WO2023163001A1 - Composition, organic electroluminescent element and method for producing same, display device, and lighting device - Google Patents
Composition, organic electroluminescent element and method for producing same, display device, and lighting device Download PDFInfo
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- WO2023163001A1 WO2023163001A1 PCT/JP2023/006325 JP2023006325W WO2023163001A1 WO 2023163001 A1 WO2023163001 A1 WO 2023163001A1 JP 2023006325 W JP2023006325 W JP 2023006325W WO 2023163001 A1 WO2023163001 A1 WO 2023163001A1
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- 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
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- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H05B33/00—Electroluminescent light sources
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- H10K50/15—Hole transporting layers
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- the present invention relates to a composition, an organic electroluminescent element and its manufacturing method, a display device, and a lighting device.
- organic electroluminescent elements instead of those using inorganic materials, organic electroluminescent elements using organic thin films have been developed.
- An organic electroluminescent device usually has a charge injection layer, a charge transport layer, an organic light emitting layer, an electron transport layer, etc. between an anode and a cathode, and materials suitable for each layer are being developed. Emission colors are also being developed into red, green, and blue.
- quantum dot light-emitting devices using "quantum dots", which are inorganic light-emitting substances, in the light-emitting layer of organic electroluminescence devices have also been developed.
- Methods for forming the organic layer of the organic electroluminescence device include a vacuum deposition method and a wet film forming method (coating method).
- the vacuum vapor deposition method facilitates lamination, and thus has the advantage of improving charge injection from the anode and/or cathode and facilitating confinement of excitons in the light-emitting layer.
- the wet film-forming method does not require a vacuum process and can easily be applied to a large area. There is an advantage that a layer containing the material can be formed. Therefore, in recent years, research and development of organic electroluminescence elements by film formation by a coating method have been vigorously carried out.
- Patent Document 1 discloses an organic electroluminescence device having a composition containing an arylamine polymer compound containing a cross-linking group and an electron-accepting compound.
- Patent Document 2 discloses an organic electroluminescence device having a composition containing a fluorine-containing arylamine polymer compound and an electron-accepting compound.
- Patent Literature 1 discloses that this technique was used to successfully reduce the hole injection barrier.
- the HOMO Highest Occupied Molecular Orbital
- an ion complex is formed from an organic electron donor of an arylamine polymer compound having fluorine and an organic electron acceptor.
- an organic electron acceptor that does not contain a cross-linking group is used as a photopolymerization initiator, and the diffusion of the organic electron acceptor to the light-emitting layer is not sufficiently prevented, and the luminous efficiency and driving life cannot be improved.
- the present invention has been made in view of the above-mentioned conventional circumstances, and an object of the present invention is to provide a composition for obtaining an organic electroluminescent device having a low driving voltage, a high luminous efficiency, and a long driving life. .
- the present inventors have found that a hole injection layer and/or a hole transport layer containing a cross-linking reaction product of an arylamine polymer compound with a specific structure and an electron-accepting compound with a specific structure can be used. Therefore, the inventors have found that the above problems can be solved in an organic electroluminescence device (OLED) or a quantum dot light-emitting device containing quantum dots in the light-emitting layer of the organic electroluminescence device, and have completed the present invention.
- OLED organic electroluminescence device
- quantum dot light-emitting device containing quantum dots in the light-emitting layer of the organic electroluminescence device
- the gist of the present invention is as follows in aspects 1 to 19.
- Aspect 1 of the present invention has a repeating unit represented by the following formula (1), has a fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group.
- a composition comprising a polymer compound and an electron-accepting compound having a cross-linking group represented by the following formula (81).
- Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group
- G represents a divalent group represented by any one of formulas (1-1) to (1-3)
- "*" represents the bonding position with the adjacent structure
- Each substituent A is independently a fluorine atom, CF3 , or SF5 .
- Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms.
- a plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group, m is an integer from 1 to 4, n is an integer of 1-6.
- R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
- Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
- X + represents a counter cation.
- Aspect 2 of the present invention is the composition according to Aspect 1, comprising the electron-accepting compound represented by the formula (81) having at least two cross-linking groups.
- Aspect 3 of the present invention is Aspect 1, wherein the compound represented by the formula (1) and the compound represented by the formula (81) each independently have a cross-linking group selected from the following cross-linking group group T: or a composition according to 2. ⁇ Crosslinking Group T>
- R 110 in formula (X4), formula (X5), formula (X6) and formula (X10) represents a hydrogen atom or an optionally substituted alkyl group.
- the benzene ring and naphthalene ring may have a substituent. Also, the substituents may be combined with each other to form a ring.
- the cyclobutene ring may have a substituent.
- Aspect 4 of the present invention is the composition according to any one of Aspects 1 to 3, wherein said G is represented by any of the following formulas.
- Aspect 5 of the present invention is the composition according to any one of Aspects 1 to 3, wherein [-G-Ar 2 ] is represented by any one of the following formulas.
- Ar 1 has one partial structure selected from the following formulas (2-1) to (2-3), or the following formulas (2-1) to (2- 3) having a bonding structure in which two or more selected from the following formulas (2-1) to (2-3) are bonded to each other, and the bonding structure bonds two or more structures of at least one type selected from the following formulas (2-1) to (2-3) 6.
- the composition of any one of aspects 1-5 which may contain a structure comprising:
- R 1 and R 2 each independently represent a hydrogen atom, a deuterium atom, a halogen atom, or an optionally substituted carbon number of 6 ⁇ 18 aromatic hydrocarbon groups, optionally substituted C3-C12 aromatic heterocyclic groups, C1-C12 alkyl groups, and "*" with the adjacent structure represents the binding position.
- Aspect 7 of the present invention is the composition according to any one of Aspects 1 to 6, wherein the polymer compound further has a repeating unit represented by the following formula (3).
- Ar 3 is an optionally substituted 2-fluorenyl group.
- Ar 4 is an optionally substituted divalent aromatic hydrocarbon group, A divalent aromatic heterocyclic group which may have a substituent, or a divalent aromatic hydrocarbon group which may have a substituent and a divalent which may have a substituent represents a divalent group in which at least two groups selected from the group consisting of aromatic heterocyclic groups are linked directly or via a linking group.
- Aspect 8 of the present invention is the composition according to any one of aspects 1 to 7, further comprising a solvent.
- Aspect 9 of the present invention is a method for manufacturing an organic electroluminescence device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode, wherein the organic layer is the A method for producing an organic electroluminescence device, comprising a step of forming by a wet film-forming method using the composition of
- a tenth aspect of the present invention is the method for producing an organic electroluminescent device according to Aspect 9, wherein the organic layer is an organic layer between the anode and the light-emitting layer.
- Embodiment 11 of the present invention is an organic electroluminescence device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode,
- the organic layer has a repeating unit represented by the following formula (1), has fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group.
- Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group
- G represents a divalent group represented by any one of formulas (1-1) to (1-3)
- "*" represents the binding site with the adjacent structure
- Each substituent A is independently a fluorine atom, CF3 , or SF5 .
- Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms.
- a plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group, m is an integer from 1 to 4, n is an integer of 1-6.
- R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
- Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
- X + represents a counter cation.
- Aspect 12 of the present invention is the organic electroluminescence device according to Aspect 11, wherein the G is represented by any one of the following formulas.
- Aspect 13 of the present invention is the organic electroluminescence device according to Aspect 11, wherein [-G-Ar 2 ] is represented by any one of the following formulas.
- Ar 1 has one partial structure selected from the following formulas (2-1) to (2-3), or the following formulas (2-1) to (2- 3) having a bonding structure in which two or more selected from the following formulas (2-1) to (2-3) are bonded to each other, and the bonding structure bonds two or more structures of at least one type selected from the following formulas (2-1) to (2-3) 14.
- the organic electroluminescent device according to any one of aspects 11 to 13, which may contain a structure with
- R 1 and R 2 are each independently a hydrogen atom, a deuterium atom, a halogen atom, or the number of carbon atoms which may have a substituent.
- Aspect 15 of the present invention is the organic electroluminescence device according to any one of Aspects 11 to 14, wherein the polymer compound further has a repeating unit represented by the following formula (3).
- Ar 3 is an optionally substituted 2-fluorenyl group.
- Ar 4 is an optionally substituted divalent aromatic hydrocarbon group, a substituted a divalent aromatic heterocyclic group optionally having a group, or a divalent aromatic hydrocarbon group optionally having a substituent and a divalent It represents a divalent group in which at least two groups selected from the group consisting of aromatic heterocyclic groups are linked directly or via a linking group.
- a sixteenth aspect of the present invention is an organic electroluminescent device manufactured by the method for manufacturing an organic electroluminescent device according to the ninth or tenth aspect.
- Aspect 17 of the present invention is the organic electroluminescent device according to any one of Aspects 11 to 16, which contains quantum dots in the light-emitting layer.
- Aspect 18 of the present invention is a display device comprising the organic electroluminescent element according to any one of Aspects 11 to 17.
- a nineteenth aspect of the present invention is a lighting device comprising the organic electroluminescent element according to any one of aspects 11 to 17.
- composition of the present invention can provide an organic electroluminescent device with low driving voltage, high luminous efficiency, and long driving life.
- FIG. 1 is a schematic cross-sectional view showing a structural example of the organic electroluminescence device of the present invention.
- the aromatic hydrocarbon group refers to a monovalent, divalent, or trivalent or higher aromatic hydrocarbon ring structure depending on the bonding state in the structure of the compound to be described later.
- the number of carbon atoms is usually not limited, but preferably 6 or more and 60 or less, and the upper limit of the carbon number is more preferably 48 or less, more preferably 48 or less. It has 30 or less carbon atoms.
- six-membered rings such as 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 ring.
- a monocyclic or 2 to 5 condensed ring group, or a structure in which a plurality of groups selected from these are linked together may be mentioned.
- a structure in which 2 to 10 rings are linked is usually mentioned, and a structure in which 2 to 5 rings are linked is preferable.
- a plurality of aromatic hydrocarbon rings are linked the same structure may be linked, or different structures may be linked.
- Preferred aromatic hydrocarbon ring structures include a benzene ring, a biphenyl ring, i.e., a structure in which two benzene rings are linked, a terphenyl ring, i.e., a structure in which three benzene rings are linked, a quaterphenylene ring, i.e., a structure in which four benzene rings are linked, and a naphthalene ring.
- the aromatic heterocyclic group refers to a monovalent, divalent, or trivalent or higher aromatic heterocyclic structure depending on the bonding state in the structure of the compound to be described later.
- the number of carbon atoms is generally not limited, but preferably 3 or more and 60 or less, and more preferably 48 or less as the upper limit of the carbon number, more preferably 48 or less. It has 30 or less carbon atoms.
- a plurality of aromatic heterocycles When a plurality of aromatic heterocycles are linked, the same structure may be linked, or different structures may be linked. When a plurality of aromatic heterocycles are linked, a structure in which 2 to 10 are linked is usually mentioned, and a structure in which 2 to 5 are linked is preferable.
- the aromatic heterocyclic ring structure is preferably a thiophene ring, a benzothiophene ring, a pyrimidine ring, a triazine ring, a carbazole ring, a dibenzofuran ring, or a dibenzothiophene ring.
- the substituent is an arbitrary group, preferably a group selected from the following substituent group Z and a bridging group.
- substituent group Z a group selected from the following substituent group Z and a bridging group.
- substituents are also as described in Substituent Group Z below.
- 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 diphenylamino group, a ditolylamino group, an N-carbazolyl group and the like. an arylalkylamino group having 7 or more and 36 or less, preferably 24 or less carbon atoms;
- a specific example is a phenylmethylamino group.
- Specific examples include an acetyl group and a benzoyl group.
- halogen atoms such as fluorine and chlorine atoms; A fluorine atom is preferred.
- the above substituents may have any structure of linear, branched or cyclic. When the above substituents are adjacent to each other, the adjacent substituents may be combined to form a ring.
- Preferred ring sizes are 4-, 5-, and 6-membered rings, and specific examples include cyclobutane, cyclopentane, and cyclohexane rings.
- alkyl groups alkyl groups, alkoxy groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups are preferred.
- each substituent in the substituent group Z may further have a substituent.
- substituents include the same as those in the above-mentioned substituent group Z or a bridging group.
- it has no further substituents, or an alkyl group with up to 8 carbon atoms, an alkoxy group with up to 8 carbon atoms, or a phenyl group, more preferably an alkyl group with up to 6 carbon atoms, or an alkoxy group with up to 6 carbon atoms. or a phenyl group. From the viewpoint of charge transport properties, it is more preferable not to have additional substituents.
- the crosslinkable group is preferably a crosslinkable group selected from the following crosslinkable group T.
- a substituent that preferably further has a bridging group is an alkyl group or an aromatic hydrocarbon 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.
- cross-linking groups represented by any one of the following formulas (X1) to (X18) in the following cross-linking group group T are preferable.
- R 110 in formula (X4), formula (X5), formula (X6) and formula (X10) represents a hydrogen atom or an optionally substituted alkyl group.
- the benzene ring and naphthalene ring may have a substituent. Also, the substituents may be combined with each other to form a ring.
- the cyclobutene ring may have a substituent.
- the linking group is not particularly limited, but is preferably an alkylene group, a divalent oxygen atom, or a divalent aromatic hydrocarbon group which may have a substituent.
- the alkylene group is generally an alkylene group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms.
- the divalent aromatic hydrocarbon group usually has 6 or more carbon atoms and usually 36 or less carbon atoms, preferably 30 or less, more preferably 24 or less, and the aromatic hydrocarbon ring structure is benzene A ring is preferred, and the substituents which may be present can be selected from the substituent group Z described above.
- the alkyl group represented by R 110 has a linear, branched or cyclic structure and has 1 or more carbon atoms, preferably 24 or less, more preferably 12 or less, and still more preferably 8 or less.
- the benzene ring and naphthalene ring of formulas (X1) to (X4) and the substituents that R 110 of formulas (X4) to (X6) and (X10) may have are preferably an alkyl group and an aromatic They are a hydrocarbon group, an alkyloxy group and an aralkyl group.
- the alkyl group as a substituent has a linear, branched or cyclic structure, and preferably has 24 or less carbon atoms, more preferably 12 or less carbon atoms, still more preferably 8 or less carbon atoms, and preferably 1 or more carbon atoms.
- the number of carbon atoms in the aromatic hydrocarbon group as a substituent is preferably 24 or less, more preferably 18 or less, still more preferably 12 or less, and preferably 6 or more.
- the aromatic hydrocarbon group may further have the aforementioned alkyl group as a substituent.
- the number of carbon atoms in the alkyloxy group as a substituent is preferably 24 or less, more preferably 12 or less, still more preferably 8 or less, and preferably 1 or more.
- the number of carbon atoms in the aralkyl group as a substituent is preferably 30 or less, more preferably 24 or less, even more preferably 14 or less, and preferably 7 or more.
- the alkylene group contained in the aralkyl group preferably has a linear or branched structure.
- the aryl group contained in the aralkyl group may further have the aforementioned alkyl group as a substituent.
- the substituent that the cyclobutene ring of formulas (X1) and (X2) may have is preferably an alkyl group.
- R 110 in formula (X4) is preferably a hydrogen atom or an unsubstituted alkyl group.
- R 110 in formulas (X5), (X6) and (X10) is preferably an optionally substituted alkyl group, more preferably an unsubstituted alkyl group.
- the alkyl group as a substituent has a linear, branched or cyclic structure, and preferably has 24 or less carbon atoms, more preferably 12 or less carbon atoms, still more preferably 8 or less carbon atoms, and preferably 1 or more carbon atoms.
- cross-linking group a cross-linking group represented by any one of the formulas (X1) to (X3) is preferable because the cross-linking reaction proceeds only with heat, the polarity is small, and the effect on charge transport is small.
- the cyclobutene ring is opened by heat, and the ring-opened groups bond to each other to form a bridging structure, as shown in the following formula.
- the linking group Q in formulas (X1) to (X4) and the like is omitted.
- the cyclobutene ring of the bridging group represented by formula (X2) is opened by heat, and the ring-opened groups bond to each other to form a bridging structure.
- the cyclobutene ring of the bridging group represented by formula (X3) is opened by heat, and the ring-opened groups bond to each other to form a bridging structure.
- the cyclobutene ring is opened by heat, and the ring-opened group reacts with the double bond when a double bond exists nearby. to form a crosslinked structure.
- cross-linking group represented by formula (X1) and the cross-linking group represented by formula (X4) having a double bond site form a cross-linked structure is shown below.
- the group containing a double bond capable of reacting with the cross-linking group represented by any one of formulas (X1) to (X3) includes, in addition to the cross-linking group represented by formula (X4), formula (X5), A cross-linking group represented by any one of formula (X6), formula (X12), formula (X15), formula (X16), formula (X17) and formula (X18) can be mentioned.
- a group containing these double bonds is used as a cross-linking group in an electron-accepting compound, other components forming a hole-injecting layer and/or a hole-transporting layer, such as a hole-transporting compound, are added with the formula (X1 ) to (X3) is preferable because the possibility of forming a crosslinked structure increases.
- cross-linking group a radically polymerizable cross-linking group represented by any one of the formulas (X4), (X5), and (X6) is preferred because it has a low polarity and does not easily interfere with charge transport.
- the cross-linking group represented by the formula (X7) is preferable from the viewpoint of enhancing the electron-accepting property.
- the cross-linking group represented by formula (X7) is used, the following cross-linking reaction proceeds.
- a cross-linking group represented by either formula (X8) or formula (X9) is preferable in terms of high reactivity.
- the cross-linking group represented by formula (X8) and the cross-linking group represented by formula (X9) are used, the following cross-linking reaction proceeds.
- cross-linking group a cationic polymerizable cross-linking group represented by any one of the formula (X10), the formula (X11), and the formula (X12) is preferable because of its high reactivity.
- a charge transport material used in the present invention is a material capable of transporting holes and/or electrons. Further, the charge transport material used in the present invention is preferably a material that transports holes and is oxidized by an electron-accepting compound to form a cation radical.
- the charge-transporting material is preferably a polymer compound, preferably a hole-transporting polymer compound, and preferably a polymer compound containing an arylamine structure as a repeating unit.
- the charge is usually holes
- the charge transport is the transport of holes
- the charge transport film is the hole transport film
- the charge injection layer is the hole injection layer.
- composition of the present invention has a repeating unit represented by the following formula (1), has a fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group.
- a polymer compound hereinafter sometimes referred to as "the fluorine-containing arylamine polymer compound of the present invention”
- an electron-accepting compound having a cross-linking group represented by the following formula (81) (hereinafter, " It is a composition containing the "electron-accepting compound of the present invention”.
- Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group
- G represents a divalent group represented by any one of formulas (1-1) to (1-3)
- "*" represents the bonding position with the adjacent structure
- Each substituent A is independently a fluorine atom, CF3 , or SF5 .
- Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms.
- a plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group, m is an integer from 1 to 4, n is an integer of 1-6.
- R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
- Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
- X + represents a counter cation.
- the composition of the present invention comprises a polymer compound having a repeating unit represented by the following formula (1) and having a cross-linking group, and an electron acceptor having at least two cross-linking groups represented by the following formula (81). It may be a composition containing a sexual compound.
- Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group
- G represents a divalent group represented by any one of formulas (1-1) to (1-3)
- Each substituent A is independently a fluorine atom, CF3 , or SF5 .
- Ar 2 is a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heterocyclic group having 3 to 50 carbon atoms, or a monovalent group selected from an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group linked directly or via a linking group. represents the group, m is an integer from 1 to 4, n is an integer of 1-6. )
- R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
- Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
- X + represents a counter cation.
- the polymer compound having a cross-linking group is preferably a polymer compound having a cross-linking group and having a repeating unit represented by the above formula (1) and containing an arylamine structure as a repeating unit. This polymer compound is included as a charge transport material in the composition of the present invention.
- the number of carbon atoms in the aromatic hydrocarbon group is preferably 6-60, more preferably 6-30, still more preferably 6-18.
- Specific examples of aromatic hydrocarbon groups include benzene ring, naphthalene ring, fluorene ring, anthracene ring, tetraphenylene ring, phenanthrene ring, chrysene ring, pyrene ring, benzanthracene ring, or perylene ring.
- a structure in which 2 to 8 rings are linked is usually mentioned, and a structure in which 2 to 5 rings are linked is preferable.
- a plurality of aromatic hydrocarbon rings are linked, the same structure may be linked, or different structures may be linked.
- the number of carbon atoms in the aromatic heterocyclic group is preferably 3-50, more preferably 3-30, still more preferably 3-18.
- Specific examples of the aromatic heterocyclic group include triazine ring, pyrimidine ring, pyridine ring, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, carbazole ring, etc., having usually 3 or more, usually 30 or less, preferably 18 carbon atoms.
- Ar 1 is an optionally substituted divalent aromatic hydrocarbon having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterohydrocarbon having 3 to 50 carbon atoms.
- a divalent group in which one or more groups selected from cyclic groups are bonded directly or via a linking group is preferable, and the hole transport property is improved.
- aromatic hydrocarbon group which may have a substituent is preferred, and the aromatic hydrocarbon group preferably has 1 to 4 benzene rings, 1 or 2 naphthalene rings, 1 or 2 fluorene A divalent group formed by chaining or branching a plurality of structures selected from a ring, one or two phenanthrene rings, and one tetraphenylene ring in any order, or 1,4-phenylene group, 1,3-phenylene group, 2,7-fluorenylene group, divalent spirobisfluorene group, more preferably 1 to 4 benzene rings, and 1 or 2 A divalent group formed by binding a plurality of structures selected from fluorene rings in a chain or branched manner in any order, particularly preferably one or two phenylene groups, 2,7-fluorenylene a divalent group in which one or two phenylene groups are bonded in this order in a chain, a phenylene group, a biphenylene group, a p
- aromatic hydrocarbon structures may have substituents.
- Substituents which may be present are as described above, and specifically can be selected from the substituent group Z.
- Preferred substituents are the preferred substituents of the substituent group Z described above.
- Ar 1 preferably has at least one structure selected from the following formulas (2-1) to (2-7) from the viewpoint of the solubility and durability of the polymer compound.
- * represents a bond with an adjacent structure or a hydrogen atom
- at least one of the two * represents a bonding position with an adjacent structure
- At least one of two arbitrary * selected from four * represents a binding position to an adjacent structure.
- R 1 and R 2 each independently represent a hydrogen atom, a deuterium atom, a halogen atom, an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or an optionally substituted It is preferably an aromatic heterocyclic group having 3 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms.
- Ar 1 has one partial structure selected from the above formulas (2-1) to (2-3), or two or more selected from the above formulas (2-1) to (2-3) are bonded to each other, and the bonding structure contains a structure in which two or more of at least one structure selected from the above formulas (2-1) to (2-3) are bonded good too.
- the bond structure may include, for example, a structure in which two or more structures of (2-1) above are bonded.
- R 1 and R 2 each independently represent a hydrogen atom, a deuterium atom, a halogen atom, an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, a substituent an aromatic heterocyclic group having 3 to 12 carbon atoms and an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 6 to 12 carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, and an aryl group.
- R 1 and R 2 may combine together to form a ring.
- aromatic hydrocarbon ring structure a phenyl group or a group in which a plurality of phenyl groups are linked is more preferable.
- substituents may have substituents.
- the substituents that may be present are as described above, and specifically, they can be selected from the substituent group Z or the bridging group.
- the partial structure is more preferably a structure selected from formulas (2-1) to (2-7), more preferably a structure selected from formulas (2-1) to (2-5), Structures selected from formulas (2-1) to (2-4) are particularly preferred. It is most preferable to have partial structures represented by formulas (2-2) and (2-3) because of their excellent charge transport properties.
- Formula (2-1) is preferably a 1,3-phenylene group or a 1,4-phenylene group.
- Formula (2-2) is preferably the following formula (2-2-2).
- Formula (2-2) is more preferably formula (2-2-3) below.
- Ar 1 preferably has a partial structure represented by formula (2-1) and a partial structure represented by formula (2-2) from the viewpoint of compound solubility and durability.
- the partial structure represented by formula (2-1) and the partial structure represented by formula (2-2) As the partial structure having the partial structure represented by formula (2-1) and the partial structure represented by formula (2-2), the partial structure represented by formula (2-1) and the partial structure represented by formula (2-2 A partial structure represented by at least one selected from the following formulas (2-8) to (2-11), which is a structure containing a plurality of structures selected from the partial structures represented by ), is more preferable. .
- the partial structure represented by formula (2-1) and the partial structures represented by formulas (2-3) and (2-4) the partial structure represented by formula (2-1) and a structure including a plurality of structures selected from partial structures represented by formulas (2-3) and (2-4), selected from the following formulas (2-12) to (2-15)
- a partial structure represented by at least one is more preferable.
- (G) G represents a divalent group represented by any one of the above formulas (1-1) to (1-3), and each substituent A is independently a fluorine atom, CF 3 , or SF 5 be. Among the above, the substituent A is preferably a fluorine atom or CF3 from the viewpoint of not reducing the charge transport ability. From the same point of view, m and n in formulas (1-1) to (1-3) are preferably integers of 1-2.
- G is preferably a group represented by any of the following formulas.
- Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms.
- a plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group.
- the plurality of Ar 2 when a plurality of Ar 2 are present, the plurality of Ar 2 may be the same or different.
- monovalent aromatic hydrocarbon groups include benzene ring, azulene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring and acenaphthene. 6-membered monocyclic or 2-5 condensed monovalent groups such as ring, fluoranthene ring, and fluorene ring.
- monovalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolo imidazole 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, pyridazine ring, 5- or 6-membered monocyclic ring or 2-4 condensed ring such as pyrimidine ring, triazine ring, quinoline ring, iso
- the linking group includes, for example, an oxygen atom or a carbonyl group. Since the triplet level can be increased by constructing a non-conjugated structure with an aromatic ring, a structure in which phenylene rings are linked by an oxygen atom or a carbonyl group can also be used. A structure in which they are directly linked without a linking group is preferred. The same applies to the linking group in Ar 1 .
- a monovalent aromatic hydrocarbon group is preferable, a monovalent group of a benzene ring or a fluorene ring is more preferable, and a phenyl group or a fluorenyl group is further preferable.
- a fluorenyl group is particularly preferred, and a 2-fluorenyl group is most preferred.
- Ar 2 is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms from the viewpoint of solubility in a coating solvent, and a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms. Especially preferred. Furthermore, Ar 2 is preferably a 9-alkyl-2-fluorenyl group in which a 2-fluorenyl group is substituted with an alkyl group at the 9-position, and particularly a 9,9-dialkyl-2-fluorenyl group in which an alkyl group is disubstituted. preferable. Ar 2 is preferably a fluorenyl group substituted with an alkyl group, because the solubility in a solvent is improved.
- a monovalent group in which a plurality of groups selected from an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group As can be used a monovalent group in which a plurality of groups selected from the aromatic hydrocarbon group and the aromatic heterocyclic group are linked directly or via a linking group.
- (-G- Ar2 ) [-G-Ar 2 ] is preferably a group represented by any one of the following formulae.
- a polymer compound having a cross-linking group has fluorene which may have a substituent in at least one of the main chain and the side chain.
- the above substituent is preferably a linear or branched alkyl group having 1 to 12 carbon atoms.
- the above substituents are preferably introduced into the 5-membered ring portion of fluorene. Examples of the polymer compound having fluorene in which the substituent is introduced into the 5-membered ring portion include polymer compound P-1 described later.
- Ar 51 represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a group in which a plurality of groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group are linked
- Ar 52 represents a divalent aromatic At least one group selected from the group consisting of a hydrocarbon group, a divalent aromatic heterocyclic group, or the divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group is directly or a linking group represents a divalent group in which a plurality of groups are linked via Ar 51 and Ar 52 may form a ring via a single bond or a linking group.
- Ar 51 and Ar 52 may have a substituent.
- the substituent that Ar 51 and Ar 52 may have is preferably a substituent selected from the substituent group Z or a cross-linking group.
- the cross-linking group is preferably a cross-linking group selected from the above-described cross-linking group T.
- the substituents 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 polymer compound used in the present invention.
- 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 preferably a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms, from the viewpoint of solubility in a solvent. . 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 solvents.
- repeating unit represented by the formula (50) examples include repeating units represented by the following formula (3).
- Ar 3 is an optionally substituted 2-fluorenyl group.
- Ar 4 is an optionally substituted divalent aromatic hydrocarbon group, a substituted a divalent aromatic heterocyclic group optionally having a group, or a divalent aromatic hydrocarbon group optionally having a substituent and a divalent It represents a divalent group in which at least two groups selected from the group consisting of aromatic heterocyclic groups are linked directly or via a linking group.
- Ar 51 in the repeating unit represented by the formula (50) is a group represented by the following formula (51), 52) or a repeating unit that is a group represented by the following formula (53).
- Ar 53 and Ar 54 are each independently a divalent aromatic hydrocarbon group optionally having a substituent, an aromatic heterocyclic group optionally having a substituent, or having a substituent represents a divalent group in which a plurality of optionally substituted aromatic heterocyclic groups or aromatic hydrocarbon groups are linked directly or via a linking group
- Ar 55 is an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, an optionally substituted aromatic hydrocarbon group or an aromatic represents a monovalent group in which multiple heterocyclic groups are linked 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 a substituent.
- the substituent that may be present is preferably a group selected from the above-described substituent group Z or a cross-linking group.
- Ar 53 is preferably a group in which 1 to 6 divalent aromatic hydrocarbon groups are linked, more preferably a group in which 2 to 4 divalent aromatic hydrocarbon groups are linked, especially 1 to 4 phenylene rings A group in which two phenylene rings are linked is more preferable, and a biphenylene group in which two phenylene rings are linked is particularly preferable.
- These groups may have a substituent.
- the substituent that may be present is preferably a group selected from the above-described substituent group Z or a cross-linking group.
- Ar 53 has no substituents.
- divalent aromatic hydrocarbon groups or divalent aromatic heterocyclic groups when a plurality of these divalent aromatic hydrocarbon groups or divalent aromatic heterocyclic groups are linked, it is preferably a group in which a plurality of 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, more preferably a 1,3- It is a group in which a plurality of phenylene groups or unsubstituted 1,3-phenylene groups are linked.
- Ar 54 is preferably a group in which one or more divalent aromatic hydrocarbon groups, which may be the same or different, are linked, and the divalent aromatic group hydrocarbon group may have a substituent. When multiple groups are linked, the number of linked groups is preferably 2 to 10, more preferably 6 or less, and particularly preferably 3 or less from the viewpoint of film stability.
- Preferred aromatic hydrocarbon ring structures are benzene ring, naphthalene ring, anthracene ring and fluorene ring, and more preferred are benzene ring and fluorene ring.
- a group in which 1 to 4 phenylene rings are linked or a group in which a phenylene ring and a fluorene ring are linked are preferable as the group in which a plurality of rings are linked.
- a biphenylene group in which two phenylene rings are linked is particularly preferable from the viewpoint of expanding LUMO.
- substituents may have substituents.
- the substituent that may be present is preferably a group selected from the above-described substituent group Z or a cross-linking group.
- Preferred substituents are phenyl, naphthyl and fluorenyl groups. Moreover, it is also preferable not to have a substituent.
- Ar 55 is an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, an optionally substituted aromatic hydrocarbon group or A monovalent group in which a plurality of aromatic heterocyclic groups are linked directly or via a linking group.
- it is a monovalent aromatic hydrocarbon group or a group in which a plurality of monovalent aromatic hydrocarbon groups are linked.
- the substituent that may be present is preferably a group selected from the above-described substituent group Z or a cross-linking group.
- 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 one of Schemes 2A, 2B and 2C below.
- "-*" represents the binding position to Ar 54 , and when there are multiple "-*"s, one of them represents the binding position to Ar 54 .
- These structures may have a substituent.
- the substituent that these structures may have is preferably a group or a cross-linking group selected from the substituent group Z, and when a cross-linking group is included, the cross-linking group is selected from the cross-linking group T groups are preferred.
- R 31 and R 32 in Schemes 2A and 2B 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, but all R 31 and R 32 are are preferably the same groups.
- Ar d18 in Scheme 2B is independently an aromatic hydrocarbon group or an aromatic heterocyclic group.
- Ar d18 is preferably an aromatic hydrocarbon group, more preferably a phenyl group, from the viewpoint of stability. These groups may further have a substituent.
- the substituent that may be present is preferably a group selected from the above-described substituent group Z or a cross-linking group.
- Ar 55 includes the above a-1 to a-4, b-1 to b-9, c-1 to c-4, d-1 to d-18, and e- 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, d-17, Structures selected from d-18, and e-1 through e-4 are preferred.
- a-1 to a-4, d-1 to d-12, d-17, d-18, and e- Structures selected from 1 to e-4 are preferred.
- d-1, d-10, d-17, d-18 and e-1 are more preferable, d-1 benzene ring structure, d-6 fluorene A ring structure or a d-17 carbazole structure is particularly preferred.
- the 9,9'-position may have a substituent, and the substituent that may have is preferably a group or a cross-linking group selected from the substituent group Z, and when having a cross-linking group, as a cross-linking group is preferably a group selected from the above-mentioned cross-linking group T.
- substituents an alkyl group is preferable.
- Ar 56 represents a hydrogen atom or a substituent.
- Ar 56 is not particularly limited, but is preferably an aromatic hydrocarbon group, an aromatic heterocyclic group or a bridging group. It may have a substituent selected from group Z or a cross-linking group selected from group T of cross-linking groups.
- Ar 56 is a cross-linking group, it is preferably a cross-linking group selected from the cross-linking group T.
- Ar 56 When Ar 56 is a substituent, it is preferably bonded to the 3-position of the carbazole structure to which Ar 56 is bonded in formula (51) from the viewpoint of improving durability.
- Ar 56 is preferably a hydrogen atom from the viewpoint of ease of synthesis and charge transport properties.
- Ar 56 is preferably an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group from the viewpoint of durability improvement and charge transport property. , is more preferably an aromatic hydrocarbon group which may have a substituent.
- Ar 56 is preferably a hydrogen atom from the viewpoint of ease of synthesis and charge transport properties.
- Ar 61 and Ar 62 each independently represent an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or a substituent
- Ar 63 to Ar 65 are each independently a hydrogen atom or a substituent. * represents the bonding position to the nitrogen atom of the main chain in formula (50).
- Ar 63 to Ar 65 are each independently the same as Ar 56 above.
- Ar 63 to Ar 64 are preferably hydrogen atoms.
- Ar 62 is an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or optionally substituted It is a divalent group in which a plurality of aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked 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.
- the substituents which the aromatic hydrocarbon group may have and the substituents which the aromatic heterocyclic group may have are preferably the same groups as those in the substituent group Z or the bridging groups.
- the cross-linking group a group selected from the cross-linking group T is preferable.
- a specific structure of Ar 62 is similar to that of Ar 54 .
- a specific preferred group for Ar 62 is a divalent group of a benzene ring, a naphthalene ring, 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 plurality of these It is a linked group, and particularly preferably a 1,4-phenylene group in which benzene rings are linked at the 1,4-position divalents, a 2,7-fluorenylene group in which the 2,7-positions of a fluorene ring are linked at a divalence, Or a group in which a plurality of these are linked, most preferably a group containing "1,4-phenylene group-2,7-fluorenylene group-1,4-phenylene group-".
- 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.
- the substituent is preferably a substituent or a cross-linking group selected from the substituent group Z, and more preferably an alkyl group. These substituents may be further substituted with a bridging group.
- the cross-linking group a cross-linking group selected from the cross-linking group T is preferable.
- a substituent selected from the substituent group Z is preferable.
- Ar61 Ar 61 is the same group as Ar 53 , and the preferred structure is also the same.
- Ar 71 represents a divalent aromatic hydrocarbon group
- Ar 72 and Ar 73 are each independently an aromatic hydrocarbon group, an aromatic heterocyclic group, or two or more groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group directly or via a linking group.
- Ring HA is an aromatic heterocycle containing a nitrogen atom
- X 2 and Y 2 each independently represent a carbon atom or a nitrogen atom, and when at least one of X 2 and Y 2 is a carbon atom, the carbon atom may have a substituent.
- the substituent that may be present is preferably a group selected from the substituent group Z or a cross-linking group.
- the cross-linking group is preferably a group selected from the above-mentioned cross-linking group T.
- Ar 71 is the same group as Ar 53 above.
- 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. .
- any one of the substituent group Z or a combination thereof can be used.
- the preferred range of the substituent that Ar 71 may have is the same as the substituent that Ar 53 may have when it is an aromatic hydrocarbon group.
- X2 and Y2 > X2 and Y2 each independently represent a C (carbon) atom or an N (nitrogen) atom.
- X 2 and Y 2 When at least one of X 2 and 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 the localization of LUMO around ring HA.
- any one of the substituent group Z or a combination thereof can be used as the substituent which may be possessed.
- X 2 and Y 2 more preferably have no substituents.
- Ar 72 and Ar 73 are each independently an aromatic hydrocarbon group, an aromatic heterocyclic group, or two or more groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group directly or via a linking group. is a monovalent group in which a plurality of groups are linked by These groups may have a substituent, and the substituent which may have is preferably a group selected from the substituent group Z or a bridging group. When it has a cross-linking group, the cross-linking group is preferably a group selected from the cross-linking group T described above.
- Ar 72 and Ar 73 are each independently a-1 to a-4, b-1 to b-9, c-1 to c-4 shown in Schemes 2A to 2C above. , d-1 to d-16, and e-1 to e-4.
