immersed for preferably 2 minutes or longer, more preferably 5 minutes or longer, still more preferably 10 minutes or longer, and even more preferably 15 minutes or longer.
  • the atmospheric pressure and temperature are assumed to be 1 Pa or more and 50° C. or less, respectively.
  • “until the solvent evaporates” means until the entire solvent contained in the second composition evaporates. That is, when the solvent contained in the second composition is only the first solvent component, it means until the first solvent component evaporates and disappears, and the solvent contained in the second composition is the first solvent component. In the case of one solvent component and a second solvent component, it means until all of them have evaporated. In addition, it is not necessary that the amount of residual solvent is strictly zero when the solvent evaporates. Since residual solvent may remain depending on the boiling point of the solvent, if the concentration in the second functional film on a volume basis is 100 ppm or less, it can be considered that the solvent has evaporated.
  • the first functional film does not need to be insolubilized at all positions in its cross-sectional direction. Even with polymeric materials that do not form chemical bonds due to cross-linking groups, etc., if an arylamine polymer with an appropriate molecular structure and molecular weight is thermally treated, the rearrangement proceeds on the surface and interface ahead of the bulk portion, Forms a surface that is difficult to be eluted by the solvent during coating of the upper layer. At this time, most of the thin film maintains an amorphous state and dissolves rapidly after the surface is eluted.
  • the first functional film it is possible to use a low-molecular weight functional material that is advantageous for simpler heat treatment such as low temperature and short time, high definition, and flexibility in film thickness design within the range where this insolubility can be achieved.
  • the effect of the second composition on the durability time until the first functional film starts dissolving depends on the solvent molecules contained in the second composition, especially the first solvent component. It varies depending on the volume, surface area, internal degrees of freedom, intermolecular forces between solvent molecules, etc. Although there is little correlation with the Hansen solubility parameter .delta.P of solvent molecules, solvent molecules having .delta.P larger than a certain value tend to shorten the durability time and should be avoided.
  • the present inventors have experimentally clarified the criteria for selecting preferred solvent molecules, and established a judgment formula. This is the following relational expression (A) mentioned above. 32 x viscosity - 4.3 x theoretical surface area + 5.4 x volume - boiling point > 150 (A) Also, this judgment can be made simply by the viscosity of the solvent.
  • the second composition as a whole must have a viscosity suitable for ejection, that is, 15 mPa ⁇ It is required to have a viscosity of s or less.
  • 15 mPa ⁇ s or less is not essential.
  • the content of the first functional material or the second functional material contained in the first functional film or the second functional film is usually 70% by weight or more, preferably 80% by weight. Above, more preferably 90% by weight or more, particularly preferably 95% by weight or more, most preferably substantially 100% by weight, the upper limit is 100% by weight. Substantially 100% by weight means that the functional film may contain trace amounts of additives, residual solvents and impurities. When the content of the functional material in the functional film is within this range, the function of the functional material can be exhibited more effectively.
  • organic electroluminescent device (hereinafter referred to as "organic electroluminescent device in the present embodiment") ) will be described with reference to FIG. 1 .
  • FIG. 1 is a schematic cross-sectional view showing a structural example of an organic electroluminescence device 10 according to this embodiment.
  • 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 each represent a cathode.
  • the organic electroluminescent element in this embodiment has the anode 2, the light emitting layer 5 and the cathode 9 as essential constituent layers, but if necessary, as shown in FIG. It may have another functional layer between it and the layer 5 .
  • the substrate 1 serves as a support for the organic electroluminescence device.
  • a quartz or glass plate, a metal plate or metal foil, a plastic film or sheet, or the like is used as the substrate 1.
  • Glass plates; transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate and polysulfone are particularly preferred.
  • the gas barrier property of the substrate is large, because deterioration of the organic electroluminescence element due to outside air passing through the substrate is unlikely to occur. Therefore, a method of providing a dense silicon oxide film or the like on at least one surface of a synthetic resin substrate to ensure gas barrier properties is also one of the preferable methods.
  • the anode 2 is an electrode that plays a role of injecting holes into the layer on the light-emitting layer 5 side.
  • the anode 2 is generally made of metal such as aluminum, gold, silver, nickel, palladium, platinum, metal oxide such as indium and/or tin oxide, metal halide such as copper iodide, carbon black, or poly (3-methylthiophene), polypyrrole, polyaniline, and other conductive polymers.
  • Formation of the anode 2 is usually carried out by a method such as a sputtering method, a vacuum deposition method, or the like.
  • a method such as a sputtering method, a vacuum deposition method, or the like.
  • metal fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc.
  • the anode 2 can also be formed by dispersing it in a binder resin solution and coating it on the substrate 1 .
  • a conductive polymer a thin film can be formed directly on the substrate 1 by electrolytic polymerization.
  • the anode 2 can be formed by coating the substrate 1 with a conductive polymer (Appl. Phys. Lett., Vol. 60, p. 2711, 1992).
  • the anode 2 usually has a single-layer structure, but it can also have a laminated structure consisting of multiple materials, if desired.
  • the thickness of the anode 2 may be appropriately selected according to the required transparency and the like.
  • the visible light transmittance is usually 60% or more, preferably 80% or more.
  • 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 is arbitrary as long as it is opaque.
  • a substrate 1 that also functions as the anode 2 may be used. It is also possible to laminate different conductive materials on top of the anode 2 described above.
  • the surface of the anode 2 is treated with ultraviolet (UV)/ozone, oxygen plasma, or argon plasma. It is also preferable to
  • the hole injection layer 3 is a layer into which holes flow from the electrode when transporting holes from the anode 2 to the light emitting layer 5 .
  • the hole injection layer 3 is usually formed on the anode 2 .
  • a method for forming the hole injection layer 3 may be a vacuum deposition method or a wet film formation method, and is not particularly limited.
  • the hole injection layer 3 is preferably formed by a wet film formation method from the viewpoint of reducing dark spots.
  • the thickness of the hole injection layer 3 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
  • the composition for forming a hole injection layer usually contains a hole transport material and a solvent as constituent materials of the hole injection layer 3 .
  • the hole-transporting material is a compound having a hole-transporting property that is usually used in the hole-injection layer 3 of an organic electroluminescent device, and may be a polymer compound such as a polymer, or a monomer. may be a low-molecular-weight compound, but a high-molecular-weight compound is preferred.
  • a compound having an ionization potential of 4.5 eV to 6.0 eV is preferable as the hole transport material from the viewpoint of a charge injection barrier from the anode 2 to the hole injection layer 3 .
  • hole-transporting materials include aromatic amine derivatives, phthalocyanine derivatives, porphyrin derivatives, oligothiophene derivatives, polythiophene derivatives, benzylphenyl derivatives, compounds in which tertiary amines are linked with fluorene groups, hydrazone derivatives, silazane derivatives, and silanamine derivatives.