- 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.
- Structures selected from d-1 to d-12 and e-1 to e-4 are more preferred to prevent aggregation of molecules.
- the repeating unit represented by the formula (50) is preferably a repeating unit represented by the following formula (54), a repeating unit represented by the following formula (55), or a repeating unit represented by the following formula (56). , a repeating unit represented by the following formula (57), and a repeating unit represented by the following formula (60).
- Ar 51 is the same as Ar 51 in the formula (50), X is -C(R 207 )(R 208 )-, -N(R 209 )- or -C(R 211 )(R 212 )-C(R 213 )(R 214 )-; R 201 , R 202 , R 221 and R 222 are each independently an optionally substituted alkyl group, R 207 to R 209 and R 211 to R 214 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituent.
- an aromatic hydrocarbon group which may have a and b are each independently an integer of 0 to 4; c is an integer from 0 to 3, d is an integer from 0 to 4, i and j are each independently an integer from 0 to 3; )
- R201 , R202 , R221 , R222 are each independently an optionally substituted alkyl group.
- 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 201 may be the same or different, and when there is a plurality of R 202 , the plurality of R 202 may be the same or different. All R 201 and R 202 are preferably the same group because the charge can be uniformly distributed around the nitrogen atom and the synthesis is easy.
- the multiple R 221 may be the same or different, and when there is the multiple R 222 , the multiple R 222 may be the same or different. All R 221 and R 222 are preferably the same group for ease of synthesis.
- R 207 to R 209 and R 211 to R 214 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted is an aromatic hydrocarbon group which may be
- 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 207 and R 208 are preferably methyl groups or aromatic hydrocarbon groups, R 207 and R 208 are more preferably methyl groups, and R 209 is a phenyl group. is more preferable.
- the alkyl groups of R 201 , R 202 , R 221 and R 222 , the alkyl groups of R 207 to R 209 and R 211 to R 214 , the aralkyl groups and the aromatic hydrocarbon groups may have substituents.
- substituents include groups or bridging groups exemplified as preferable groups of the alkyl groups, aralkyl groups and aromatic hydrocarbon groups of R 207 to R 209 and R 211 to R 214 .
- Examples of the cross-linking group include cross-linking groups selected from the cross-linking group T described above.
- the alkyl groups represented by R 201 , R 202 , R 221 and R 222 , the alkyl groups represented by R 207 to R 209 and R 211 to R 214 , the aralkyl groups and the aromatic hydrocarbon groups are substituents from the viewpoint of voltage reduction. It is most preferred not to have
- a and b are each independently an integer of 0-4. It is preferable that a+b is 1 or more, more preferably each of a and b is 2 or less, and more preferably both a and b are 1.
- b is 1 or more
- d is also 1 or more.
- c is 2 or more
- a plurality of a's may be the same or different
- d is 2 or more
- a plurality of b's may be the same or different.
- c is an integer of 0-3 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 201 and R 202 are most preferably bonded at symmetrical positions.
- the binding of R 201 and R 202 at symmetrical positions means that the binding positions of R 201 and R 202 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.
- R 221 and R 222 are each independently preferably present at the 1-, 3-, 6-, or 8-position relative to the carbon atom of the benzene ring to which X is bonded. Due to the presence of R 221 and / or R 222 at this position, the condensed ring to which R 221 and / or R 222 is bonded and the adjacent benzene ring on the main chain are twisted due to steric hindrance, resulting in a polymer is excellent in solubility in a solvent, and a coating film formed by a wet film-forming method and then heat-treated tends to be excellent in solubility in a solvent, which is preferable.
- i+j is preferably 1 or more, i and j are each preferably 2 or less, and both i and j are more preferably 1.
- (X) X in the above formula (54) is preferably -C(R 207 )(R 208 )- or -N(R 209 )- because of its high stability during charge transport, and -C(R 207 )(R 208 )— 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 (54-8).
- R 201 and R 202 are the same, and R 201 and R 202 are 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, for example, the following structure is preferable.
- Ar 51 is the same as Ar 51 in the formula (54), R 303 and R 306 are each independently an optionally substituted alkyl group, R 304 and R 305 are each independently an optionally substituted alkyl group, an optionally substituted alkoxy group or an optionally substituted aralkyl group, l is 0 or 1, m is 1 or 2, n is 0 or 1, p is 0 or 1, q is 0 or 1; )
- R303 , R306 R 303 and R 306 in the repeating unit represented by formula (55) are each independently an optionally substituted alkyl group.
- alkyl group examples include the same as those for R 201 and R 202 in the formula (54), and the same substituents and preferred structures as those for R 201 and R 202 may be mentioned.
- the plurality of R 303 may be the same or different, and when there is a plurality of R 306 , the plurality of R 306 may be the same or different.
- R304 , R305 ) R 304 and R 305 in the repeating unit represented by the formula (55) are each independently an optionally substituted alkyl group, an optionally substituted alkoxy group, or a substituted It is an aralkyl group which may have a group. An optionally substituted alkyl group is preferred. R 304 and R 304 are preferably the same.
- 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, it preferably has 5 or more carbon atoms, 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 substituents that the alkyl group, alkoxy group and aralkyl group of R 304 and R 305 may have are the preferred groups of the alkyl group, aralkyl group and aromatic hydrocarbon group of R 207 to R 209 and R 211 to R 214
- Examples of the cross-linking group include cross-linking groups selected from the cross-linking group group T described above.
- the alkyl group, alkoxy group and aralkyl group of R 304 and R 305 most preferably have no substituent from the viewpoint of voltage reduction.
- the cross-linking group is preferably bonded to R 304 and R 305 .
- l and n are each independent, and l+n is preferably 1 or more, more preferably 1 or 2, and still more preferably 2.
- l+n is within the above range, the solubility of the polymer tends to be high and precipitation from the composition of the present invention containing the polymer can be suppressed.
- n 1 or 2
- the organic electroluminescent device manufactured using the composition of the present invention can be driven at a low voltage, and the hole injection ability, transport ability, and durability tend to be improved. is preferably
- (p and q) p represents 0 or 1; q represents 0 or 1;
- l 2 or more, multiple p may be the same or different, and when n is 2 or more, multiple q may be the same or different.
- p and q are not 0 at the same time, the solubility of the polymer is increased, and precipitation from the composition of the present invention containing the polymer tends to be suppressed.
- p+q 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.
- Heat-treated coatings tend to be excellent in solvent insolubility. Therefore, when p + q is 1 or more, when forming another organic layer (for example, a light-emitting layer) on this coating film by a wet film-forming method, a composition for forming another organic layer containing an organic solvent elution of the polymer is suppressed.
- another organic layer for example, a light-emitting layer
- 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 (54), Ar 41 is an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or the aforementioned divalent aromatic hydrocarbon group and at least one group selected from the group consisting of the divalent aromatic heterocyclic groups is a divalent group in which a plurality of groups are linked directly or via a linking group, R 441 and R 442 are each independently an optionally substituted alkyl group, t is 1 or 2; u is 0 or 1, r and s are each independently an integer of 0-4. )
- R441 , R442 ) R 441 and R 442 in the repeating unit represented by formula (56) are each independently an optionally substituted alkyl group.
- 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.
- the plurality of R 441 and R 442 may be the same or different.
- r and s are each independently an integer of 0-4.
- t is 2 or more, multiple r may be the same or different, and when u is 2 or more, multiple s may be the same or different.
- r+s is preferably 1 or more, and r and s are each preferably 2 or less. When r+s is 1 or more, the drive life of the organic electroluminescence device is considered to be longer 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 an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or the aforementioned divalent aromatic hydrocarbon group and a divalent group in which at least one group selected from the group consisting of the above divalent aromatic heterocyclic groups is linked 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). Further, the aromatic hydrocarbon group and the substituent which the aromatic hydrocarbon group may have are preferably groups selected from the above substituent group Z, and the substituent which may be further included in the above substituent group Z is preferably the same as
- Ar 51 is the same as Ar 51 in the formula (54), R 517 to R 519 each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aralkyl group, or a substituent represents an aromatic hydrocarbon group which may have or an aromatic heterocyclic group which may have a substituent, f, g, and h each independently represent an integer of 0 to 4, e represents an integer of 0 to 3, However, when g is 1 or more, e is 1 or more. )
- R 517 to R 519 The aromatic hydrocarbon group and aromatic heterocyclic group in R 517 to R 519 are each independently the same groups as those listed for Ar 51 above, and the substituents these groups may have The group is preferably a group or a cross-linking group selected from the same groups as in the substituent group Z, and the cross-linking group is preferably a cross-linking group selected from the cross-linking group T.
- the alkyl group and aralkyl group for R 517 to R 519 are preferably the same groups as those mentioned for R 207 above, and the substituents which may be further included are preferably the same groups as those for R 207 above.
- the alkoxy groups in R 517 to R 519 are preferably the alkoxy groups listed in the above substituent group Z, and the substituents which may be further included are preferably groups selected from the above substituent group Z.
- (f, g, h) f, g, and h each independently represent an integer of 0-4.
- e is 2 or more, multiple g's may be the same or different.
- f+g+h is preferably 1 or more.
- f + h is preferably 1 or more, f + h is 1 or more, and f, g and h are more preferably 2 or less, It is more preferable that f+h is 1 or more, and f and h are 1 or less, Most preferably, both f and h are 1.
- R 517 and R 519 are preferably bonded at symmetrical positions.
- R 517 and R 519 are preferably the same,
- g is two. when g is 2, the two R 518 are most preferably attached to each other in the para position; When g is 2, the two R 518 are most preferably identical.
- binding positions of R 517 and R 519 that 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 the formula (57) is preferably a repeating unit represented by the following formula (58).
- the binding positions are the 2nd and 5th positions.
- g 0, i.e., when there is no steric hindrance by R 518
- R 517 and R 519 can be bonded at symmetrical positions.
- the binding positions are the 2nd and 5th positions.
- g 0, i.e., when there is no steric hindrance by R 518
- R 517 and R 519 can be combined at symmetrical positions.
- main chain of repeating unit represented by formula (57) is not particularly limited, and examples thereof include the following structures.
- Ar 51 is the same as Ar 51 in the formula (50), n 60 represents an integer of 1-5. )
- n60 represents an integer of 1-5, preferably an integer of 1-4, more preferably an integer of 1-3.
- the terminal group refers to the structure of the terminal portion of the polymer compound formed by the end capping agent used at the end of polymerization of the polymer compound.
- the terminal group of the polymer compound containing the repeating unit represented by formula (1) 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 group examples include 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 pheny
- hydrocarbon groups may further have a substituent, and the substituent that may further have is preferably an alkyl group or an aromatic hydrocarbon group. Further, when there are a plurality of substituents which may be possessed, they may be combined with each other to form a ring. When these hydrocarbon groups are groups other than cross-linking groups, the substituent may further have a cross-linking group selected from the above-described cross-linking group T.
- the terminal group is preferably an alkyl group, an aromatic hydrocarbon group, or a cross-linking group that is a hydrocarbon group in the cross-linking group group T, more preferably an aromatic
- the weight-average molecular weight (Mw) of the fluorine-containing arylamine polymer compound is usually 1,000,000 or less, preferably 500,000 or less, more preferably 100,000 or less, and still more preferably 70,000 or less. Particularly preferably, it is 50,000 or less. Moreover, the weight average molecular weight is usually 5,000 or more, preferably 10,000 or more, more preferably 12,000 or more, and particularly preferably 15,000 or more.
- the weight-average molecular weight of the fluorine-containing arylamine polymer compound is equal to or less than the above upper limit, solubility in a solvent is obtained, and film-forming properties tend to be excellent. Further, when the weight average molecular weight of the polymer compound is at least the above lower limit, the decrease in the glass transition temperature, melting point and vaporization temperature of the polymer compound may be suppressed and the heat resistance may be improved. In addition, in some cases, the coating film after the cross-linking reaction is sufficiently insoluble in organic solvents.
- the number average molecular weight (Mn) of the fluorine-containing arylamine polymer compound is generally 750,000 or less, preferably 250,000 or less, more preferably 100,000 or less, and particularly preferably 50,000 or less. be. Moreover, 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 polydispersity (Mw/Mn) of the fluorine-containing arylamine polymer compound 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 compound are determined by SEC (size exclusion chromatography) measurement.
- SEC size exclusion chromatography
- the weight average molecular weight and number average molecular weight are calculated.
- the content of the repeating unit represented by formula (1) is not particularly limited, but the repeating unit represented by formula (1) is usually 10 mol per 100 mol% of all repeating units in the polymer compound. % 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 (1). It may have a repeating unit other than the repeating unit shown. In that case, the content of the repeating unit represented by formula (1) in the polymer is usually 99 mol % or less, preferably 95 mol % or less.
- These polymer compounds 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 polymer compound contained in the composition of the present invention 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. Moreover, it can be manufactured by the manufacturing method similar to the manufacturing method of the polymer as described in WO2019/177175, WO2020/171190, and WO2021/125011.
- an aryl dihalide represented by the following formula (2a) Z represents a halogen atom such as I, Br, Cl, F
- a polymer containing a repeating unit represented by the formula (54) is synthesized by reacting it with a primary aminoaryl represented by the formula (2b).
- an aryl dihalide represented by the formula (3a) Z represents a halogen atom such as I, Br, Cl, F
- a polymer containing a repeating unit represented by formula (55) is synthesized by reacting it with a primary aminoaryl represented by formula (3b).
- 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 fluorine-containing arylamine polymer compound of the present invention is preferably 10% by mass or more, and preferably 25% by mass. The above is more preferable, and 30% by mass or more is even more preferable.
- the content of the fluorine-containing arylamine polymer compound of the present invention in the composition of the present invention is 99% in terms of the composition ratio of the solid components of the composition. It is preferably 90% by mass or less, more preferably 80% by mass or less.
- a hole injection layer or a hole In order to improve the hole injection property from the anode to the hole injection layer or the hole transport layer, or to improve the charge transport property in the hole injection layer or the hole transport layer, a hole injection layer or a hole
- the charge transport material contained in the transport layer preferably contains cation radical sites.
- An electron-accepting compound is used when forming a hole-injecting layer or a hole-transporting layer in order to convert the charge-transporting material into cation radicals.
- an ionic compound composed of a tetraarylborate ion, which is an anion having an ion valence of 1, and a counter cation, which will be described later, is preferable because of its high stability.
- Cation radicalization of the charge transport material is carried out as follows.
- a hole-injecting layer or a hole-transporting layer can be formed by using a tetraarylborate having a diaryliodonium as a counter cation as an electron-accepting compound.
- the counter cation can change from a diaryliodonium to an arylamine cation, as in the formula below.
- Ar, Ar 1′ to Ar 4′ each independently represent an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, or a substituent It is a monovalent group in which a plurality of structures selected from an optionally substituted aromatic hydrocarbon ring group and an optionally substituted aromatic heterocyclic group are linked.
- the tetraarylborate used as the arylamine ion counter cation is an electron-accepting compound.
- a compound composed of tetraarylborate ions, which are cations and anions of the charge-transporting material is referred to as a charge-transporting ionic compound. Details will be described later.
- the hole injection layer and/or the hole transport layer of the organic electroluminescent device of the present invention is preferably obtained by wet film formation of the composition of the present invention. It is preferably a composition obtained through a step of dissolving or dispersing an electron-accepting compound having a tetraarylborate ion structure and a charge-transporting material described later in an organic solvent.
- a charge-transporting ionic compound having the tetraarylborate ion structure of the present invention described later as an anion and the cation of the charge transport material of the present invention as a counter cation is used. preferably included.
- the composition of the present invention contains a polymer compound having a cross-linking group and an electron-accepting compound having a cross-linking group. Therefore, the organic layer formed by the wet film-forming method using the composition of the present invention contains a cross-linked reaction product of a polymer compound having a cross-linking group and an electron-accepting compound having a cross-linking group. Furthermore, as will be described later, the electron-accepting compound of the present invention is preferably an ionic compound consisting of a tetraarylborate ion and a counter cation, and the tetraarylborate ion preferably has a cross-linking group.
- the organic layer can contain a cross-linking reactant containing the following cross-linked structure.
- ⁇ Crosslinked structure between polymer compound and electron-accepting compound ⁇ Crosslinked structure between crosslinkable groups of polymer compound
- ⁇ Crosslinked structure between electron-accepting compounds ⁇ Crosslinked structure between electron-accepting compound and tetraarylborate ion ⁇ Tetraarylborate
- the tetraarylborate ion is an anion structural site that constitutes the electron-accepting compound.
- the tetraarylborate ion is a tetraarylborate ion ionically bonded to the cation radical of the polymer compound. Details will be described later.
- the “tetraarylborate ion in the present invention” refers to the case where it exists as an electron-accepting compound that is an ionic compound consisting of a tetraarylborate ion and a counter cation described later, and a tetraarylborate ion described later. and the cation of the charge-transporting material as a charge-transporting ionic compound.
- the two cross-linking groups that undergo a cross-linking reaction may be the same cross-linking group or different cross-linking groups as long as they are cross-linkable.
- the electron-accepting compound which is an ionic compound composed of a tetraarylborate ion and a counter cation, is an electron-accepting ionic compound composed of a counter anion, which is a non-coordinating anion represented by the following formula (81), and a counter cation, , has a bridging group.
- the non-coordinating anion represented by formula (81) below preferably has formula (83), which will be described later, as a tetraarylborate ion.
- the electron-accepting compound used in the present invention may be called an electron-accepting ion compound.
- R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
- Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
- X + represents a counter cation.
- the electron-accepting compound represented by formula (81) has a cross-linking group, and the number of cross-linking groups is preferably two or more.
- the bridging group is preferably provided in the anion portion of the electron-accepting compound represented by the formula (81), that is, the compound represented by the below-described formula (82), which is a tetraarylborate ion.
- a tetraarylborate ion is an anion of the above formula (81) represented by the following formula (82).
- R 81 to R 84 are the same as R 81 to R 84 in formula (81).
- Ph 1 to Ph 4 are the same as Ph 1 to Ph 4 in formula (81), and are symbols indicating four benzene rings.
- the aromatic hydrocarbon group used for R 81 to R 84 preferably has 6 to 50 carbon atoms.
- As the aromatic hydrocarbon ring structure a single ring, 2 to 6 condensed rings, and a structure in which 2 to 8 of these are linked are preferable.
- aromatic hydrocarbon groups 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
- aromatic hydrocarbon groups 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
- the aromatic heterocyclic group used for R 81 to R 84 preferably has 3 to 50 carbon atoms.
- the aromatic heterocyclic ring structure a single ring, 2 to 6 condensed rings, and a structure in which 2 to 8 of these are linked are preferable.
- aromatic heterocyclic groups include 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, pyridazine ring, pyrimidine ring, a single monovalent group of triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinox
- the aromatic heterocyclic group referred to herein may contain at least one of these independent structures, and the connecting structure may contain an aromatic hydrocarbon ring structure.
- the connecting structure may contain an aromatic hydrocarbon ring structure.
- it may have a structure in which 2 to 8 of the above aromatic heterocycles and aromatic hydrocarbon rings are combined.
- the aromatic hydrocarbon ring a single structure of the aromatic hydrocarbon ring used for R 81 to R 84 can be used.
- monovalent groups such as benzene, naphthalene, fluorene, pyridine or carbazole rings, or biphenyl groups in which 2 to 5 of these groups are linked. groups are more preferred.
- a monovalent group of a benzene ring or a group in which 2 to 5 benzene rings are linked is particularly preferred, and specific examples thereof include a phenyl group, a biphenyl group and a terphenyl group.
- the aromatic hydrocarbon group is a biphenyl group, a terphenyl group, or a quaterphenyl group, it is regarded as a structure in which two, three, or four phenyl groups are linked, respectively.
- R 81 to R 84 may have, a group selected from the substituent group Z or the bridging group group T is preferable.
- R 81 to R 84 are each independently preferably a fluorine atom or a fluorine-substituted alkyl group from the viewpoint of increasing the stability of the anion and improving the effect of stabilizing the cation. Moreover, it preferably contains two or more fluorine atoms or fluorine-substituted alkyl groups, more preferably three or more, and most preferably four.
- the fluorine-substituted alkyl group used for R 81 to R 84 is preferably a linear or branched alkyl group having 1 to 12 carbon atoms and is substituted with a fluorine atom, more preferably a perfluoroalkyl group.
- a linear or branched perfluoroalkyl group having 1 to 5 carbon atoms is more preferable, a linear or branched perfluoroalkyl group having 1 to 3 carbon atoms is particularly preferable, and a perfluoromethyl group is most preferable.
- the reason for this is that the charge injection layer containing the cross-linking reaction product of the electron-accepting compound having a cross-linking group and the coating film laminated thereon are stabilized.
- the fluorine-substituted alkyl group is preferably attached to the para-position of the boron atom.
- the tetraarylborate ion further increases the stability of the anion and further improves the effect of stabilizing the cation.
- At least one of (R 82 ) 5 , *-Ph 3 -(R 83 ) 5 , *-Ph 4 -(R 84 ) 5 (* represents a bond with boron B in formula (82)) It is preferably a group represented by the following formula (84) having four fluorine atoms, and in terms of improving the stability of the anion, it is preferable that at least two of them are groups represented by the same formula (84). More preferably, at least three of them are the same group represented by the following formula (84) from the viewpoint of further improving the stability of the anion.
- the aromatic hydrocarbon group that can be used for R 85 preferably has 3 to 40 carbon atoms.
- the aromatic hydrocarbon ring structure a single ring, 2 to 6 condensed rings, and a structure in which 2 to 5 of these are linked are preferable.
- the cross-linking group which the aromatic hydrocarbon group may have is preferably a cross-linking group selected from the above-described cross-linking
- the cross-linking group that can be used for R 85 is preferably a cross-linking group selected from the above-described cross-linking group T.
- the aromatic hydrocarbon group and the substituent which is not a cross-linking group which the aromatic hydrocarbon group may have are preferably groups selected from the substituent group Z, among which the aromatic hydrocarbon group is preferred from the viewpoint of stability. from the viewpoint of solubility, and an alkyl group is preferred from the viewpoint of solubility.
- a tetraarylborate ion is used as an electron-accepting ion compound containing a tetraarylborate ion.
- the counter cation is preferably an iodonium cation, a sulfonium cation, a carbocation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a ferrocenium cation having a transition metal. Ammonium cations are more preferred, and iodonium cations are particularly preferred.
- the structure represented by the following formula (83) is preferable as the iodonium cation, and the more preferable structure is the same.
- iodonium cations include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, 4-tert-butoxyphenylphenyliodonium cation, 4-methoxyphenylphenyliodonium cation, 4-isopropylphenyl-4-methyl Phenyliodonium cations and the like are preferred.
- sulfonium cations include triphenylsulfonium cation, 4-hydroxyphenyldiphenylsulfonium cation, 4-cyclohexylphenyldiphenylsulfonium cation, 4-methanesulfonylphenyldiphenylsulfonium cation, (4-tert-butoxyphenyl)diphenylsulfonium cation, Bis(4-tert-butoxyphenyl)phenylsulfonium cation, 4-cyclohexylsulfonylphenyldiphenylsulfonium cation and the like are preferred.
- trisubstituted carbocations such as triphenyl carbocation, tri(methylphenyl) carbocation, and tri(dimethylphenyl) carbocation are preferred as carbocations.
- ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri(n-butyl)ammonium cation; N,N-diethylanilinium cation, N , N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.
- phosphonium cations include tetraarylphosphonium cations such as tetraphenylphosphonium cations, tetrakis(methylphenyl)phosphonium cations and tetrakis(dimethylphenyl)phosphonium cations; tetraalkylphosphonium cations such as tetrabutylphosphonium cations and tetrapropylphosphonium cations. etc. are preferred.
- iodonium cations iodonium cations, carbocations, and sulfonium cations are preferred, and iodonium cations are more preferred, in terms of film stability of the compound.
- the counter cation X + in formula (81) is preferably an iodonium cation having the structure of formula (83) below.
- Ar 81 and Ar 82 are each independently an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms.
- the aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and most preferably a phenyl group.
- the substituent which may be present is a group selected from the above-described substituent group Z, most preferably an alkyl group.
- aromatic hydrocarbon groups include phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, triphenylene, and naphthylphenyl groups. preferable.
- the molecular weight of the electron-accepting compound of the present invention is usually 900 or more, preferably 1000 or more, more preferably 1200 or more, and usually 10000 or less, preferably 5000 or less, more preferably 3000 or less. If the molecular weight is too small, the delocalization of the positive and negative charges is insufficient, which may reduce the electron-accepting ability. If the molecular weight is too large, the charge transport may be hindered.
- composition ratio/content of fluorine-containing arylamine polymer compound and electron-accepting compound in composition the content of the polymer compound of the present invention is 99% by mass or less with respect to the total amount of the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention. is preferred, 97% by mass or less is more preferred, and 95% by mass or less is even more preferred. Moreover, it is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more.
- the film formed using the composition of the present invention is sufficiently crosslinked to be insolubilized, and the film formed using the composition of the present invention can be directly wet-coated to form a film.
- the film formed using the composition of the present invention is used as a charge injection film, the injection barrier in the charge transport layer is reduced, the charge transport property is excellent, and the stability during charge transport is improved. It is believed that the durability of the device containing the film formed using the composition of the present invention is improved.
- composition of the present invention may further contain a solvent, and may contain a polymerization initiator, additives and the like.
- the composition of the present invention preferably contains the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention. Furthermore, it is preferable that a solvent is included. In particular, when the composition of the present invention is used to form a charge transport film by a wet film-forming method, a solvent is used to combine the fluorine-containing arylamine polymer compound of the present invention with the electron-accepting compound of the present invention. It is preferably in a dissolved state.
- the type of solvent contained in the composition of the present invention is not particularly limited as long as it can dissolve both the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention.
- the fluorine-containing arylamine polymer compound of the present invention and the solvent for dissolving the electron-accepting compound of the present invention preferably contain 0.005% by mass or more of the fluorine-containing arylamine polymer compound of the present invention. More preferably 0.5% by mass or more, more preferably 1% by mass or more is a solvent that dissolves.
- the solvent preferably dissolves the electron-accepting compound in an amount of 0.001% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.2% by mass or more.
- Preferred solvents include, for example, aromatic hydrocarbon solvents, ether solvents and ester solvents.
- aromatic hydrocarbon solvents include toluene, xylene, mesitylene, tetralin, and cyclohexylbenzene.
- ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole , 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, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole , phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole
- ester solvents include aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoic acid; aromatic esters such as n-butyl;
- aromatic hydrocarbon solvents such as benzene, toluene, and xylene have low ability to dissolve electron-accepting compounds and free carriers (cation radicals), so they can be used by mixing with ether solvents and ester solvents. preferable.
- the solvent concentration relative to the composition of the present invention is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more.
- the concentration of the solvent in the composition is preferably 99.999% by mass or less, more preferably 99.99% by mass or less, and still more preferably 99.9% by mass or less.
- the total of these solvents should satisfy this range.
- each layer is required to be a uniform layer because the organic electroluminescent element is formed by laminating a large number of layers composed of organic compounds. .
- a layer is formed by a wet film-forming method, if water is present in the solution (composition) for thin film formation, the water will be mixed in the coating film and the uniformity of the film will be impaired. Less is better.
- the presence of moisture is not preferable from the viewpoint of deterioration of the element, because organic electroluminescence elements generally use many materials, such as cathodes, that are significantly deteriorated by moisture.
- the amount of water contained in the composition of the present invention is preferably 1% by mass or less, more preferably 0.1% by mass or less, and more preferably 0.05% by mass or less.
- Examples of methods for reducing the amount of water in the composition include sealing with nitrogen gas, using a desiccant, dehydrating the solvent in advance, and using a solvent with low water solubility. Among them, it is preferable to use a solvent with low water solubility from the viewpoint of preventing the solution coating film from whitening due to absorption of moisture in the atmosphere during the coating process.
- the composition of the present invention is a solvent having a low water solubility, specifically, a water solubility at 25° C. of 1% by mass or less, preferably 0.1% by mass. % or less, preferably 10% by mass or more, more preferably 30% by mass or more, particularly preferably 50% by mass or more, based on the total composition.
- Charge-transporting film composition (A) a composition containing the electron-accepting ionic compound and the fluorine-containing arylamine polymer compound of formula (1) (hereinafter referred to as , appropriately referred to as "charge-transporting film composition (A)"), or a cation radical of an arylamine polymer compound containing fluorine having a cross-linking group described later and a counter anion which is a part of the electron-accepting ion compound.
- compositions containing a charge-transporting ionic compound consisting of
- a charge-transporting ionic compound consisting of
- a charge-transporting property comprising a cation radical of an arylamine polymer compound containing fluorine having a group and a cation radical of the arylamine polymer compound containing fluorine having a crosslinking group described later and a counter anion which is a part of the electron-accepting ion compound.
- compositions comprising ionic compounds.
- compositions (A) and (B) are compositions (compositions for charge transport materials) that can be widely used as charge transport materials. However, since it is usually formed into a film and used as a hole injection layer and/or a hole transport layer, that is, as a "charge transport film” that transports holes, which are charges, in this specification, the term “charge transport film will be referred to as the "composition for
- the charge-transporting film composition (A) comprises the fluorine-containing arylamine polymer compound having a cross-linking group, the electron-accepting compound having a cross-linking group, and a solvent.
- the fluorine-containing arylamine polymer compound may be contained singly or in combination of two or more kinds.
- the charge-transporting film composition (A) is prepared by mixing at least the fluorine-containing arylamine polymer compound of the present invention with the electron-accepting compound having a cross-linking group. At this time, the charge-transporting film composition (A) contains a solvent, and the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound having a cross-linking group are dissolved in the solvent and mixed. is preferred.
- the content of the electron-accepting compound having a crosslinkable group of the present invention in the composition (A) for a charge transport film is usually 0.1% by mass or more in terms of the fluorine-containing arylamine polymer compound of the present invention. , preferably 1% by mass or more, and usually 100% by mass or less, preferably 40% by mass or less. If the content of the electron-accepting compound is at least the above lower limit, free carriers (cation radicals of the fluorine-containing arylamine polymer compound of the present invention) can be sufficiently generated, and if it is at most the above upper limit, it is sufficient. It is preferable because the charge transport ability can be ensured. When two or more electron-accepting compounds are used in combination, the total content of these should be within the above range. The same applies to charge-transporting compounds.
- the charge-transporting film composition (B) contains, as described above, a charge-transporting ionic compound comprising a cation radical of the fluorine-containing arylamine polymer compound of the present invention and a counter anion of the electron-accepting ionic compound. It is a composition that
- the cation radical of the fluorine-containing arylamine polymer compound of the present invention which is the cation of the charge-transporting ionic compound, is obtained from the electrically neutral compound shown in the fluorine-containing arylamine polymer compound of the present invention. It is a chemical species with one electron removed.
- the cation radical of the fluorine-containing arylamine polymer compound of the present invention is a fluorine-containing arylamine polymer compound having a structure represented by the following formula (110).
- Ar 1a , Ar 2a and G 1a are respectively the same as Ar 1 , Ar 2 and G in the formula (1).
- Formula (110) is particularly a fluorine-containing arylamine polymer compound having a structure represented by the following formula (110-1). It is preferable because it is
- Ar 1b is an aromatic hydrocarbon group, and the number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-24, still more preferably 6-18.
- Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a fluorene ring, a tetraphenylene ring, and the like, having usually 6 or more and usually 30 or less, preferably 18 or less, more preferably 14 or less carbon atoms.
- a bivalent group having a certain aromatic hydrocarbon ring structure, or a bivalent group having a structure in which a plurality of structures selected from these structures are bonded in a chain or branched manner is exemplified.
- Ar 2a and G 1a are the same as Ar 2 and G in formula (1) above, respectively. ]
- Ar 1b is preferably an aromatic hydrocarbon group having a substituent, and specific examples thereof, preferred groups, examples of optionally substituted substituents and examples of preferred substituents are selected from the substituent group Z is preferred. Particularly preferred is an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.
- Ar 1b is preferably a phenylene group, a biphenylene group, or a phenylfluorene group, more preferably a phenylene group or a biphenylene group, from the viewpoints of charge transport and that the partial structure represented by formula (110-1) tends to become a cation radical. and a phenylene group is particularly preferred.
- the charge-transporting ionic compound is a compound in which the cation radical of the fluorine-containing arylamine polymer compound of the present invention is ionically bonded to a counter anion that is a part of the electron-accepting ionic compound.
- a charge-transporting ionic compound can be obtained by mixing an arylamine polymer compound containing fluorine and an electron-accepting ionic compound, and is easily dissolved in various solvents. Specifically, it can be obtained by the method described in ⁇ Method for preparing composition (B) for charge transport film> described below.
- the weight average molecular weight (Mw) of the charge-transporting ionic compound is usually 1,000,000 or less, preferably 500,000 or less, more preferably 100,000 or less, still more preferably 70,000 or less, particularly preferably 50,000 or less. 000 or less. Moreover, the weight average molecular weight is usually 5,000 or more, preferably 10,000 or more, more preferably 12,000 or more, and particularly preferably 15,000 or more.
- the charge-transporting ionic compound (B) is preferably prepared by dissolving and mixing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting ionic compound in a solvent.
- the fluorine-containing arylamine polymer compound of the present invention is oxidized by the electron-accepting ion compound to form a cation radical, and the counter anion of the electron-accepting ion compound and the fluorine-containing arylamine of the present invention are converted into cation radicals.
- a charge-transporting ionic compound, which is an ionic compound with the cation radical of the polymer compound, is produced.
- This mixture is preferably a film formed by coating and drying a solution obtained by dissolving a mixture of an electron-accepting ionic compound and the fluorine-containing polymer compound of the present invention in a solvent.
- the heating temperature at this time is preferably a temperature at which the cross-linking groups of the composition do not undergo a cross-linking reaction. It is formed.
- the charge-transporting film composition (B) may contain one type of charge-transporting ionic compound described above, or may contain two or more types. It is preferable to contain one or two types of charge-transporting ionic compounds, and it is more preferable to contain one type alone. This is because the ionization potential of the charge-transporting ionic compound has little variation and the hole-transporting property is excellent.
- a composition containing one type of charge-transporting ionic compound alone or two types is defined as a composition prepared by using only two or three types in total of the electron-accepting ionic compound and the fluorine-containing polymer compound of the present invention.
- the composition is prepared using at least one electron-accepting ion compound and at least one fluorine-containing polymer compound of the present invention.
- the charge-transporting film formed from the charge-transporting-film composition (B) exhibits a high hole injection/transport capability due to positive charge transfer from the charge-transporting ionic compound to a nearby neutral charge-transporting compound. Demonstrate.
- the mass ratio of the charge-transporting ionic compound and the neutral fluorine-containing polymer compound of the present invention is preferably about 1:100 to 100:1, more preferably about 1:20 to 20:1. is more preferable.
- composition for charge transport film (A) and (B) The charge transport film formed from the charge transport film composition (A) has excellent heat resistance and high hole injection/transport capability. The reason why such excellent properties are obtained will be explained below.
- the charge-transporting film composition (A) contains the electron-accepting compound and the charge-transporting compound described above.
- the cation in the electron-accepting ionic compound has a hypervalent central atom and its positive charge is widely delocalized, so it has a high electron-accepting property.
- electron transfer occurs from the charge-transporting compound to the cation of the electron-accepting ionic compound, and a charge-transporting ionic compound composed of the cation radical of the charge-transporting compound and the counter anion is generated. Since the cation radicals of the charge-transporting compound serve as charge carriers, the electrical conductivity of the charge-transporting film can be increased. That is, it is considered that when the charge transport film composition (A) is prepared, a charge transporting ionic compound at least partially composed of the cation radical of the charge transporting compound and the counter anion of the electron accepting ion compound is produced.
- the charge-transporting compound represented by the formula (9) A charge-transporting ionic compound consisting of a cation radical and a counter-anion is produced.
- the composition of the present invention is prepared by mixing a functional material containing the fluorine-containing arylamine polymer compound of the present invention, the electron-accepting compound of the present invention, preferably the above-mentioned electron-accepting compound, with a solvent, followed by heating for a certain period of time. It can be prepared by heating to dissolve or disperse. In order to uniformly dissolve or disperse the functional material in the solvent, the heating temperature is preferably 80.degree. C. or higher, more preferably 90.degree. The heating time is preferably 30 minutes or longer, more preferably 45 minutes or longer, and even more preferably 60 minutes or longer, for example 60 to 180 minutes.
- the composition after heating can be filtered using a membrane filter, depth filter, etc. to remove coarse particles before use.
- the pore size of the filter is preferably 0.5 ⁇ m or less, more preferably 0.2 ⁇ m or less, and even more preferably 0.1 ⁇ m or less.
- the composition of the present invention is preferably a solution containing a solvent, and the composition of the present invention is preferably used for wet film formation.
- the wet film formation method is a method in which a composition containing a solvent is applied onto a substrate and the solvent is removed by drying to form a film.
- the coating method is not particularly limited, but for example, spin coating, dip coating, die coating, bar coating, blade coating, roll coating, spray coating, capillary coating, inkjet, screen printing, A gravure printing method, a flexographic printing method, and the like can be mentioned.
- Heat drying is usually used to remove the solvent by drying.
- heating means used in the heating step include clean ovens, hot plates, and infrared heating.
- infrared heating a halogen heater, a ceramic-coated halogen heater, a ceramic heater, or the like can be used.