  • phosphamine derivatives quinacridone derivatives, polyaniline derivatives, polypyrrole derivatives, polyphenylenevinylene derivatives, polythienylenevinylene derivatives, polyquinoline derivatives, polyquinoxaline derivatives, carbon and the like.
  • Derivatives in the present specification include, for example, aromatic amine derivatives, aromatic amines themselves and compounds having an aromatic amine as a main skeleton. may be
  • the hole-transporting material used as the material for the hole-injection layer 3 may contain any one of such compounds alone, or may contain two or more of them. When two or more hole-transporting materials are contained, the combination is arbitrary, but one or two or more aromatic tertiary amine polymer compounds and one or two other hole-transporting materials It is preferable to use the above together.
  • aromatic amine compounds are preferable, and aromatic tertiary amine compounds are particularly preferable, in terms of amorphousness and visible light transmittance.
  • the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and includes compounds having a group derived from an aromatic tertiary amine.
  • the type of the aromatic tertiary amine compound is not particularly limited, but from the viewpoint of uniform light emission due to the surface smoothing effect, a polymer compound (polymeric compound in which repeating units are linked) having a weight average molecular weight of 1000 or more and 1000000 or less is further used. preferable.
  • Preferred examples of aromatic tertiary amine polymer compounds include polymer compounds having repeating units represented by the following formula (1) or (11).
  • Ar 3 represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group
  • Ar 4 represents an optionally substituted divalent aromatic hydrocarbon group represents a divalent group in which one or more groups selected from at least one of and a divalent aromatic heterocyclic group are linked, and the linking is performed directly or via a linking group.
  • Ar 4 in the formula (1) is an aromatic carbonized aromatic compound in which a plurality of Ar 4 in the formula (1) are linked via a linking group represented by the following formula (2) in terms of excellent hole injection into the light-emitting layer.
  • a hydrogen group or an aromatic heterocyclic group is preferred.
  • R 8 and R 9 each independently represent a hydrogen atom or an optionally substituted alkyl group, aromatic hydrocarbon group, or aromatic heterocyclic group. When multiple R 8 and R 9 are present, they may be the same or different. )
  • Ar 11 , Ar 12 and Ar 14 each independently represent an optionally substituted divalent aromatic ring group having 30 or less carbon atoms, and Ar 13 has 30 carbon atoms which may be substituted.
  • aromatic ring group refers to at least one of an aromatic hydrocarbon ring group and an aromatic heterocyclic group.
  • aromatic ring groups for Ar 11 , Ar 12 and Ar 14 include monocyclic rings, 2 to 6 condensed rings, and groups in which two or more of these aromatic rings are linked.
  • monocyclic or 2- to 6-condensed aromatic ring groups include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring and acenaphthene ring.
  • fluoranthene ring fluorene ring, biphenyl group, terphenyl group, quaterphenyl group, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, Divalent groups derived from pyridazine ring, pyrimidine ring, triazinzin
  • a divalent group derived from a benzene ring, a naphthalene ring, a fluorene ring, a pyridine ring or a carbazole ring, or a biphenyl group is preferable because it efficiently delocalizes a negative charge and is excellent in stability and heat resistance.
  • the aromatic ring group for Ar 13 are the same as those for Ar 11 , Ar 12 and Ar 14 .
  • R 11 represents an alkyl group, an aromatic ring group, or a trivalent group consisting of an alkyl group having 40 or less carbon atoms and an aromatic ring group, which may have a substituent.
  • R 12 represents an alkyl group, an aromatic ring group, or a divalent group consisting of an alkyl group having 40 or less carbon atoms and an aromatic ring group, which may have a substituent.
  • Ar 31 is a monovalent represents an aromatic ring group or a monovalent bridging group, and these groups may have a substituent.
  • q' represents an integer of 1 to 4.When q'is 2 or more, multiple R 12 may be the same or different, and a plurality of Ar 31 may be the same or different.
  • the asterisk (*) indicates a bond with the nitrogen atom of formula (11).
  • the aromatic ring group for R 11 is preferably one monocyclic or condensed ring aromatic ring group having 3 to 30 carbon atoms, or a group in which 2 to 6 of them are linked, and specific examples include benzene. Trivalent groups derived from rings, fluorene rings, naphthalene rings, carbazole rings, dibenzofuran rings, dibenzothiophene rings and groups in which 2 to 6 of these are linked.
  • the alkyl group for R 11 is preferably a linear, branched, or cyclic alkyl group having 1 to 12 carbon atoms, and specific examples thereof include methane, ethane, propane, isopropane, butane, isobutane, pentane, and hexane.
  • the group consisting of an alkyl group having 40 or less carbon atoms and an aromatic ring group for R 11 is preferably a linear, branched or ring-containing alkyl group having 1 to 12 carbon atoms and a single alkyl group having 3 to 30 carbon atoms. Examples thereof include groups in which one or two to six aromatic ring groups, which are rings or condensed rings, are linked.
  • aromatic ring group for R 12 examples include a benzene ring, a fluorene ring, a naphthalene ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, and a divalent group derived from a linking ring having 30 or less carbon atoms to which these are linked. be done.
  • alkyl group for R 12 include bivalent groups derived from methane, ethane, propane, isopropane, butane, isobutane, pentane, hexane and octane.
  • aromatic ring group for Ar 31 examples include a benzene ring, a fluorene ring, a naphthalene ring, a carbazole ring, a dibenzofuran ring, a dibenzothiophene ring, and a monovalent group derived from a linking ring having 30 or less carbon atoms in which these are linked. be done.
  • Preferred examples of the structure of formula (12) include the following structure, and the benzene ring or fluorene ring of the main chain in the structure below which is the partial structure of R 11 may further have a substituent.
  • Examples of the cross-linking group for Ar 31 include a group derived from a benzocyclobutene ring, a naphthocyclobutene ring or an oxetane ring, a vinyl group, an acryl group, and the like.
  • a group derived from a benzocyclobutene ring or a naphthocyclobutene ring is preferred from the viewpoint of compound stability.
  • x and y each independently represent an integer of 0 or more.
  • Ar 21 and Ar 23 each independently represent a divalent aromatic ring group, and these groups are substituents.
  • Ar 22 represents a monovalent aromatic ring group which may have a substituent
  • R 13 represents an alkyl group, an aromatic ring group, or a divalent group consisting of an alkyl group and an aromatic ring group. These groups may have substituents
  • Ar 32 represents a monovalent aromatic ring group or a monovalent bridging group, and these groups may have substituents.
  • (*) indicates a bond with the nitrogen atom of formula (11).)
  • Examples of the aromatic ring groups of Ar 21 and Ar 23 are the same as those of Ar 11 , Ar 12 and Ar 14 .
  • aromatic ring groups for Ar 22 and Ar 32 include monocyclic rings, 2 to 6 condensed rings, and groups in which two or more of these aromatic rings are linked. Specific examples include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, biphenyl group and terphenyl group.