- infrared heating gives heat energy directly to the substrate or film
- drying can be done in a short time compared to heating using an oven or hot plate. Therefore, the influence of gases (moisture and oxygen) in the heating atmosphere and the influence of fine dust can be minimized, and productivity is improved, which is preferable.
- the heating temperature is usually 80°C or higher, preferably 100°C or higher, more preferably 150°C or higher. Also, the heating temperature is usually 300° C. or lower, preferably 280° C. or lower, more preferably 260° C. or lower.
- the heating time is usually 10 seconds or more, preferably 60 seconds or more, more preferably 90 seconds or more, and usually 120 minutes or less, preferably 60 minutes or less, more preferably 30 minutes or less. It is also preferable to perform vacuum drying before heat drying.
- the film thickness of the organic layer formed by forming the composition of the present invention by a wet film-forming method is usually 5 nm or more, preferably 10 nm or more, and more preferably 20 nm or more. Also, the film thickness is usually 1000 nm or less, preferably 500 nm or less, more preferably 300 nm or less.
- a film using the composition of the present invention and a film formed using the composition of the present invention can be suitably used as a charge transport layer.
- This charge transport layer is particularly preferably used as a charge transport film of an organic electroluminescence device.
- the organic electroluminescent device is, for example, an organic electroluminescent device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode, and the organic layer is formed using the composition of the present invention. It is preferably formed by a wet film-forming method.
- the organic layer is preferably an organic layer between the anode and the light-emitting layer.
- a device using "quantum dots", which are inorganic light-emitting substances, in the light-emitting layer of the organic electroluminescent device is also called a quantum dot light-emitting device.
- the organic layer has a repeating unit represented by the formula (1), has a fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group. It preferably contains a crosslinked reaction product of a polymer compound and an electron-accepting compound having a crosslinkable group represented by the above formula (81).
- FIG. 1 shows a schematic diagram (cross section) of a structural example of the organic electroluminescence device 8 .
- 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 an electron transport layer
- 7 is a cathode.
- the substrate 1 serves as a support for the organic electroluminescence element, and is usually made of a quartz or glass plate, a metal plate or metal foil, a plastic film or sheet, or the like. Among these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate and polysulfone are preferred.
- the substrate is preferably made of a material having a high gas barrier property because deterioration of the organic electroluminescence element due to outside air is unlikely to occur. Therefore, especially when using a material having low gas barrier properties such as a synthetic resin substrate, it is preferable to provide a dense silicon oxide film or the like on at least one side of the substrate to improve the gas barrier properties.
- the anode 2 has the function of injecting holes into the layer on the light-emitting layer 5 side.
- Anode 2 is typically made of metals such as aluminum, gold, silver, nickel, palladium, platinum; metal oxides such as indium and/or tin oxide; metal halides such as copper iodide; carbon black and poly(3 -methylthiophene), polypyrrole, and polyaniline.
- metals such as aluminum, gold, silver, nickel, palladium, platinum
- metal oxides such as indium and/or tin oxide
- metal halides such as copper iodide
- the formation of the anode 2 is usually carried out by dry methods such as sputtering and vacuum deposition.
- an appropriate binder resin solution may be used. It can also be formed by dispersing and coating on a substrate.
- a conductive polymer a thin film can be formed directly on a substrate by electrolytic polymerization, or an anode can be formed by coating a conductive polymer on a substrate (Appl. Phys. Lett., 60 2711, 1992).
- the anode 2 usually has a single-layer structure, but may have a laminated structure as appropriate. When the anode 2 has a laminated structure, different conductive materials may be laminated on the first layer of the anode.
- the thickness of the anode 2 may be determined according to the required transparency and material. When particularly high transparency is required, the thickness is preferably such that the visible light transmittance is 60% or more, and more preferably the thickness is such that the visible light transmittance is 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 may be arbitrarily set according to the required strength, etc. In this case, the thickness of the anode 2 may be the same as that of the substrate.
- the impurity on the anode 2 is removed and its ionization potential is changed by treating with ultraviolet rays/ozone, oxygen plasma, argon plasma, etc. before the film formation. is preferably adjusted to improve the hole injection property.
- a layer that functions to transport holes from the anode 2 side to the light emitting layer 5 side is usually called a hole injection transport layer or a hole transport layer.
- the layer closer to the anode side may be called the hole injection layer 3 .
- the hole injection layer 3 is preferably formed in order to enhance the function of transporting holes from the anode 2 to the light emitting layer 5 side.
- the hole injection layer 3 is usually formed on the anode 2 .
- the hole injection layer 3 formed using the composition of the present invention contains a crosslinked reaction product of the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention.
- the method for forming the hole injection layer 3 is not particularly limited, and examples thereof include a vacuum deposition method and a wet film formation method.
- the composition of the present invention is prepared, applied onto the anode 2 by a wet film-forming method such as a spin coating method or a dip coating method, and dried to form a hole injection layer 3. form.
- a composition containing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention it is particularly preferable to use a composition containing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention, and to use the fluorine-containing arylamine of the present invention. It is to use a film formed using a composition containing a polymer compound and the electron-accepting compound of the present invention.
- the film thickness of the hole injection layer 3 thus formed is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
- a method for forming the hole injection layer may be a vacuum deposition method or a wet film formation method. From the viewpoint of excellent film-forming properties, it is preferable to form the film by a wet film-forming method.
- the solvent include ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, amide-based solvents, and the like.
- ether-based solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and anisole. , 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, propylene glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and anisole.
- PGMEA propylene glycol-1-monomethyl ether acetate
- 1,2-dimethoxybenzene 1,3-dimethoxybenzen
- 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, cyclohexylbenzene, and methylnaphthalene. be done.
- amide-based solvents examples include N,N-dimethylformamide and N,N-dimethylacetamide.
- dimethyl sulfoxide and the like can also be used.
- Formation of the hole injection layer 3 by a wet film-forming method is usually carried out by preparing a composition for forming a hole injection layer and then applying it on a layer corresponding to the lower layer of the hole injection layer 3 (usually the anode 2). It is carried out by coating and forming a film on the surface and drying it.
- the coating film is usually dried by heating, drying under reduced pressure, or the like.
- the hole transport layer 4 is a layer that functions to transport holes from the anode 2 side to the light emitting layer 5 side.
- the hole transport layer 4 is not an essential layer in the organic electroluminescent device of the present invention, but it is preferable to form this layer in terms of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5. .
- the hole transport layer 4 is usually formed between the anode 2 and the light emitting layer 5 . Further, when the hole injection layer 3 described above is present, it is formed between the hole injection layer 3 and the light emitting layer 5 .
- the film thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and is usually 300 nm or less, preferably 100 nm or less.
- a material that forms the hole transport layer 4 is preferably a material that has a high hole transport property and can efficiently transport the injected holes. Furthermore, it is preferable that the injection barrier from the hole injection layer to the hole transport layer is low. Therefore, it is preferable that the ionization potential is appropriate, the transparency to visible light is high, the hole mobility is large, the stability is excellent, and impurities that become traps are less likely to occur during manufacture and use. In many cases, since the hole transport layer 4 is in contact with the light emitting layer 5, it does not quench the light emitted from the light emitting layer 5 or form an exciplex with the light emitting layer 5 to reduce the efficiency. is preferred.
- any material can be used as long as it is a material conventionally used as a constituent material for a hole transport layer.
- compounds include those exemplified.
- polyvinylcarbazole derivatives polyarylamine derivatives, polyvinyltriphenylamine derivatives, polyfluorene derivatives, polyarylene derivatives, polyarylene ether sulfone derivatives containing tetraphenylbenzidine, polyarylene vinylene derivatives, polysiloxane derivatives, polythiophenes. derivatives, poly(p-phenylene vinylene) derivatives and the like.
- These may be alternating copolymers, random polymers, block polymers or graft copolymers.
- a polymer having a branched main chain and three or more terminal portions, or a so-called dendrimer may be used.
- polyarylamine derivatives and polyarylene derivatives are preferred.
- a polymer containing a repeating unit represented by the following formula (I) is preferred.
- a polymer composed of repeating units represented by the following formula (I) is preferable, and in this case, Ar a ' or Ar b ' may be different in each repeating unit.
- Ar a ' and Ar b ' are each independently an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group represents.
- polyarylene derivatives include polymer compounds having an arylene group such as an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group as a repeating unit. be done.
- polystyrene resin As the polyarylene derivative, a polymer compound having a repeating unit represented by the following formula (II-1) and/or the following formula (II-2) is preferable.
- R a , R b , R c and R d are each independently an alkyl group, an alkoxy group, a phenylalkyl group, a phenylalkoxy group, a phenyl group, a phenoxy group, an alkylphenyl group, represents an alkoxyphenyl group, an alkylcarbonyl group, an alkoxycarbonyl group or a carboxy group, x11 and x12 each independently represent an integer of 0 to 3. When x11 or x12 is 2 or more, a plurality of groups contained in one molecule may be the same or different, and adjacent Ra or Rb may form a ring. )
- R e and R f are each independently synonymous with R a , R b , R c or R d in formula (II-1) above.
- x13 and x14 are each independently represents an integer of 0 to 3.
- a plurality of R e and R f contained in one molecule may be the same or different, and adjacent R e or R f may form a ring together, and L represents an atom or a group of atoms constituting a 5- or 6-membered ring.
- L include an oxygen atom, an optionally substituted boron atom, an optionally substituted nitrogen atom, an optionally substituted silicon atom, and an optionally substituted an optionally substituted phosphorus atom, an optionally substituted sulfur atom, an optionally substituted carbon atom, or a group formed by combining these atoms.
- polyarylene derivative has a repeating unit represented by the following formula (III-3) in addition to the repeating unit represented by the above formula (II-1) and/or the above formula (II-2). is preferred.
- Ar c to Ar i each independently represent an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group; x15 and x16 each independently represent 0 or 1.
- a composition for forming a hole transport layer is prepared in the same manner as in the formation of the hole injection layer 3, and after wet film formation, heat drying is performed. .
- the hole-transporting layer-forming composition contains a solvent in addition to the hole-transporting compound described above.
- the solvent to be used is the same as that used for the composition for forming the hole injection layer.
- the film formation conditions, heat drying conditions, etc. are the same as in the case of forming the hole injection layer 3 .
- the film forming conditions and the like are the same as in the case of forming the hole injection layer 3 described above.
- the hole-transporting layer 4 may contain various light-emitting materials, electron-transporting compounds, binder resins, coatability improvers, etc., in addition to the above hole-transporting compounds.
- the hole transport layer 4 may be a layer formed by cross-linking a cross-linking compound.
- the crosslinkable compound is a compound having a crosslinkable group, and forms a network polymer compound by crosslinking.
- crosslinkable groups include groups derived from cyclic ethers such as oxetane and epoxy; groups derived from unsaturated double bonds such as vinyl, trifluorovinyl, styryl, acryl, methacryloyl, and cinnamoyl; Examples thereof include groups derived from cyclobutene.
- the crosslinkable compound may be a monomer, oligomer, or polymer.
- the crosslinkable compound may have only one type, or may have two or more types in any combination and ratio.
- a hole-transporting compound having a crosslinkable group is preferably used as the crosslinkable compound.
- the hole-transporting compound include those exemplified above, and examples of the cross-linking compound include those in which a cross-linking group is bonded to the main chain or side chain of these hole-transporting compounds. be done.
- the crosslinkable group is preferably bonded to the main chain via a linking group such as an alkylene group.
- the hole-transporting compound is preferably a polymer containing a repeating unit having a crosslinkable group. is preferably a polymer compound having repeating units linked directly or via a linking group.
- a composition for forming a hole transport layer is usually prepared by dissolving or dispersing the cross-linking compound in a solvent, and the film is formed by wet film formation. to cross-link.
- the film thickness of the hole transport layer 4 thus formed is usually 5 nm or more, preferably 10 nm or more, and usually 300 nm or less, preferably 150 nm or less.
- the light-emitting layer 5 is a layer that functions to emit light by being excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 7 when an electric field is applied between a pair of electrodes. .
- the light-emitting layer 5 is a layer formed between the anode 2 and the cathode 7, and the light-emitting layer is formed between the hole-injection layer and the cathode, if there is a hole-injection layer on the anode, and the anode If there is a hole-transport layer on top, it is formed between the hole-transport layer and the cathode.
- the organic electroluminescent element in the present invention preferably contains a light-emitting layer-forming material suitable for the light-emitting layer.
- the film thickness of the light-emitting layer 5 is arbitrary as long as it does not significantly impair the effects of the present invention, but a thicker film is preferable because defects are less likely to occur in the film, and a thinner film is preferable because a low driving voltage can be easily achieved. . Therefore, it is preferably 3 nm or more, more preferably 5 nm or more, and on the other hand, it is usually preferably 200 nm or less, more preferably 100 nm or less.
- the light-emitting layer 5 contains at least a material having light-emitting properties (light-emitting material), and preferably contains one or more host materials.
- the light-emitting layer in the present invention contains a light-emitting material and a charge transport material.
- the luminescent material may be a phosphorescent luminescent material or a fluorescent luminescent material.
- Charge Transport Film Preferably, the red-emitting material and the green-emitting material are phosphorescent materials, and the blue-emitting material is a fluorescent material.
- 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 materials include those described in International Publication No. 2014/024889, International Publication No. 2015-087961, International Publication No. 2016/194784, and JP-A-2014-074000.
- 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 which may have a substituent.
- R 101 and R 102 each independently represent a structure represented by formula (202), and "*" represents the bonding position with ring A1 or ring A2.
- R 101 and R 102 may be the same or different, and when multiple R 101 and R 102 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 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 may be bonded to each other to form a ring.
- B 201 -L 200 -B 202 represents an anionic bidentate ligand.
- B 201 and B 202 each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may be atoms constituting a ring.
- L 200 represents a single bond or 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 Unless otherwise specified, a group selected from the following Substituent Group S is preferable as the substituent in the material for forming the light-emitting layer.
- 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 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 preferred are alkyl groups, arylamino groups, aralkyl groups, alkenyl groups, aryl groups, heteroaryl groups, and groups in which one or more hydrogen atoms of these groups are replaced with fluorine atoms, fluorine atoms, cyano a group, or —SF 5 , more preferably an alkyl group, an alkoxy group, an aryloxy group, an arylamino group, an aralkyl group, an alken
- 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 which may have 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. 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 1-12, more preferably 1-8, more preferably 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 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 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 substituents.
- Group S but 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, where the tertiary butyl group is substituted for Ar 203 if Ar 203 is present, Ar 202 if Ar 203 is absent, or Ar 201 if Ar 202 and Ar 203 are absent. preferably.
- the compound represented by the 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 1 to 6, and at least one of the benzene rings is in the ortho or meta position. It is preferred that the sites are linked to adjacent structures. 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 ⁇ 6, Ar 202 is an aliphatic hydrocarbon structure, i2 is 1 to 12, preferably 3 to 8, Ar 203 is a benzene ring structure, i3 is 0 or 1, preferably Ar 201 is the aromatic hydrocarbon structure It is a hydrogen 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.
- phosphorescent material represented by the formula (201) is not particularly limited, the following are preferred.
- a phosphorescent material represented by the following formula (205) is also preferable.
- M2 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, there are no R94 and R95 . ]
- 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 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. Furthermore, 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 charge-transporting material contained in the light-emitting layer is a polymeric material, the molecular weight is preferably 5,000 or more and 1,000,000 or less, more preferably 10,000 or more and 500,000 or less, and still more preferably 10,000 or less. 000 or more and 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, represents an aromatic hydrocarbon group, a heteroaromatic 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 1-4, preferably 1-3, more preferably 1-2, 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 heteroaromatic group for Ar 242 and Ar 243 is preferably a heteroaromatic group having 3 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 5 to 24 carbon atoms, specifically a carbazolyl group, A dibenzofuranyl group and a dibenzothiophenyl group are preferred, and a dibenzofuranyl group is more preferred.
- the substituent that Ar 241 , Ar 242 , and Ar 243 may have is preferably a group selected from the substituent group S, more preferably a hydrocarbon group included 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 each independently represent a structure represented by formula (213), R 253 represents a substituent, and when there are multiple R 253 , they may be the same or different. and n43 is an integer from 0 to 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 which may have 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 0 to An integer of 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 C 12 It is an aromatic heterocyclic ring structure that is a condensed ring.
- 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 substituent group S described above. 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 molecular weights of the fluorescence-emitting material and charge-transporting material are 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.
- the light-emitting layer preferably contains quantum dots as light-emitting substances. Quantum dots are luminescent semiconductor nanoparticles, typically ranging in diameter from 1 to 20 nm.
- the quantum dots are preferably composed of II-VI group compounds, III-V group compounds, IV-VI group compounds, IV group elements, IV group compounds, or combinations thereof.
- II-VI group compounds include CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, AgInS, CuInS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HeSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HeZnSe, HeZnTe, MgZnSe, MgZnS, HgZnTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHg SeS, CdHgSeTe, CdHgSTe, HgZnSe
- III-V compounds include GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, ALPSB, INGAP, Innp, Innas, Innsb, Inpasb, INPSB, GAALNAS, GAALNAS, GAALNSB, GAALPAS, GAALPSB, GAINNP, GAINNAS, GAINNSB, GAINNSB, GAINSB. Pas, GAINPSB, Inalnp, Inalnasb, Inalpasb, and Inalpsb are listed.
- SNS Sns, Snse, Snte, PBS, PBS, PBSE, PBSE, SnSes, Snset, SnSETE, SNSETE, PBSETE, PBSETE, SNPBSETE, SNPBSE, SNPBTE, SNPBSSE, SNPBSSE, SNPBSSE. , SnpbSete and Snpbste are listed.
- Group IV elements include Si and Ge, and Group IV compounds include SiC and SiGe.
- a quantum dot may have a homogeneous single structure or a core/shell dual structure. It may also have a triple or quadruple or more structure such as core/shell/shell.
- the materials that make up the core and shell consist of different compounds.
- the energy bandgap of the shell compound is preferably larger than the energy bandgap of the core compound.
- structures such as ZnTeSe/ZnSe/ZnS, CdSe/ZnS, and InP/ZnS are preferred.
- composition for forming a light-emitting layer containing quantum dots The method for forming the light-emitting layer containing quantum dots may be either a vacuum deposition method or a wet film formation method, but the wet film formation method is preferred. In the case of the wet film-forming method, the light-emitting layer is formed by coating and drying a composition for forming a light-emitting layer containing an organic solvent. The composition for forming a light-emitting layer containing quantum dots contains quantum dots and an organic solvent.
- Organic solvent contained in the composition for forming a light-emitting layer containing quantum dots is a volatile liquid component used for forming a layer containing quantum dots by wet film formation.
- the organic solvent is not particularly limited as long as it is an organic solvent in which the solute quantum dots are well dissolved.
- Preferred organic solvents include, for example, alkanes such as n-decane, cyclohexane, ethylcyclohexane, decalin and bicyclohexane; aromatic hydrocarbons such as toluene, xylene, mesitylene, phenylcyclohexane, tetralin and methylnaphthalene; Halogenated aromatic hydrocarbons such as chlorobenzene and trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3 - aromatic ethers such as dimethylanisole, 2,4-dimethylanisole and diphenyl ether; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, prop
- alkanes, aromatic hydrocarbons, and aromatic esters are preferable from the viewpoint of viscosity and boiling point.
- One type of these organic solvents may be used alone, or two or more types may be used in any combination and ratio.
- the boiling point of the organic solvent used is usually 80°C or higher, preferably 100°C or higher, more preferably 120°C or higher, and usually 350°C or lower, preferably 330°C or lower, more preferably 300°C or lower. If the boiling point of the organic solvent is below this range, the film formation stability may decrease due to evaporation of the solvent from the composition for forming the light-emitting layer during wet film formation. If the boiling point of the organic solvent exceeds this range, there is a possibility that the film formation stability will decrease due to the solvent remaining after film formation during wet film formation.
- the content of quantum dots in the composition for forming a light-emitting layer containing quantum dots is usually 0.001% by mass or more, preferably 0.01% by mass or more, usually 30.0% by mass or less, preferably 20.0% by mass. % or less.
- the content in this range holes and electrons are efficiently injected from adjacent layers (for example, a hole-transporting layer and a hole-blocking layer) to the light-emitting layer, thereby reducing the driving voltage. can be done.
- 1 type of quantum dots may be contained in the composition for light emitting layer formation, and 2 or more types may be combined and contained.
- the content of the organic solvent contained in the light-emitting layer-forming composition containing quantum dots is usually 10% by mass or more, preferably 50% by mass or more, particularly preferably 80% by mass or more, and usually 99.95% by mass or less. , preferably 99.9% by mass or less, particularly preferably 99.8% by mass or less. If the content of the organic solvent is at least the above lower limit, the composition will have an appropriate viscosity and coatability will be improved.
- composition for forming a light-emitting layer containing quantum dots may contain other compounds in addition to the above compounds, if necessary.
- Other compounds preferably include dibutylhydroxytoluene, which is known as an antioxidant, phenols such as dibutylphenol, and known charge-transporting compounds.
- the method for forming the light-emitting layer containing quantum dots is preferably a wet film-forming method.
- the wet film-forming method is a method of applying a composition to form a liquid film, drying it to remove the organic solvent, and forming a light-emitting layer film.
- coating methods include spin coating, dip coating, die coating, bar coating, blade coating, roll coating, spray coating, capillary coating, inkjet, nozzle printing, screen printing, and gravure.
- a wet film-forming method such as a printing method or a flexographic printing method is employed, and the coating film is dried to form a film.
- the spin coating method, the spray coating method, the inkjet method, the nozzle printing method, and the like are preferable.
- an inkjet method or a nozzle printing method is preferable, and an inkjet method is particularly preferable.
- drying method is not particularly limited, natural drying, reduced pressure drying, heat drying, or reduced pressure drying while heating can be used as appropriate. Heat drying may be carried out in order to further remove residual organic solvent after natural drying or vacuum drying.
- the heating method is not particularly limited, but heating with a hot plate, heating in an oven, infrared heating, etc. can be used.
- the heating temperature is usually 80° C. or higher, preferably 100° C. or higher, more preferably 110° C. or higher, and preferably 200° C. or lower, more preferably 150° C. or lower.
- the heating time is usually 1 minute or more, preferably 2 minutes or more, usually 60 minutes or less, preferably 30 minutes or less, and more preferably 20 minutes or less.
- a hole-blocking layer may be provided between the light-emitting layer 5 and an electron-injecting layer, which will be described later.
- the hole-blocking layer 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 7 side.
- This hole-blocking layer has the role of blocking holes moving from the anode 2 from reaching the cathode 7 and the role of efficiently transporting electrons injected from the cathode 7 toward the light-emitting layer 5.
- Physical properties required for the material constituting the hole blocking layer include high electron mobility and low hole mobility, a large energy gap (difference between HOMO and LUMO), and an excited triplet level (T 1 ). is high.
- Examples of materials for the hole blocking layer that satisfy 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-quinolato) aluminum binuclear metal complexes such as metal complexes, distyrylbiphenyl derivatives and the like Styryl compounds (JP-A-11-242996), triazole derivatives such as 3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole ( 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 WO 2005/022962 is also preferable as a material for the hole blocking layer.
- the hole blocking layer There are no restrictions on the method of forming the hole blocking layer. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.
- the thickness of the hole-blocking layer is arbitrary as long as it does not significantly impair the effects of the present invention. .
- the electron transport layer 6 is provided between the light emitting layer 5 and the cathode 7 for the purpose of further improving the current efficiency of the device.
- the electron transport layer 6 is made of a compound that can efficiently transport electrons injected from the cathode 7 toward the light emitting layer 5 between electrodes to which an electric field is applied.
- the electron-transporting compound used in the electron-transporting layer 6 is a compound that has high electron injection efficiency from the cathode 7, high electron mobility, and can efficiently transport the injected electrons. is necessary.
- the electron-transporting compound used in the electron-transporting layer include, for example, a metal complex such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), 10-hydroxybenzo[h] quinoline metal complexes, oxadiazole derivatives, distyrylbiphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Patent No. 5645948), quinoxaline compounds (Japanese Patent Laid-Open No.
- the film thickness of the electron transport layer 6 is usually 1 nm or more, preferably 5 nm or more, and is usually 300 nm or less, preferably 100 nm or less.
- the electron transport layer 6 is formed on the hole blocking layer by a wet film forming method or a vacuum vapor deposition method in the same manner as described above.
- a vacuum deposition method is usually used.
- the electron-transporting layer can be formed on the light-emitting layer containing a suitable material for forming the light-emitting layer by a wet film-forming method.
- the electron injection layer may be provided to efficiently inject electrons injected from the cathode 7 into the electron transport layer 6 or the light emitting layer 5 .
- the material forming the electron injection layer be a metal with a low work function.
- examples thereof include alkali metals such as sodium and cesium, alkaline earth metals such as barium and calcium, and the like.
- the film thickness is preferably 0.1 nm or more and 5 nm or less.
- an organic electron-transporting material typified by a nitrogen-containing heterocyclic compound such as bathophenanthroline or a metal complex such as an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium or rubidium ( JP-A-10-270171, JP-A-2002-100478, JP-A-2002-100482, etc.) also improves electron injection and transport properties and achieves excellent film quality. It is preferable because it enables
- the thickness of the electron injection layer is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.
- the electron injection layer is formed by laminating the light emitting layer 5 or the hole blocking layer or the electron transport layer 6 thereon by a wet film forming method or a vacuum deposition method.
- the details of the wet film formation method are the same as those of the light-emitting layer described above.
- the hole-blocking layer, electron-transporting layer, and electron-injecting layer are formed into a single layer by co-doping the electron-transporting material and the lithium complex.
- the cathode 7 plays a role of injecting electrons into a layer (an electron injection layer, a light-emitting layer, or the like) on the light-emitting layer 5 side.
- the material of the cathode 7 it is possible to use the material used for the anode 2, but in terms of efficient electron injection, it is preferable to use a metal with a low work function, such as tin or magnesium. , indium, calcium, aluminum, and silver, or alloys thereof. Specific examples include low work function alloy electrodes such as magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys.
- the cathode made of a metal with a low work function by stacking a metal layer that has a high work function and is stable against the atmosphere on the cathode.
- Metals to be laminated include, for example, metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum.
- the film thickness of the cathode is usually the same as that of the anode.
- the organic electroluminescence device of the present invention may further have other layers as long as they do not significantly impair the effects of the present invention. That is, it may have any of the other layers described above between the anode and cathode.
- the organic electroluminescence device of the present invention has a structure opposite to that described above. It is also possible to laminate the injection layer and the anode in this order.
- the organic electroluminescent element of the present invention When the organic electroluminescent element of the present invention is applied to an organic electroluminescent device, it may be used as a single organic electroluminescent element or may be used in a configuration in which a plurality of organic electroluminescent elements are arranged in an array. A configuration in which anodes and cathodes are arranged in an XY matrix may be used.
- the display device (organic electroluminescent element display device) of the present invention comprises the organic electroluminescent element of the present invention.
- the device can be assembled according to a conventional method using the organic electroluminescence device of the present invention.
- the organic EL display device of the present invention can be manufactured by the method described in "Organic EL Display” (Ohmsha, August 20, 2004, by Shizuo Tokito, Chihaya Adachi, and Hideyuki Murata). can be formed.
- the lighting device (organic electroluminescent element lighting device) of the present invention comprises the organic electroluminescent element of the present invention.
- the device can be assembled using the organic electroluminescence device of the present invention in a conventional manner.
- the quantum dot display device (quantum dot light emitting device display device) of the present invention comprises the quantum dot light emitting device of the present invention.
- the type and structure of the quantum dot display device of the present invention are not particularly limited, and the quantum dot light emitting device of the present invention can be assembled according to a conventional method.
- the organic light-emitting layer is The quantum dot display device of the present invention.
- the quantum dot lighting device (quantum dot light emitting element lighting device) of the present invention comprises the quantum dot light emitting device of the present invention.
- quantum dot lighting device of the present invention There are no particular restrictions on the type and structure of the quantum dot lighting device of the present invention, and it can be assembled using the quantum dot light emitting device of the present invention in accordance with conventional methods.
- 3-bromo-3′-iodo-1,1-biphenyl (29.4 g, 81.9 mmol), commercially available compound 2 (20.0 g, 81.9 mmol), potassium phosphate (2 M aqueous solution, 103 g, 205 mmol) ), toluene (200 mL), and ethanol (100 mL) were charged into a flask, the system was sufficiently purged with nitrogen, and heated to 60°C. Tetrakis(triphenylphosphine)palladium(0) (2.37 g, 2.05 mmol) was added and stirred at 85° C. for 6 hours. Water was added to the reaction solution, and extraction was performed with toluene.
- Solution B1 was added to solution A1 in a nitrogen stream, and the mixture was heated under reflux for 1.0 hour. After confirming that compound 1 had disappeared, 4,4'-dibromobiphenyl (0.668 g, 2.14 mmol) was added. After heating under reflux for 2 hours, bromobenzene (1.3 g, 8.2 mmol) was added and the reaction was carried out under heating under reflux for 2 hours. The reaction solution was allowed to cool and added dropwise to an ethanol/water (210 mL/30 mL) solution to obtain an end-capped crude polymer.
- Solution B2 was added to solution A2 in a nitrogen stream, and the mixture was heated under reflux for 1.0 hour. After confirming that compound 1 had disappeared, 4,4'-dibromobiphenyl (0.668 g, 2.14 mmol) was added. After heating under reflux for 2 hours, bromobenzene (1.3 g, 8.2 mmol) was added and the reaction was carried out under heating under reflux for 2 hours. The reaction solution was allowed to cool and added dropwise to an ethanol/water (210 mL/30 mL) solution to obtain an end-capped crude polymer.
- Solution B3 was added to solution A3 in a nitrogen stream, and the mixture was heated under reflux for 2.0 hours. After confirming that 4,4′-dibromobiphenyl had disappeared, compound 1 (1.811 g, 2.69 mmol) was added. After heating under reflux for 2 hours, bromobenzene (3.0 g, 19.11 mmol) was added, and the reaction was carried out under heating under reflux for 2 hours. The reaction solution was allowed to cool and added dropwise to an ethanol/water (255 mL/60 mL) solution to obtain an end-capped crude polymer.
- Solution B4 was added to solution A4 in a nitrogen stream, and the mixture was heated under reflux for 1.0 hour. After confirming that 4,4'-dibromobiphenyl had disappeared, 4,4'-dibromobiphenyl (2.415 g, 7.74 mmol) was added. After heating under reflux for 2 hours, bromobenzene (2.94 g, 18.7 mmol) was added and the reaction was carried out under heating under reflux for 2 hours. The reaction solution was allowed to cool and added dropwise to an ethanol/water (315 mL/50 mL) solution to obtain an end-capped crude polymer.
- Polymer compound Pa was synthesized according to the following reaction scheme.
- Solution B5 was added to solution A5 in a nitrogen stream, and the mixture was heated under reflux for 1.0 hour. After confirming that compound 5 had disappeared, 2,7-bis(4-bromophenyl)9,9-dihexylfluorene (3.54 g, 5.49 mmol) was added. After heating under reflux for 2 hours, bromobenzene (3.52 g, 22.42 mmol) was added, and the reaction was heated under reflux for 2 hours. The reaction mixture was allowed to cool and added dropwise to an ethanol/water (275 ml/50 ml) solution to obtain an end-capped crude polymer.
- a polymer compound P-5 was synthesized in the same manner as the polymer compound P-1.
- Example 1 An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate to a thickness of 50 nm (manufactured by Geomatec, a sputter-deposited product) was subjected to a 2 mm-wide stripe using ordinary photolithography and etching with hydrochloric acid. was patterned to form an anode. The substrate on which the ITO pattern is formed in this manner is washed with ultrasonic waves using an aqueous solution of surfactant, washed with ultrapure water, ultrasonically washed with ultrapure water, and washed with ultrapure water in this order, and then dried with compressed air. , and finally performed ultraviolet ozone cleaning.
- ITO indium tin oxide
- composition for forming a hole injection layer 3.1% by mass of a hole-transporting polymer compound having a structure of the following formula (P-1) and 0.6% by mass of an electron-accepting compound (HI-1) below. was dissolved in ethyl benzoate to prepare a composition.
- This composition was spin-coated on the substrate in the atmosphere and dried on a hot plate in the atmosphere at 230° C. for 30 minutes to form a uniform thin film with a thickness of 40 nm, which was used as a hole injection layer.
- a charge-transporting polymer compound having the following structural formula (HT-1) was dissolved in 1,3,5-trimethylbenzene to prepare a 2.0% by mass solution.
- This solution was spin-coated on the substrate on which the hole injection layer was coated in a nitrogen glove box, and dried on a hot plate in the nitrogen glove box at 230° C. for 30 minutes to form a uniform thin film with a thickness of 40 nm. was formed to form a hole transport layer.
- a host compound having the following structural formula (BH-1) and a dopant compound having the following structural formula (BD-1) were dissolved in cyclohexylbenzene in parts by weight of 100:10 to give 4.4% by weight. was prepared.
- a uniform thin film of 40 nm was formed by spin coating in a nitrogen glove box on the substrate on which the film up to the hole transport layer had been applied and formed as a light-emitting layer. It was dried on a hot plate in a nitrogen glove box at 120° C. for 20 minutes to form a light-emitting layer.
- the substrate on which up to the light-emitting layer was formed was placed in a vacuum deposition apparatus, and the inside of the apparatus was evacuated to 2 ⁇ 10 ⁇ 4 Pa or less.
- a compound represented by the following structural formula (ET-1) and 8-hydroxyquinolinolatritium are co-deposited on the light-emitting layer at a film thickness ratio of 2:3 by a vacuum vapor deposition method to obtain a film thickness.
- a 30 nm electron transport layer was formed.
- a striped shadow mask with a width of 2 mm was adhered to the substrate so as to be orthogonal to the ITO stripes of the anode as a mask for cathode evaporation, and aluminum was heated by a molybdenum boat by vacuum evaporation to obtain a film thickness of 80 nm. was formed to form a cathode.
- an organic electroluminescence device having a light-emitting area of 2 mm ⁇ 2 mm was obtained.
- a moisture and oxygen adsorbent is attached to the inside of a glass substrate having a hollow structure, and the surface of the glass substrate having the organic electroluminescent element and the moisture and oxygen adsorbent of the hollow glass are provided.
- the surfaces were made to face each other, and an ultraviolet curable resin was applied so as to surround the outer periphery of the organic electroluminescence element portion, and the surfaces were bonded to each other. Further, a structure was formed in which the ultraviolet curable resin portion was irradiated with ultraviolet rays to isolate the organic electroluminescence element portion from the external space.
- the surface of the organic electroluminescent device can be isolated from moisture and oxygen without any structure directly touching it, and the performance of the organic electroluminescent device can be evaluated by excluding the influence of moisture and oxygen. be able to.
- Example 2 As the composition for forming a hole injection layer, 3.1% by mass of the hole-transporting polymer compound having the structure of the formula (P-2) and 0.6% by mass of the electron-accepting compound (HI-1) alone.
- An organic electroluminescence device was produced in the same manner as in Example 1, except that a composition dissolved in ethyl benzoate was prepared and used.
- Example 3 As a composition for forming a hole injection layer, 3.1% by mass of a hole-transporting polymer compound having the structure of formula (P-4) and 0.6% by mass of an electron-accepting compound (HI-1) are mixed. An organic electroluminescence device was produced in the same manner as in Example 1, except that a composition dissolved in ethyl benzoate was prepared and used.
- Comparative Example 1 As a composition for forming a hole injection layer, 3.1% by mass of a hole-transporting polymer compound having a structure of the above formula P-5 and 0.6% by mass of an electron-accepting compound (HI-1) are combined with benzoin. An organic electroluminescence device was produced in the same manner as in Example 1, except that a composition dissolved in ethyl acetate was prepared and used.
- the time (hr) for the brightness of the device to decrease to 95% of the initial brightness was measured when a current density of 15 mA/cm 2 was continuously applied to these organic electroluminescence devices. Let this value be LT95.
- the ratio of LT95 of the organic electroluminescent devices of other examples and comparative examples, that is, “of each organic electroluminescent device other than Comparative Example 1 LT95/LT95 of the organic electroluminescence device of Comparative Example 1 (hereinafter referred to as “relative life”) was determined and shown in Table 1.
- Example 4 An electroluminescence device was produced in the same manner as in Example 1, except that the structure of the light emitting layer in Example 1 was changed to the light emitting layer 5 as described below.
- This solution was spin-coated in a nitrogen glove box onto the substrate on which the hole transport layer had been applied and dried on a hot plate in the nitrogen glove box at 120° C. for 20 minutes to form a uniform thin film with a thickness of 70 nm.
- a light-emitting layer 5 was formed.
- Example 5 An organic electroluminescence device was produced in the same manner as in Example 4 except that the compound represented by the above formula (P-1) was changed to the compound represented by the above formula (P-2).
- Example 6 An organic electroluminescence device was produced in the same manner as in Example 4, except that the compound represented by the above formula (P-1) was changed to the compound represented by the above formula (P-4).
- the time (hr) for the brightness of the device to decrease to 95% of the initial brightness was measured when a current density of 15 mA/cm 2 was continuously applied to these organic electroluminescence devices. Let this value be LT95.
- the ratio of LT95 of the organic electroluminescent devices of other examples and comparative examples, that is, “of each organic electroluminescent device other than Comparative Example 2 LT95/LT95 of the organic electroluminescence device of Comparative Example 1 (hereinafter referred to as “relative life”) was obtained and shown in Table 2.
- the green phosphorescent organic electroluminescent device formed using the composition of the present invention containing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound having a cross-linking group exhibited a low voltage. It was found that the current luminous efficiency and life were good.
- Example 7 As an electron-accepting compound contained in the composition for forming a hole injection layer, a compound represented by the following formula (HI-2) instead of the compound represented by the above formula (HI-1) is used for hole injection. A layer-forming composition was prepared, and an organic electroluminescence device was produced in the same manner as in Example 4, except that this composition was used.
- Example 8 Using the compound represented by the above formula (P-2) instead of the compound represented by the above formula (P-1) as the hole-transporting polymer compound contained in the composition for forming a hole injection layer A composition for forming a hole injection layer was prepared, and an organic electroluminescence device was produced in the same manner as in Example 7, except that this composition was used.
- Example 9 Using the compound represented by the above formula (P-4) instead of the compound represented by the above formula (P-1) as the hole-transporting polymer compound contained in the composition for forming a hole injection layer A composition for forming a hole injection layer was prepared, and an organic electroluminescence device was produced in the same manner as in Example 7, except that this composition was used.
- Example 10 As a hole-transporting polymer compound contained in the composition for forming a hole injection layer, a compound represented by the following formula (Pa) is used instead of the compound represented by the above formula (P-1). A composition for forming a hole injection layer was prepared, and an organic electroluminescence device was produced in the same manner as in Example 4, except that this composition was used.
- Example or Table 3 shows the current luminous efficiency of the organic electroluminescent device of Comparative Example/current luminous efficiency of the organic electroluminescent device of Comparative Example 4 (hereinafter referred to as "relative current luminous efficiency").
- the ratio of the LT95 of the organic electroluminescent devices of Examples and Comparative Examples that is, the LT95 of the organic electroluminescent devices of Examples and Comparative Examples, respectively / LT95 of the organic electroluminescence device of the comparative example (hereinafter referred to as "relative life") was determined and shown in Table 3.
- the phosphorescent organic electroluminescent device using the fluorine-free polymer compound and the electron-accepting compound not containing the cross-linking group has the fluorine-containing arylamine polymer compound of the present invention and the cross-linking group. It was found that the phosphorescent organic electroluminescent device formed using the composition of the present invention containing an electron-accepting compound exhibits good current luminescence efficiency and lifetime.
- Ionization potential (IP) measurements are performed by photoelectron yield spectroscopy (PYS).
- the measurement is preferably performed using PCR-101 manufactured by Optel, but is not limited as long as equivalent measurement can be performed.
- a sample coating liquid is prepared by dissolving the host material in a suitable solvent.
- the solvent is not limited, and those exemplified as the solvent used for the composition for forming the light-emitting layer can be used, but the solvent used when actually forming the light-emitting layer is preferable.
- the concentration of the sample coating liquid is not particularly limited, it may be a concentration at which a film thickness of 50 nm is formed after film formation and drying.
- a film is formed on a quartz substrate from the prepared sample coating liquid. The film formation is preferably performed in the same manner as the method described in the film formation process of the light-emitting layer.
- This measurement sample is set on a substrate holder in the measurement chamber of the measurement device (Optel PCR-101), and the door of the measurement chamber is closed.
- the measuring chamber is evacuated to below 10 ⁇ 1 Pa by a turbomolecular pump.
- a voltage of ⁇ 50 V is applied to the sample, the excitation light from the deuterium lamp is made monochromatic and is incident on the sample, and the photoelectrons emitted from the sample due to the excitation are detected by a microammeter.
- the ionization potential is determined from a plot of monochromatic excitation light energy versus photoelectron detection.
- the prepared sample is used to measure the absorption curve of the thin film with an ultraviolet-visible spectrophotometer as described in ⁇ Method for Measuring Ionization Potential>.
- a tangent line is drawn at the short-wavelength side rise of the thin film, and the obtained wavelength ( ⁇ ) nm at the crossing point is substituted into the following equation to obtain the target value.
- the value thus obtained is Eg (eV).
- Eg 1240/ ⁇
- Ea (electron affinity) is Ip minus Eg.
- the absolute value of the HOMO energy level corresponds to the ionization potential
- the absolute value of the LUMO energy level corresponds to the electron affinity.
- P-2, P-3, P-4, Pa and P-5 are shown in Table 4.
- the HOMO of the fluorine-containing arylamine polymer compound of the present invention is deeper than that of the fluorine-free polymer P-5. A high current luminous efficiency and lifetime can be expected.
Abstract
The present invention relates to a composition that comprises: a polymer compound having a repeat unit given by formula (1), having possibly substituted fluorene in the main chain and/or in side chain position, and having a crosslinking group; and an electron-accepting compound given by formula (81) and having a crosslinking group. (In formula (1) and formula (81), Ar1, G, *, Ar2, m, n, R81 to R84, Ph1 to Ph4, and X+ each have the definitions provided in the Description.)
Description
本発明は、組成物、有機電界発光素子及びその製造方法、表示装置、並びに照明装置に関する。
The present invention relates to a composition, an organic electroluminescent element and its manufacturing method, a display device, and a lighting device.
近年、薄膜型の電界発光素子としては、無機材料を用いたものに代わり、有機薄膜を用いた有機電界発光素子の開発が行われるようになっている。有機電界発光素子(OLED)は、通常、陽極と陰極の間に、電荷注入層、電荷輸送層、有機発光層、電子輸送層などを有し、この各層に適した材料が開発されつつあり、発光色も赤、緑、青と、それぞれに開発が進んでいる。また近年、有機電界発光素子の発光層に無機発光物質である「量子ドット」を用いた量子ドット発光素子も開発が進んでいる。
In recent years, as thin-film electroluminescent elements, instead of those using inorganic materials, organic electroluminescent elements using organic thin films have been developed. An organic electroluminescent device (OLED) usually has a charge injection layer, a charge transport layer, an organic light emitting layer, an electron transport layer, etc. between an anode and a cathode, and materials suitable for each layer are being developed. Emission colors are also being developed into red, green, and blue. In recent years, quantum dot light-emitting devices using "quantum dots", which are inorganic light-emitting substances, in the light-emitting layer of organic electroluminescence devices have also been developed.
有機電界発光素子の有機層の形成方法としては、真空蒸着法と湿式成膜法(塗布法)が挙げられる。真空蒸着法は積層化が容易であるため、陽極及び/又は陰極からの電荷注入の改善、励起子の発光層封じ込めが容易であるという利点を有する。一方で、湿式成膜法は真空プロセスが要らず、大面積化が容易で、様々な機能をもった複数の材料を混合した塗布液を用いることにより、容易に、様々な機能をもった複数の材料を含有する層を形成できる等の利点がある。そのため、近年では塗布法での製膜による有機電界発光素子の研究開発が精力的に行われている。
Methods for forming the organic layer of the organic electroluminescence device include a vacuum deposition method and a wet film forming method (coating method). The vacuum vapor deposition method facilitates lamination, and thus has the advantage of improving charge injection from the anode and/or cathode and facilitating confinement of excitons in the light-emitting layer. On the other hand, the wet film-forming method does not require a vacuum process and can easily be applied to a large area. There is an advantage that a layer containing the material can be formed. Therefore, in recent years, research and development of organic electroluminescence elements by film formation by a coating method have been vigorously carried out.
特許文献1には、架橋基を含むアリールアミン高分子化合物と電子受容性化合物を含む組成物を有する有機電界発光素子が開示されている。特許文献2、特許文献3及び特許文献4には、フッ素を含むアリールアミン高分子化合物と電子受容性化合物を含む組成物を有する有機電界発光素子が開示されている。
Patent Document 1 discloses an organic electroluminescence device having a composition containing an arylamine polymer compound containing a cross-linking group and an electron-accepting compound. Patent Document 2, Patent Document 3, and Patent Document 4 disclose an organic electroluminescence device having a composition containing a fluorine-containing arylamine polymer compound and an electron-accepting compound.
一般的に、アリールアミン類の有機電子供与体と有機電子受容体とを適切な比率で混合し、アリールアミンの有するN原子が部分的に有機電子受容体とイオン錯体を形成すると、このイオン錯体が形成されることで陽極からの正孔注入障壁が低減するので、安定なイオン錯体を形成する材料が注目されている。特許文献1には、この技術を利用して正孔注入障壁が低減することを成功したことが開示されている。しかしながら、特許文献1に開示されたアリールアミン高分子化合物では分子のHOMO(Highest Occupied Molecular Orbital、最高被占軌道)が浅く、HOMO深い正孔輸送材料を用いた正孔輸送層において電荷注入障壁が生じ、有機電界発光素子の駆動電圧の低減が不十分である。特許文献2~4に開示された材料や技術では、フッ素を有するアリールアミン高分子化合物の有機電子供与体と、有機電子受容体からイオン錯体を形成させている。しかしながら、このイオン錯体を含有する電荷注入層の膜を形成したが、有機電界発光素子の駆動電圧の低減が不十分である。また、架橋基を含まない有機電子受容体が光重合開始剤として使用されており、発光層まで有機電子受容体の拡散防止が不十分であり、発光効率及び駆動寿命を向上させることができなかった。
In general, an arylamine organic electron donor and an organic electron acceptor are mixed in an appropriate ratio, and when the N atoms of the arylamine partially form an ionic complex with the organic electron acceptor, this ionic complex The formation of a lowers the hole injection barrier from the anode, so materials that form stable ionic complexes are attracting attention. Patent Literature 1 discloses that this technique was used to successfully reduce the hole injection barrier. However, in the arylamine polymer compound disclosed in Patent Document 1, the HOMO (Highest Occupied Molecular Orbital) of the molecule is shallow, and a charge injection barrier is formed in the hole transport layer using a hole transport material with a deep HOMO. Therefore, the driving voltage of the organic electroluminescence device is insufficiently reduced. In the materials and techniques disclosed in Patent Documents 2 to 4, an ion complex is formed from an organic electron donor of an arylamine polymer compound having fluorine and an organic electron acceptor. However, although the film of the charge injection layer containing this ion complex is formed, the reduction of the driving voltage of the organic electroluminescence device is insufficient. In addition, an organic electron acceptor that does not contain a cross-linking group is used as a photopolymerization initiator, and the diffusion of the organic electron acceptor to the light-emitting layer is not sufficiently prevented, and the luminous efficiency and driving life cannot be improved. Ta.
本発明は、上記従来の実情に鑑みてなされたものであって、駆動電圧が低く、発光効率が高く、駆動寿命が長い有機電界発光素子を得るための組成物を提供することを課題とする。
The present invention has been made in view of the above-mentioned conventional circumstances, and an object of the present invention is to provide a composition for obtaining an organic electroluminescent device having a low driving voltage, a high luminous efficiency, and a long driving life. .
本発明者らは、鋭意検討した結果、特定の構造のアリールアミン高分子化合物および特定の構造の電子受容性化合物の架橋反応物を含有する正孔注入層及び/又は正孔輸送層を用いることで、有機電界発光素子(OLED)、または有機電界発光素子の発光層に量子ドットを含有する量子ドット発光素子においても上記課題を解決し得ることを見出し、本発明を完成するに至った。
As a result of extensive studies, the present inventors have found that a hole injection layer and/or a hole transport layer containing a cross-linking reaction product of an arylamine polymer compound with a specific structure and an electron-accepting compound with a specific structure can be used. Therefore, the inventors have found that the above problems can be solved in an organic electroluminescence device (OLED) or a quantum dot light-emitting device containing quantum dots in the light-emitting layer of the organic electroluminescence device, and have completed the present invention.
即ち、本発明の要旨は、次の態様1~19のとおりである。
That is, the gist of the present invention is as follows in aspects 1 to 19.
本発明の態様1は、下記式(1)で表される繰り返し単位を有し、主鎖及び側鎖の少なくとも1つに置換基を有していてもよいフルオレンを有し、架橋基を有する高分子化合物、および下記式(81)で表される、架橋基を有する電子受容性化合物を含む、組成物である。
Aspect 1 of the present invention has a repeating unit represented by the following formula (1), has a fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group. A composition comprising a polymer compound and an electron-accepting compound having a cross-linking group represented by the following formula (81).
(式(1)中、
Ar1は、置換基を有していてもよい炭素数6~60の2価の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Gは、式(1-1)~式(1-3)のいずれかで表される2価の基を表し、
“*”は隣接する構造との結合位置を表し、
置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
Ar2は、水素原子、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表し、
mは、1~4の整数であり、
nは、1~6の整数である。) (In formula (1),
Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group ,
G represents a divalent group represented by any one of formulas (1-1) to (1-3),
"*" represents the bonding position with the adjacent structure,
Each substituent A is independently a fluorine atom, CF3 , or SF5 .
Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms. A plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group,
m is an integer from 1 to 4,
n is an integer of 1-6. )
Ar1は、置換基を有していてもよい炭素数6~60の2価の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Gは、式(1-1)~式(1-3)のいずれかで表される2価の基を表し、
“*”は隣接する構造との結合位置を表し、
置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
Ar2は、水素原子、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表し、
mは、1~4の整数であり、
nは、1~6の整数である。) (In formula (1),
Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group ,
G represents a divalent group represented by any one of formulas (1-1) to (1-3),
"*" represents the bonding position with the adjacent structure,
Each substituent A is independently a fluorine atom, CF3 , or SF5 .
Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms. A plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group,
m is an integer from 1 to 4,
n is an integer of 1-6. )
(式(81)中、
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) (In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. )
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) (In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. )
本発明の態様2は、少なくとも2つの架橋基を有する前記式(81)で表される電子受容性化合物を含む、態様1に記載の組成物である。
Aspect 2 of the present invention is the composition according to Aspect 1, comprising the electron-accepting compound represented by the formula (81) having at least two cross-linking groups.
本発明の態様3は、前記式(1)で表される化合物及び前記式(81)で表される化合物が、各々独立に、下記架橋基群Tから選択される架橋基を有する、態様1又は2に記載の組成物である。
<架橋基群T> Aspect 3 of the present invention isAspect 1, wherein the compound represented by the formula (1) and the compound represented by the formula (81) each independently have a cross-linking group selected from the following cross-linking group group T: or a composition according to 2.
<Crosslinking Group T>
<架橋基群T> Aspect 3 of the present invention is
<Crosslinking Group T>
(上記式中、
Qは直接結合又は連結基を表す。
“*”は結合位置を表す。
式(X4)、式(X5)、式(X6)及び式(X10)中のR110は、水素原子又は置換基を有していてもよいアルキル基を表す。
式(X1)~(X4)中、ベンゼン環及びナフタレン環は、置換基を有していてもよい。また、置換基は互いに結合して環を形成してもよい。
式(X1)、(X2)中、シクロブテン環は置換基を有していてもよい。) (In the above formula,
Q represents a direct bond or a linking group.
"*" represents the binding position.
R 110 in formula (X4), formula (X5), formula (X6) and formula (X10) represents a hydrogen atom or an optionally substituted alkyl group.
In formulas (X1) to (X4), the benzene ring and naphthalene ring may have a substituent. Also, the substituents may be combined with each other to form a ring.
In formulas (X1) and (X2), the cyclobutene ring may have a substituent. )
Qは直接結合又は連結基を表す。
“*”は結合位置を表す。
式(X4)、式(X5)、式(X6)及び式(X10)中のR110は、水素原子又は置換基を有していてもよいアルキル基を表す。
式(X1)~(X4)中、ベンゼン環及びナフタレン環は、置換基を有していてもよい。また、置換基は互いに結合して環を形成してもよい。
式(X1)、(X2)中、シクロブテン環は置換基を有していてもよい。) (In the above formula,
Q represents a direct bond or a linking group.
"*" represents the binding position.
R 110 in formula (X4), formula (X5), formula (X6) and formula (X10) represents a hydrogen atom or an optionally substituted alkyl group.
In formulas (X1) to (X4), the benzene ring and naphthalene ring may have a substituent. Also, the substituents may be combined with each other to form a ring.
In formulas (X1) and (X2), the cyclobutene ring may have a substituent. )
本発明の態様4は、前記Gが下記式のいずれかで表される、態様1~3のいずれか1つに記載の組成物である。
Aspect 4 of the present invention is the composition according to any one of Aspects 1 to 3, wherein said G is represented by any of the following formulas.
(上記式中、“*”は隣接する構造との結合位置を表す。)
(In the above formula, "*" represents the bonding position with the adjacent structure.)
本発明の態様5は、前記[-G-Ar2]が下記式のいずれかで表される、態様1~3のいずれか1つに記載の組成物である。
Aspect 5 of the present invention is the composition according to any one of Aspects 1 to 3, wherein [-G-Ar 2 ] is represented by any one of the following formulas.
(上記式中、“*”は隣接する構造との結合位置を表す。)
(In the above formula, "*" represents the bonding position with the adjacent structure.)
本発明の態様6は、前記Ar1が、下記式(2-1)~(2-3)から選択される1つの部分構造を有するか、または、下記式(2-1)~(2-3)から選択される2以上が互いに結合してなる結合構造を有し、前記結合構造が下記式(2-1)~(2-3)から選択される少なくとも1種の構造を2以上結合した構造を含有してもよい、態様1~5のいずれか1つに記載の組成物である。
In aspect 6 of the present invention, Ar 1 has one partial structure selected from the following formulas (2-1) to (2-3), or the following formulas (2-1) to (2- 3) having a bonding structure in which two or more selected from the following formulas (2-1) to (2-3) are bonded to each other, and the bonding structure bonds two or more structures of at least one type selected from the following formulas (2-1) to (2-3) 6. The composition of any one of aspects 1-5, which may contain a structure comprising:
(上記式(2-1)~(2-3)それぞれにおいて、R1およびR2は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~18の芳香族炭化水素基、置換基を有していてもよい炭素数3~12の芳香族複素環基、炭素数1~12のアルキル基であり、“*”は隣接する構造との結合位置を表す。)
(In each of the above formulas (2-1) to (2-3), R 1 and R 2 each independently represent a hydrogen atom, a deuterium atom, a halogen atom, or an optionally substituted carbon number of 6 ~18 aromatic hydrocarbon groups, optionally substituted C3-C12 aromatic heterocyclic groups, C1-C12 alkyl groups, and "*" with the adjacent structure represents the binding position.)
本発明の態様7は、前記高分子化合物が、さらに、下記式(3)で表される繰り返し単位を有する、態様1~6のいずれか1つに記載の組成物である。
Aspect 7 of the present invention is the composition according to any one of Aspects 1 to 6, wherein the polymer compound further has a repeating unit represented by the following formula (3).
(上記式(3)中、Ar3は、置換基を有していてもよい2-フルオレニル基である。Ar4は、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は前記置換基を有していてもよい2価の芳香族炭化水素基及び前記置換基を有していてもよい2価の芳香族複素環基からなる群から選択される少なくとも2つの基が直接若しくは連結基を介して複数個連結した2価の基を表す。)
(In the above formula (3), Ar 3 is an optionally substituted 2-fluorenyl group. Ar 4 is an optionally substituted divalent aromatic hydrocarbon group, A divalent aromatic heterocyclic group which may have a substituent, or a divalent aromatic hydrocarbon group which may have a substituent and a divalent which may have a substituent represents a divalent group in which at least two groups selected from the group consisting of aromatic heterocyclic groups are linked directly or via a linking group.)
本発明の態様8は、更に溶媒を含有する、態様1~7のいずれか1つに記載の組成物である。
Aspect 8 of the present invention is the composition according to any one of aspects 1 to 7, further comprising a solvent.
本発明の態様9は、基板上に、陽極及び陰極を有し、該陽極と該陰極の間に有機層を有する有機電界発光素子の製造方法であって、該有機層を、態様8に記載の組成物を用いて湿式成膜法にて形成する工程を有する、有機電界発光素子の製造方法である。
Aspect 9 of the present invention is a method for manufacturing an organic electroluminescence device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode, wherein the organic layer is the A method for producing an organic electroluminescence device, comprising a step of forming by a wet film-forming method using the composition of
本発明の態様10は、前記有機層が前記陽極と発光層の間にある有機層である、態様9に記載の有機電界発光素子の製造方法である。
A tenth aspect of the present invention is the method for producing an organic electroluminescent device according to Aspect 9, wherein the organic layer is an organic layer between the anode and the light-emitting layer.
本発明の態様11は、基板上に、陽極及び陰極を有し、該陽極と該陰極の間に有機層を有する有機電界発光素子であって、
該有機層が、下記式(1)で表される繰り返し単位を有し、主鎖及び側鎖の少なくとも1つに置換基を有していてもよいフルオレンを有し、架橋基を有する高分子化合物と、下記式(81)で表される、架橋基を有する電子受容性化合物との架橋反応物を含有する、有機電界発光素子である。 Embodiment 11 of the present invention is an organic electroluminescence device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode,
The organic layer has a repeating unit represented by the following formula (1), has fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group. An organic electroluminescence device containing a cross-linking reaction product of a compound and an electron-accepting compound having a cross-linking group represented by the following formula (81).
該有機層が、下記式(1)で表される繰り返し単位を有し、主鎖及び側鎖の少なくとも1つに置換基を有していてもよいフルオレンを有し、架橋基を有する高分子化合物と、下記式(81)で表される、架橋基を有する電子受容性化合物との架橋反応物を含有する、有機電界発光素子である。 Embodiment 11 of the present invention is an organic electroluminescence device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode,
The organic layer has a repeating unit represented by the following formula (1), has fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group. An organic electroluminescence device containing a cross-linking reaction product of a compound and an electron-accepting compound having a cross-linking group represented by the following formula (81).
(式(1)中、
Ar1は、置換基を有していてもよい炭素数6~60の2価の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Gは、式(1-1)~式(1-3)のいずれかで表される2価の基を表し、
“*”は隣接する構造との結合部位を表し、
置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
Ar2は、水素原子、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表し、
mは、1~4の整数であり、
nは、1~6の整数である。) (In formula (1),
Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group ,
G represents a divalent group represented by any one of formulas (1-1) to (1-3),
"*" represents the binding site with the adjacent structure,
Each substituent A is independently a fluorine atom, CF3 , or SF5 .
Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms. A plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group,
m is an integer from 1 to 4,
n is an integer of 1-6. )
Ar1は、置換基を有していてもよい炭素数6~60の2価の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Gは、式(1-1)~式(1-3)のいずれかで表される2価の基を表し、
“*”は隣接する構造との結合部位を表し、
置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
Ar2は、水素原子、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表し、
mは、1~4の整数であり、
nは、1~6の整数である。) (In formula (1),
Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group ,
G represents a divalent group represented by any one of formulas (1-1) to (1-3),
"*" represents the binding site with the adjacent structure,
Each substituent A is independently a fluorine atom, CF3 , or SF5 .
Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms. A plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group,
m is an integer from 1 to 4,
n is an integer of 1-6. )
(式(81)中、
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) (In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. )
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) (In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. )
本発明の態様12は、前記Gが下記式のいずれかで表される、態様11に記載の有機電界発光素子である。
Aspect 12 of the present invention is the organic electroluminescence device according to Aspect 11, wherein the G is represented by any one of the following formulas.
(上記式中、“*”は隣接する構造との結合位置を表す。)
(In the above formula, "*" represents the bonding position with the adjacent structure.)
本発明の態様13は、前記[-G-Ar2]が下記式のいずれかで表される、態様11に記載の有機電界発光素子である。
Aspect 13 of the present invention is the organic electroluminescence device according to Aspect 11, wherein [-G-Ar 2 ] is represented by any one of the following formulas.
(上記式中、“*”は隣接する構造との結合位置を表す。)
(In the above formula, "*" represents the bonding position with the adjacent structure.)
本発明の態様14は、前記Ar1が、下記式(2-1)~(2-3)から選択される1つの部分構造を有するか、または、下記式(2-1)~(2-3)から選択される2以上が互いに結合してなる結合構造を有し、前記結合構造が下記式(2-1)~(2-3)から選択される少なくとも1種の構造を2以上結合した構造を含有してもよい、態様11~13のいずれか1つに記載の有機電界発光素子である。
In embodiment 14 of the present invention, Ar 1 has one partial structure selected from the following formulas (2-1) to (2-3), or the following formulas (2-1) to (2- 3) having a bonding structure in which two or more selected from the following formulas (2-1) to (2-3) are bonded to each other, and the bonding structure bonds two or more structures of at least one type selected from the following formulas (2-1) to (2-3) 14. The organic electroluminescent device according to any one of aspects 11 to 13, which may contain a structure with
(上記式(2-1)~式(2-3)それぞれにおいて、R1およびR2は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~18の芳香族炭化水素基、置換基を有していてもよい炭素数3~12の芳香族複素環基、炭素数1~12のアルキル基であり、*は隣接する構造との結合位置を表す。)
(In each of the above formulas (2-1) to (2-3), R 1 and R 2 are each independently a hydrogen atom, a deuterium atom, a halogen atom, or the number of carbon atoms which may have a substituent. an aromatic hydrocarbon group of 6 to 18, an aromatic heterocyclic group of 3 to 12 carbon atoms which may have a substituent, an alkyl group of 1 to 12 carbon atoms, and * is a bond with an adjacent structure position.)
本発明の態様15は、前記高分子化合物が、さらに、下記式(3)で表される繰り返し単位を有する、態様11~14のいずれか1つに記載の有機電界発光素子である。
Aspect 15 of the present invention is the organic electroluminescence device according to any one of Aspects 11 to 14, wherein the polymer compound further has a repeating unit represented by the following formula (3).
(式(3)中、Ar3が、置換基を有していてもよい2-フルオレニル基である。Ar4は、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は前記置換基を有していてもよい2価の芳香族炭化水素基及び前記置換基を有していてもよい2価の芳香族複素環基からなる群から選択される少なくとも2つの基が直接若しくは連結基を介して複数個連結した2価の基を表す。)
(In formula (3), Ar 3 is an optionally substituted 2-fluorenyl group. Ar 4 is an optionally substituted divalent aromatic hydrocarbon group, a substituted a divalent aromatic heterocyclic group optionally having a group, or a divalent aromatic hydrocarbon group optionally having a substituent and a divalent It represents a divalent group in which at least two groups selected from the group consisting of aromatic heterocyclic groups are linked directly or via a linking group.)
本発明の態様16は、態様9又は10に記載の有機電界発光素子の製造方法で製造された、有機電界発光素子である。
A sixteenth aspect of the present invention is an organic electroluminescent device manufactured by the method for manufacturing an organic electroluminescent device according to the ninth or tenth aspect.
本発明の態様17は、発光層に量子ドットを含有する、態様11~16のいずれか1つに記載の有機電界発光素子である。
Aspect 17 of the present invention is the organic electroluminescent device according to any one of Aspects 11 to 16, which contains quantum dots in the light-emitting layer.
本発明の態様18は、態様11~17のいずれか1つに記載の有機電界発光素子を有する、表示装置である。
Aspect 18 of the present invention is a display device comprising the organic electroluminescent element according to any one of Aspects 11 to 17.
本発明の態様19は、態様11~17のいずれか1つに記載の有機電界発光素子を有する、照明装置である。
A nineteenth aspect of the present invention is a lighting device comprising the organic electroluminescent element according to any one of aspects 11 to 17.
本発明の組成物は、駆動電圧が低く、発光効率が高く、駆動寿命が長い有機電界発光素子を提供することができる。
The composition of the present invention can provide an organic electroluminescent device with low driving voltage, high luminous efficiency, and long driving life.
以下に、本発明の一実施形態である組成物、有機電界発光素子及びその製造方法、表示装置、並びに照明装置の実施態様を詳細に説明する。以下の説明は、本発明の実施態様の一例(代表例)である第一の実施形態であるが、本発明は、その要旨を超えない限り、これらの内容に特定されない。
In the following, embodiments of the composition, the organic electroluminescence device and its manufacturing method, the display device, and the lighting device, which are one embodiment of the present invention, will be described in detail. Although the following description is a first embodiment which is an example (representative example) of embodiments of the present invention, the present invention is not specified by these contents unless it exceeds the gist thereof.
本発明において、「置換基を有していてもよい」とは、置換基を1以上有していてもよいことを意味するものとする。
In the present invention, "optionally having a substituent" means that it may have one or more substituents.
[定義]
以下、本発明で用いるフッ素を有するアリールアミン高分子化合物、架橋基を有する電子受容性化合物及び電荷輸送性高分子化合物の構造を詳細に説明するにあたり、共通する部分構造は特段の断りが無い限り、以下の構造であるとする。 [definition]
Hereinafter, in describing in detail the structures of the fluorine-containing arylamine polymer compound, the electron-accepting compound having a cross-linking group, and the charge-transporting polymer compound used in the present invention, common partial structures are as follows unless otherwise specified. , with the following structure:
以下、本発明で用いるフッ素を有するアリールアミン高分子化合物、架橋基を有する電子受容性化合物及び電荷輸送性高分子化合物の構造を詳細に説明するにあたり、共通する部分構造は特段の断りが無い限り、以下の構造であるとする。 [definition]
Hereinafter, in describing in detail the structures of the fluorine-containing arylamine polymer compound, the electron-accepting compound having a cross-linking group, and the charge-transporting polymer compound used in the present invention, common partial structures are as follows unless otherwise specified. , with the following structure:
<芳香族炭化水素基>
芳香族炭化水素基とは、後述の説明対象となる化合物の構造の中での結合状態に応じて、芳香族炭化水素環構造の1価、2価、又は3価以上の構造を指す。 <Aromatic hydrocarbon group>
The aromatic hydrocarbon group refers to a monovalent, divalent, or trivalent or higher aromatic hydrocarbon ring structure depending on the bonding state in the structure of the compound to be described later.
芳香族炭化水素基とは、後述の説明対象となる化合物の構造の中での結合状態に応じて、芳香族炭化水素環構造の1価、2価、又は3価以上の構造を指す。 <Aromatic hydrocarbon group>
The aromatic hydrocarbon group refers to a monovalent, divalent, or trivalent or higher aromatic hydrocarbon ring structure depending on the bonding state in the structure of the compound to be described later.
芳香族炭化水素環の構造において、通常、炭素数は制限されるものではないが、好ましくは炭素数6以上、60以下であり、炭素数の上限としてさらに好ましくは炭素数48以下、より好ましくは炭素数30以下である。具体的には、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環等の、6員環の単環若しくは2~5縮合環の基、又はこれらから選択される複数の基が複数連結した構造が挙げられる。芳香族炭化水素環が複数個連結する場合は、通常、2~10個連結した構造が挙げられ、2~5個連結した構造であることが好ましい。芳香族炭化水素環が複数個連結する場合、同一の構造が連結してもよく、異なる構造が連結してもよい。
In the structure of the aromatic hydrocarbon ring, the number of carbon atoms is usually not limited, but preferably 6 or more and 60 or less, and the upper limit of the carbon number is more preferably 48 or less, more preferably 48 or less. It has 30 or less carbon atoms. Specifically, six-membered rings such as 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 ring. A monocyclic or 2 to 5 condensed ring group, or a structure in which a plurality of groups selected from these are linked together may be mentioned. When a plurality of aromatic hydrocarbon rings are linked, a structure in which 2 to 10 rings are linked is usually mentioned, and a structure in which 2 to 5 rings are linked is preferable. When a plurality of aromatic hydrocarbon rings are linked, the same structure may be linked, or different structures may be linked.
芳香族炭化水素環構造として好ましくは、ベンゼン環、ビフェニル環すなわちベンゼン環が2連結した構造、ターフェニル環すなわちベンゼン環が3連結した構造、クォーターフェニレン環すなわちベンゼン環が4連結した構造、ナフタレン環、フルオレン環である。
Preferred aromatic hydrocarbon ring structures include a benzene ring, a biphenyl ring, i.e., a structure in which two benzene rings are linked, a terphenyl ring, i.e., a structure in which three benzene rings are linked, a quaterphenylene ring, i.e., a structure in which four benzene rings are linked, and a naphthalene ring. , is a fluorene ring.
<芳香族複素環基>
芳香族複素環基とは、後述の説明対象となる化合物の構造の中での結合状態に応じて、芳香族複素環構造の1価、2価、又は3価以上構造を指す。 <Aromatic heterocyclic group>
The aromatic heterocyclic group refers to a monovalent, divalent, or trivalent or higher aromatic heterocyclic structure depending on the bonding state in the structure of the compound to be described later.
芳香族複素環基とは、後述の説明対象となる化合物の構造の中での結合状態に応じて、芳香族複素環構造の1価、2価、又は3価以上構造を指す。 <Aromatic heterocyclic group>
The aromatic heterocyclic group refers to a monovalent, divalent, or trivalent or higher aromatic heterocyclic structure depending on the bonding state in the structure of the compound to be described later.
芳香族複素環の構造において、通常、炭素数は制限されるものではないが、好ましくは、炭素数3以上、60以下であり、炭素数の上限としてさらに好ましくは炭素数48以下、より好ましくは炭素数30以下である。具体的には、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シンノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環等の、5~6員環の単環若しくは2~4縮合環の2価の基又はこれらが複数連結した基が挙げられる。芳香族複素環が複数個連結する場合、同一の構造が連結してもよく、異なる構造が連結してもよい。芳香族複素環が複数個連結される場合は、通常、2~10個連結した構造が挙げられ、2~5個連結した構造であることが好ましい。
In the structure of the aromatic heterocyclic ring, the number of carbon atoms is generally not limited, but preferably 3 or more and 60 or less, and more preferably 48 or less as the upper limit of the carbon number, more preferably 48 or less. It has 30 or less carbon atoms. Specifically, 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, benzoisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring , a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a benzimidazole ring, a perimidine ring, a quinazoline ring, a quinazolinone ring, an azulene ring, a 5- to 6-membered monocyclic ring or a 2- to 4-condensed divalent group or A group in which a plurality of these are linked is exemplified. When a plurality of aromatic heterocycles are linked, the same structure may be linked, or different structures may be linked. When a plurality of aromatic heterocycles are linked, a structure in which 2 to 10 are linked is usually mentioned, and a structure in which 2 to 5 are linked is preferable.
芳香族複素環構造として好ましくは、チオフェン環、ベンゾチオフェン環、ピリミジン環、トリアジン環、カルバゾール環、ジベンゾフラン環、ジベンゾチオフェン環である。
The aromatic heterocyclic ring structure is preferably a thiophene ring, a benzothiophene ring, a pyrimidine ring, a triazine ring, a carbazole ring, a dibenzofuran ring, or a dibenzothiophene ring.
<置換基>
特に断りの無い場合、置換基とは任意の基であるが、好ましくは、下記置換基群Zから選択される基、及び架橋基である。また、有してよい置換基が置換基群Zから選択される、と記されている場合、好ましい置換基も下記置換基群Zに記されている通りである。 <Substituent>
Unless otherwise specified, the substituent is an arbitrary group, preferably a group selected from the following substituent group Z and a bridging group. In addition, when it is described that the substituent that may be present is selected from Substituent Group Z, preferred substituents are also as described in Substituent Group Z below.
特に断りの無い場合、置換基とは任意の基であるが、好ましくは、下記置換基群Zから選択される基、及び架橋基である。また、有してよい置換基が置換基群Zから選択される、と記されている場合、好ましい置換基も下記置換基群Zに記されている通りである。 <Substituent>
Unless otherwise specified, the substituent is an arbitrary group, preferably a group selected from the following substituent group Z and a bridging group. In addition, when it is described that the substituent that may be present is selected from Substituent Group Z, preferred substituents are also as described in Substituent Group Z below.
<置換基群Z>
置換基群Zは、アルキル基、アルケニル基、アルキニル基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルコキシカルボニル基、ジアルキルアミノ基、ジアリールアミノ基、アリールアルキルアミノ基、アシル基、ハロゲン原子、ハロアルキル基、アルキルチオ基、アリールチオ基、シリル基、シロキシ基、シアノ基、芳香族炭化水素基、及び芳香族複素環基よりなる群である。これらの置換基は直鎖、分岐及び環状のいずれの構造を含んでいてもよい。 <Substituent Group Z>
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.
置換基群Zは、アルキル基、アルケニル基、アルキニル基、アルコキシ基、アリールオキシ基、ヘテロアリールオキシ基、アルコキシカルボニル基、ジアルキルアミノ基、ジアリールアミノ基、アリールアルキルアミノ基、アシル基、ハロゲン原子、ハロアルキル基、アルキルチオ基、アリールチオ基、シリル基、シロキシ基、シアノ基、芳香族炭化水素基、及び芳香族複素環基よりなる群である。これらの置換基は直鎖、分岐及び環状のいずれの構造を含んでいてもよい。 <Substituent Group Z>
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.