  • a monovalent group derived from a benzene ring, a naphthalene ring, a fluorene ring, a pyridine ring, or a carbazole ring, or a biphenyl group is preferable because it efficiently delocalizes a negative charge and is excellent in stability and heat resistance.
  • Examples of the alkyl group or aromatic ring group for R 13 are the same as those for R 12 .
  • the cross-linking group for Ar 32 is not particularly limited, but preferred examples include a group derived from a benzocyclobutene ring, naphthocyclobutene ring or oxetane ring, vinyl group, acryl group and the like.
  • Each of Ar 11 to Ar 14 , R 11 to R 13 , Ar 21 to Ar 23 , Ar 31 to Ar 32 , Q 11 and Q 12 further has a substituent as long as it does not contradict the spirit of the present invention.
  • the molecular weight of the substituent is preferably 400 or less, more preferably 250 or less.
  • the type of substituent is not particularly limited, but examples thereof include one or more selected from the following substituent group W.
  • an alkyl group or an alkoxy group is preferable from the viewpoint of improving solubility, and an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable from the viewpoint of charge transportability and stability.
  • a polymer compound having a repeating unit represented by the following formula (14) exhibits extremely high hole injection/transport properties. preferable.
  • R 21 to R 25 each independently represent an arbitrary substituent. Specific examples of the substituents of R 21 to R 25 are described in [Substituent Group W] above. is the same as for the substituents s and t each independently represent an integer of 0 or more and 5 or less. u, v, and w each independently represent an integer of 0 to 4; )
  • aromatic tertiary amine polymer compounds include polymer compounds containing repeating units represented by the following formula (15) and/or formula (16).
  • each of Ar 45 , Ar 47 and Ar 48 independently has an optionally substituted monovalent aromatic hydrocarbon group or a substituent
  • Ar 44 and Ar 46 each independently represents a monovalent aromatic heterocyclic group which may be substituted, or a divalent aromatic hydrocarbon group which may be substituted or each of R 41 to R 43 independently represents a hydrogen atom or any substituent.
  • R 41 to R 43 are preferably a hydrogen atom or a substituent described in [Substituent group W] above, more preferably a hydrogen atom, an alkyl group, an alkoxy group, an amino group, or an aromatic hydrocarbon. or an aromatic heterocyclic group.
  • the hole injection layer-forming composition preferably contains an electron-accepting compound as a constituent material of the hole injection layer 3 .
  • the electron-accepting compound is preferably a compound that has oxidizing power and the ability to accept one electron from the above-mentioned hole-transporting material.
  • a compound having an electron affinity of 4.0 eV or more is preferable, and a compound having an electron affinity of 5.0 eV or more is more preferable.
  • electron-accepting compounds include the group consisting of triarylboron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids.
  • the electron-accepting compound includes an onium salt substituted with an organic group such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis(pentafluorophenyl)borate, triphenylsulfonium tetrafluoroborate (international publication No. 2005/089024, International Publication No. 2017/164268); iron (III) chloride (Japanese Patent Laid-Open No.
  • high-valent inorganic compounds such as ammonium peroxodisulfate; cyano such as tetracyanoethylene compounds, aromatic boron compounds such as tris(pentafluorophenyl)borane (Japanese Patent Laid-Open No. 2003-31365); fullerene derivatives; iodine; ions and the like.
  • the electron-accepting compound can improve the electrical conductivity of the hole-injection layer 3 by oxidizing the hole-transporting material.
  • the material of the hole injection layer 3 may contain other components in addition to the above-mentioned hole transporting material and electron accepting compound as long as the effects of the present invention are not significantly impaired.
  • At least one of the solvents of the composition for forming a hole injection layer used in the wet film-forming method is preferably a compound capable of dissolving the constituent material of the hole injection layer 3 described above.
  • the solvent is the first solvent component or the second solvent component in the present embodiment.
  • solvents examples include ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, and amide-based solvents.
  • ether-based solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, aromatic ethers such as phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole;
  • aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA)
  • 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole aromatic ethers such as phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxy
  • ester-based solvents include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.
  • aromatic hydrocarbon solvents examples include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, and methylnaphthalene.
  • amide solvents examples include N,N-dimethylformamide and N,N-dimethylacetamide.
  • dimethylsulfoxide and the like can also be used.
  • aromatic esters and aromatic ethers are preferred.
  • One type of these solvents may be used alone, or two or more types may be used in any combination and ratio.
  • the concentration of the hole-transporting material in the hole-injection layer-forming composition is arbitrary as long as it does not significantly impair the effects of the present invention.
  • the concentration of the hole transport material in the composition for forming a hole injection layer is preferably 0.01% by weight or more, more preferably 0.1% by weight or more, and still more preferably 0, from the viewpoint of uniformity of the film thickness. .5% by weight or more.
  • the concentration of the hole transport material in the composition for forming a hole injection layer is preferably 70% by weight or less, more preferably 60% by weight or less, and even more preferably 50% by weight or less. It is preferable that this density is small in that film thickness unevenness is less likely to occur.
  • the concentration is preferably large from the viewpoint that defects are less likely to occur in the formed hole injection layer.
  • the hole injection layer 3 is formed by a wet film formation method
  • the material constituting the hole injection layer 3 is usually mixed with an appropriate solvent (solvent for the hole injection layer) to form a film formation composition
  • a film formation composition A composition for forming a hole injection layer
  • this composition for forming a hole injection layer 3 is applied on a layer corresponding to the lower layer of the hole injection layer (usually, the anode 2) by an appropriate method.
  • the hole injection layer 3 is formed by forming a film using a heat treatment and drying it.
  • the hole injection layer 3 can be formed, for example, as follows.
  • One or two or more of the constituent materials of the hole injection layer 3 (the aforementioned hole transport material, electron-accepting compound, etc.) are placed in a crucible placed in a vacuum vessel (when two or more materials are used, each crucible), and the inside of the vacuum chamber is evacuated to about 10 ⁇ 4 Pa by a suitable vacuum pump.
  • the crucible is heated (each crucible is heated when two or more materials are used) to control the evaporation amount (when two or more materials are used, each evaporation amount is independent controlled evaporation) to form a hole injection layer 3 on the anode 2 of the substrate 1 placed opposite the crucible.
  • a mixture thereof can be placed in a crucible, heated and evaporated to form the hole injection layer 3 .
  • the degree of vacuum during vapor deposition is not limited as long as it does not significantly impair the effects of the present invention.
  • the degree of vacuum during vapor deposition is usually 0.1 ⁇ 10 ⁇ 6 Torr (0.13 ⁇ 10 ⁇ 4 Pa) or more and 9.0 ⁇ 10 ⁇ 6 Torr (12.0 ⁇ ⁇ 4 Pa) or less.
  • the vapor deposition rate is not limited as long as it does not significantly impair the effects of the present invention.