置換基群Zとして、より具体的には、以下の構造が挙げられる。
炭素数が1以上であり、好ましくは4以上であり、24以下、好ましくは12以下であり、さらに好ましくは8以下であり、より好ましくは6以下である、直鎖、分岐、又は環状のアルキル基。具体例としてはメチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、tert-ブチル基、n-ヘキシル基、シクロヘキシル基、ドデシル基等が挙げられる。
炭素数が通常2以上であり、通常24以下、好ましくは12以下である、直鎖、分岐、又は環状のアルケニル基;具体例としては、ビニル基等が挙げられる。
炭素数が通常2以上であり、通常24以下、好ましくは12以下である、直鎖又は分岐のアルキニル基;具体例としては、エチニル基等が挙げられる。
炭素数が1以上、24以下、好ましくは12以下であるアルコキシ基。具体例としては、メトキシ基、エトキシ基等が挙げられる。
炭素数4以上、好ましくは5以上であり、36以下、好ましくは24以下である、アリールオキシ基若しくはヘテロアリールオキシ基。具体例としては、フェノキシ基、ナフトキシ基、ピリジルオキシ基等が挙げられる。
炭素数2以上、24以下、好ましくは12以下であるアルコキシカルボニル基。具体例としては、メトキシカルボニル基、エトキシカルボニル基等が挙げられる。
炭素数2以上、24以下、好ましくは12以下であるジアルキルアミノ基。具体例としては、ジメチルアミノ基、ジエチルアミノ基等が挙げられる。
炭素数10以上、好ましくは12以上であり、36以下、好ましくは24以下のジアリールアミノ基。具体例としては、ジフェニルアミノ基、ジトリルアミノ基、N-カルバゾリル基等が挙げられる。
炭素数7以上、36以下、好ましくは24以下であるアリールアルキルアミノ基。具体例としては、フェニルメチルアミノ基が挙げられる。
炭素数2以上、24以下、好ましくは12以下であるアシル基。具体例としては、アセチル基、ベンゾイル基が挙げられる。
フッ素原子、塩素原子等のハロゲン原子。好ましくはフッ素原子である。;
炭素数1以上、12以下、好ましくは6以下のハロアルキル基。具体例としては、トリフルオロメチル基等が挙げられる。
炭素数1以上であり、通常24以下、好ましくは12以下のアルキルチオ基。具体例としては、メチルチオ基、エチルチオ基等が挙げられる。
炭素数4以上、好ましくは5以上であり、36以下、好ましくは24以下であるアリールチオ基。具体的には、フェニルチオ基、ナフチルチオ基、ピリジルチオ基等が挙げられる。
炭素数が通常2以上、好ましくは3以上であり、通常36以下、好ましくは24以下であるシリル基。具体例としては、トリメチルシリル基、トリフェニルシリル基等が挙げられる。
炭素数2以上、好ましくは3以上であり、通常36以下、好ましくは24以下であるシロキシ基。具体例としては、トリメチルシロキシ基、トリフェニルシロキシ基等が挙げられる。
シアノ基。
炭素数6以上、36以下、好ましくは24以下である芳香族炭化水素基。具体例としては、フェニル基、ナフチル基、複数のフェニル基が連結した基、等が挙げられる。
炭素数3以上、好ましくは4以上であり、36以下、好ましくは24以下である芳香族複素環基。具体例としては、チエニル基、ピリジル基等が挙げられる。 More specific examples of the 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.
A linear, branched or cyclic alkenyl group having usually 2 or more carbon atoms and usually 24 or less, preferably 12 or less carbon atoms; specific examples thereof include vinyl groups and the like.
A linear or branched alkynyl group having usually 2 or more carbon atoms and usually 24 or less, preferably 12 or less carbon atoms; specific examples thereof include ethynyl groups and the like.
an alkoxy group having 1 or more and 24 or less, preferably 12 or less carbon atoms; Specific examples include a methoxy group, an ethoxy group, and the like.
an aryloxy group or heteroaryloxy group having 4 or more, preferably 5 or more carbon atoms and 36 or less, preferably 24 or less carbon atoms; Specific examples include phenoxy group, naphthoxy group, pyridyloxy group and the like.
an alkoxycarbonyl group having 2 or more and 24 or less, preferably 12 or less carbon atoms; Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and the like.
A dialkylamino group having 2 or more and 24 or less, preferably 12 or less carbon atoms. Specific examples include a dimethylamino group and a diethylamino group.
A diarylamino group having 10 or more, preferably 12 or more, and 36 or less, preferably 24 or less carbon atoms. Specific examples include a diphenylamino group, a ditolylamino group, an N-carbazolyl group and the like.
an arylalkylamino group having 7 or more and 36 or less, preferably 24 or less carbon atoms; A specific example is a phenylmethylamino group.
an acyl group having 2 or more and 24 or less, preferably 12 or less carbon atoms; Specific examples include an acetyl group and a benzoyl group.
halogen atoms such as fluorine and chlorine atoms; A fluorine atom is preferred. ;
A haloalkyl group having 1 or more and 12 or less, preferably 6 or less carbon atoms. Specific examples include a trifluoromethyl group and the like.
an alkylthio group having 1 or more carbon atoms and usually 24 or less, preferably 12 or less; 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.
A silyl group having usually 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less carbon atoms. Specific examples include a trimethylsilyl group and a triphenylsilyl group.
A siloxy group having 2 or more carbon atoms, preferably 3 or more carbon atoms, and usually 36 or less, preferably 24 or less carbon atoms. Specific examples include a trimethylsiloxy group and a triphenylsiloxy group.
Cyano group.
An aromatic hydrocarbon group having 6 or more and 36 or less, preferably 24 or less carbon atoms. Specific examples include a phenyl group, a naphthyl group, a group in which multiple phenyl groups are linked, 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.
炭素数が1以上であり、好ましくは4以上であり、24以下、好ましくは12以下であり、さらに好ましくは8以下であり、より好ましくは6以下である、直鎖、分岐、又は環状のアルキル基。具体例としてはメチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、tert-ブチル基、n-ヘキシル基、シクロヘキシル基、ドデシル基等が挙げられる。
炭素数が通常2以上であり、通常24以下、好ましくは12以下である、直鎖、分岐、又は環状のアルケニル基;具体例としては、ビニル基等が挙げられる。
炭素数が通常2以上であり、通常24以下、好ましくは12以下である、直鎖又は分岐のアルキニル基;具体例としては、エチニル基等が挙げられる。
炭素数が1以上、24以下、好ましくは12以下であるアルコキシ基。具体例としては、メトキシ基、エトキシ基等が挙げられる。
炭素数4以上、好ましくは5以上であり、36以下、好ましくは24以下である、アリールオキシ基若しくはヘテロアリールオキシ基。具体例としては、フェノキシ基、ナフトキシ基、ピリジルオキシ基等が挙げられる。
炭素数2以上、24以下、好ましくは12以下であるアルコキシカルボニル基。具体例としては、メトキシカルボニル基、エトキシカルボニル基等が挙げられる。
炭素数2以上、24以下、好ましくは12以下であるジアルキルアミノ基。具体例としては、ジメチルアミノ基、ジエチルアミノ基等が挙げられる。
炭素数10以上、好ましくは12以上であり、36以下、好ましくは24以下のジアリールアミノ基。具体例としては、ジフェニルアミノ基、ジトリルアミノ基、N-カルバゾリル基等が挙げられる。
炭素数7以上、36以下、好ましくは24以下であるアリールアルキルアミノ基。具体例としては、フェニルメチルアミノ基が挙げられる。
炭素数2以上、24以下、好ましくは12以下であるアシル基。具体例としては、アセチル基、ベンゾイル基が挙げられる。
フッ素原子、塩素原子等のハロゲン原子。好ましくはフッ素原子である。;
炭素数1以上、12以下、好ましくは6以下のハロアルキル基。具体例としては、トリフルオロメチル基等が挙げられる。
炭素数1以上であり、通常24以下、好ましくは12以下のアルキルチオ基。具体例としては、メチルチオ基、エチルチオ基等が挙げられる。
炭素数4以上、好ましくは5以上であり、36以下、好ましくは24以下であるアリールチオ基。具体的には、フェニルチオ基、ナフチルチオ基、ピリジルチオ基等が挙げられる。
炭素数が通常2以上、好ましくは3以上であり、通常36以下、好ましくは24以下であるシリル基。具体例としては、トリメチルシリル基、トリフェニルシリル基等が挙げられる。
炭素数2以上、好ましくは3以上であり、通常36以下、好ましくは24以下であるシロキシ基。具体例としては、トリメチルシロキシ基、トリフェニルシロキシ基等が挙げられる。
シアノ基。
炭素数6以上、36以下、好ましくは24以下である芳香族炭化水素基。具体例としては、フェニル基、ナフチル基、複数のフェニル基が連結した基、等が挙げられる。
炭素数3以上、好ましくは4以上であり、36以下、好ましくは24以下である芳香族複素環基。具体例としては、チエニル基、ピリジル基等が挙げられる。 More specific examples of the 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.
A linear, branched or cyclic alkenyl group having usually 2 or more carbon atoms and usually 24 or less, preferably 12 or less carbon atoms; specific examples thereof include vinyl groups and the like.
A linear or branched alkynyl group having usually 2 or more carbon atoms and usually 24 or less, preferably 12 or less carbon atoms; specific examples thereof include ethynyl groups and the like.
an alkoxy group having 1 or more and 24 or less, preferably 12 or less carbon atoms; Specific examples include a methoxy group, an ethoxy group, and the like.
an aryloxy group or heteroaryloxy group having 4 or more, preferably 5 or more carbon atoms and 36 or less, preferably 24 or less carbon atoms; Specific examples include phenoxy group, naphthoxy group, pyridyloxy group and the like.
an alkoxycarbonyl group having 2 or more and 24 or less, preferably 12 or less carbon atoms; Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group, and the like.
A dialkylamino group having 2 or more and 24 or less, preferably 12 or less carbon atoms. Specific examples include a dimethylamino group and a diethylamino group.
A diarylamino group having 10 or more, preferably 12 or more, and 36 or less, preferably 24 or less carbon atoms. Specific examples include a diphenylamino group, a ditolylamino group, an N-carbazolyl group and the like.
an arylalkylamino group having 7 or more and 36 or less, preferably 24 or less carbon atoms; A specific example is a phenylmethylamino group.
an acyl group having 2 or more and 24 or less, preferably 12 or less carbon atoms; Specific examples include an acetyl group and a benzoyl group.
halogen atoms such as fluorine and chlorine atoms; A fluorine atom is preferred. ;
A haloalkyl group having 1 or more and 12 or less, preferably 6 or less carbon atoms. Specific examples include a trifluoromethyl group and the like.
an alkylthio group having 1 or more carbon atoms and usually 24 or less, preferably 12 or less; 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.
A silyl group having usually 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less carbon atoms. Specific examples include a trimethylsilyl group and a triphenylsilyl group.
A siloxy group having 2 or more carbon atoms, preferably 3 or more carbon atoms, and usually 36 or less, preferably 24 or less carbon atoms. Specific examples include a trimethylsiloxy group and a triphenylsiloxy group.
Cyano group.
An aromatic hydrocarbon group having 6 or more and 36 or less, preferably 24 or less carbon atoms. Specific examples include a phenyl group, a naphthyl group, a group in which multiple phenyl groups are linked, 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.
上記置換基は、直鎖、分岐又は環状のいずれの構造を含んでいてもよい。
上記置換基が隣接する場合、隣接した置換基同士が結合して環を形成してもよい。好ましい環の大きさは、4員環、5員環、6員環であり、具体例としては、シクロブタン環、シクロペンタン環、シクロヘキサン環である。 The above substituents may have any structure of linear, branched or cyclic.
When the above substituents are adjacent to each other, the adjacent substituents may be combined to form a ring. Preferred ring sizes are 4-, 5-, and 6-membered rings, and specific examples include cyclobutane, cyclopentane, and cyclohexane rings.
上記置換基が隣接する場合、隣接した置換基同士が結合して環を形成してもよい。好ましい環の大きさは、4員環、5員環、6員環であり、具体例としては、シクロブタン環、シクロペンタン環、シクロヘキサン環である。 The above substituents may have any structure of linear, branched or cyclic.
When the above substituents are adjacent to each other, the adjacent substituents may be combined to form a ring. Preferred ring sizes are 4-, 5-, and 6-membered rings, and specific examples include cyclobutane, cyclopentane, and cyclohexane rings.
上記の置換基群Zの中でも、好ましくは、アルキル基、アルコキシ基、芳香族炭化水素基、芳香族複素環基である。
Among the above substituent groups Z, alkyl groups, alkoxy groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups are preferred.
また、上記置換基群Zの各置換基は更に置換基を有していてもよい。それら置換基としては、上記置換基群Zと同じのもの又は架橋基が挙げられる。好ましくは、更なる置換基は有さないか、炭素数8以下のアルキル基、炭素数8以下のアルコキシ基、またはフェニル基、より好ましくは炭素数6以下のアルキル基、炭素数6以下のアルコキシ基、またはフェニル基である。電荷輸送性の観点からは、さらなる置換基を有さないことがより好ましい。
Further, each substituent in the substituent group Z may further have a substituent. Examples of these substituents include the same as those in the above-mentioned substituent group Z or a bridging group. Preferably, it has no further substituents, or an alkyl group with up to 8 carbon atoms, an alkoxy group with up to 8 carbon atoms, or a phenyl group, more preferably an alkyl group with up to 6 carbon atoms, or an alkoxy group with up to 6 carbon atoms. or a phenyl group. From the viewpoint of charge transport properties, it is more preferable not to have additional substituents.
上記置換基群Zの各置換基が更に有してよい置換基が架橋基である場合の架橋基は、下記架橋基群Tから選択される架橋基が好ましい。架橋基を更に有することが好ましい置換基は、アルキル基又は芳香族炭化水素基である。
When the substituent that each substituent of the substituent group Z may further have is a crosslinkable group, the crosslinkable group is preferably a crosslinkable group selected from the following crosslinkable group T. A substituent that preferably further has a bridging group is an alkyl group or an aromatic hydrocarbon group.
<架橋基>
ここで架橋基とは、熱及び/又は活性エネルギー線の照射により、該架橋基の近傍に位置する他の架橋基と反応して、新規な化学結合を生成する基のことをいう。この場合、反応する基は架橋基と同一の基あるいは異なった基の場合もある。 <Crosslinking group>
Here, 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. In this case, the reactive group may be the same group as the bridging group or a different group.
ここで架橋基とは、熱及び/又は活性エネルギー線の照射により、該架橋基の近傍に位置する他の架橋基と反応して、新規な化学結合を生成する基のことをいう。この場合、反応する基は架橋基と同一の基あるいは異なった基の場合もある。 <Crosslinking group>
Here, 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. In this case, the reactive group may be the same group as the bridging group or a different group.
架橋基としては、限定されないが、アルケニル基を含む基、共役ジエン構造を含む基、アルキニル基を含む基、オキシラン構造を含む基、オキセタン構造を含む基、アジリジン構造を含む基、アジド基、無水マレイン酸構造を含む基、芳香族環に結合したアルケニル基を含む基、芳香族環に縮環したシクロブテン環などが挙げられる。好ましい架橋基の具体例としては下記架橋基群Tにおける下記式(X1)~(X18)のいずれかで表される架橋基が好ましい。
Examples of 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. As specific examples of preferred cross-linking groups, cross-linking groups represented by any one of the following formulas (X1) to (X18) in the following cross-linking group group T are preferable.
<架橋基群T>
<Crosslinking Group T>
(上記式中、
Qは直接結合又は連結基を表す。
“*”は結合位置を表す。
式(X4)、式(X5)、式(X6)及び式(X10)中のR110は、水素原子又は置換基を有していてもよいアルキル基を表す。
式(X1)~(X4)中、ベンゼン環及びナフタレン環は、置換基を有していてもよい。また、置換基は互いに結合して環を形成してもよい。
式(X1)、(X2)中、シクロブテン環は置換基を有していてもよい。) (In the above formula,
Q represents a direct bond or a linking group.
"*" represents the binding position.
R 110 in formula (X4), formula (X5), formula (X6) and formula (X10) represents a hydrogen atom or an optionally substituted alkyl group.
In formulas (X1) to (X4), the benzene ring and naphthalene ring may have a substituent. Also, the substituents may be combined with each other to form a ring.
In formulas (X1) and (X2), the cyclobutene ring may have a substituent. )
Qは直接結合又は連結基を表す。
“*”は結合位置を表す。
式(X4)、式(X5)、式(X6)及び式(X10)中のR110は、水素原子又は置換基を有していてもよいアルキル基を表す。
式(X1)~(X4)中、ベンゼン環及びナフタレン環は、置換基を有していてもよい。また、置換基は互いに結合して環を形成してもよい。
式(X1)、(X2)中、シクロブテン環は置換基を有していてもよい。) (In the above formula,
Q represents a direct bond or a linking group.
"*" represents the binding position.
R 110 in formula (X4), formula (X5), formula (X6) and formula (X10) represents a hydrogen atom or an optionally substituted alkyl group.
In formulas (X1) to (X4), the benzene ring and naphthalene ring may have a substituent. Also, the substituents may be combined with each other to form a ring.
In formulas (X1) and (X2), the cyclobutene ring may have a substituent. )
(Q)
Qが連結基である場合、連結基は特に限定はされないが、好ましくは、アルキレン基、2価の酸素原子又は置換基を有してもよい2価の芳香族炭化水素基である。
該アルキレン基としては、通常、炭素数1~12、好ましくは炭素数1~8、さらに好ましくは炭素数1~6のアルキレン基である。
該2価の芳香族炭化水素基としては、通常、炭素数6以上であり、通常炭素数36以下、好ましくは30以下、さらに好ましくは24以下であり、芳香族炭化水素環の構造としてはベンゼン環が好ましく、有してもよい置換基は、前述の置換基群Zから選択することが出来る。 (Q)
When Q is a linking group, the linking group is not particularly limited, but is preferably an alkylene group, a divalent oxygen atom, or a divalent aromatic hydrocarbon group which may have a substituent.
The alkylene group is generally an alkylene group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms.
The divalent aromatic hydrocarbon group usually has 6 or more carbon atoms and usually 36 or less carbon atoms, preferably 30 or less, more preferably 24 or less, and the aromatic hydrocarbon ring structure is benzene A ring is preferred, and the substituents which may be present can be selected from the substituent group Z described above.
Qが連結基である場合、連結基は特に限定はされないが、好ましくは、アルキレン基、2価の酸素原子又は置換基を有してもよい2価の芳香族炭化水素基である。
該アルキレン基としては、通常、炭素数1~12、好ましくは炭素数1~8、さらに好ましくは炭素数1~6のアルキレン基である。
該2価の芳香族炭化水素基としては、通常、炭素数6以上であり、通常炭素数36以下、好ましくは30以下、さらに好ましくは24以下であり、芳香族炭化水素環の構造としてはベンゼン環が好ましく、有してもよい置換基は、前述の置換基群Zから選択することが出来る。 (Q)
When Q is a linking group, the linking group is not particularly limited, but is preferably an alkylene group, a divalent oxygen atom, or a divalent aromatic hydrocarbon group which may have a substituent.
The alkylene group is generally an alkylene group having 1 to 12 carbon atoms, preferably 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms.
The divalent aromatic hydrocarbon group usually has 6 or more carbon atoms and usually 36 or less carbon atoms, preferably 30 or less, more preferably 24 or less, and the aromatic hydrocarbon ring structure is benzene A ring is preferred, and the substituents which may be present can be selected from the substituent group Z described above.
R110で表されるアルキル基は直鎖、分岐又は環状構造であり、炭素数は1以上であり、好ましくは24以下、より好ましくは12以下、さらに好ましくは8以下である。
The alkyl group represented by R 110 has a linear, branched or cyclic structure and has 1 or more carbon atoms, preferably 24 or less, more preferably 12 or less, and still more preferably 8 or less.
式(X1)~(X4)のベンゼン環及びナフタレン環、及び、式(X4)~(X6)、(X10)のR110が有していてもよい置換基として好ましくは、アルキル基、芳香族炭化水素基、アルキルオキシ基、アラルキル基である。
The benzene ring and naphthalene ring of formulas (X1) to (X4) and the substituents that R 110 of formulas (X4) to (X6) and (X10) may have are preferably an alkyl group and an aromatic They are a hydrocarbon group, an alkyloxy group and an aralkyl group.
置換基としてのアルキル基は直鎖、分岐又は環状構造であり、炭素数は好ましくは24以下、より好ましくは12以下、さらに好ましくは8以下であり、好ましくは1以上である。
The alkyl group as a substituent has a linear, branched or cyclic structure, and preferably has 24 or less carbon atoms, more preferably 12 or less carbon atoms, still more preferably 8 or less carbon atoms, and preferably 1 or more carbon atoms.
置換基としての芳香族炭化水素基の炭素数は、好ましくは24以下、より好ましくは18以下、さらに好ましくは12以下であり、好ましくは6以上である。芳香族炭化水素基はさらに前記アルキル基を置換基として有してもよい。
The number of carbon atoms in the aromatic hydrocarbon group as a substituent is preferably 24 or less, more preferably 18 or less, still more preferably 12 or less, and preferably 6 or more. The aromatic hydrocarbon group may further have the aforementioned alkyl group as a substituent.
置換基としてのアルキルオキシ基の炭素数は、好ましくは炭素数24以下、より好ましくは12以下、さらに好ましくは8以下であり、好ましくは1以上である。
The number of carbon atoms in the alkyloxy group as a substituent is preferably 24 or less, more preferably 12 or less, still more preferably 8 or less, and preferably 1 or more.
置換基としてのアラルキル基の炭素数は、好ましくは炭素数30以下、より好ましくは24以下、さらに好ましくは14以下であり、好ましくは7以上である。アラルキル基に含まれるアルキレン基は直鎖又は分岐構造が好ましい。アラルキル基に含まれるアリール基はさらに前記アルキル基を置換基として有してもよい。
The number of carbon atoms in the aralkyl group as a substituent is preferably 30 or less, more preferably 24 or less, even more preferably 14 or less, and preferably 7 or more. The alkylene group contained in the aralkyl group preferably has a linear or branched structure. The aryl group contained in the aralkyl group may further have the aforementioned alkyl group as a substituent.
式(X1)、(X2)のシクロブテン環が有していてもよい置換基として好ましくは、アルキル基である。
The substituent that the cyclobutene ring of formulas (X1) and (X2) may have is preferably an alkyl group.
式(X4)のR110として好ましくは水素原子又は置換基を有しないアルキル基である。式(X5)、(X6)、(X10)のR110として好ましくは置換基を有してよいアルキル基であり、さらに好ましくは置換基を有しないアルキル基である。
R 110 in formula (X4) is preferably a hydrogen atom or an unsubstituted alkyl group. R 110 in formulas (X5), (X6) and (X10) is preferably an optionally substituted alkyl group, more preferably an unsubstituted alkyl group.
置換基としてのアルキル基は直鎖、分岐又は環状構造であり、炭素数は好ましくは24以下、より好ましくは12以下、さらに好ましくは8以下であり、好ましくは1以上である。
The alkyl group as a substituent has a linear, branched or cyclic structure, and preferably has 24 or less carbon atoms, more preferably 12 or less carbon atoms, still more preferably 8 or less carbon atoms, and preferably 1 or more carbon atoms.
架橋基としては、式(X1)~(X3)のいずれかで表される架橋基が、熱のみで架橋反応が進行し、極性が小さく、電荷輸送に影響が小さい点で好ましい。
As the cross-linking group, a cross-linking group represented by any one of the formulas (X1) to (X3) is preferable because the cross-linking reaction proceeds only with heat, the polarity is small, and the effect on charge transport is small.
式(X1)で表される架橋基は下記式のように、熱によりシクロブテン環が開環し、開環した基同士で結合し、架橋構造を形成する。なお、以下において、式(X1)~式(X4)等における連結基Qは記載を省略している。
In the bridging group represented by formula (X1), the cyclobutene ring is opened by heat, and the ring-opened groups bond to each other to form a bridging structure, as shown in the following formula. In the following description, the linking group Q in formulas (X1) to (X4) and the like is omitted.
式(X2)で表される架橋基は下記式のように、熱によりシクロブテン環が開環し、開環した基同士で結合し、架橋構造を形成する。
As shown in the following formula, the cyclobutene ring of the bridging group represented by formula (X2) is opened by heat, and the ring-opened groups bond to each other to form a bridging structure.
式(X3)で表される架橋基は下記式のように、熱によりシクロブテン環が開環し、開環した基同士で結合し、架橋構造を形成する。
As shown in the following formula, the cyclobutene ring of the bridging group represented by formula (X3) is opened by heat, and the ring-opened groups bond to each other to form a bridging structure.
式(X1)~(X3)のいずれかで表される架橋基は、熱によりシクロブテン環が開環し、開環した基は、近傍に二重結合が存在する場合は、二重結合と反応して架橋構造を形成する。
In the bridging group represented by any one of formulas (X1) to (X3), the cyclobutene ring is opened by heat, and the ring-opened group reacts with the double bond when a double bond exists nearby. to form a crosslinked structure.
下記に、式(X1)で表される架橋基が開環した基と二重結合部位を有する式(X4)で表される架橋基が架橋構造を形成する例を示す。
An example in which the cross-linking group represented by formula (X1) and the cross-linking group represented by formula (X4) having a double bond site form a cross-linked structure is shown below.
式(X1)~(X3)のいずれかで表される架橋基と反応し得る二重結合を含有する基としては、式(X4)で表される架橋基の他に、式(X5)、式(X6)、式(X12)、式(X15)、式(X16)、式(X17)、式(X18)のいずれかで表される架橋基が挙げられる。これらの二重結合を含有する基を電子受容性化合物における架橋基として用いる場合、正孔輸送性化合物などの正孔注入層及び、又は正孔輸送層を形成する他の成分に、式(X1)~(X3)のいずれかで表される架橋基を含有させることが、架橋構造を形成する可能性が高まり、好ましい。
The group containing a double bond capable of reacting with the cross-linking group represented by any one of formulas (X1) to (X3) includes, in addition to the cross-linking group represented by formula (X4), formula (X5), A cross-linking group represented by any one of formula (X6), formula (X12), formula (X15), formula (X16), formula (X17) and formula (X18) can be mentioned. When a group containing these double bonds is used as a cross-linking group in an electron-accepting compound, other components forming a hole-injecting layer and/or a hole-transporting layer, such as a hole-transporting compound, are added with the formula (X1 ) to (X3) is preferable because the possibility of forming a crosslinked structure increases.
架橋基としては、ラジカル重合性の式(X4)、式(X5)、式(X6)のいずれかで表される架橋基が、極性が小さく、電荷輸送の妨げとなりにくいため、好ましい。
As the cross-linking group, a radically polymerizable cross-linking group represented by any one of the formulas (X4), (X5), and (X6) is preferred because it has a low polarity and does not easily interfere with charge transport.
架橋基としては、式(X7)で表される架橋基が、電子受容性を高める点で好ましい。なお、式(X7)で表される架橋基を用いると、下記のような架橋反応が進行する。
As the cross-linking group, the cross-linking group represented by the formula (X7) is preferable from the viewpoint of enhancing the electron-accepting property. When the cross-linking group represented by formula (X7) is used, the following cross-linking reaction proceeds.
式(X8)、式(X9)のいずれかで表される架橋基は、反応性が高い点で好ましい。なお、式(X8)で表される架橋基、及び式(X9)で表される架橋基を用いると、下記のような架橋反応が進行する。
A cross-linking group represented by either formula (X8) or formula (X9) is preferable in terms of high reactivity. When the cross-linking group represented by formula (X8) and the cross-linking group represented by formula (X9) are used, the following cross-linking reaction proceeds.
架橋基としては、カチオン重合性の式(X10)、式(X11)、式(X12)のいずれかで表される架橋基が、反応性が高い点で好ましい。
As the cross-linking group, a cationic polymerizable cross-linking group represented by any one of the formula (X10), the formula (X11), and the formula (X12) is preferable because of its high reactivity.
<電荷輸送材料>
本発明で用いる電荷輸送材料とは、正孔及び/又は電子を輸送することのできる材料である。また、本発明で用いる電荷輸送材料は正孔輸送性であることが好ましく、電子受容性化合物によって酸化され、カチオンラジカル化する材料であることが好ましい。本発明においては、電荷輸送性材料としては高分子化合物が好ましく、正孔輸送性高分子化合物が好ましく、アリールアミン構造を繰返し単位として含む高分子化合物が好ましい。この場合、電荷とは通常正孔であり、電荷を輸送するとは正孔を輸送することであり、電荷輸送膜とは正孔輸送膜であり、電荷注入層とは正孔注入層である。 <Charge transport material>
A charge transport material used in the present invention is a material capable of transporting holes and/or electrons. Further, the charge transport material used in the present invention is preferably a material that transports holes and is oxidized by an electron-accepting compound to form a cation radical. In the present invention, the charge-transporting material is preferably a polymer compound, preferably a hole-transporting polymer compound, and preferably a polymer compound containing an arylamine structure as a repeating unit. In this case, the charge is usually holes, the charge transport is the transport of holes, the charge transport film is the hole transport film, and the charge injection layer is the hole injection layer.
本発明で用いる電荷輸送材料とは、正孔及び/又は電子を輸送することのできる材料である。また、本発明で用いる電荷輸送材料は正孔輸送性であることが好ましく、電子受容性化合物によって酸化され、カチオンラジカル化する材料であることが好ましい。本発明においては、電荷輸送性材料としては高分子化合物が好ましく、正孔輸送性高分子化合物が好ましく、アリールアミン構造を繰返し単位として含む高分子化合物が好ましい。この場合、電荷とは通常正孔であり、電荷を輸送するとは正孔を輸送することであり、電荷輸送膜とは正孔輸送膜であり、電荷注入層とは正孔注入層である。 <Charge transport material>
A charge transport material used in the present invention is a material capable of transporting holes and/or electrons. Further, the charge transport material used in the present invention is preferably a material that transports holes and is oxidized by an electron-accepting compound to form a cation radical. In the present invention, the charge-transporting material is preferably a polymer compound, preferably a hole-transporting polymer compound, and preferably a polymer compound containing an arylamine structure as a repeating unit. In this case, the charge is usually holes, the charge transport is the transport of holes, the charge transport film is the hole transport film, and the charge injection layer is the hole injection layer.
[本発明の組成物]
本発明の組成物は、下記式(1)で表される繰り返し単位を有し、主鎖及び側鎖の少なくとも1つに置換基を有していてもよいフルオレンを有し、架橋基を有する高分子化合物(以下、「本発明のフッ素を含むアリールアミン高分子化合物」と称す場合がある。)、および下記式(81)で表される、架橋基を有する電子受容性化合物(以下、「本発明の電子受容性化合物」と称す場合がある。)を含む組成物である。 [Composition of the present invention]
The composition of the present invention has a repeating unit represented by the following formula (1), has a fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group. A polymer compound (hereinafter sometimes referred to as "the fluorine-containing arylamine polymer compound of the present invention"), and an electron-accepting compound having a cross-linking group represented by the following formula (81) (hereinafter, " It is a composition containing the "electron-accepting compound of the present invention".
本発明の組成物は、下記式(1)で表される繰り返し単位を有し、主鎖及び側鎖の少なくとも1つに置換基を有していてもよいフルオレンを有し、架橋基を有する高分子化合物(以下、「本発明のフッ素を含むアリールアミン高分子化合物」と称す場合がある。)、および下記式(81)で表される、架橋基を有する電子受容性化合物(以下、「本発明の電子受容性化合物」と称す場合がある。)を含む組成物である。 [Composition of the present invention]
The composition of the present invention has a repeating unit represented by the following formula (1), has a fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group. A polymer compound (hereinafter sometimes referred to as "the fluorine-containing arylamine polymer compound of the present invention"), and an electron-accepting compound having a cross-linking group represented by the following formula (81) (hereinafter, " It is a composition containing the "electron-accepting compound of the present invention".
(式(1)中、
Ar1は、置換基を有していてもよい炭素数6~60の2価の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Gは、式(1-1)~式(1-3)のいずれかで表される2価の基を表し、
“*”は隣接する構造との結合位置を表し、
置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
Ar2は、水素原子、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表し、
mは、1~4の整数であり、
nは、1~6の整数である。) (In formula (1),
Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group ,
G represents a divalent group represented by any one of formulas (1-1) to (1-3),
"*" represents the bonding position with the adjacent structure,
Each substituent A is independently a fluorine atom, CF3 , or SF5 .
Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms. A plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group,
m is an integer from 1 to 4,
n is an integer of 1-6. )
Ar1は、置換基を有していてもよい炭素数6~60の2価の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Gは、式(1-1)~式(1-3)のいずれかで表される2価の基を表し、
“*”は隣接する構造との結合位置を表し、
置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
Ar2は、水素原子、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表し、
mは、1~4の整数であり、
nは、1~6の整数である。) (In formula (1),
Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group ,
G represents a divalent group represented by any one of formulas (1-1) to (1-3),
"*" represents the bonding position with the adjacent structure,
Each substituent A is independently a fluorine atom, CF3 , or SF5 .
Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms. A plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group,
m is an integer from 1 to 4,
n is an integer of 1-6. )
(式(81)中、
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) (In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. )
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) (In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. )
本発明の組成物は、下記式(1)で表される繰り返し単位を有し、架橋基を有する高分子化合物、および下記式(81)で表される、少なくとも2つの架橋基を有する電子受容性化合物を含む組成物であってもよい。
The composition of the present invention comprises a polymer compound having a repeating unit represented by the following formula (1) and having a cross-linking group, and an electron acceptor having at least two cross-linking groups represented by the following formula (81). It may be a composition containing a sexual compound.
(式(1)中、
Ar1は、置換基を有していてもよい炭素数6~60の2価の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Gは、式(1-1)~式(1-3)のいずれかで表される2価の基を表し、
置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
Ar2は、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表し、
mは、1~4の整数であり、
nは、1~6の整数である。) (In formula (1),
Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group ,
G represents a divalent group represented by any one of formulas (1-1) to (1-3),
Each substituent A is independently a fluorine atom, CF3 , or SF5 .
Ar 2 is a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heterocyclic group having 3 to 50 carbon atoms, or a monovalent group selected from an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group linked directly or via a linking group. represents the group,
m is an integer from 1 to 4,
n is an integer of 1-6. )
Ar1は、置換基を有していてもよい炭素数6~60の2価の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Gは、式(1-1)~式(1-3)のいずれかで表される2価の基を表し、
置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
Ar2は、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表し、
mは、1~4の整数であり、
nは、1~6の整数である。) (In formula (1),
Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group ,
G represents a divalent group represented by any one of formulas (1-1) to (1-3),
Each substituent A is independently a fluorine atom, CF3 , or SF5 .
Ar 2 is a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heterocyclic group having 3 to 50 carbon atoms, or a monovalent group selected from an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group linked directly or via a linking group. represents the group,
m is an integer from 1 to 4,
n is an integer of 1-6. )
(式(81)中、
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) (In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. )
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) (In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. )
<架橋基を有する高分子化合物>
架橋基を有する高分子化合物は、上記式(1)で表される繰り返し単位を有する、アリールアミン構造を繰返し単位として含む、架橋基を有する高分子化合物が好ましい。この高分子化合物は本発明の組成物中に電荷輸送材料として含有される。 <Polymer compound having a cross-linking group>
The polymer compound having a cross-linking group is preferably a polymer compound having a cross-linking group and having a repeating unit represented by the above formula (1) and containing an arylamine structure as a repeating unit. This polymer compound is included as a charge transport material in the composition of the present invention.
架橋基を有する高分子化合物は、上記式(1)で表される繰り返し単位を有する、アリールアミン構造を繰返し単位として含む、架橋基を有する高分子化合物が好ましい。この高分子化合物は本発明の組成物中に電荷輸送材料として含有される。 <Polymer compound having a cross-linking group>
The polymer compound having a cross-linking group is preferably a polymer compound having a cross-linking group and having a repeating unit represented by the above formula (1) and containing an arylamine structure as a repeating unit. This polymer compound is included as a charge transport material in the composition of the present invention.
(Ar1)
芳香族炭化水素基の炭素数は、好ましくは6~60、より好ましくは6~30、さらに好ましくは6~18である。芳香族炭化水素基としては、具体的には、ベンゼン環、ナフタレン環、フルオレン環、アントラセン環、テトラフェニレン環、フェナントレン環、クリセン環、ピレン環、ベンゾアントラセン環、又はペリレン環等の、炭素数が通常6以上、通常30以下、好ましくは18以下、さらに好ましくは14以下である芳香族炭化水素環構造の2価の基、又は、これらの構造から選択された複数の構造が鎖状に又は分岐して結合した構造の2価の基が挙げられる。芳香族炭化水素環が複数個連結する場合は、通常、2~8個連結した構造が挙げられ、2~5個連結した構造であることが好ましい。芳香族炭化水素環が複数個連結する場合、同一の構造が連結してもよく、異なる構造が連結してもよい。 (Ar 1 )
The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-60, more preferably 6-30, still more preferably 6-18. Specific examples of aromatic hydrocarbon groups include benzene ring, naphthalene ring, fluorene ring, anthracene ring, tetraphenylene ring, phenanthrene ring, chrysene ring, pyrene ring, benzanthracene ring, or perylene ring. is usually 6 or more, usually 30 or less, preferably 18 or less, more preferably 14 or less divalent group of aromatic hydrocarbon ring structure, or a plurality of structures selected from these structures are chained or A divalent group having a branched and bonded structure can be mentioned. When a plurality of aromatic hydrocarbon rings are linked, a structure in which 2 to 8 rings are linked is usually mentioned, and a structure in which 2 to 5 rings are linked is preferable. When a plurality of aromatic hydrocarbon rings are linked, the same structure may be linked, or different structures may be linked.