  • the deposition rate is usually 0.1 ⁇ /second or more and 5.0 ⁇ /second or less.
  • the film formation temperature during vapor deposition is not limited as long as it does not significantly impair the effects of the present invention.
  • the film forming temperature during vapor deposition is preferably 10° C. or higher and 50° C. or lower.
  • the hole transport layer 4 is a layer that transports from the anode 2 to the light emitting layer 5 .
  • the hole transport layer 4 is formed on the hole injection layer 3 when the hole injection layer 3 is present, or on the anode 2 when the hole injection layer 3 is not present.
  • the method for forming the hole transport layer 4 may be a vacuum deposition method or a wet film formation method, and is not particularly limited. From the viewpoint of reducing dark spots, the hole transport layer 4 is preferably formed by a wet film formation method.
  • the hole transport layer 4 contains a hole transport material.
  • the hole transport material forming the hole transport layer 4 a material having high hole transport properties and capable of efficiently transporting injected holes is preferable. Therefore, the hole-transporting material forming the hole-transporting layer 4 has a small ionization potential, a high transparency to visible light, a large hole mobility, an excellent stability, and an impurity that acts as a trap. is less likely to occur during manufacture or use.
  • the hole-transporting layer 4 is in contact with the light-emitting layer 5, so that the hole-transporting layer 4 does not quench light emitted from the light-emitting layer 5 or form an exciplex with the light-emitting layer 5 to reduce efficiency. preferable.
  • any material conventionally used as a constituent material for the hole-transporting layer 4 may be used.
  • Materials for the hole transport layer 4 include, for example, arylamine derivatives, fluorene derivatives, spiro derivatives, carbazole derivatives, pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, phthalocyanine derivatives, porphyrin derivatives, and silole derivatives. , oligothiophene derivatives, condensed polycyclic aromatic derivatives, and metal complexes.
  • the hole-transporting material for forming the hole-transporting layer 4 the hole-transporting material used in the composition for forming the hole-injection layer can be used.
  • hole transport materials for the hole transport layer 4 include polyvinylcarbazole derivatives, polyarylamine derivatives (arylamine polymers), polyvinyltriphenylamine derivatives, polyfluorene derivatives, polyarylene derivatives, and polyarylene containing tetraphenylbenzidine.
  • polyarylamine derivatives and polyarylene derivatives are preferable as the hole transport material for the hole transport layer 4 .
  • Specific examples of polyarylamine derivatives and polyarylene derivatives include those described in Japanese Patent Application Laid-Open No. 2008-98619.
  • As the polyarylamine derivative it is preferable to use an aromatic tertiary amine polymer compound represented by formula (50).
  • a composition for forming a hole transport layer is prepared in the same manner as in the formation of the hole injection layer 3, followed by wet film formation and drying.
  • the composition for forming a hole transport layer contains a solvent in addition to the hole transport material described above.
  • the solvent to be used is the same as that used for the composition for forming the hole injection layer.
  • the film forming conditions, drying conditions, etc. are the same as those for forming the hole injection layer 3 .
  • the hole transport layer-forming composition is the second composition in the present embodiment
  • the solvent is the first solvent component or the second solvent component in the present embodiment.
  • the film forming conditions and the like are the same as those for forming the hole injection layer 3 described above.
  • the film thickness of the hole-transporting layer 4 is usually 5 nm or more, preferably 10 nm or more, and usually 300 nm or less, taking into consideration factors such as penetration of the low-molecular-weight material into the light-emitting layer 5 and swelling of the hole-transporting material. It is preferably 200 nm or less.
  • the light-emitting layer 5 is a layer that is excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 between electrodes to which an electric field is applied, and becomes a main light source.
  • the light-emitting layer 5 is generally formed on the hole-transport layer 4 when the hole-transport layer 4 is present and on the hole-injection layer 3 when the hole-injection layer 3 is present. If neither the hole-transporting layer 4 nor the hole-injecting layer 3 is present above, they are formed on the anode 2 .
  • the light-emitting layer material usually contains a light-emitting material and a charge-transporting material serving as a host.
  • the light-emitting material any known material that is usually used as a light-emitting material for organic electroluminescence devices can be applied, and there is no particular limitation. Substances can be used.
  • the light-emitting material may be a fluorescent light-emitting material or a phosphorescent light-emitting material, but is preferably a phosphorescent light-emitting material from the viewpoint of internal quantum efficiency. More preferably, the red emitting material and the green emitting material are phosphorescent emitting materials, and the blue emitting material is fluorescent emitting material.
  • the second composition in the present embodiment is a composition for forming a light-emitting layer
  • a phosphorescent material is a material that emits light from an excited triplet state.
  • metal complex compounds containing Ir, Pt, Eu, etc. are typical examples, and materials containing metal complexes are preferable as the structure of the material.
  • the long-period periodic table (unless otherwise specified, the long-period periodic table ) include Werner-type complexes or organometallic complex compounds containing a metal selected from Groups 7 to 11 as a central metal.
  • phosphorescent light-emitting materials include, for example, International Publication No. 2014/024889, International Publication No. 2015-087961, International Publication No. 2016/194784, and phosphorescent materials described in Japanese Patent Application Laid-Open No. 2014-074000. is mentioned.
  • a compound represented by the following formula (201) or a compound represented by the following formula (205) is preferable, and a compound represented by the following formula (201) is more preferable.
  • ring A1 represents an optionally substituted aromatic hydrocarbon ring structure or an optionally substituted aromatic heterocyclic ring structure.
  • Ring A2 represents an aromatic heterocyclic structure optionally having a substituent.
  • R 201 and R 202 each independently represent a structure represented by formula (202), and "*" represents the bonding position with ring A1 or ring A2.
  • R 201 and R 202 may be the same or different, and when multiple R 201 and R 202 are present, they may be the same or different.
  • Ar 201 and Ar 203 each independently represent an optionally substituted aromatic hydrocarbon ring structure or an optionally substituted aromatic heterocyclic ring structure.
  • Ar 202 is an optionally substituted aromatic hydrocarbon ring structure, an optionally substituted aromatic heterocyclic ring structure, or an optionally substituted aliphatic hydrocarbon structure represents In formula (201), the substituents bonded to ring A1, the substituents bonded to ring A2, or the substituents bonded to ring A1 and the substituents bonded to ring A2 are bonded to each other to form a ring.
  • B 201 -L 200 -B 202 represents an anionic bidentate ligand.
  • B 201 and B 202 each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring.
  • L 200 represents a single bond or an atomic group forming a bidentate ligand together with B 201 and B 202 .
  • B 201 -L 200 -B 202 When there are multiple groups of B 201 -L 200 -B 202 , they may be the same or different.
  • i1 and i2 each independently represent an integer of 0 to 12
  • i3 represents an integer of 0 or more with the upper limit of the number that can be substituted for Ar 202
  • i4 represents an integer of 0 or more with the upper limit of the number that can be substituted for Ar 201
  • k1 and k2 each independently represent an integer of 0 or more, with the upper limit being the number that can be substituted on ring A1 and ring A2
  • z represents an integer of 1 to 3;
  • substituent is preferably a group selected from the following substituent group S.
  • 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 still more 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 an aryloxy group having 6 carbon atoms; aryloxy group.
  • 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, more preferably an alkylamino group having 1 to 12 carbon atoms;
  • An arylamino group preferably an arylamino group having 6 to 36 carbon atoms, 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 still more preferably an aralkyl group having 7 to 12 carbon atoms.
  • a 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, still more preferably an alkenyl group having 2 to 8 carbon atoms, particularly preferably an alkenyl group having 2 to 6 carbon atoms .
  • an alkynyl group preferably an alkynyl group having 2 to 20 carbon atoms, 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, still more preferably an aryl group having 6 to 18 carbon atoms, 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, particularly preferably 3 to 3 carbon atoms 14 heteroaryl groups.
  • An 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 in which the aryl group has 6 to 20 carbon atoms, more preferably an arylsilyl group in which the aryl group has 6 to 14 carbon atoms.
  • an alkylcarbonyl group preferably an alkylcarbonyl group having 2 to 20 carbon atoms
  • - an arylcarbonyl group preferably an arylcarbonyl group having 7 to 20 carbon atoms
  • One or more hydrogen atoms in the above substituent group S may be replaced with fluorine atoms, or one or more hydrogen atoms may be replaced with deuterium atoms.
  • aryl is an aromatic hydrocarbon ring and heteroaryl is a heteroaromatic ring.
  • substituent group S 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 groups thereof a group in which one or more hydrogen atoms of is replaced with a fluorine atom, a fluorine atom, a cyano group, or -SF5 , More 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 a group substituted with a fluorine atom, a fluorine atom, a cyano group, or —SF5
  • substituent groups S may further have a substituent selected from the substituent group S as a substituent.
  • Preferred groups, more preferred groups, further preferred groups, particularly preferred groups, and most preferred groups of the substituents which may be present are the same as the preferred groups in the substituent group S.
  • Ring A1 represents an optionally substituted aromatic hydrocarbon ring structure or an optionally substituted aromatic heterocyclic ring structure.
  • the aromatic hydrocarbon ring is preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms. Specifically, benzene ring, naphthalene ring, anthracene ring, triphenylyl ring, acenaphthene ring, fluoranthene ring, and fluorene ring are preferred.
  • an aromatic heterocyclic ring having 3 to 30 carbon atoms containing any one of a nitrogen atom, an oxygen atom, or a sulfur atom as a heteroatom is preferable.
  • furan ring benzofuran ring, thiophene ring and benzothiophene ring.
  • Ring A1 is more preferably a benzene ring, a naphthalene ring or a fluorene ring, particularly preferably a benzene ring or a fluorene ring, most preferably a benzene ring.
  • Ring A2 represents an aromatic heterocyclic structure optionally having a substituent.
  • the aromatic heterocyclic ring is preferably an aromatic heterocyclic ring having 3 to 30 carbon atoms containing a nitrogen atom, an oxygen atom or a sulfur atom as a heteroatom.
  • Ring A1 and Ring A2 Preferred combinations of ring A1 and ring A2 are represented by (ring A1-ring A2), (benzene ring-pyridine ring), (benzene ring-quinoline ring), (benzene ring-quinoxaline ring), (benzene ring- quinazoline ring), (benzene ring-benzothiazole ring), (benzene ring-imidazole ring), (benzene ring-pyrrole ring), (benzene ring-diazole ring), and (benzene ring-thiophene ring).
  • Ring A1 and the ring A2 may have may be optionally selected, but one or more substituents selected from the substituent group S are preferable.
  • Ar201 and Ar 203 each independently represent an optionally substituted aromatic hydrocarbon ring structure or an optionally substituted aromatic heterocyclic ring structure.
  • Ar 202 is an optionally substituted aromatic hydrocarbon ring structure, an optionally substituted aromatic heterocyclic ring structure, or an optionally substituted aliphatic hydrocarbon structure represents
  • the aromatic hydrocarbon ring structure is preferably an aromatic ring structure having 6 to 30 carbon atoms. is a group hydrocarbon ring. Specifically, benzene ring, naphthalene ring, anthracene ring, triphenylyl ring, acenaphthene ring, fluoranthene ring and fluorene ring are preferred, benzene ring, naphthalene ring and fluorene ring are more preferred, and benzene ring is most preferred.
  • Ar 201 or Ar 202 is an optionally substituted benzene ring
  • at least one benzene ring is preferably bonded to the adjacent structure at the ortho- or meta-position, and at least one More preferably, one benzene ring is attached to the adjacent structure at the meta position.
  • Ar 201 , Ar 202 and Ar 203 is a fluorene ring optionally having a substituent
  • the 9- and 9′-positions of the fluorene ring have a substituent or are bonded to the adjacent structure. preferably.
  • Ar 201 , Ar 202 and Ar 203 is an aromatic heterocyclic structure which may have a substituent
  • the aromatic heterocyclic structure preferably contains a nitrogen atom, an oxygen atom, or
  • Ar 201 , Ar 202 and Ar 203 is a carbazole ring optionally having a substituent
  • the N-position of the carbazole ring may have a substituent or be bonded to an adjacent structure. preferable.
  • Ar 202 is an optionally substituted aliphatic hydrocarbon structure, it is an aliphatic hydrocarbon structure having a linear, branched or cyclic structure, preferably having 1 to 24 carbon atoms. more preferably 1 or more and 12 or less carbon atoms, more preferably 1 or more and 8 or less carbon atoms.
  • i1 and i2 each independently represent an integer of 0-12, preferably an integer of 1-12, more preferably an integer of 1-8, more preferably an integer of 1-6. Within this range, an improvement in solubility and an improvement in charge transport properties can be expected.
  • i3 preferably represents an integer of 0-5, more preferably an integer of 0-2, more preferably 0 or 1.
  • i4 preferably represents an integer of 0 to 2, more preferably 0 or 1.
  • Each of k1 and k2 independently represents an integer of preferably 0 to 3, more preferably an integer of 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 above substituent group S, and preferred groups are also the above-mentioned substituents.
  • group S more preferably unsubstituted (hydrogen atom), alkyl group or aryl group, particularly preferably unsubstituted (hydrogen atom) or alkyl group, most preferably unsubstituted (hydrogen atom ) or a tertiary butyl group.
  • the tertiary butyl group preferably substitutes for Ar 203 when Ar 203 exists, for Ar 202 when Ar 203 does not exist, and for Ar 201 when Ar 202 and Ar 203 do not exist.
  • the compound represented by the above formula (201) is preferably a compound satisfying any one or more of the following (I) to (IV).