芳香族炭化水素基の炭素数は、好ましくは6~60、より好ましくは6~30、さらに好ましくは6~18である。芳香族炭化水素基としては、具体的には、ベンゼン環、ナフタレン環、フルオレン環、アントラセン環、テトラフェニレン環、フェナントレン環、クリセン環、ピレン環、ベンゾアントラセン環、又はペリレン環等の、炭素数が通常6以上、通常30以下、好ましくは18以下、さらに好ましくは14以下である芳香族炭化水素環構造の2価の基、又は、これらの構造から選択された複数の構造が鎖状に又は分岐して結合した構造の2価の基が挙げられる。芳香族炭化水素環が複数個連結する場合は、通常、2~8個連結した構造が挙げられ、2~5個連結した構造であることが好ましい。芳香族炭化水素環が複数個連結する場合、同一の構造が連結してもよく、異なる構造が連結してもよい。 (Ar 1 )
The number of carbon atoms in the aromatic hydrocarbon group is preferably 6-60, more preferably 6-30, still more preferably 6-18. Specific examples of aromatic hydrocarbon groups include benzene ring, naphthalene ring, fluorene ring, anthracene ring, tetraphenylene ring, phenanthrene ring, chrysene ring, pyrene ring, benzanthracene ring, or perylene ring. is usually 6 or more, usually 30 or less, preferably 18 or less, more preferably 14 or less divalent group of aromatic hydrocarbon ring structure, or a plurality of structures selected from these structures are chained or A divalent group having a branched and bonded structure can be mentioned. When a plurality of aromatic hydrocarbon rings are linked, a structure in which 2 to 8 rings are linked is usually mentioned, and a structure in which 2 to 5 rings are linked is preferable. When a plurality of aromatic hydrocarbon rings are linked, the same structure may be linked, or different structures may be linked.
芳香族複素環基の炭素数は、好ましくは3~50、より好ましくは3~30、さらに好ましくは3~18である。芳香族複素環基としては、具体的には、トリアジン環、ピリミジン環、ピリジン環、ベンゾフラン、ベンゾチオフェン、ジベンゾフラン、ジベンゾチオフェン、カルバゾール環等の炭素数が通常3以上、通常30以下、好ましくは18以下、さらに好ましくは12以下である芳香族複素環構造の2価の基、又は、これらの構造から選択された複数の構造が鎖状に又は分岐して結合した構造の2価の基が挙げられる。
The number of carbon atoms in the aromatic heterocyclic group is preferably 3-50, more preferably 3-30, still more preferably 3-18. Specific examples of the aromatic heterocyclic group include triazine ring, pyrimidine ring, pyridine ring, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, carbazole ring, etc., having usually 3 or more, usually 30 or less, preferably 18 carbon atoms. Hereinafter, more preferably, a divalent group having an aromatic heterocyclic structure of 12 or less, or a divalent group having a structure in which a plurality of structures selected from these structures are bonded in a chain or branched manner. be done.
Ar1は、置換基を有していてもよい炭素数は6~60の2価の芳香族炭化水素、置換基を有していてもよい炭素数は3~50の2価の芳香族複素環基から選ばれる1または複数の基が直接または連結基を介して結合した2価の基であることが好ましく、正孔輸送性が向上することから、窒素原子に直接結合する基としては、置換基を有していてもよい芳香族炭化水素基が好ましく、芳香族炭化水素基としては、好ましくは、1~4個のベンゼン環、1又は2個のナフタレン環、1又は2個のフルオレン環、1又は2個の複数のフェナントレン環、及び、1つのテトラフェニレン環から選択される複数の構造が任意の順序で鎖状又は分岐して結合して形成された2価の基、又は、1,4-フェニレン基、1,3-フェニレン基、2,7-フルオレニレン基、2価のスピロビスフルオレン基であり、さらに好ましくは、1~4個のベンゼン環、及び、1又は2個のフルオレン環から選択される複数の構造が任意の順序で鎖状又は分岐して結合して形成された2価の基であり、特に好ましくは、1又は2個のフェニレン基、2,7-フルオレニレン基、1又は2個のフェニレン基がこの順に鎖状に結合した2価の基、フェニレン基、ビフェニレン基、パラターフェニレン基、又は2,7-フルオレニレン基である。フルオレン構造は、9,9’位に置換基を有してよく、有してよい置換基は前記置換基群Zから選択される基が好ましい。
Ar 1 is an optionally substituted divalent aromatic hydrocarbon having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterohydrocarbon having 3 to 50 carbon atoms. A divalent group in which one or more groups selected from cyclic groups are bonded directly or via a linking group is preferable, and the hole transport property is improved. An aromatic hydrocarbon group which may have a substituent is preferred, and the aromatic hydrocarbon group preferably has 1 to 4 benzene rings, 1 or 2 naphthalene rings, 1 or 2 fluorene A divalent group formed by chaining or branching a plurality of structures selected from a ring, one or two phenanthrene rings, and one tetraphenylene ring in any order, or 1,4-phenylene group, 1,3-phenylene group, 2,7-fluorenylene group, divalent spirobisfluorene group, more preferably 1 to 4 benzene rings, and 1 or 2 A divalent group formed by binding a plurality of structures selected from fluorene rings in a chain or branched manner in any order, particularly preferably one or two phenylene groups, 2,7-fluorenylene a divalent group in which one or two phenylene groups are bonded in this order in a chain, a phenylene group, a biphenylene group, a p-terphenylene group, or a 2,7-fluorenylene group. The fluorene structure may have substituents at the 9 and 9′ positions, and the substituents that may have are preferably groups selected from the substituent group Z described above.
これらの芳香族炭化水素構造は置換基を有してもよい。有してよい置換基は前述の通りであり、具体的には置換基群Zから選択することが出来る。好ましい置換基は前記置換基群Zの好ましい置換基である。
These aromatic hydrocarbon structures may have substituents. Substituents which may be present are as described above, and specifically can be selected from the substituent group Z. Preferred substituents are the preferred substituents of the substituent group Z described above.
(Ar1の好ましい範囲)
Ar1は、高分子化合物の溶解性及び耐久性の観点から、下記式(2-1)~(2-7)から選択される少なくとも1つの構造を有することが好ましい。 (Preferred range of Ar 1 )
Ar 1 preferably has at least one structure selected from the following formulas (2-1) to (2-7) from the viewpoint of the solubility and durability of the polymer compound.
Ar1は、高分子化合物の溶解性及び耐久性の観点から、下記式(2-1)~(2-7)から選択される少なくとも1つの構造を有することが好ましい。 (Preferred range of Ar 1 )
Ar 1 preferably has at least one structure selected from the following formulas (2-1) to (2-7) from the viewpoint of the solubility and durability of the polymer compound.
上記式(2-1)~式(2-7)それぞれにおいて、*は隣接する構造との結合又は水素原子を表し、2つ存在する*の少なくとも一方は隣接する構造との結合位置を表し、4つ存在する*から選択される任意2つの*の少なくとも一方は隣接する構造との結合位置を表す。以降の記載においても、特に断りの無い限り*の定義は同様である。R1およびR2は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~18の芳香族炭化水素基、置換基を有していてもよい炭素数3~12の芳香族複素環基、炭素数1~12のアルキル基である。
In each of the above formulas (2-1) to (2-7), * represents a bond with an adjacent structure or a hydrogen atom, and at least one of the two * represents a bonding position with an adjacent structure, At least one of two arbitrary * selected from four * represents a binding position to an adjacent structure. In the following description, the definition of * is the same unless otherwise specified. R 1 and R 2 each independently represent a hydrogen atom, a deuterium atom, a halogen atom, an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, or an optionally substituted It is preferably an aromatic heterocyclic group having 3 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms.
Ar1は、上記式(2-1)~(2-3)から選択される1つの部分構造を有するか、または、上記式(2-1)~(2-3)から選択される2以上が互いに結合してなる結合構造を有することが好ましく、前記結合構造が上記式(2-1)~(2-3)から選択される少なくとも1種の構造を2以上結合した構造を含有してもよい。
Ar 1 has one partial structure selected from the above formulas (2-1) to (2-3), or two or more selected from the above formulas (2-1) to (2-3) are bonded to each other, and the bonding structure contains a structure in which two or more of at least one structure selected from the above formulas (2-1) to (2-3) are bonded good too.
すなわち、前記結合構造は、例えば、上記(2-1)の構造が2以上結合した構造を含んでいてもよい。
That is, the bond structure may include, for example, a structure in which two or more structures of (2-1) above are bonded.
(R1、R2)
R1、R2は、各々独立に、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~18の芳香族炭化水素基、置換基を有していてもよい炭素数3~12の芳香族複素環基、炭素数1~12のアルキル基であり、好ましくは、炭素数6~12のアルキル基、アルケニル基、アルキニル基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アシル基、ハロゲン原子、ハロアルキル基、アルキルチオ基、アリールチオ基、シリル基、シロキシ基、シアノ基、アラルキル基、又は炭素数6~30の1価の芳香族炭化水素基を表し、R1、R2は共に結合して環を形成してもよい。芳香族炭化水素環構造としてはフェニル基又はフェニル基が複数連結した基がさらに好ましい。 (R 1 , R 2 )
R 1 and R 2 each independently represent a hydrogen atom, a deuterium atom, a halogen atom, an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, a substituent an aromatic heterocyclic group having 3 to 12 carbon atoms and an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 6 to 12 carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, and an aryl group. an oxy group, an alkoxycarbonyl group, an acyl group, a halogen atom, a haloalkyl group, an alkylthio group, an arylthio group, a silyl group, a siloxy group, a cyano group, an aralkyl group, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms; and R 1 and R 2 may combine together to form a ring. As the aromatic hydrocarbon ring structure, a phenyl group or a group in which a plurality of phenyl groups are linked is more preferable.
R1、R2は、各々独立に、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~18の芳香族炭化水素基、置換基を有していてもよい炭素数3~12の芳香族複素環基、炭素数1~12のアルキル基であり、好ましくは、炭素数6~12のアルキル基、アルケニル基、アルキニル基、アルコキシ基、アリールオキシ基、アルコキシカルボニル基、アシル基、ハロゲン原子、ハロアルキル基、アルキルチオ基、アリールチオ基、シリル基、シロキシ基、シアノ基、アラルキル基、又は炭素数6~30の1価の芳香族炭化水素基を表し、R1、R2は共に結合して環を形成してもよい。芳香族炭化水素環構造としてはフェニル基又はフェニル基が複数連結した基がさらに好ましい。 (R 1 , R 2 )
R 1 and R 2 each independently represent a hydrogen atom, a deuterium atom, a halogen atom, an optionally substituted aromatic hydrocarbon group having 6 to 18 carbon atoms, a substituent an aromatic heterocyclic group having 3 to 12 carbon atoms and an alkyl group having 1 to 12 carbon atoms, preferably an alkyl group having 6 to 12 carbon atoms, an alkenyl group, an alkynyl group, an alkoxy group, and an aryl group. an oxy group, an alkoxycarbonyl group, an acyl group, a halogen atom, a haloalkyl group, an alkylthio group, an arylthio group, a silyl group, a siloxy group, a cyano group, an aralkyl group, or a monovalent aromatic hydrocarbon group having 6 to 30 carbon atoms; and R 1 and R 2 may combine together to form a ring. As the aromatic hydrocarbon ring structure, a phenyl group or a group in which a plurality of phenyl groups are linked is more preferable.
これらの基は置換基を有してもよい。有してよい置換基は前述の通りであり、具体的には置換基群Z又は架橋基から選択することが出来る。好ましくは前記置換基群Zの好ましい置換基、架橋基を有してもよい炭素数6~50の芳香族炭化水素基、又は架橋基である。
These groups may have substituents. The substituents that may be present are as described above, and specifically, they can be selected from the substituent group Z or the bridging group. Preferably, it is a preferable substituent of the substituent group Z, an aromatic hydrocarbon group having 6 to 50 carbon atoms which may have a cross-linking group, or a cross-linking group.
部分構造として、より好ましくは式(2-1)~(2-7)から選択される構造であり、さらに好ましくは式(2-1)~(2-5)から選択される構造であり、特に好ましくは式(2-1)~(2-4)から選択される構造である。電荷輸送性が優れることから、式(2-2)および(2-3)で表される部分構造を有することが最も好ましい。
The partial structure is more preferably a structure selected from formulas (2-1) to (2-7), more preferably a structure selected from formulas (2-1) to (2-5), Structures selected from formulas (2-1) to (2-4) are particularly preferred. It is most preferable to have partial structures represented by formulas (2-2) and (2-3) because of their excellent charge transport properties.
式(2-1)として好ましくは、1,3-フェニレン基又は1,4-フェニレン基である。
Formula (2-1) is preferably a 1,3-phenylene group or a 1,4-phenylene group.
式(2-2)として好ましくは下記式(2-2-2)である。
Formula (2-2) is preferably the following formula (2-2-2).
式(2-2)としてよりさらに好ましくは、下記式(2-2-3)である。
Formula (2-2) is more preferably formula (2-2-3) below.
また、化合物の溶解性及び耐久性の観点からAr1は部分構造として、式(2-1)で表される部分構造及び式(2-2)で表される部分構造を有することが好ましい。
Ar 1 preferably has a partial structure represented by formula (2-1) and a partial structure represented by formula (2-2) from the viewpoint of compound solubility and durability.
式(2-1)で表される部分構造及び式(2-2)で表される部分構造を有する部分構造としては、式(2-1)で表される部分構造及び式(2-2)で表される部分構造から選択される構造を複数含む構造である、下記式(2-8)~下記式(2-11)から選択される少なくとも1つで表される部分構造がさらに好ましい。
As the partial structure having the partial structure represented by formula (2-1) and the partial structure represented by formula (2-2), the partial structure represented by formula (2-1) and the partial structure represented by formula (2-2 A partial structure represented by at least one selected from the following formulas (2-8) to (2-11), which is a structure containing a plurality of structures selected from the partial structures represented by ), is more preferable. .
式(2-1)で表される部分構造及び式(2-3)、(2-4)で表される部分構造を有する部分構造としては、式(2-1)で表される部分構造及び式(2-3)、(2-4)で表される部分構造から選択される構造を複数含む構造である、下記式(2-12)~下記式(2-15)から選択される少なくとも1つで表される部分構造がさらに好ましい。
As the partial structure having the partial structure represented by formula (2-1) and the partial structures represented by formulas (2-3) and (2-4), the partial structure represented by formula (2-1) and a structure including a plurality of structures selected from partial structures represented by formulas (2-3) and (2-4), selected from the following formulas (2-12) to (2-15) A partial structure represented by at least one is more preferable.
(G)
Gは、上記式(1-1)~式(1-3)のいずれかで表される2価の基を表し、置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
置換基Aは、上記の中でも、電荷輸送能力を低減させない観点からフッ素原子、CF3が好ましい。同観点で式(1-1)~式(1-3)のm、nは、1~2の整数が好ましい。 (G)
G represents a divalent group represented by any one of the above formulas (1-1) to (1-3), and each substituent A is independently a fluorine atom, CF 3 , or SF 5 be.
Among the above, the substituent A is preferably a fluorine atom or CF3 from the viewpoint of not reducing the charge transport ability. From the same point of view, m and n in formulas (1-1) to (1-3) are preferably integers of 1-2.
Gは、上記式(1-1)~式(1-3)のいずれかで表される2価の基を表し、置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
置換基Aは、上記の中でも、電荷輸送能力を低減させない観点からフッ素原子、CF3が好ましい。同観点で式(1-1)~式(1-3)のm、nは、1~2の整数が好ましい。 (G)
G represents a divalent group represented by any one of the above formulas (1-1) to (1-3), and each substituent A is independently a fluorine atom, CF 3 , or SF 5 be.
Among the above, the substituent A is preferably a fluorine atom or CF3 from the viewpoint of not reducing the charge transport ability. From the same point of view, m and n in formulas (1-1) to (1-3) are preferably integers of 1-2.
Gは、下記式のいずれかで表される基が好ましい。
G is preferably a group represented by any of the following formulas.
(上記式中、“*”は隣接する構造との結合位置を表す。)
(In the above formula, "*" represents the bonding position with the adjacent structure.)
(Ar2)
Ar2は、水素原子、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表す。 ( Ar2 )
Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms. A plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group.
Ar2は、水素原子、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表す。 ( Ar2 )
Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms. A plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group.
本発明で用いる高分子化合物において、Ar2が複数存在する場合、複数のAr2は同一であっても異なっていてもよい。
In the polymer compound used in the present invention, when a plurality of Ar 2 are present, the plurality of Ar 2 may be the same or different.
1価の芳香族炭化水素基としては、具体的には、ベンゼン環、アズレン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環等の、6員環の単環又は2~5縮合環の1価の基が挙げられる。
Specific examples of monovalent aromatic hydrocarbon groups include benzene ring, azulene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring and acenaphthene. 6-membered monocyclic or 2-5 condensed monovalent groups such as ring, fluoranthene ring, and fluorene ring.
1価の芳香族複素環基としては、具体的には、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シンノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環等の、5又は6員環の単環又は2~4縮合環の1価の基が挙げられる。
Specific examples of monovalent aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolo imidazole 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, pyridazine ring, 5- or 6-membered monocyclic ring or 2-4 condensed ring such as pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, etc. valence groups.
連結基としては、例えば酸素原子又はカルボニル基が挙げられる。芳香族環と非共役構造を構成することで三重項レベルを高くすることができるため、フェニレン環同士の間を酸素原子又はカルボニル基で連結している構造を用いることもできる。好ましくは、連結基を介さず直接連結する構造である。Ar1における連結基に関しても同様である。
The linking group includes, for example, an oxygen atom or a carbonyl group. Since the triplet level can be increased by constructing a non-conjugated structure with an aromatic ring, a structure in which phenylene rings are linked by an oxygen atom or a carbonyl group can also be used. A structure in which they are directly linked without a linking group is preferred. The same applies to the linking group in Ar 1 .
これらの中でも、電荷輸送性が優れる点、耐久性に優れる点から、1価の芳香族炭化水素基が好ましく、ベンゼン環又はフルオレン環の1価の基がより好ましく、フェニル基又はフルオレニル基がさらに好ましく、フルオレニル基が特に好ましく、2-フルオレニル基が最も好ましい。
Among these, from the viewpoint of excellent charge transportability and excellent durability, a monovalent aromatic hydrocarbon group is preferable, a monovalent group of a benzene ring or a fluorene ring is more preferable, and a phenyl group or a fluorenyl group is further preferable. A fluorenyl group is particularly preferred, and a 2-fluorenyl group is most preferred.
また、Ar2は、塗布溶媒への溶解性の点から、炭素数1~24のアルキル基で置換されたフルオレニル基が好ましく、炭素数4~12のアルキル基で置換された2-フルオレニル基が特に好ましい。さらに、Ar2は、2-フルオレニル基の9位にアルキル基が置換された9-アルキル-2-フルオレニル基が好ましく、アルキル基が2置換された9、9-ジアルキル-2-フルオレニル基が特に好ましい。Ar2は、アルキル基で置換されたフルオレニル基であることにより、溶媒に対する溶解性が向上し好ましい。
Ar 2 is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms from the viewpoint of solubility in a coating solvent, and a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms. Especially preferred. Furthermore, Ar 2 is preferably a 9-alkyl-2-fluorenyl group in which a 2-fluorenyl group is substituted with an alkyl group at the 9-position, and particularly a 9,9-dialkyl-2-fluorenyl group in which an alkyl group is disubstituted. preferable. Ar 2 is preferably a fluorenyl group substituted with an alkyl group, because the solubility in a solvent is improved.
置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される複数の基が直接若しくは連結基を介して連結した1価の基としては、上記芳香族炭化水素基と上記芳香族複素環基から選択される複数の基を直接若しくは連結基を介して連結した1価の基を用いることができる。
A monovalent group in which a plurality of groups selected from an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group As can be used a monovalent group in which a plurality of groups selected from the aromatic hydrocarbon group and the aromatic heterocyclic group are linked directly or via a linking group.
(-G-Ar2)
[-G-Ar2]は下記式のいずれかで表される基が好ましい。 (-G- Ar2 )
[-G-Ar 2 ] is preferably a group represented by any one of the following formulae.
[-G-Ar2]は下記式のいずれかで表される基が好ましい。 (-G- Ar2 )
[-G-Ar 2 ] is preferably a group represented by any one of the following formulae.
(上記式中、“*”は隣接する構造との結合位置を表す。)
(In the above formula, "*" represents the bonding position with the adjacent structure.)
(具体例)
以下に、本発明で用いる上記式(1)で表される繰り返し単位の具体例を示すが、これらに限定されるものではない。 (Concrete example)
Specific examples of the repeating unit represented by formula (1) used in the present invention are shown below, but the invention is not limited thereto.
以下に、本発明で用いる上記式(1)で表される繰り返し単位の具体例を示すが、これらに限定されるものではない。 (Concrete example)
Specific examples of the repeating unit represented by formula (1) used in the present invention are shown below, but the invention is not limited thereto.
<置換基を有していてもよいフルオレン>
架橋基を有する高分子化合物は、主鎖及び側鎖の少なくとも1つに置換基を有していてもよいフルオレンを有する。
上記置換基は、炭素数1~12の直鎖又は分岐のアルキル基が好ましい。上記置換基は、フルオレンの5員環部分に導入されることが好ましい。上記置換基が5員環部分に導入されたフルオレンを有する高分子化合物としては、例えば、後述の高分子化合物P-1が挙げられる。 <Fluorene which may have a substituent>
A polymer compound having a cross-linking group has fluorene which may have a substituent in at least one of the main chain and the side chain.
The above substituent is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The above substituents are preferably introduced into the 5-membered ring portion of fluorene. Examples of the polymer compound having fluorene in which the substituent is introduced into the 5-membered ring portion include polymer compound P-1 described later.
架橋基を有する高分子化合物は、主鎖及び側鎖の少なくとも1つに置換基を有していてもよいフルオレンを有する。
上記置換基は、炭素数1~12の直鎖又は分岐のアルキル基が好ましい。上記置換基は、フルオレンの5員環部分に導入されることが好ましい。上記置換基が5員環部分に導入されたフルオレンを有する高分子化合物としては、例えば、後述の高分子化合物P-1が挙げられる。 <Fluorene which may have a substituent>
A polymer compound having a cross-linking group has fluorene which may have a substituent in at least one of the main chain and the side chain.
The above substituent is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The above substituents are preferably introduced into the 5-membered ring portion of fluorene. Examples of the polymer compound having fluorene in which the substituent is introduced into the 5-membered ring portion include polymer compound P-1 described later.
<本発明で用いる上記式(1)で表される繰返し単位と組み合わせる、好ましい繰り返し単位であるアリールアミン構造>
本発明で用いる上記式(1)で表される繰返し単位と組み合わせる、好ましいアリールアミン構造を繰り返し単位として有する、高分子化合物のアリールアミン構造の繰返し単位は下記式(50)で表される。 <Arylamine structure which is a preferred repeating unit to be combined with the repeating unit represented by formula (1) used in the present invention>
The repeating unit of the arylamine structure of the polymer compound having the preferable arylamine structure as a repeating unit, which is combined with the repeating unit represented by the above formula (1) used in the present invention, is represented by the following formula (50).
本発明で用いる上記式(1)で表される繰返し単位と組み合わせる、好ましいアリールアミン構造を繰り返し単位として有する、高分子化合物のアリールアミン構造の繰返し単位は下記式(50)で表される。 <Arylamine structure which is a preferred repeating unit to be combined with the repeating unit represented by formula (1) used in the present invention>
The repeating unit of the arylamine structure of the polymer compound having the preferable arylamine structure as a repeating unit, which is combined with the repeating unit represented by the above formula (1) used in the present invention, is represented by the following formula (50).
(式(50)中、
Ar51は、芳香族炭化水素基、芳香族複素環基、又は芳香族炭化水素基及び芳香族複素環基から選択される複数の基が連結した基を表し、Ar52は、2価の芳香族炭化水素基、2価の芳香族複素環基、又は前記2価の芳香族炭化水素基及び前記2価の芳香族複素環基からなる群から選択される少なくとも1つの基が直接若しくは連結基を介して複数個連結した2価の基を表す。
Ar51とAr52は単結合又は連結基を介して環を形成していてもよい。
Ar51、Ar52は置換基を有してもよい。) (In formula (50),
Ar 51 represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a group in which a plurality of groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group are linked, and Ar 52 represents a divalent aromatic At least one group selected from the group consisting of a hydrocarbon group, a divalent aromatic heterocyclic group, or the divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group is directly or a linking group represents a divalent group in which a plurality of groups are linked via
Ar 51 and Ar 52 may form a ring via a single bond or a linking group.
Ar 51 and Ar 52 may have a substituent. )
Ar51は、芳香族炭化水素基、芳香族複素環基、又は芳香族炭化水素基及び芳香族複素環基から選択される複数の基が連結した基を表し、Ar52は、2価の芳香族炭化水素基、2価の芳香族複素環基、又は前記2価の芳香族炭化水素基及び前記2価の芳香族複素環基からなる群から選択される少なくとも1つの基が直接若しくは連結基を介して複数個連結した2価の基を表す。
Ar51とAr52は単結合又は連結基を介して環を形成していてもよい。
Ar51、Ar52は置換基を有してもよい。) (In formula (50),
Ar 51 represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a group in which a plurality of groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group are linked, and Ar 52 represents a divalent aromatic At least one group selected from the group consisting of a hydrocarbon group, a divalent aromatic heterocyclic group, or the divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group is directly or a linking group represents a divalent group in which a plurality of groups are linked via
Ar 51 and Ar 52 may form a ring via a single bond or a linking group.
Ar 51 and Ar 52 may have a substituent. )
Ar51、Ar52が有していてもよい置換基は、前記置換基群Zから選択される置換基又は架橋基が好ましい。
The substituent that Ar 51 and Ar 52 may have is preferably a substituent selected from the substituent group Z or a cross-linking group.
Ar51、Ar52が架橋基を有する場合、架橋基としては、前記架橋基群Tから選択される架橋基が好ましい。
When Ar 51 and Ar 52 have a cross-linking group, the cross-linking group is preferably a cross-linking group selected from the above-described cross-linking group T.
Ar51の芳香族炭化水素基及び芳香族複素環基が有してもよい置換基としては、本発明で用いる高分子化合物の特性を著しく低減させないものであれば、特に制限はない。当該置換基は、好ましくは、後述の置換基群Zから選ばれる基が挙げられ、アルキル基、アルコキシ基、芳香族炭化水素基、芳香族複素環基がより好ましく、アルキル基がさらに好ましい。
The substituents 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 polymer compound used in the present invention. 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.
Ar51は、溶媒への溶解性の点から、炭素数1~24のアルキル基で置換されたフルオレニル基が好ましく、特に、炭素数4~12のアルキル基で置換された2-フルオレニル基が好ましい。さらに、2-フルオレニル基の9位がアルキル基で置換された9-アルキル-2-フルオレニル基が好ましく、特に、アルキル基で2置換された9,9’-ジアルキル-2-フルオレニル基が好ましい。
Ar 51 is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms, particularly preferably a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms, from the viewpoint of solubility in a solvent. . 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.
9位及び9’位の少なくとも一方がアルキル基で置換されたフルオレニル基であることにより、溶媒に対する溶解性及びフルオレン環の耐久性が向上する傾向にある。さらに、9位及び9’位の両方がアルキル基で置換されたフルオレニル基であることにより、溶媒に対する溶解性及びフルオレン環の耐久性がさらに向上する傾向にある。
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.
また、Ar51は、溶媒への溶解性の点から、スピロビフルオレニル基であることも好ましい。
Ar 51 is also preferably a spirobifluorenyl group from the viewpoint of solubility in solvents.
前記式(50)で表される繰り返し単位としては、例えば、下記式(3)で表される繰り返し単位が挙げられる。
Examples of the repeating unit represented by the formula (50) include repeating units represented by the following formula (3).
(式(3)中、Ar3は、置換基を有していてもよい2-フルオレニル基である。Ar4は、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は前記置換基を有していてもよい2価の芳香族炭化水素基及び前記置換基を有していてもよい2価の芳香族複素環基からなる群から選択される少なくとも2つの基が直接若しくは連結基を介して複数個連結した2価の基を表す。)
(In formula (3), Ar 3 is an optionally substituted 2-fluorenyl group. Ar 4 is an optionally substituted divalent aromatic hydrocarbon group, a substituted a divalent aromatic heterocyclic group optionally having a group, or a divalent aromatic hydrocarbon group optionally having a substituent and a divalent It represents a divalent group in which at least two groups selected from the group consisting of aromatic heterocyclic groups are linked directly or via a linking group.)
また、前記式(50)で表される繰り返し単位を含む重合体としては、前記式(50)で表される繰り返し単位におけるAr51が、下記式(51)で表される基、下記式(52)で表される基、又は下記式(53)で表される基である繰返し単位を含むことが好ましい。
Further, as the polymer containing the repeating unit represented by the formula (50), Ar 51 in the repeating unit represented by the formula (50) is a group represented by the following formula (51), 52) or a repeating unit that is a group represented by the following formula (53).
<式(51)で表される基>
<Group Represented by Formula (51)>
(式(51)中、
*は式(50)の主鎖の窒素原子との結合を表し、
Ar53、Ar54は、それぞれ独立に、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Ar55は置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは芳香族複素環基が直接若しくは連結基を介して複数個連結した1価の基を表し、
Ar56は水素原子、又は置換基を表す。) (In formula (51),
* represents a bond to the nitrogen atom of the main chain of formula (50),
Ar 53 and Ar 54 are each independently a divalent aromatic hydrocarbon group optionally having a substituent, an aromatic heterocyclic group optionally having a substituent, or having a substituent represents a divalent group in which a plurality of optionally substituted aromatic heterocyclic groups or aromatic hydrocarbon groups are linked directly or via a linking group,
Ar 55 is an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, an optionally substituted aromatic hydrocarbon group or an aromatic represents a monovalent group in which multiple heterocyclic groups are linked directly or via a linking group,
Ar 56 represents a hydrogen atom or a substituent. )
*は式(50)の主鎖の窒素原子との結合を表し、
Ar53、Ar54は、それぞれ独立に、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Ar55は置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは芳香族複素環基が直接若しくは連結基を介して複数個連結した1価の基を表し、
Ar56は水素原子、又は置換基を表す。) (In formula (51),
* represents a bond to the nitrogen atom of the main chain of formula (50),
Ar 53 and Ar 54 are each independently a divalent aromatic hydrocarbon group optionally having a substituent, an aromatic heterocyclic group optionally having a substituent, or having a substituent represents a divalent group in which a plurality of optionally substituted aromatic heterocyclic groups or aromatic hydrocarbon groups are linked directly or via a linking group,
Ar 55 is an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, an optionally substituted aromatic hydrocarbon group or an aromatic represents a monovalent group in which multiple heterocyclic groups are linked directly or via a linking group,
Ar 56 represents a hydrogen atom or a substituent. )
ここで、各芳香族炭化水素基及び各芳香族複素環基は、置換基を有してもよい。有してもよい置換基は前記置換基群Zから選択される基又は架橋基が好ましく、架橋基を有する場合、架橋基としては、前記架橋基群Tから選ばれる基が好ましい。
Here, each aromatic hydrocarbon group and each aromatic heterocyclic group may have a substituent. The substituent that may be present is preferably a group selected from the above-described substituent group Z or a cross-linking group.
(Ar53)
Ar53は、2価の芳香族炭化水素基が1~6個連結した基が好ましく、2価の芳香族炭化水素基が2~4個連結した基がさらに好ましく、中でもフェニレン環が1~4個連結した基がより好ましく、フェニレン環が2個連結したビフェニレン基が特に好ましい。 ( Ar53 )
Ar 53 is preferably a group in which 1 to 6 divalent aromatic hydrocarbon groups are linked, more preferably a group in which 2 to 4 divalent aromatic hydrocarbon groups are linked, especially 1 to 4 phenylene rings A group in which two phenylene rings are linked is more preferable, and a biphenylene group in which two phenylene rings are linked is particularly preferable.
Ar53は、2価の芳香族炭化水素基が1~6個連結した基が好ましく、2価の芳香族炭化水素基が2~4個連結した基がさらに好ましく、中でもフェニレン環が1~4個連結した基がより好ましく、フェニレン環が2個連結したビフェニレン基が特に好ましい。 ( Ar53 )
Ar 53 is preferably a group in which 1 to 6 divalent aromatic hydrocarbon groups are linked, more preferably a group in which 2 to 4 divalent aromatic hydrocarbon groups are linked, especially 1 to 4 phenylene rings A group in which two phenylene rings are linked is more preferable, and a biphenylene group in which two phenylene rings are linked is particularly preferable.
これらの基は置換基を有していてもよい。有していてもよい置換基は、前記置換基群Zから選ばれる基又は架橋基が好ましく、架橋基を有する場合、架橋基としては、前記架橋基群Tから選ばれる基が好ましい。好ましくは、Ar53は置換基を有さない。
These groups may have a substituent. The substituent that may be present is preferably a group selected from the above-described substituent group Z or a cross-linking group. Preferably Ar 53 has no substituents.
また、これら2価の芳香族炭化水素基又は2価の芳香族複素環基が複数連結する場合、好ましくは複数連結した2価の芳香族炭化水素基が共役しないように結合した基である。具体的には、1,3-フェニレン基、又は置換基を有し置換基の立体効果によって捻じれ構造となる基を含むことが好ましく、さらに好ましくは、置換基を有さない1,3-フェニレン基又は置換基を有さない1,3-フェニレン基が複数連結した基である。
In addition, when a plurality of these divalent aromatic hydrocarbon groups or divalent aromatic heterocyclic groups are linked, it is preferably a group in which a plurality of 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, more preferably a 1,3- It is a group in which a plurality of phenylene groups or unsubstituted 1,3-phenylene groups are linked.
(Ar54)
Ar54は電荷輸送性が優れる点、耐久性に優れる点から、同一であっても異なっていてもよい2価の芳香族炭化水素基が1または複数連結した基が好ましく、該2価の芳香族炭化水素基は置換基を有していてもよい。複数連結する場合、連結する基の数は、2~10が好ましく、6以下がさらに好ましく、3以下が膜の安定性の観点からは特に好ましい。好ましい芳香族炭化水素環構造としては、ベンゼン環、ナフタレン環、アントラセン環、フルオレン環であり、より好ましくはベンゼン環およびフルオレン環である。複数連結した基としては、フェニレン環が1~4個連結した基、または、フェニレン環とフルオレン環が連結した基が好ましい。LUMOが広がる観点からフェニレン環が2個連結したビフェニレン基が特に好ましい。 ( Ar54 )
Ar 54 is preferably a group in which one or more divalent aromatic hydrocarbon groups, which may be the same or different, are linked, and the divalent aromatic group hydrocarbon group may have a substituent. When multiple groups are linked, the number of linked groups is preferably 2 to 10, more preferably 6 or less, and particularly preferably 3 or less from the viewpoint of film stability. Preferred aromatic hydrocarbon ring structures are benzene ring, naphthalene ring, anthracene ring and fluorene ring, and more preferred are benzene ring and fluorene ring. A group in which 1 to 4 phenylene rings are linked or a group in which a phenylene ring and a fluorene ring are linked are preferable as the group in which a plurality of rings are linked. A biphenylene group in which two phenylene rings are linked is particularly preferable from the viewpoint of expanding LUMO.
Ar54は電荷輸送性が優れる点、耐久性に優れる点から、同一であっても異なっていてもよい2価の芳香族炭化水素基が1または複数連結した基が好ましく、該2価の芳香族炭化水素基は置換基を有していてもよい。複数連結する場合、連結する基の数は、2~10が好ましく、6以下がさらに好ましく、3以下が膜の安定性の観点からは特に好ましい。好ましい芳香族炭化水素環構造としては、ベンゼン環、ナフタレン環、アントラセン環、フルオレン環であり、より好ましくはベンゼン環およびフルオレン環である。複数連結した基としては、フェニレン環が1~4個連結した基、または、フェニレン環とフルオレン環が連結した基が好ましい。LUMOが広がる観点からフェニレン環が2個連結したビフェニレン基が特に好ましい。 ( Ar54 )
Ar 54 is preferably a group in which one or more divalent aromatic hydrocarbon groups, which may be the same or different, are linked, and the divalent aromatic group hydrocarbon group may have a substituent. When multiple groups are linked, the number of linked groups is preferably 2 to 10, more preferably 6 or less, and particularly preferably 3 or less from the viewpoint of film stability. Preferred aromatic hydrocarbon ring structures are benzene ring, naphthalene ring, anthracene ring and fluorene ring, and more preferred are benzene ring and fluorene ring. A group in which 1 to 4 phenylene rings are linked or a group in which a phenylene ring and a fluorene ring are linked are preferable as the group in which a plurality of rings are linked. A biphenylene group in which two phenylene rings are linked is particularly preferable from the viewpoint of expanding LUMO.
これらの基は置換基を有していてもよい。有していてもよい置換基は、前記置換基群Zから選ばれる基又は架橋基が好ましく、架橋基を有する場合、架橋基としては、前記架橋基群Tから選ばれる基が好ましい。より好ましい置換基としては、フェニル基、ナフチル基、フルオレニル基である。また、置換基を有さないことも好ましい。
These groups may have substituents. The substituent that may be present is preferably a group selected from the above-described substituent group Z or a cross-linking group. Preferred substituents are phenyl, naphthyl and fluorenyl groups. Moreover, it is also preferable not to have a substituent.
(Ar55)
Ar55は、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは芳香族複素環基が直接若しくは連結基を介して複数個連結した1価の基である。好ましくは、1価の芳香族炭化水素基又は1価の芳香族炭化水素基が複数連結した基である。 ( Ar55 )
Ar 55 is an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, an optionally substituted aromatic hydrocarbon group or A monovalent group in which a plurality of aromatic heterocyclic groups are linked directly or via a linking group. Preferably, it is a monovalent aromatic hydrocarbon group or a group in which a plurality of monovalent aromatic hydrocarbon groups are linked.