  • the structure represented by formula (202) is a structure having a group to which benzene rings are linked, that is, a benzene ring structure, i1 is an integer of 1 to 6, and at least one of the benzene rings is in the ortho position. Alternatively, it is preferably bound to the adjacent structure at the meta position. Such a structure is expected to improve the solubility and the charge transport property.
  • Ar 201 is an aromatic hydrocarbon structure or an aromatic heterocyclic structure
  • i1 is 1
  • Ar 202 is an aliphatic hydrocarbon structure
  • i2 is an integer of 1 to 12
  • Ar 203 is a benzene ring structure
  • i3 is 0 or 1
  • Ar 201 is the above aromatic hydrocarbon structure, more preferably a structure in which 1 to 5 benzene rings are linked, more preferably one benzene ring.
  • Such a structure is expected to improve the solubility and the charge transport property.
  • B 201 -L 200 -B 202 The structure represented by B 201 -L 200 -B 202 is preferably a structure represented by the following formula (203) or the following formula (204).
  • R 211 , R 212 and R 213 each independently represent a substituent.
  • ring B3 represents an aromatic heterocyclic structure containing a nitrogen atom, which may have a substituent. Ring B3 is preferably a pyridine ring.
  • the phosphorescent material represented by the above formula (201) is not particularly limited, but the following are preferred.
  • a phosphorescent material represented by the following formula (205) is also preferable.
  • M 2 represents a metal
  • 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, R 94 and R95 are not available.
  • M 2 in formula (205) include metals selected from Groups 7 to 11 of the periodic table. Among them, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum and gold are preferred, and divalent metals such as platinum and palladium are particularly preferred.
  • R 92 and R 93 each independently represent 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, a carboxyl group, represents an alkoxy group, an alkylamino group, an aralkylamino group, a haloalkyl group, a hydroxyl group, an aryloxy group, an aromatic hydrocarbon group or an aromatic heterocyclic group;
  • R94 and R95 each independently represent a substituent represented by the same examples as R92 and R93 .
  • R 92 to R 95 may further have a substituent.
  • the substituents may be the substituents described above.
  • any two or more groups selected from R 92 to R 95 may be linked together to form a ring.
  • the molecular weight of the phosphorescent material is preferably 5,000 or less, more preferably 4,000 or less, and particularly preferably 3,000 or less. Also, the molecular weight of the phosphorescent material is preferably 800 or more, more preferably 1000 or more, and even more preferably 1200 or more. It is believed that within this molecular weight range, the phosphorescent light-emitting material is not agglomerated and uniformly mixed with the charge-transporting material, making it possible to obtain a light-emitting layer with high light-emitting efficiency.
  • the molecular weight of the phosphorescent light-emitting material has a high Tg, melting point, decomposition temperature, etc., and the phosphorescent light-emitting material and the formed light-emitting layer have excellent heat resistance, and the film quality due to gas generation, recrystallization, molecular migration, etc. A large value is preferable from the viewpoint that it is difficult to cause a decrease in the concentration of impurities and an increase in the concentration of impurities due to thermal decomposition of the material.
  • the molecular weight of the phosphorescent light-emitting material is preferably small in terms of facilitating purification of the organic compound.
  • the charge-transporting material used in the light-emitting layer is a material having a skeleton with excellent charge-transporting properties, and may be selected from electron-transporting materials, hole-transporting materials, and bipolar materials capable of transporting both electrons and holes. preferable.
  • skeletons with excellent charge transport properties include aromatic structures, aromatic amine structures, triarylamine structures, dibenzofuran structures, naphthalene structures, phenanthrene structures, phthalocyanine structures, porphyrin structures, thiophene structures, benzylphenyl structures, fluorene structure, quinacridone structure, triphenylene structure, carbazole structure, pyrene structure, anthracene structure, phenanthroline structure, quinoline structure, pyridine structure, pyrimidine structure, triazine structure, oxadiazole structure, imidazole structure, and the like.
  • a compound having a pyridine structure, a pyrimidine structure, or a triazine structure is more preferable, and a compound having a pyrimidine structure or a triazine structure, from the viewpoint of being a material having excellent electron-transporting properties and having a relatively stable structure. is more preferred.
  • a hole-transporting material is a compound having a structure having excellent hole-transporting properties.
  • a pyrene structure is preferable as a structure having excellent hole transport properties, and a carbazole structure, a dibenzofuran structure, or a triarylamine structure is more preferable.
  • the charge-transporting material used in the light-emitting layer preferably has a condensed ring structure of three or more rings, and is a compound having two or more condensed ring structures of three or more rings or a compound having at least one condensed ring of five or more rings. is more preferred. These compounds increase the rigidity of the molecules, making it easier to obtain the effect of suppressing the degree of molecular motion in response to heat. Further, the 3 or more condensed rings and the 5 or more condensed rings preferably have an aromatic hydrocarbon ring or an aromatic heterocyclic ring from the viewpoint of charge transportability and material durability.
  • condensed ring structures having three or more rings include anthracene structure, phenanthrene structure, pyrene structure, chrysene structure, naphthacene structure, triphenylene structure, fluorene structure, benzofluorene structure, indenofluorene structure, indolofluorene structure, Carbazole structure, indenocarbazole structure, indolocarbazole structure, dibenzofuran structure, dibenzothiophene structure and the like.
  • a carbazole structure or an indolocarbazole structure is more preferred from the viewpoint of durability against electric charges.
  • At least one of the charge-transporting materials in the light-emitting layer is preferably a material having a pyrimidine skeleton or a triazine skeleton, from the viewpoint of the durability of the organic electroluminescent device against charges.
  • the charge-transporting material of the light-emitting layer is preferably a polymeric material from the viewpoint of excellent flexibility.
  • a light-emitting layer formed using a material having excellent flexibility is preferable as a light-emitting layer of an organic electroluminescent device formed on a flexible substrate.
  • the weight-average molecular weight is preferably 5,000 or more, more preferably 10,000 or more, and preferably 1,000,000 or less, more preferably 500,000 or less, more preferably 100,000 or less.
  • the charge-transporting material for the light-emitting layer is A low molecular weight is preferred.
  • 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 ,000 or less, preferably 300 or more, more preferably 350 or more, and still more preferably 400 or more.
  • the fluorescent light-emitting material is not particularly limited, but a compound represented by the following formula (211) is preferable.
  • Ar 241 represents an optionally substituted aromatic hydrocarbon condensed ring structure
  • Ar 242 and Ar 243 are each independently an optionally substituted alkyl group
  • It represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a group in which these are bonded.
  • n41 is an integer of 1-4.