Ar55は、置換基を有していてもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは芳香族複素環基が直接若しくは連結基を介して複数個連結した1価の基である。好ましくは、1価の芳香族炭化水素基又は1価の芳香族炭化水素基が複数連結した基である。 ( Ar55 )
Ar 55 is an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, an optionally substituted aromatic hydrocarbon group or A monovalent group in which a plurality of aromatic heterocyclic groups are linked directly or via a linking group. Preferably, it is a monovalent aromatic hydrocarbon group or a group in which a plurality of monovalent aromatic hydrocarbon groups are linked.
これらの基は置換基を有していてもよい。有していてもよい置換基は、前記置換基群Zから選ばれる基又は架橋基が好ましく、架橋基を有する場合、架橋基としては、前記架橋基群Tから選ばれる基が好ましい。
These groups may have substituents. The substituent that may be present is preferably a group selected from the above-described substituent group Z or a cross-linking group.
これらの基が複数個連結する場合は、2~10個連結した2価の基であり、2~5個連結した1価の基であることが好ましい。芳香族炭化水素基、芳香族複素環基としては、前記Ar51と同様の芳香族炭化水素基及び芳香族複素環基を用いることが出来る。
When a plurality of these groups are linked, it is preferably a divalent group in which 2 to 10 are linked, and preferably a monovalent group in which 2 to 5 are linked. As 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.
Ar55としては、下記スキーム2A,2B,2Cのいずれかで表される構造を有することが好ましい。
Ar 55 preferably has a structure represented by any one of Schemes 2A, 2B and 2C below.
上記スキーム2A~2Cにおいて、“-*”はAr54との結合位置を表し、“-*”が複数ある場合はいずれか1つがAr54との結合位置を表す。
これらの構造は、置換基を有していてもよい。これらの構造が有していてもよい置換基としては、前記置換基群Zから選択される基又は架橋基が好ましく、架橋基を有する場合、架橋基としては前記架橋基群Tから選択される基が好ましい。 In Schemes 2A to 2C above, "-*" represents the binding position to Ar 54 , and when there are multiple "-*"s, one of them represents the binding position to Ar 54 .
These structures may have a substituent. The substituent that these structures may have is preferably a group or a cross-linking group selected from the substituent group Z, and when a cross-linking group is included, the cross-linking group is selected from the cross-linking group T groups are preferred.
これらの構造は、置換基を有していてもよい。これらの構造が有していてもよい置換基としては、前記置換基群Zから選択される基又は架橋基が好ましく、架橋基を有する場合、架橋基としては前記架橋基群Tから選択される基が好ましい。 In Schemes 2A to 2C above, "-*" represents the binding position to Ar 54 , and when there are multiple "-*"s, one of them represents the binding position to Ar 54 .
These structures may have a substituent. The substituent that these structures may have is preferably a group or a cross-linking group selected from the substituent group Z, and when a cross-linking group is included, the cross-linking group is selected from the cross-linking group T groups are preferred.
(R31及びR32)
スキーム2A,2BのR31及びR32は、各々独立に、置換基を有していてもよい直鎖、分岐又は環状のアルキル基であることが好ましい。アルキル基の炭素数は特に限定されないが、重合体の溶解性を維持するために、炭素数が1以上、6以下が好ましく、3以下がより好ましく、メチル基又はエチル基であることが更に好ましい。 (R 31 and R 32 )
Preferably, R 31 and R 32 in Schemes 2A and 2B are each independently an optionally substituted linear, branched or cyclic alkyl group. Although 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. .
スキーム2A,2BのR31及びR32は、各々独立に、置換基を有していてもよい直鎖、分岐又は環状のアルキル基であることが好ましい。アルキル基の炭素数は特に限定されないが、重合体の溶解性を維持するために、炭素数が1以上、6以下が好ましく、3以下がより好ましく、メチル基又はエチル基であることが更に好ましい。 (R 31 and R 32 )
Preferably, R 31 and R 32 in Schemes 2A and 2B are each independently an optionally substituted linear, branched or cyclic alkyl group. Although 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. .
R31及びR32は同一であっても異なっていてもよいが、電荷を均一的に窒素原子の周りに分布することができ、更に合成も容易であることから、全てのR31及びR32は同一の基であることが好ましい。
R 31 and R 32 may be the same or different, but all R 31 and R 32 are are preferably the same groups.
(Ard18)
スキーム2BのArd18は、各々独立に、芳香族炭化水素基又は芳香族複素環基である。Ard18は、安定性の観点から芳香族炭化水素基が好ましく、さらに好ましくはフェニル基である。これらの基はさらに置換基を有してもよい。有していてもよい置換基は、前記置換基群Zから選ばれる基又は架橋基が好ましく、架橋基を有する場合、架橋基としては、前記架橋基群Tから選ばれる基が好ましい。 (Ar d18 )
Each Ar d18 in Scheme 2B is independently an aromatic hydrocarbon group or an aromatic heterocyclic group. Ar d18 is preferably an aromatic hydrocarbon group, more preferably a phenyl group, from the viewpoint of stability. These groups may further have a substituent. The substituent that may be present is preferably a group selected from the above-described substituent group Z or a cross-linking group.
スキーム2BのArd18は、各々独立に、芳香族炭化水素基又は芳香族複素環基である。Ard18は、安定性の観点から芳香族炭化水素基が好ましく、さらに好ましくはフェニル基である。これらの基はさらに置換基を有してもよい。有していてもよい置換基は、前記置換基群Zから選ばれる基又は架橋基が好ましく、架橋基を有する場合、架橋基としては、前記架橋基群Tから選ばれる基が好ましい。 (Ar d18 )
Each Ar d18 in Scheme 2B is independently an aromatic hydrocarbon group or an aromatic heterocyclic group. Ar d18 is preferably an aromatic hydrocarbon group, more preferably a phenyl group, from the viewpoint of stability. These groups may further have a substituent. The substituent that may be present is preferably a group selected from the above-described substituent group Z or a cross-linking group.
分子のLUMOを分布させる観点から、Ar55としては、上記a-1~a-4、b-1~b-9、c-1~c-4、d-1~d-18、及びe-1~e-4から選択される構造が好ましい。更に電子求引性基を有することにより分子のLUMOが広がることに促進する観点から、a-1~a-4、b-1~b-9、d-1~d-12、d-17、d-18、及びe-1~e-4から選択される構造が好ましい。更に三重項レベルが高い、発光層に形成された励起子を閉じ込む効果の観点から、a-1~a-4、d-1~d-12、d-17、d-18、及びe-1~e-4から選択される構造が好ましい。また、簡易に合成でき、安定性に優れる観点から、d-1、d-10、d-17、d-18及びe-1がさらに好ましく、d-1のベンゼン環構造、d-6のフルオレン環構造又はd-17のカルバゾール構造が特に好ましい。
From the viewpoint of distributing the LUMO of the molecule, Ar 55 includes the above a-1 to a-4, b-1 to b-9, c-1 to c-4, d-1 to d-18, and e- 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, d-17, Structures selected from d-18, and e-1 through e-4 are preferred. Furthermore, from the viewpoint of the effect of confining the excitons formed in the light-emitting layer, which have a higher triplet level, a-1 to a-4, d-1 to d-12, d-17, d-18, and e- Structures selected from 1 to e-4 are preferred. Further, from the viewpoint of easy synthesis and excellent stability, d-1, d-10, d-17, d-18 and e-1 are more preferable, d-1 benzene ring structure, d-6 fluorene A ring structure or a d-17 carbazole structure is particularly preferred.
Ar55がd-6で表されるフルオレン構造の場合、2-フルオレニル基が好ましい。さらに、9,9’位には置換基を有してもよく、有してよい置換基は、前記置換基群Zから選ばれる基又は架橋基が好ましく、架橋基を有する場合、架橋基としては、前記架橋基群Tから選ばれる基が好ましい。置換基としては中でもアルキル基が好ましい。
When Ar 55 is a fluorene structure represented by d-6, a 2-fluorenyl group is preferred. Furthermore, the 9,9'-position may have a substituent, and the substituent that may have is preferably a group or a cross-linking group selected from the substituent group Z, and when having a cross-linking group, as a cross-linking group is preferably a group selected from the above-mentioned cross-linking group T. Among these substituents, an alkyl group is preferable.
(Ar56)
Ar56は、水素原子、又は置換基を表す。Ar56が置換基である場合、特に限定はされないが、好ましくは芳香族炭化水素基、芳香族複素環基又は架橋基であり、芳香族炭化水素基又は芳香族複素環基の場合は更に置換基群Zから選択される置換基又は架橋基群Tから選択される架橋基を有していてもよい。Ar56が架橋基の場合、好ましくは前記架橋基群Tから選択される架橋基である。 ( Ar56 )
Ar 56 represents a hydrogen atom or a substituent. When Ar 56 is a substituent, it is not particularly limited, but is preferably an aromatic hydrocarbon group, an aromatic heterocyclic group or a bridging group. It may have a substituent selected from group Z or a cross-linking group selected from group T of cross-linking groups. When Ar 56 is a cross-linking group, it is preferably a cross-linking group selected from the cross-linking group T.
Ar56は、水素原子、又は置換基を表す。Ar56が置換基である場合、特に限定はされないが、好ましくは芳香族炭化水素基、芳香族複素環基又は架橋基であり、芳香族炭化水素基又は芳香族複素環基の場合は更に置換基群Zから選択される置換基又は架橋基群Tから選択される架橋基を有していてもよい。Ar56が架橋基の場合、好ましくは前記架橋基群Tから選択される架橋基である。 ( Ar56 )
Ar 56 represents a hydrogen atom or a substituent. When Ar 56 is a substituent, it is not particularly limited, but is preferably an aromatic hydrocarbon group, an aromatic heterocyclic group or a bridging group. It may have a substituent selected from group Z or a cross-linking group selected from group T of cross-linking groups. When Ar 56 is a cross-linking group, it is preferably a cross-linking group selected from the cross-linking group T.
Ar56が置換基である場合、式(51)においてAr56が結合しているカルバゾール構造の3位に結合していることが、耐久性向上の観点から好ましい。Ar56は、合成のし易さ及び電荷輸送性の観点からは、水素原子であることが好ましい。Ar56は、耐久性向上及び電荷輸送性の観点からは、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基であることが好ましく、置換基を有していてもよい芳香族炭化水素基であることがさらに好ましい。
When Ar 56 is a substituent, it is preferably bonded to the 3-position of the carbazole structure to which Ar 56 is bonded in formula (51) from the viewpoint of improving durability. Ar 56 is preferably a hydrogen atom from the viewpoint of ease of synthesis and charge transport properties. Ar 56 is preferably an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group from the viewpoint of durability improvement and charge transport property. , is more preferably an aromatic hydrocarbon group which may have a substituent.
Ar56は、合成のし易さ及び電荷輸送性の観点からは、水素原子であることが好ましい。
Ar 56 is preferably a hydrogen atom from the viewpoint of ease of synthesis and charge transport properties.
(式(51)で表される基の具体例)
式(51)で表される基の具体例を以下に挙げるが、式(51)で表される基はこれらに限定されるものではない。 (Specific examples of groups represented by formula (51))
Specific examples of the group represented by formula (51) are shown below, but the group represented by formula (51) is not limited thereto.
式(51)で表される基の具体例を以下に挙げるが、式(51)で表される基はこれらに限定されるものではない。 (Specific examples of groups represented by formula (51))
Specific examples of the group represented by formula (51) are shown below, but the group represented by formula (51) is not limited thereto.
<式(52)で表される基>
<Group Represented by Formula (52)>
(式(52)中、
Ar61及びAr62は、それぞれ独立に、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有してもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基であり、
Ar63~Ar65は、それぞれ独立に、水素原子又は置換基である。
*は式(50)中の主鎖の窒素原子への結合位置を表す。) (In formula (52),
Ar 61 and Ar 62 each independently represent an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or a substituent A divalent group in which a plurality of aromatic hydrocarbon groups or aromatic heterocyclic groups optionally having a substituent are linked 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 of the main chain in formula (50). )
Ar61及びAr62は、それぞれ独立に、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有してもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基であり、
Ar63~Ar65は、それぞれ独立に、水素原子又は置換基である。
*は式(50)中の主鎖の窒素原子への結合位置を表す。) (In formula (52),
Ar 61 and Ar 62 each independently represent an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or a substituent A divalent group in which a plurality of aromatic hydrocarbon groups or aromatic heterocyclic groups optionally having a substituent are linked 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 of the main chain in formula (50). )
(Ar63~Ar65)
Ar63~Ar65は、それぞれ独立して、前記Ar56と同様である。
Ar63~Ar64は、好ましくは水素原子である。 (Ar 63 -Ar 65 )
Ar 63 to Ar 65 are each independently the same as Ar 56 above.
Ar 63 to Ar 64 are preferably hydrogen atoms.
Ar63~Ar65は、それぞれ独立して、前記Ar56と同様である。
Ar63~Ar64は、好ましくは水素原子である。 (Ar 63 -Ar 65 )
Ar 63 to Ar 65 are each independently the same as Ar 56 above.
Ar 63 to Ar 64 are preferably hydrogen atoms.
(Ar62)
Ar62は、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基である。好ましくは、置換基を有していてもよい2価の芳香族炭化水素基又は置換基を有していてもよい2価の芳香族炭化水素基が複数連結した基である。ここで、芳香族炭化水素基が有してもよい置換基及び芳香族複素環基が有してもよい置換基は前記置換基群Zと同様の基又は架橋基が好ましい。架橋基としては、前記架橋基群Tから選ばれる基が好ましい。 ( Ar62 )
Ar 62 is an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or optionally substituted It is a divalent group in which a plurality of aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked 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. Here, the substituents which the aromatic hydrocarbon group may have and the substituents which the aromatic heterocyclic group may have are preferably the same groups as those in the substituent group Z or the bridging groups. As the cross-linking group, a group selected from the cross-linking group T is preferable.
Ar62は、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基である。好ましくは、置換基を有していてもよい2価の芳香族炭化水素基又は置換基を有していてもよい2価の芳香族炭化水素基が複数連結した基である。ここで、芳香族炭化水素基が有してもよい置換基及び芳香族複素環基が有してもよい置換基は前記置換基群Zと同様の基又は架橋基が好ましい。架橋基としては、前記架橋基群Tから選ばれる基が好ましい。 ( Ar62 )
Ar 62 is an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or optionally substituted It is a divalent group in which a plurality of aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked 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. Here, the substituents which the aromatic hydrocarbon group may have and the substituents which the aromatic heterocyclic group may have are preferably the same groups as those in the substituent group Z or the bridging groups. As the cross-linking group, a group selected from the cross-linking group T is preferable.
Ar62の具体的な構造は、Ar54と同様である。
A specific structure of Ar 62 is similar to that of Ar 54 .
Ar62の具体的な好ましい基は、ベンゼン環、ナフタレン環、アントラセン環、フルオレン環の2価の基又はこれらが複数連結した基であり、より好ましくは、ベンゼン環の2価の基又はこれが複数連結した基であり、特に好ましくは、ベンゼン環が1,4位の2価で連結した1,4-フェニレン基、フルオレン環の2,7位の2価で連結した2,7-フルオレニレン基、又はこれらが複数連結した基であり、最も好ましくは、“1,4-フェニレン基-2,7-フルオレニレン基-1,4-フェニレン基-”を含む基である。
A specific preferred group for Ar 62 is a divalent group of a benzene ring, a naphthalene ring, 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 plurality of these It is a linked group, and particularly preferably a 1,4-phenylene group in which benzene rings are linked at the 1,4-position divalents, a 2,7-fluorenylene group in which the 2,7-positions of a fluorene ring are linked at a divalence, Or a group in which a plurality of these are linked, most preferably a group containing "1,4-phenylene group-2,7-fluorenylene group-1,4-phenylene group-".
Ar62のこれら好ましい構造において、フェニレン基は連結位置以外に置換基を有さないことが、置換基の立体効果によるAr62のねじれが生じず好ましい。また、フルオレニレン基は、9,9’位に置換基を有している方が、溶解性及びフルオレン構造の耐久性向上の観点から好ましい。置換基としては前記置換基群Zから選択される置換基又は架橋基が好ましく、中でもアルキル基がより好ましい。これら置換基はさらに架橋基で置換されていてもよい。架橋基としては前記架橋基群Tから選択される架橋基が好ましい。好ましくは置換基群Zから選択される置換基である。
In these preferred structures of Ar 62 , 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. Further, the fluorenylene group preferably has substituents at the 9 and 9′ positions from the viewpoint of improving solubility and durability of the fluorene structure. The substituent is preferably a substituent or a cross-linking group selected from the substituent group Z, and more preferably an alkyl group. These substituents may be further substituted with a bridging group. As the cross-linking group, a cross-linking group selected from the cross-linking group T is preferable. A substituent selected from the substituent group Z is preferable.
(Ar61)
Ar61は、前記Ar53と同様の基であり、好ましい構造も同様である。 ( Ar61 )
Ar 61 is the same group as Ar 53 , and the preferred structure is also the same.
Ar61は、前記Ar53と同様の基であり、好ましい構造も同様である。 ( Ar61 )
Ar 61 is the same group as Ar 53 , and the preferred structure is also the same.
(式(52)で表される基の具体例)
式(52)で表される基の具体例を以下に挙げるが、式(52)で表される基としてはこれらに限定されるものではない。 (Specific examples of groups represented by formula (52))
Specific examples of the group represented by formula (52) are shown below, but the group represented by formula (52) is not limited to these.
式(52)で表される基の具体例を以下に挙げるが、式(52)で表される基としてはこれらに限定されるものではない。 (Specific examples of groups represented by formula (52))
Specific examples of the group represented by formula (52) are shown below, but the group represented by formula (52) is not limited to these.
<式(53)で表される基>
<Group Represented by Formula (53)>
(式(53)中、
*は式(50)の主鎖の窒素原子との結合を表し、
Ar71は、2価の芳香族炭化水素基を表し、
Ar72及びAr73は、それぞれ独立に、芳香族炭化水素基、芳香族複素環基、或いは、芳香族炭化水素基及び芳香族複素環基から選ばれる2以上の基が直接若しくは連結基を介して複数個連結した1価の基を表し、これらの基は置換基を有していてもよく、
環HAは窒素原子を含む芳香族複素環であり、
X2、Y2は、それぞれ独立に、炭素原子又は窒素原子を表し、X2及びY2の少なくとも一方が、炭素原子の場合は、当該炭素原子は置換基を有していてもよい。) (In formula (53),
* represents a bond to the nitrogen atom of the main chain of formula (50),
Ar 71 represents a divalent aromatic hydrocarbon group,
Ar 72 and Ar 73 are each independently an aromatic hydrocarbon group, an aromatic heterocyclic group, or two or more groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group directly or via a linking group. represents a monovalent group in which a plurality of are linked, and these groups may have a substituent,
Ring HA is an aromatic heterocycle containing a nitrogen atom;
X 2 and Y 2 each independently represent a carbon atom or a nitrogen atom, and when at least one of X 2 and Y 2 is a carbon atom, the carbon atom may have a substituent. )
*は式(50)の主鎖の窒素原子との結合を表し、
Ar71は、2価の芳香族炭化水素基を表し、
Ar72及びAr73は、それぞれ独立に、芳香族炭化水素基、芳香族複素環基、或いは、芳香族炭化水素基及び芳香族複素環基から選ばれる2以上の基が直接若しくは連結基を介して複数個連結した1価の基を表し、これらの基は置換基を有していてもよく、
環HAは窒素原子を含む芳香族複素環であり、
X2、Y2は、それぞれ独立に、炭素原子又は窒素原子を表し、X2及びY2の少なくとも一方が、炭素原子の場合は、当該炭素原子は置換基を有していてもよい。) (In formula (53),
* represents a bond to the nitrogen atom of the main chain of formula (50),
Ar 71 represents a divalent aromatic hydrocarbon group,
Ar 72 and Ar 73 are each independently an aromatic hydrocarbon group, an aromatic heterocyclic group, or two or more groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group directly or via a linking group. represents a monovalent group in which a plurality of are linked, and these groups may have a substituent,
Ring HA is an aromatic heterocycle containing a nitrogen atom;
X 2 and Y 2 each independently represent a carbon atom or a nitrogen atom, and when at least one of X 2 and Y 2 is a carbon atom, the carbon atom may have a substituent. )
上記有していてもよい置換基は、前記置換基群Zから選ばれる基又は架橋基が好ましい。架橋基を有する場合、架橋基としては、前記架橋基群Tから選ばれる基が好ましい。
The substituent that may be present is preferably a group selected from the substituent group Z or a cross-linking group. When it has a cross-linking group, the cross-linking group is preferably a group selected from the above-mentioned cross-linking group T.
<Ar71>
Ar71は、前記Ar53と同様の基である。 <Ar71>
Ar 71 is the same group as Ar 53 above.
Ar71は、前記Ar53と同様の基である。 <Ar71>
Ar 71 is the same group as Ar 53 above.
Ar71としては、特に、置換基を有していてもよいベンゼン環が2~6個連結した基が好ましく、置換基を有していてもよいベンゼン環が4個連結したクアテルフェニレン基が最も好ましい。
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.
また、Ar71は非共役部位である1,3位で連結したベンゼン環を少なくとも1つ含むことが好ましく、2以上含むことが更に好ましい。
In addition, 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.
Ar71が置換基を有していてもよい2価の芳香族炭化水素基が複数連結した基の場合、電荷輸送性又は耐久性の観点から、全て直接結合して連結していることが好ましい。
When 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. .
このため、Ar71として、重合体の主鎖の窒素原子と前記式(53)中の環HAとの間を繋ぐ好ましい構造は、下記のスキーム2-1及びスキーム2-2に挙げられる通りである。“-*”は、重合体の主鎖の窒素原子又は前記式(53)の環HAとの結合部位を表す。2つの“-*”のうち、いずれかが重合体の主鎖の窒素原子と結合していても、環HAと結合していてもよい。
Therefore, preferred structures for Ar 71 connecting the nitrogen atom of the main chain of the polymer and the ring HA in the formula (53) are as shown in Schemes 2-1 and 2-2 below. be. "-*" represents the nitrogen atom of the main chain of the polymer or the bonding site with the ring HA of the formula (53). Either of the two "-*" may be bonded to the nitrogen atom of the main chain of the polymer or may be bonded to the ring HA.
Ar71が有していてもよい置換基としては、前記置換基群Zのいずれか又はこれらの組み合わせを用いることができる。Ar71が有していてもよい置換基の好ましい範囲は、前述のAr53が芳香族炭化水素基である場合に有してもよい置換基と同様である。
As the substituent that Ar 71 may have, any one of the substituent group Z or a combination thereof can be used. The preferred range of the substituent that Ar 71 may have is the same as the substituent that Ar 53 may have when it is an aromatic hydrocarbon group.
<X2及びY2>
X2及びY2は、それぞれ独立に、C(炭素)原子又はN(窒素)原子を表す。X2及びY2の少なくとも一方が、C原子の場合は、置換基を有していてもよい。 < X2 and Y2 >
X2 and Y2 each independently represent a C (carbon) atom or an N (nitrogen) atom. When at least one of X 2 and Y 2 is a C atom, it may have a substituent.
X2及びY2は、それぞれ独立に、C(炭素)原子又はN(窒素)原子を表す。X2及びY2の少なくとも一方が、C原子の場合は、置換基を有していてもよい。 < X2 and Y2 >
X2 and Y2 each independently represent a C (carbon) atom or an N (nitrogen) atom. When at least one of X 2 and Y 2 is a C atom, it may have a substituent.
環HAの周辺にLUMOをより局在化させやすい観点からX2及びY2はいずれもN原子であることが好ましい。
Both X 2 and Y 2 are preferably N atoms from the viewpoint of facilitating the localization of LUMO around ring HA.
X2及びY2の少なくとも一方がC原子の場合に有していてもよい置換基としては、前記置換基群Zのいずれか又はこれらの組み合わせを用いることができる。電荷輸送性の観点からは、X2及びY2は置換基を有さないことが更に好ましい。
When at least one of X 2 and Y 2 is a C atom, any one of the substituent group Z or a combination thereof can be used as the substituent which may be possessed. From the viewpoint of charge transport properties, X 2 and Y 2 more preferably have no substituents.
<Ar72及びAr73>
Ar72及びAr73は、それぞれ独立に、芳香族炭化水素基、芳香族複素環基、或いは、芳香族炭化水素基及び芳香族複素環基から選ばれる2以上の基が直接若しくは連結基を介して複数個連結した1価の基である。これらの基は置換基を有していてもよく、有していてもよい置換基は前記置換基群Zから選ばれる基又は架橋基が好ましい。架橋基を有する場合、架橋基として架橋基は、前記架橋基群Tから選ばれる基が好ましい。 <Ar 72 and Ar 73 >
Ar 72 and Ar 73 are each independently an aromatic hydrocarbon group, an aromatic heterocyclic group, or two or more groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group directly or via a linking group. is a monovalent group in which a plurality of groups are linked by These groups may have a substituent, and the substituent which may have is preferably a group selected from the substituent group Z or a bridging group. When it has a cross-linking group, the cross-linking group is preferably a group selected from the cross-linking group T described above.
Ar72及びAr73は、それぞれ独立に、芳香族炭化水素基、芳香族複素環基、或いは、芳香族炭化水素基及び芳香族複素環基から選ばれる2以上の基が直接若しくは連結基を介して複数個連結した1価の基である。これらの基は置換基を有していてもよく、有していてもよい置換基は前記置換基群Zから選ばれる基又は架橋基が好ましい。架橋基を有する場合、架橋基として架橋基は、前記架橋基群Tから選ばれる基が好ましい。 <Ar 72 and Ar 73 >
Ar 72 and Ar 73 are each independently an aromatic hydrocarbon group, an aromatic heterocyclic group, or two or more groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group directly or via a linking group. is a monovalent group in which a plurality of groups are linked by These groups may have a substituent, and the substituent which may have is preferably a group selected from the substituent group Z or a bridging group. When it has a cross-linking group, the cross-linking group is preferably a group selected from the cross-linking group T described above.
分子のLUMOを分布させる観点から、Ar72及びAr73は、それぞれ独立に、前記スキーム2A~2Cに示すa-1~a-4、b-1~b-9、c-1~c-4、d-1~d-16、及びe-1~e-4から選択される構造を有することが好ましい。
From the viewpoint of distributing the LUMO of the molecule, Ar 72 and Ar 73 are each independently a-1 to a-4, b-1 to b-9, c-1 to c-4 shown in Schemes 2A to 2C above. , d-1 to d-16, and e-1 to e-4.
更に電子求引性基を有することにより分子のLUMOが広がることに促進する観点から、a-1~a-4、b-1~b-9、c-1~c-5、d-1~d-12、及びe-1~e-4から選択される構造が好ましい。
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.
更に三重項レベルが高い、発光層に形成された励起子を閉じ込める効果の観点から、a-1~a-4、d-1~d-12、及びe-1~e-4から選択される構造が好ましい。
further selected from a-1 to a-4, d-1 to d-12, and e-1 to e-4 from the viewpoint of the effect of confining excitons formed in the light-emitting layer, which have a higher triplet level Structure is preferred.
分子の凝集を防ぐため、d-1~d-12、及びe-1~e-4から選択される構造が更に好ましい。簡易に合成でき、安定性に優れる観点からAr72=Ar73=d-1又はd-10が好ましく、d-1のベンゼン環構造が特に好ましい。
またこれら構造に置換基を有していてもよい。 Structures selected from d-1 to d-12 and e-1 to e-4 are more preferred to prevent aggregation of molecules. Ar 72 =Ar 73 =d-1 or d-10 is preferable from the viewpoint of easy synthesis and excellent stability, and a benzene ring structure of d-1 is particularly preferable.
Further, these structures may have substituents.
またこれら構造に置換基を有していてもよい。 Structures selected from d-1 to d-12 and e-1 to e-4 are more preferred to prevent aggregation of molecules. Ar 72 =Ar 73 =d-1 or d-10 is preferable from the viewpoint of easy synthesis and excellent stability, and a benzene ring structure of d-1 is particularly preferable.
Further, these structures may have substituents.
(式(53)で表される基の具体例)
式(53)で表される基の具体例を以下に挙げるが、式(53)で表される基としてはこれらに限定されるものではない。 (Specific examples of groups represented by formula (53))
Specific examples of the group represented by formula (53) are shown below, but the group represented by formula (53) is not limited thereto.
式(53)で表される基の具体例を以下に挙げるが、式(53)で表される基としてはこれらに限定されるものではない。 (Specific examples of groups represented by formula (53))
Specific examples of the group represented by formula (53) are shown below, but the group represented by formula (53) is not limited thereto.
(好ましい式(50)で表される繰り返し単位)
前記式(50)で表される繰り返し単位として好ましくは、下記式(54)で表される繰り返し単位、下記式(55)で表される繰り返し単位、下記式(56)で表される繰り返し単位、下記式(57)で表される繰り返し単位、及び下記式(60)で表される繰り返しから選択される繰返し単位である。 (preferred repeating unit represented by formula (50))
The repeating unit represented by the formula (50) is preferably a repeating unit represented by the following formula (54), a repeating unit represented by the following formula (55), or a repeating unit represented by the following formula (56). , a repeating unit represented by the following formula (57), and a repeating unit represented by the following formula (60).
前記式(50)で表される繰り返し単位として好ましくは、下記式(54)で表される繰り返し単位、下記式(55)で表される繰り返し単位、下記式(56)で表される繰り返し単位、下記式(57)で表される繰り返し単位、及び下記式(60)で表される繰り返しから選択される繰返し単位である。 (preferred repeating unit represented by formula (50))
The repeating unit represented by the formula (50) is preferably a repeating unit represented by the following formula (54), a repeating unit represented by the following formula (55), or a repeating unit represented by the following formula (56). , a repeating unit represented by the following formula (57), and a repeating unit represented by the following formula (60).
<式(54)で表される繰り返し単位>
<Repeating Unit Represented by Formula (54)>
(式(54)中、
Ar51は、前記式(50)におけるAr51と同様であり、
Xは、-C(R207)(R208)-、-N(R209)-又は-C(R211)(R212)-C(R213)(R214)-であり、
R201、R202、R221及びR222は、それぞれ独立して、置換基を有していてもよいアルキル基であり、
R207~R209及びR211~R214は、それぞれ独立して、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアラルキル基、又は、置換基を有していてもよい芳香族炭化水素基であり、
a及びbは、それぞれ独立して、0~4の整数であり、
cは、0~3の整数であり、
dは、0~4の整数であり、
i及びjはそれぞれ独立して0~3の整数である。) (In formula (54),
Ar 51 is the same as Ar 51 in the formula (50),
X is -C(R 207 )(R 208 )-, -N(R 209 )- or -C(R 211 )(R 212 )-C(R 213 )(R 214 )-;
R 201 , R 202 , R 221 and R 222 are each independently an optionally substituted alkyl group,
R 207 to R 209 and R 211 to R 214 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituent. an aromatic hydrocarbon group which may have
a and b are each independently an integer of 0 to 4;
c is an integer from 0 to 3,
d is an integer from 0 to 4,
i and j are each independently an integer from 0 to 3; )
Ar51は、前記式(50)におけるAr51と同様であり、
Xは、-C(R207)(R208)-、-N(R209)-又は-C(R211)(R212)-C(R213)(R214)-であり、
R201、R202、R221及びR222は、それぞれ独立して、置換基を有していてもよいアルキル基であり、
R207~R209及びR211~R214は、それぞれ独立して、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアラルキル基、又は、置換基を有していてもよい芳香族炭化水素基であり、
a及びbは、それぞれ独立して、0~4の整数であり、
cは、0~3の整数であり、
dは、0~4の整数であり、
i及びjはそれぞれ独立して0~3の整数である。) (In formula (54),
Ar 51 is the same as Ar 51 in the formula (50),
X is -C(R 207 )(R 208 )-, -N(R 209 )- or -C(R 211 )(R 212 )-C(R 213 )(R 214 )-;
R 201 , R 202 , R 221 and R 222 are each independently an optionally substituted alkyl group,
R 207 to R 209 and R 211 to R 214 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituent. an aromatic hydrocarbon group which may have
a and b are each independently an integer of 0 to 4;
c is an integer from 0 to 3,
d is an integer from 0 to 4,
i and j are each independently an integer from 0 to 3; )
(R201、R202、R221、R222)
上記式(54)で表される繰り返し単位中のR201、R202、R221及びR222は、それぞれ独立して、置換基を有していてもよいアルキル基である。 ( R201 , R202 , R221 , R222 )
R 201 , R 202 , R 221 and R 222 in the repeating unit represented by formula (54) are each independently an optionally substituted alkyl group.
上記式(54)で表される繰り返し単位中のR201、R202、R221及びR222は、それぞれ独立して、置換基を有していてもよいアルキル基である。 ( R201 , R202 , R221 , R222 )
R 201 , R 202 , R 221 and R 222 in the repeating unit represented by formula (54) are each independently an optionally substituted alkyl group.
該アルキル基は、直鎖、分岐又は環状のアルキル基である。アルキル基の炭素数は特に限定されないが、重合体の溶解性を維持するために、1以上が好ましく、また、8以下が好ましく、6以下がより好ましく、3以下がさらに好ましい。該アルキル基は、メチル基又はエチル基であることがさらに好ましい。
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.
R201が複数ある場合は、複数のR201は同一であっても異なっていてもよく、R202が複数ある場合は、複数のR202は同一であっても異なっていてもよい。電荷を均一的に窒素原子の周りに分布することができ、さらに合成も容易であることから、全てのR201とR202は同一の基であることが好ましい。
When there is a plurality of R 201 , the plurality of R 201 may be the same or different, and when there is a plurality of R 202 , the plurality of R 202 may be the same or different. All R 201 and R 202 are preferably the same group because the charge can be uniformly distributed around the nitrogen atom and the synthesis is easy.
R221が複数ある場合は、複数のR221は同一であっても異なっていてもよく、R222が複数ある場合は、複数のR222は同一であっても異なっていてもよい。合成が容易であることから、全てのR221とR222は同一の基であることが好ましい。
When there are multiple R 221 , the multiple R 221 may be the same or different, and when there is the multiple R 222 , the multiple R 222 may be the same or different. All R 221 and R 222 are preferably the same group for ease of synthesis.
(R207~R209及びR211~R214)
R207~R209及びR211~R214は、それぞれ独立して、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアラルキル基、又は置換基を有していてもよい芳香族炭化水素基である。 (R 207 to R 209 and R 211 to R 214 )
R 207 to R 209 and R 211 to R 214 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted is an aromatic hydrocarbon group which may be
R207~R209及びR211~R214は、それぞれ独立して、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアラルキル基、又は置換基を有していてもよい芳香族炭化水素基である。 (R 207 to R 209 and R 211 to R 214 )
R 207 to R 209 and R 211 to R 214 are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aralkyl group, or a substituted is an aromatic hydrocarbon group which may be
該アルキル基は特に限定されないが、重合体の溶解性を向上できる傾向にあるため、炭素数は1以上が好ましく、また、24以下が好ましく、8以下がより好ましく、6以下がさらに好ましい。また、該アルキル基は直鎖、分岐又は環状の各構造であってもよい。
Although 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.
該アルキル基として、具体的には、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、tert-ブチル基、n-ヘキシル基、n-オクチル基、シクロヘキシル基、ドデシル基等が挙げられる。
Specific examples of the alkyl group 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.
該アラルキル基は特に限定されないが、重合体の溶解性を向上できる傾向にあるため、炭素数は5以上が好ましく、また、60以下が好ましく、40以下がより好ましい。
Although 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.
該アラルキル基として、具体的には、1,1-ジメチル-1-フェニルメチル基、1,1-ジ(n-ブチル)-1-フェニルメチル基、1,1-ジ(n-ヘキシル)-1-フェニルメチル基、1,1-ジ(n-オクチル)-1-フェニルメチル基、フェニルメチル基、フェニルエチル基、3-フェニル-1-プロピル基、4-フェニル-1-n-ブチル基、1-メチル-1-フェニルエチル基、5-フェニル-1-n-プロピル基、6-フェニル-1-n-ヘキシル基、6-ナフチル-1-n-ヘキシル基、7-フェニル-1-n-ヘプチル基、8-フェニル-1-n-オクチル基、4-フェニルシクロヘキシル基等が挙げられる。
Specific examples of the aralkyl group 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.
該芳香族炭化水素基としては特に限定されないが、重合体の溶解性を向上できる傾向にあるため、炭素数は6以上が好ましく、また、60以下が好ましく、30以下がより好ましい。
Although 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.
該芳香族炭化水素基として、具体的には、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環等の、6員環の単環若しくは2~5縮合環の1価の基、又はこれらが複数連結した基等が挙げられる。
Specific examples of the aromatic hydrocarbon group 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.
電荷輸送性及び耐久性向上の観点から、R207及びR208はメチル基又は芳香族炭化水素基が好ましく、R207及びR208はメチル基であることがより好ましく、R209はフェニル基であることがより好ましい。
From the viewpoint of improving charge transport properties and durability, R 207 and R 208 are preferably methyl groups or aromatic hydrocarbon groups, R 207 and R 208 are more preferably methyl groups, and R 209 is a phenyl group. is more preferable.