  • Ar 241 preferably represents an aromatic hydrocarbon condensed ring structure having 10 to 30 carbon atoms, and specific ring structures include naphthalene, acenaphthene, fluorene, anthracene, phenathrene, fluoranthene, pyrene, tetracene, chrysene, perylene and the like. mentioned. Ar 241 is more preferably an aromatic hydrocarbon condensed ring structure having 12 to 20 carbon atoms, and specific ring structures include acenaphthene, fluorene, anthracene, phenathrene, fluoranthene, pyrene, tetracene, chrysene, and perylene. . Ar 241 is more preferably an aromatic hydrocarbon condensed ring structure having 16 to 18 carbon atoms, and specific ring structures include fluoranthene, pyrene and chrysene.
  • n41 is an integer of 1-4, preferably an integer of 1-3, more preferably 1 or 2, most preferably 2.
  • the alkyl group for Ar 242 and Ar 243 is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.
  • the aromatic hydrocarbon group for Ar 242 and Ar 243 is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 24 carbon atoms, most preferably a phenyl group. , is a naphthyl group.
  • the aromatic heterocyclic group for Ar 242 and Ar 243 is preferably an aromatic heterocyclic group having 3 to 30 carbon atoms, more preferably an aromatic heterocyclic group having 5 to 24 carbon atoms, specifically carbazolyl. group, dibenzofuranyl group and dibenzothiophenyl group are preferred, and dibenzofuranyl group is more preferred.
  • the substituent that Ar 241 , Ar 242 , and Ar 243 may have is preferably a group selected from the above substituent group S, more preferably a hydrocarbon group contained in the substituent group S, and still more preferably is a hydrocarbon group among preferred groups for the group S of substituents.
  • the charge-transporting material used together with the fluorescent light-emitting material is not particularly limited, but is preferably represented by the following formula (212).
  • R 251 and R 252 are each independently a structure represented by the following formula (213), R 253 represents a substituent, and when there are multiple R 253 , they are the same.
  • n43 is an integer of 0-8.
  • Ar 254 and Ar 255 are each independently an aromatic hydrocarbon structure optionally having a substituent, or a substituted represents a heteroaromatic ring structure optionally having a group, Ar 254 and Ar 255 may be the same or different when there are a plurality of each, n44 is an integer of 1 to 5, n45 is An integer from 0 to 5.
  • Ar 254 is preferably an optionally substituted monocyclic or condensed ring aromatic hydrocarbon structure having 6 to 30 carbon atoms, more preferably optionally substituted , is a monocyclic or condensed ring aromatic hydrocarbon structure having 6 to 12 carbon atoms.
  • Ar 255 is preferably an optionally substituted monocyclic or condensed ring aromatic hydrocarbon structure having 6 to 30 carbon atoms, or an optionally substituted carbon number of 6 to 30 is an aromatic heterocyclic ring structure that is a condensed ring of Ar 255 is more preferably an optionally substituted monocyclic or condensed ring aromatic hydrocarbon structure having 6 to 12 carbon atoms, or an optionally substituted carbon number of 6 to It is an aromatic heterocyclic ring structure with 12 condensed rings.
  • n44 is preferably an integer of 1-3, more preferably 1 or 2.
  • n45 is preferably an integer of 0-3, more preferably an integer of 0-2.
  • the substituent that the substituents R 253 , Ar 254 and Ar 255 may have is preferably a group selected from the above substituent group S. More preferably, it is a hydrocarbon group contained in the substituent group S, and more preferably a hydrocarbon group among groups preferable as the substituent group S.
  • the weight molecular weight of the fluorescence emitting material and the charge transport 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. Also, it is preferably 300 or more, more preferably 350 or more, and still more preferably 400 or more.
  • a hole blocking layer 6 may be provided between the light emitting layer 5 and an electron injection layer 8 which will be described later.
  • the hole-blocking layer 6 is a layer of the electron-transporting layer that also plays a role of blocking holes moving from the anode 2 from reaching the cathode 9 .
  • the hole blocking layer 6 is a layer laminated on the light emitting layer 5 so as to be in contact with the interface of the light emitting layer 5 on the cathode 9 side.
  • the hole-blocking layer 6 has a role of blocking holes moving from the anode 2 from reaching the cathode 9 and a role of efficiently transporting electrons injected from the cathode 9 toward the light-emitting layer 5. have.
  • Physical properties required for the material constituting the hole blocking layer 6 include high electron mobility and low hole mobility, a large energy gap (difference between HOMO and LUMO), and an excited triplet energy level (T1 ) is high.
  • Examples of materials for the hole blocking layer 6 satisfying these conditions include bis(2-methyl-8-quinolinolato)(phenolato)aluminum, bis(2-methyl-8-quinolinolato)(triphenylsilanolate)aluminum, and the like.
  • mixed ligand complexes bis (2-methyl-8-quinolato) aluminum- ⁇ -oxo-bis- (2-methyl-8-quinolinolato) aluminum binuclear metal complexes such as metal complexes, distyrylbiphenyl derivatives and the like Styryl compounds (Japanese Patent Laid-Open No. 11-242996), triazole derivatives such as 3-(4-biphenylyl)-4-phenyl-5(4-tert-butylphenyl)-1,2,4-triazole (Japan JP-A-7-41759), phenanthroline derivatives such as bathocuproine (JP-A-10-79297), and the like.
  • the compound having at least one pyridine ring substituted at the 2,4,6 positions described in International Publication No. 2005/022962 is also preferable as the material for the hole blocking layer 6 .
  • the method for forming the hole blocking layer 6 is not limited.
  • the hole blocking layer 6 can be formed by a wet film forming method, a vapor deposition method, or other methods.
  • the film thickness of the hole blocking layer 6 is arbitrary as long as it does not significantly impair the effects of the present invention.
  • the thickness of the hole blocking layer 6 is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less.
  • the electron transport layer 7 is a layer for transporting electrons provided between the light emitting layer 5 and the cathode 9 .
  • the electron injection efficiency from the cathode 9 or the adjacent layer on the cathode 9 side is usually high, and the injected electrons having high electron mobility can be efficiently transported.
  • a compound that can Compounds satisfying these conditions include, for example, metal complexes such as aluminum complexes and lithium complexes of 8-hydroxyquinoline (JP-A-59-194393), metal complexes of 10-hydroxybenzo[h]quinoline, Oxadiazole derivatives, distyrylbiphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Pat.
  • Electron transporting materials used in the electron transporting layer 7 include electron transporting organic compounds typified by nitrogen-containing heterocyclic compounds such as bathophenanthroline and metal complexes such as aluminum complexes of 8-hydroxyquinoline, sodium, potassium, and cesium.
  • Lithium by doping an alkali metal such as rubidium (described in JP-A-10-270171, JP-A-2002-100478, JP-A-2002-100482, etc.), electron injection It is preferable because it makes it possible to achieve both transportability and excellent film quality. It is also effective to dope the electron-transporting organic compound with an inorganic salt such as lithium fluoride or cesium carbonate.
  • the method for forming the electron transport layer 7 is not limited.
  • the electron transport layer 7 can be formed by a wet film-forming method, a vapor deposition method, or other methods.
  • the film thickness of the electron transport layer 7 is arbitrary as long as it does not significantly impair the effects of the present invention.
  • the 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.
  • an electron injection layer 8 may be provided between the electron transport layer 7 and the cathode 9, which will be described later.
  • the electron injection layer 8 is made of an inorganic salt or the like.
  • Examples of materials for the electron injection layer 8 include lithium fluoride (LiF), magnesium fluoride (MgF 2 ), lithium oxide (Li 2 O), cesium (II) carbonate (CsCO 3 ), and the like (Applied Physics Letters). , 1997, Vol.70, pp.152; Japanese Patent Laid-Open No. 10-74586; IEEE Transactions on Electron Devices, 1997, Vol.44, pp.1245; SID 04 Digest, pp.154, etc.).
  • the electron injection layer 8 Since the electron injection layer 8 often does not have a charge transport property, it is preferably used as an extremely thin film in order to efficiently perform electron injection, and the film thickness is usually 0.1 nm or more, preferably 5 nm or less. be.
  • the cathode 9 is an electrode that plays a role of injecting electrons into the layer on the light emitting layer 5 side.
  • Materials for the cathode 9 generally include metals such as aluminum, gold, silver, nickel, palladium and platinum, metal oxides such as indium and/or tin oxides, metal halides such as copper iodide, carbon black, Alternatively, conductive polymers such as poly(3-methylthiophene), polypyrrole, polyaniline, and the like can be used. Among these, metals having a low work function are preferred for efficient electron injection, and suitable metals such as tin, magnesium, indium, calcium, aluminum and silver, or alloys thereof are used. Specific examples include low work function alloy electrodes such as magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys.
  • Only one material may be used for the cathode 9, or two or more materials may be used in any combination and ratio.
  • the film thickness of the cathode 9 varies depending on the required transparency.
  • the visible light transmittance is usually 60% or more, preferably 80% or more.
  • the thickness of the cathode 9 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 cathode 9 can be arbitrary as long as it can be opaque, and the cathode can be the same as the substrate.
  • a metal having a high work function and being stable to the atmosphere is used for the purpose of protecting the cathode made of a low work function metal such as an alkali metal such as sodium or cesium, or an alkaline earth metal such as barium or calcium.
  • a metal having a high work function and being stable to the atmosphere is used for the purpose of protecting the cathode made of a low work function metal such as an alkali metal such as sodium or cesium, or an alkaline earth metal such as barium or calcium.
  • Lamination of metal layers is preferable because it increases the stability of the device.
  • Metals such as aluminum, silver, copper, nickel, chromium, gold, platinum, etc. are used for this purpose. These materials may be used alone, or two or more of them may be used in any combination and ratio.
  • the organic electroluminescence element in this embodiment may have another configuration without departing from the spirit thereof.
  • any layer may be provided between the anode 2 and the cathode 9 in addition to the layers described above. It may be omitted.
  • the layer structure described above it is also possible to stack components other than the substrate in the reverse order.
  • the injection layer 3 and the anode 2 may be provided in this order.
  • the organic electroluminescent element in the present embodiment may be configured as a single organic electroluminescent element, or may be applied to a configuration in which a plurality of organic electroluminescent elements are arranged in an array. It may be applied to a configuration arranged in a -Y matrix.
  • Each layer described above may contain components other than those described as materials as long as the effects of the present invention are not significantly impaired.
  • Organic electroluminescence device such as an organic EL display device or an organic EL lighting can be formed by providing two or more organic electroluminescence elements that emit light in different colors.
  • this organic electroluminescence device by using at least one, preferably all organic electroluminescence elements as the organic electroluminescence elements of the present embodiment, a high-quality organic electroluminescence device can be provided.
  • Organic EL display device There are no particular restrictions on the type and structure of the organic EL display device using the organic electroluminescence device of the present embodiment, and the organic electroluminescence device of the present embodiment can be assembled according to a conventional method.
  • an organic EL display device can be formed by a method as described in "Organic EL Display” (Ohmsha, August 20, 2004, written by Shizuo Tokito, Chihaya Adachi, and Hideyuki Murata). can.
  • Arylamine polymer 1 represented by the above formula was synthesized by a conventionally known method.
  • the weight average molecular weight was 29140
  • the molecular weight distribution represented by weight average molecular weight/number average molecular weight was 1.25
  • the glass transition point was 229°C.
  • a glass substrate having a thickness of 0.7 mm and a size of 25 ⁇ 37 mm was washed with UV/ozone.
  • a first composition was prepared by dissolving the arylamine polymer 1 produced above as a first functional material in anisole as a solvent, and a film was formed on the entire surface of a glass substrate by spin coating.
  • the content of the arylamine polymer in the first composition is 3.2 wt%. This was heated at 220° C. for 30 minutes in an N 2 atmosphere to obtain an insolubilized first functional film with a thickness of 100 nm.
  • the holding time (immersion time), the viscosity of the solvent component at 23° C., and the Hansen solubility parameter ⁇ P of the solvent component are as shown in Table 1, and the structural formula of each solvent component is also shown.
  • the second composition above contains only the solvent component. Therefore, the viscosity of the second composition at 23 ° C. is the same as the viscosity of the solvent component and the viscosity of the second composition when there is only one solvent component, that is, in the cases of Examples 1 to 8 and Comparative Examples 1 to 4. Viscosity is the same.
  • the viscosity of Example 8 is more than 15 mPa s, when actually obtaining an organic semiconductor device, the addition of a low-viscosity solvent, the decrease in the solid content concentration in the second composition, and the increase in viscosity It is preferable to set the viscosity of the second composition to 15 mPa ⁇ s or less by using a low-molecular-weight solid content that is difficult to dissolve.
  • the viscosity of the second composition is determined by the viscosity of the two solvent components and their content ratio.
  • the film thickness of the first functional film was determined by a reflection spectroscopic film thickness meter OPTM. Reflection spectra were measured at eight in-plane locations of the first functional film, and the measurement locations were the same among the substrates, and the reflection spectra were measured before and after ⁇ immersion of the first functional film>.
  • the concentration of the arylamine polymer in the first composition and the number of spin-coating rotations in advance nine types of thin films having different thicknesses of the first functional film were prepared, and the KOSAKA Surfcoder was used.
  • a calibrated optical model was generated by correlating the step thickness and reflectance spectra measured by . From the measured reflection spectrum, an optical model was used to calculate the optical film thickness at eight locations.
  • E-type viscometer RE85L manufactured by Toki Sangyo Co., Ltd.
  • Example 9 and Example 10 which contain the first solvent component of Example 5 and the second solvent component of Comparative Example 5, the residual film rate is high, and the appropriate solvent is included as the first solvent. Thus, it was found that the elution of the first functional material can be suppressed even in the presence of the second solvent.

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