R201、R202、R221、R222のアルキル基、R207~R209及びR211~R214のアルキル基、アラルキル基及び芳香族炭化水素基は、置換基を有していてもよい。置換基は、前記R207~R209及びR211~R214のアルキル基、アラルキル基及び芳香族炭化水素基の好ましい基として挙げた基又は架橋基が挙げられる。架橋基としては、前記架橋基群Tから選択される架橋基が挙げられる。
The alkyl groups of R 201 , R 202 , R 221 and R 222 , the alkyl groups of R 207 to R 209 and R 211 to R 214 , the aralkyl groups and the aromatic hydrocarbon groups may have substituents. Examples of substituents include groups or bridging groups exemplified as preferable groups of the alkyl groups, aralkyl groups and aromatic hydrocarbon groups of R 207 to R 209 and R 211 to R 214 . Examples of the cross-linking group include cross-linking groups selected from the cross-linking group T described above.
R201、R202、R221、R222のアルキル基、R207~R209及びR211~R214のアルキル基、アラルキル基及び芳香族炭化水素基は、低電圧化の観点からは、置換基を有さないことが最も好ましい。
The alkyl groups represented by R 201 , R 202 , R 221 and R 222 , the alkyl groups represented by R 207 to R 209 and R 211 to R 214 , the aralkyl groups and the aromatic hydrocarbon groups are substituents from the viewpoint of voltage reduction. It is most preferred not to have
式(54)で表される繰返し単位の主鎖構造に架橋基が結合する場合、架橋基は、アルキル基、アラルキル基または芳香族炭化水素基である場合の、R207~R209、R211~R213、又はR214に結合していることが好ましい。
When a bridging group is bonded to the main chain structure of the repeating unit represented by formula (54), R 207 to R 209 and R 211 when the bridging group is an alkyl group, an aralkyl group or an aromatic hydrocarbon group ~ R 213 or R 214 is preferred.
(a、b、c、d、i及びj)
上記式(54)で表される繰り返し単位中において、a及びbはそれぞれ独立して、0~4の整数である。a+bは1以上であることが好ましく、さらに、a及びbは、各々2以下であることが好ましく、aとbの両方が1であることがより好ましい。ここで、bが1以上である場合、dも1以上である。また、cが2以上の場合、複数のaは同じであっても異なってもよく、dが2以上の場合、複数のbは同じであっても異なってもよい。 (a, b, c, d, i and j)
In the repeating unit represented by the above formula (54), a and b are each independently an integer of 0-4. It is preferable that a+b is 1 or more, more preferably each of a and b is 2 or less, and more preferably both a and b are 1. Here, when b is 1 or more, d is also 1 or more. Moreover, when c is 2 or more, a plurality of a's may be the same or different, and when d is 2 or more, a plurality of b's may be the same or different.
上記式(54)で表される繰り返し単位中において、a及びbはそれぞれ独立して、0~4の整数である。a+bは1以上であることが好ましく、さらに、a及びbは、各々2以下であることが好ましく、aとbの両方が1であることがより好ましい。ここで、bが1以上である場合、dも1以上である。また、cが2以上の場合、複数のaは同じであっても異なってもよく、dが2以上の場合、複数のbは同じであっても異なってもよい。 (a, b, c, d, i and j)
In the repeating unit represented by the above formula (54), a and b are each independently an integer of 0-4. It is preferable that a+b is 1 or more, more preferably each of a and b is 2 or less, and more preferably both a and b are 1. Here, when b is 1 or more, d is also 1 or more. Moreover, when c is 2 or more, a plurality of a's may be the same or different, and when d is 2 or more, a plurality of b's may be the same or different.
a+bが1以上であると、主鎖の芳香環が立体障害により捻じれ、重合体の溶媒への溶解性が優れると共に、湿式成膜法で形成し加熱処理された塗膜は溶媒への不溶性に優れる傾向にある。したがって、a+bが1以上であると、この塗膜上へ湿式成膜法で別の有機層(例えば発光層)を形成する場合には、有機溶媒を含む該別の有機層形成用組成物への重合体の溶出が抑えられる。
When 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. tend to be superior to Therefore, when a + b is 1 or more, when another organic layer (for example, a light-emitting layer) is formed on this coating film by a wet film-forming method, a composition for forming another organic layer containing an organic solvent is used. elution of the polymer is suppressed.
上記式(54)で表される繰り返し単位中において、cは0~3の整数であり、dは0~4の整数である。c及びdは、各々2以下であることが好ましく、cとdは等しいことがさらに好ましく、cとdの両方が1であるか、又はcとdの両方が2であることが特に好ましい。
In the repeating unit represented by the above formula (54), c is an integer of 0-3 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.
上記式(54)で表される繰り返し単位中のcとdの両方が1であるか又はcとdの両方が2であり、且つ、aとbの両方が2又は1である場合、R201とR202は、互いに対称な位置に結合していることが最も好ましい。
When 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 201 and R 202 are most preferably bonded at symmetrical positions.
ここで、R201とR202とが互いに対称な位置に結合するとは、式(54)におけるフルオレン環、カルバゾール環又は9,10-ジヒドロフェナントレン誘導体構造に対して、R201とR202の結合位置が対称であることをいう。このとき、主鎖を軸とする180度回転は同一構造とみなす。
Here, the binding of R 201 and R 202 at symmetrical positions means that the binding positions of R 201 and R 202 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.
R221とR222は存在する場合それぞれ独立に、Xが結合しているベンゼン環の炭素原子を基準として、1位、3位、6位、又は8位に存在することが好ましい。この位置にR221及び/又はR222が存在することで、R221及び/又はR222が結合している縮合環と、主鎖上の隣のベンゼン環とが立体障害により捻じれ、重合体の溶媒への溶解性が優れると共に、湿式成膜法で形成し加熱処理された塗膜は溶媒への不溶性に優れる傾向にあり、好ましい。
When present, R 221 and R 222 are each independently preferably present at the 1-, 3-, 6-, or 8-position relative to the carbon atom of the benzene ring to which X is bonded. Due to the presence of R 221 and / or R 222 at this position, the condensed ring to which R 221 and / or R 222 is bonded and the adjacent benzene ring on the main chain are twisted due to steric hindrance, resulting in a polymer is excellent in solubility in a solvent, and a coating film formed by a wet film-forming method and then heat-treated tends to be excellent in solubility in a solvent, which is preferable.
a及びbは0の場合に、分子のエネルギーレベルを高めるため、ねじれ構造が好ましい。そのため、i+jは1以上であることが好ましく、さらに、i及びjは、各々2以下であることが好ましく、iとjの両方が1であることがより好ましい。
When a and b are 0, a twisted structure is preferred because it increases the energy level of the molecule. Therefore, i+j is preferably 1 or more, i and j are each preferably 2 or less, and both i and j are more preferably 1.
(X)
上記式(54)におけるXは、電荷輸送時の安定性が高いことから、-C(R207)(R208)-又は-N(R209)-であることが好ましく、-C(R207)(R208)-であることがより好ましい。 (X)
X in the above formula (54) is preferably -C(R 207 )(R 208 )- or -N(R 209 )- because of its high stability during charge transport, and -C(R 207 )(R 208 )— is more preferred.
上記式(54)におけるXは、電荷輸送時の安定性が高いことから、-C(R207)(R208)-又は-N(R209)-であることが好ましく、-C(R207)(R208)-であることがより好ましい。 (X)
X in the above formula (54) is preferably -C(R 207 )(R 208 )- or -N(R 209 )- because of its high stability during charge transport, and -C(R 207 )(R 208 )— is more preferred.
(好ましい繰り返し単位)
上記式(54)で表される繰り返し単位は、下記式(54-1)~(54-8)のいずれかで示される繰り返し単位であることが特に好ましい。 (preferred repeating unit)
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 (54-8).
上記式(54)で表される繰り返し単位は、下記式(54-1)~(54-8)のいずれかで示される繰り返し単位であることが特に好ましい。 (preferred repeating unit)
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 (54-8).
上記式において、R201及びR202は同一であり、且つ、R201とR202は互いに対称な位置に結合している。
In the formula above, R 201 and R 202 are the same, and R 201 and R 202 are bonded at symmetrical positions.
<式(54)で表される繰り返し単位の主鎖の好ましい例>
上記式(54)中の窒素原子を除いた主鎖構造は特に限定されないが、例えば以下のような構造が好ましい。 <Preferred example of 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, for example, the following structure is preferable.
上記式(54)中の窒素原子を除いた主鎖構造は特に限定されないが、例えば以下のような構造が好ましい。 <Preferred example of 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, for example, the following structure is preferable.
<式(55)で表される繰り返し単位>
<Repeating Unit Represented by Formula (55)>
(式(55)中、
Ar51は前記式(54)におけるAr51と同様であり、
R303及びR306は、それぞれ独立して、置換基を有していてもよいアルキル基であり、
R304及びR305は、それぞれ独立して、置換基を有していてもよいアルキル基、
置換基を有していてもよいアルコキシ基又は置換基を有していてもよいアラルキル基であり、
lは、0又は1であり、
mは、1又は2であり、
nは、0又は1であり、
pは、0又は1であり、
qは、0又は1である。) (In formula (55),
Ar 51 is the same as Ar 51 in the formula (54),
R 303 and R 306 are each independently an optionally substituted alkyl group,
R 304 and R 305 are each independently an optionally substituted alkyl group,
an optionally substituted alkoxy group or an optionally substituted aralkyl group,
l is 0 or 1,
m is 1 or 2,
n is 0 or 1,
p is 0 or 1,
q is 0 or 1; )
Ar51は前記式(54)におけるAr51と同様であり、
R303及びR306は、それぞれ独立して、置換基を有していてもよいアルキル基であり、
R304及びR305は、それぞれ独立して、置換基を有していてもよいアルキル基、
置換基を有していてもよいアルコキシ基又は置換基を有していてもよいアラルキル基であり、
lは、0又は1であり、
mは、1又は2であり、
nは、0又は1であり、
pは、0又は1であり、
qは、0又は1である。) (In formula (55),
Ar 51 is the same as Ar 51 in the formula (54),
R 303 and R 306 are each independently an optionally substituted alkyl group,
R 304 and R 305 are each independently an optionally substituted alkyl group,
an optionally substituted alkoxy group or an optionally substituted aralkyl group,
l is 0 or 1,
m is 1 or 2,
n is 0 or 1,
p is 0 or 1,
q is 0 or 1; )
(R303、R306)
上記式(55)で表される繰り返し単位中のR303及びR306は、それぞれ独立して、置換基を有していてもよいアルキル基である。 ( R303 , R306 )
R 303 and R 306 in the repeating unit represented by formula (55) are each independently an optionally substituted alkyl group.
上記式(55)で表される繰り返し単位中のR303及びR306は、それぞれ独立して、置換基を有していてもよいアルキル基である。 ( R303 , R306 )
R 303 and R 306 in the repeating unit represented by formula (55) are each independently an optionally substituted alkyl group.
アルキル基としては、前記式(54)におけるR201及びR202と同様のものが挙げられ、有していてもよい置換基及び好ましい構造もR201及びR202と同様のものが挙げられる。
Examples of the alkyl group include the same as those for R 201 and R 202 in the formula (54), and the same substituents and preferred structures as those for R 201 and R 202 may be mentioned.
R303が複数ある場合は、複数のR303は同一であっても異なっていてもよく、R306が複数ある場合は、複数のR306は同一であっても異なっていてもよい。
When there are a plurality of R 303 , the plurality of R 303 may be the same or different, and when there is a plurality of R 306 , the plurality of R 306 may be the same or different.
(R304、R305)
上記式(55)で表される繰り返し単位中のR304及びR305は、それぞれ独立して、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基又は置換基を有していてもよいアラルキル基である。好ましくは置換基を有していてもよいアルキル基である。
R304とR304は同一であることが好ましい。 ( R304 , R305 )
R 304 and R 305 in the repeating unit represented by the formula (55) are each independently an optionally substituted alkyl group, an optionally substituted alkoxy group, or a substituted It is an aralkyl group which may have a group. An optionally substituted alkyl group is preferred.
R 304 and R 304 are preferably the same.
上記式(55)で表される繰り返し単位中のR304及びR305は、それぞれ独立して、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基又は置換基を有していてもよいアラルキル基である。好ましくは置換基を有していてもよいアルキル基である。
R304とR304は同一であることが好ましい。 ( R304 , R305 )
R 304 and R 305 in the repeating unit represented by the formula (55) are each independently an optionally substituted alkyl group, an optionally substituted alkoxy group, or a substituted It is an aralkyl group which may have a group. An optionally substituted alkyl group is preferred.
R 304 and R 304 are preferably the same.
該アルキル基は、直鎖、分岐又は環状のアルキル基である。該アルキル基の炭素数は特に限定されないが、重合体の溶解性を向上できる傾向にあるため、1以上が好ましく、また、24以下が好ましく、8以下がより好ましく、6以下がさらに好ましい。
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 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.
該アルキル基としては、具体的には、メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、tert-ブチル基、n-ヘキシル基、n-オクチル基、シクロヘキシル基、ドデシル基等が挙げられる。
Specific examples of the alkyl group 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.
該アルコキシ基は特に限定されず、アルコキシ基(-OR10)のR10で表されるアルキル基は、直鎖、分岐又は環状のいずれの構造であってもよく、重合体の溶解性を向上できる傾向にあるため、炭素数は、1以上が好ましく、また、24以下が好ましく、12以下がより好ましい。
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.
該アルコキシ基としては、具体的には、メトキシ基、エトキシ基、n-プロポキシ基、n-ブトキシ基、ヘキシロキシ基、1-メチルペンチルオキシ基、シクロヘキシルオキシ基等が挙げられる。
Specific examples of the alkoxy group include methoxy group, ethoxy group, n-propoxy group, n-butoxy group, hexyloxy group, 1-methylpentyloxy group, cyclohexyloxy group and the like.
該アラルキル基は特に限定されないが、重合体の溶解性を向上できる傾向にあるため、炭素数5以上が好ましく、また、60以下が好ましく、40以下がより好ましい。
Although the aralkyl group is not particularly limited, it preferably has 5 or more carbon atoms, preferably 60 or less, and more preferably 40 or less, because it tends to improve the solubility of the polymer.
該アラルキル基としては、具体的には、1,1-ジメチル-1-フェニルメチル基、1,1-ジ(n-ブチル)-1-フェニルメチル基、1,1-ジ(n-ヘキシル)-1-フェニルメチル基、1,1-ジ(n-オクチル)-1-フェニルメチル基、フェニルメチル基、フェニルエチル基、3-フェニル-1-プロピル基、4-フェニル-1-n-ブチル基、1-メチル-1-フェニルエチル基、5-フェニル-1-n-プロピル基、6-フェニル-1-n-ヘキシル基、6-ナフチル-1-n-ヘキシル基、7-フェニル-1-n-ヘプチル基、8-フェニル-1-n-オクチル基、4-フェニルシクロヘキシル基などが挙げられる。
Specific examples of the aralkyl group 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.
R304、R305のアルキル基、アルコキシ基及びアラルキル基が有してよい置換基は、前記R207~R209及びR211~R214のアルキル基、アラルキル基及び芳香族炭化水素基の好ましい基として挙げた基が挙げられ、架橋基としては前記架橋基群Tから選択される架橋基が挙げられる。
The substituents that the alkyl group, alkoxy group and aralkyl group of R 304 and R 305 may have are the preferred groups of the alkyl group, aralkyl group and aromatic hydrocarbon group of R 207 to R 209 and R 211 to R 214 Examples of the cross-linking group include cross-linking groups selected from the cross-linking group group T described above.
R304、R305のアルキル基、アルコキシ基及びアラルキル基は、低電圧化の観点からは、置換基を有さないことが最も好ましい。
The alkyl group, alkoxy group and aralkyl group of R 304 and R 305 most preferably have no substituent from the viewpoint of voltage reduction.
式(55)で表される繰返し単位の主鎖構造に架橋基が結合する場合、架橋基は、R304及びR305に結合していることが好ましい。
When a cross-linking group is bonded to the main chain structure of the repeating unit represented by formula (55), the cross-linking group is preferably bonded to R 304 and R 305 .
(l、m及びn)
lは0又は1を表し、nは0又は1を表す。 (l, m and n)
l represents 0 or 1; n represents 0 or 1;
lは0又は1を表し、nは0又は1を表す。 (l, m and n)
l represents 0 or 1; n represents 0 or 1;
l及びnは各々独立であり、l+nは1以上が好ましく、1又は2がより好ましく、2がさらに好ましい。l+nが上記範囲であることで、該重合体の溶解性を高くし、該重合体を含有する本発明の組成物からの析出も抑制できる傾向にある。
l and n are each independent, and l+n is preferably 1 or more, more preferably 1 or 2, and still more preferably 2. When l+n is within the above range, the solubility of the polymer tends to be high and precipitation from the composition of the present invention containing the polymer can be suppressed.
mは1又は2を表し、本発明の組成物を用いて製造される有機電界発光素子を低電圧で駆動でき、正孔注入能、輸送能、耐久性も向上する傾向にあることから、1であることが好ましい。
m represents 1 or 2, and the organic electroluminescent device manufactured using the composition of the present invention can be driven at a low voltage, and the hole injection ability, transport ability, and durability tend to be improved. is preferably
(p及びq)
pは0又は1を表し、qは0又は1を表す。lが2以上の場合、複数のpは同じであっても異なってもよく、nが2以上の場合、複数のqは同じであっても異なってもよい。l=n=1の場合、pとqは同時に0となることはない。pとqが同時に0とならないことで、該重合体の溶解性を高くし、該重合体を含有する本発明の組成物からの析出も抑制できる傾向にある。また、前記a及びbと同様の理由により、p+qが1以上であると主鎖の芳香環が立体障害により捻じれ、重合体の溶媒への溶解性が優れると共に、湿式成膜法で形成し加熱処理された塗膜は溶媒への不溶性に優れる傾向にある。したがって、p+qが1以上であると、この塗膜上へ湿式成膜法で別の有機層(例えば発光層)を形成する場合には、有機溶媒を含む該別の有機層形成用組成物への重合体の溶出が抑えられる。 (p and q)
p represents 0 or 1; q represents 0 or 1; When l is 2 or more, multiple p may be the same or different, and when n is 2 or more, multiple q may be the same or different. When l=n=1, p and q cannot be 0 at the same time. When p and q are not 0 at the same time, the solubility of the polymer is increased, and precipitation from the composition of the present invention containing the polymer tends to be suppressed. In addition, for the same reason as in a and b above, when p+q 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. Heat-treated coatings tend to be excellent in solvent insolubility. Therefore, when p + q is 1 or more, when forming another organic layer (for example, a light-emitting layer) on this coating film by a wet film-forming method, a composition for forming another organic layer containing an organic solvent elution of the polymer is suppressed.
pは0又は1を表し、qは0又は1を表す。lが2以上の場合、複数のpは同じであっても異なってもよく、nが2以上の場合、複数のqは同じであっても異なってもよい。l=n=1の場合、pとqは同時に0となることはない。pとqが同時に0とならないことで、該重合体の溶解性を高くし、該重合体を含有する本発明の組成物からの析出も抑制できる傾向にある。また、前記a及びbと同様の理由により、p+qが1以上であると主鎖の芳香環が立体障害により捻じれ、重合体の溶媒への溶解性が優れると共に、湿式成膜法で形成し加熱処理された塗膜は溶媒への不溶性に優れる傾向にある。したがって、p+qが1以上であると、この塗膜上へ湿式成膜法で別の有機層(例えば発光層)を形成する場合には、有機溶媒を含む該別の有機層形成用組成物への重合体の溶出が抑えられる。 (p and q)
p represents 0 or 1; q represents 0 or 1; When l is 2 or more, multiple p may be the same or different, and when n is 2 or more, multiple q may be the same or different. When l=n=1, p and q cannot be 0 at the same time. When p and q are not 0 at the same time, the solubility of the polymer is increased, and precipitation from the composition of the present invention containing the polymer tends to be suppressed. In addition, for the same reason as in a and b above, when p+q 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. Heat-treated coatings tend to be excellent in solvent insolubility. Therefore, when p + q is 1 or more, when forming another organic layer (for example, a light-emitting layer) on this coating film by a wet film-forming method, a composition for forming another organic layer containing an organic solvent elution of the polymer is suppressed.
<式(55)で表される繰り返し単位の主鎖の具体例>
式(55)中の窒素原子を除いた主鎖構造は特に限定されないが、例えば以下のような構造が挙げられる。 <Specific example of 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.
式(55)中の窒素原子を除いた主鎖構造は特に限定されないが、例えば以下のような構造が挙げられる。 <Specific example of 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.
<式(56)で表される繰り返し単位>
<Repeating Unit Represented by Formula (56)>
(式(56)中、
Ar51は前記式(54)におけるAr51と同様であり、
Ar41は、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は前記2価の芳香族炭化水素基及び前記2価の芳香族複素環基からなる群から選択される少なくとも1つの基が直接若しくは連結基を介して複数個連結した2価の基であり、
R441及びR442は、それぞれ独立して、置換基を有していてもよいアルキル基であり、
tは、1又は2であり、
uは、0又は1であり、
r及びsは、それぞれ独立して、0~4の整数である。) (In formula (56),
Ar 51 is the same as Ar 51 in the formula (54),
Ar 41 is an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or the aforementioned divalent aromatic hydrocarbon group and at least one group selected from the group consisting of the divalent aromatic heterocyclic groups is a divalent group in which a plurality of groups are linked directly or via a linking group,
R 441 and R 442 are each independently an optionally substituted alkyl group,
t is 1 or 2;
u is 0 or 1,
r and s are each independently an integer of 0-4. )
Ar51は前記式(54)におけるAr51と同様であり、
Ar41は、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は前記2価の芳香族炭化水素基及び前記2価の芳香族複素環基からなる群から選択される少なくとも1つの基が直接若しくは連結基を介して複数個連結した2価の基であり、
R441及びR442は、それぞれ独立して、置換基を有していてもよいアルキル基であり、
tは、1又は2であり、
uは、0又は1であり、
r及びsは、それぞれ独立して、0~4の整数である。) (In formula (56),
Ar 51 is the same as Ar 51 in the formula (54),
Ar 41 is an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or the aforementioned divalent aromatic hydrocarbon group and at least one group selected from the group consisting of the divalent aromatic heterocyclic groups is a divalent group in which a plurality of groups are linked directly or via a linking group,
R 441 and R 442 are each independently an optionally substituted alkyl group,
t is 1 or 2;
u is 0 or 1,
r and s are each independently an integer of 0-4. )
(R441、R442)
上記式(56)で表される繰り返し単位中のR441、R442は、それぞれ独立して、置換基を有していてもよいアルキル基である。 ( R441 , R442 )
R 441 and R 442 in the repeating unit represented by formula (56) are each independently an optionally substituted alkyl group.
上記式(56)で表される繰り返し単位中のR441、R442は、それぞれ独立して、置換基を有していてもよいアルキル基である。 ( R441 , R442 )
R 441 and R 442 in the repeating unit represented by formula (56) are each independently an optionally substituted alkyl group.
該アルキル基は、直鎖、分岐又は環状のアルキル基である。アルキル基の炭素数は特に限定されないが、重合体の溶解性を維持するために、炭素数1以上が好ましく、また、10以下が好ましく、8以下がより好ましく、6以下がより好ましい。該アルキル基はメチル基又はヘキシル基であることがさらに好ましい。
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.
R441及びR442が上記式(56)で表される繰り返し単位中に複数ある場合は、複数のR441及びR442は同一であっても異なっていてもよい。
When a plurality of R 441 and R 442 are present in the repeating unit represented by formula (56) above, the plurality of R 441 and R 442 may be the same or different.
(r、s、t及びu)
式(56)で表される繰り返し単位中において、r及びsはそれぞれ独立して、0~4の整数である。tが2以上の場合、複数のrは同じであっても異なってもよく、uが2以上の場合、複数のsは同じであっても異なってもよい。r+sは1以上であることが好ましく、さらに、r及びsは、各々2以下であることが好ましい。r+sが1以上であると、前記式(54)におけるa及びbと同様の理由により、有機電界発光素子の駆動寿命はさらに長くなると考えられる。 (r, s, t and u)
In the repeating unit represented by formula (56), r and s are each independently an integer of 0-4. When t is 2 or more, multiple r may be the same or different, and when u is 2 or more, multiple s may be the same or different. r+s is preferably 1 or more, and r and s are each preferably 2 or less. When r+s is 1 or more, the drive life of the organic electroluminescence device is considered to be longer for the same reason as a and b in the formula (54).
式(56)で表される繰り返し単位中において、r及びsはそれぞれ独立して、0~4の整数である。tが2以上の場合、複数のrは同じであっても異なってもよく、uが2以上の場合、複数のsは同じであっても異なってもよい。r+sは1以上であることが好ましく、さらに、r及びsは、各々2以下であることが好ましい。r+sが1以上であると、前記式(54)におけるa及びbと同様の理由により、有機電界発光素子の駆動寿命はさらに長くなると考えられる。 (r, s, t and u)
In the repeating unit represented by formula (56), r and s are each independently an integer of 0-4. When t is 2 or more, multiple r may be the same or different, and when u is 2 or more, multiple s may be the same or different. r+s is preferably 1 or more, and r and s are each preferably 2 or less. When r+s is 1 or more, the drive life of the organic electroluminescence device is considered to be longer for the same reason as a and b in the formula (54).
上記式(56)で表される繰り返し単位中において、tは1又は2であり、uは0又は1である。tは1が好ましく、uは1が好ましい。
In the repeating unit represented by formula (56) above, t is 1 or 2, and u is 0 or 1. t is preferably 1 and u is preferably 1.
(Ar41)
Ar41は、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は前記2価の芳香族炭化水素基及び前記2価の芳香族複素環基からなる群から選択される少なくとも1つの基が直接若しくは連結基を介して複数個連結した2価の基である。 ( Ar41 )
Ar 41 is an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or the aforementioned divalent aromatic hydrocarbon group and a divalent group in which at least one group selected from the group consisting of the above divalent aromatic heterocyclic groups is linked directly or via a linking group.
Ar41は、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は前記2価の芳香族炭化水素基及び前記2価の芳香族複素環基からなる群から選択される少なくとも1つの基が直接若しくは連結基を介して複数個連結した2価の基である。 ( Ar41 )
Ar 41 is an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or the aforementioned divalent aromatic hydrocarbon group and a divalent group in which at least one group selected from the group consisting of the above divalent aromatic heterocyclic groups is linked directly or via a linking group.
Ar41における芳香族炭化水素基及び芳香族炭化水素基としては、前記式(50)におけるAr52と同様の基が挙げられる。また、芳香族炭化水素基及び芳香族炭化水素基が有していてもよい置換基は、前記置換基群Zから選ばれる基が好ましく、さらに有していてよい置換基も前記置換基群Zと同様であることが好ましい。
The aromatic hydrocarbon group and aromatic hydrocarbon group for Ar 41 include the same groups as for Ar 52 in the formula (50). Further, the aromatic hydrocarbon group and the substituent which the aromatic hydrocarbon group may have are preferably groups selected from the above substituent group Z, and the substituent which may be further included in the above substituent group Z is preferably the same as
<式(57)で表される繰り返し単位>
<Repeating Unit Represented by Formula (57)>
(式(57)中、
Ar51は前記式(54)におけるAr51と同様であり、
R517~R519は、各々独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアラルキル基、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表し、
f、g、hは、各々独立して、0~4の整数を表し、
eは0~3の整数を表し、
ただし、gが1以上の場合、eは1以上である。) (In formula (57),
Ar 51 is the same as Ar 51 in the formula (54),
R 517 to R 519 each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aralkyl group, or a substituent represents an aromatic hydrocarbon group which may have or an aromatic heterocyclic group which may have a substituent,
f, g, and h each independently represent an integer of 0 to 4,
e represents an integer of 0 to 3,
However, when g is 1 or more, e is 1 or more. )
Ar51は前記式(54)におけるAr51と同様であり、
R517~R519は、各々独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアラルキル基、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表し、
f、g、hは、各々独立して、0~4の整数を表し、
eは0~3の整数を表し、
ただし、gが1以上の場合、eは1以上である。) (In formula (57),
Ar 51 is the same as Ar 51 in the formula (54),
R 517 to R 519 each independently represent an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aralkyl group, or a substituent represents an aromatic hydrocarbon group which may have or an aromatic heterocyclic group which may have a substituent,
f, g, and h each independently represent an integer of 0 to 4,
e represents an integer of 0 to 3,
However, when g is 1 or more, e is 1 or more. )
(R517~R519)
R517~R519における芳香族炭化水素基、芳香族複素環基は、各々独立に、前記Ar51で挙げたものと同様の基である、また、これらの基が有していてもよい置換基は、前記置換基群Zと同様の基から選択される基又は架橋基が好ましく、架橋基としては前記架橋基群Tから選択される架橋基が好ましい。 (R 517 to R 519 )
The aromatic hydrocarbon group and aromatic heterocyclic group in R 517 to R 519 are each independently the same groups as those listed for Ar 51 above, and the substituents these groups may have The group is preferably a group or a cross-linking group selected from the same groups as in the substituent group Z, and the cross-linking group is preferably a cross-linking group selected from the cross-linking group T.
R517~R519における芳香族炭化水素基、芳香族複素環基は、各々独立に、前記Ar51で挙げたものと同様の基である、また、これらの基が有していてもよい置換基は、前記置換基群Zと同様の基から選択される基又は架橋基が好ましく、架橋基としては前記架橋基群Tから選択される架橋基が好ましい。 (R 517 to R 519 )
The aromatic hydrocarbon group and aromatic heterocyclic group in R 517 to R 519 are each independently the same groups as those listed for Ar 51 above, and the substituents these groups may have The group is preferably a group or a cross-linking group selected from the same groups as in the substituent group Z, and the cross-linking group is preferably a cross-linking group selected from the cross-linking group T.
R517~R519におけるアルキル基及びアラルキル基は、前記R207で挙げたものと同様の基が好ましく、さらに有していてもよい置換基は前記R207と同様の基が好ましい。
The alkyl group and aralkyl group for R 517 to R 519 are preferably the same groups as those mentioned for R 207 above, and the substituents which may be further included are preferably the same groups as those for R 207 above.
R517~R519におけるアルコキシ基は、前記置換基群Zで挙げたアルコキシ基が好ましく、さらに有していてもよい置換基は前記置換基群Zから選択される基が好ましい。
The alkoxy groups in R 517 to R 519 are preferably the alkoxy groups listed in the above substituent group Z, and the substituents which may be further included are preferably groups selected from the above substituent group Z.
(f、g、h)
f、g、hは、各々独立して、0~4の整数を表す。
eが2以上の場合、複数のgは同じであっても異なってもよい。
f+g+hは1以上であることが好ましい。
f+hは1以上であることが好ましく、
f+hは1以上、且つ、f、g及びhは2以下であることがより好ましく、
f+hは1以上、且つ、f、hは1以下であることがさらに好ましく、
f、hはいずれも1であることが最も好ましい。 (f, g, h)
f, g, and h each independently represent an integer of 0-4.
When e is 2 or more, multiple g's may be the same or different.
f+g+h is preferably 1 or more.
f + h is preferably 1 or more,
f + h is 1 or more, and f, g and h are more preferably 2 or less,
It is more preferable that f+h is 1 or more, and f and h are 1 or less,
Most preferably, both f and h are 1.
f、g、hは、各々独立して、0~4の整数を表す。
eが2以上の場合、複数のgは同じであっても異なってもよい。
f+g+hは1以上であることが好ましい。
f+hは1以上であることが好ましく、
f+hは1以上、且つ、f、g及びhは2以下であることがより好ましく、
f+hは1以上、且つ、f、hは1以下であることがさらに好ましく、
f、hはいずれも1であることが最も好ましい。 (f, g, h)
f, g, and h each independently represent an integer of 0-4.
When e is 2 or more, multiple g's may be the same or different.
f+g+h is preferably 1 or more.
f + h is preferably 1 or more,
f + h is 1 or more, and f, g and h are more preferably 2 or less,
It is more preferable that f+h is 1 or more, and f and h are 1 or less,
Most preferably, both f and h are 1.
f及びhがいずれも1である場合、R517とR519は互いに対称な位置に結合していることが好ましい。
また、R517とR519とは同一であることが好ましく、 When f and h are both 1, R 517 and R 519 are preferably bonded at symmetrical positions.
In addition, R 517 and R 519 are preferably the same,
また、R517とR519とは同一であることが好ましく、 When f and h are both 1, R 517 and R 519 are preferably bonded at symmetrical positions.
In addition, R 517 and R 519 are preferably the same,
gは2であることがより好ましい。
gが2である場合、2つのR518は互いにパラ位に結合していることが最も好ましく、
gが2である場合、2つのR518は同一であることが最も好ましい。 More preferably, g is two.
when g is 2, the two R 518 are most preferably attached to each other in the para position;
When g is 2, the two R 518 are most preferably identical.
gが2である場合、2つのR518は互いにパラ位に結合していることが最も好ましく、
gが2である場合、2つのR518は同一であることが最も好ましい。 More preferably, g is two.
when g is 2, the two R 518 are most preferably attached to each other in the para position;
When g is 2, the two R 518 are most preferably identical.
ここで、R517とR519が互いに対称な位置に結合するとは、下記の結合位置のことを言う。ただし、表記上、主鎖を軸とする180度回転は同一構造とみなす。
Here, the binding positions of R 517 and R 519 that 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.
また、前記式(57)で表される繰り返し単位は、下記式(58)で表される繰り返し単位であることが好ましい。
Further, the repeating unit represented by the formula (57) is preferably a repeating unit represented by the following formula (58).
前記式(58)で表される繰り返し単位の場合、g=0または2であることが好ましい。g=2の場合、結合位置は2位と5位である。g=0の場合、すなわちR518による立体障害が無い場合、及びg=2であり結合位置は2位と5位である場合、すなわち立体障害が2つのR518が結合するベンゼン環の対角位置となる場合は、R517とR519とが互いに対称な位置に結合することが可能である。
In the case of the repeating unit represented by formula (58), g=0 or 2 is preferred. When g=2, the binding positions are the 2nd and 5th positions. When g = 0, i.e., when there is no steric hindrance by R 518 , and when g = 2 and the binding positions are 2-position and 5-position, i.e., when R 518 with two steric hindrances binds to the diagonal of the benzene ring In the case of positions, R 517 and R 519 can be bonded at symmetrical positions.
また、前記式(58)で表される繰り返し単位は、e=3である下記式(59)で示される繰り返し単位であることがさらに好ましい。
Further, the repeating unit represented by the formula (58) is more preferably a repeating unit represented by the following formula (59) where e=3.
前記式(59)で表される繰り返し単位の場合、g=0または2であることが好ましい。g=2の場合、結合位置は2位と5位である。g=0の場合、すなわちR518による立体障害が無い場合、及びg=2であり結合位置は2位と5位である場合、すなわち、立体障害が2つのR518が結合するベンゼン環の対角位置となる場合は、R517とR519とが互いに対称な位置に結合することが可能である。
In the case of the repeating unit represented by formula (59), g=0 or 2 is preferred. When g=2, the binding positions are the 2nd and 5th positions. When g = 0, i.e., when there is no steric hindrance by R 518 , and when g = 2 and the binding positions are 2-position and 5-position, i. In the case of angular positions, R 517 and R 519 can be combined at symmetrical positions.
<式(57)で表される繰り返し単位の主鎖の具体例>
式(57)で表される繰り返し単位の主鎖構造は特に限定されないが、例えば以下のような構造が挙げられる。 <Specific example of main chain of repeating unit represented by formula (57)>
The main chain structure of the repeating unit represented by formula (57) is not particularly limited, and examples thereof include the following structures.
式(57)で表される繰り返し単位の主鎖構造は特に限定されないが、例えば以下のような構造が挙げられる。 <Specific example of main chain of repeating unit represented by formula (57)>
The main chain structure of the repeating unit represented by formula (57) is not particularly limited, and examples thereof include the following structures.
<式(60)で表される繰り返し単位>
<Repeating Unit Represented by Formula (60)>
(式(60)中、
Ar51は前記式(50)におけるAr51と同様であり、
n60は1~5の整数を表す。) (In formula (60),
Ar 51 is the same as Ar 51 in the formula (50),
n 60 represents an integer of 1-5. )
Ar51は前記式(50)におけるAr51と同様であり、
n60は1~5の整数を表す。) (In formula (60),
Ar 51 is the same as Ar 51 in the formula (50),
n 60 represents an integer of 1-5. )
(n60)
n60は1~5の整数を表し、好ましくは1~4の整数であり、さらに好ましくは1~3の整数である。 ( n60 )
n60 represents an integer of 1-5, preferably an integer of 1-4, more preferably an integer of 1-3.
n60は1~5の整数を表し、好ましくは1~4の整数であり、さらに好ましくは1~3の整数である。 ( n60 )
n60 represents an integer of 1-5, preferably an integer of 1-4, more preferably an integer of 1-3.
(末端基)
本明細書において、末端基とは、高分子化合物の重合終了時に用いるエンドキャップ剤によって形成された、高分子化合物の末端部の構造のことを指す。本発明の組成物において、式(1)で表される繰り返し単位を含む高分子化合物の末端基は炭化水素基であることが好ましい。炭化水素基としては、電荷輸送性の観点から、炭素数1以上60以下の炭化水素基が好ましく、炭素数1以上40以下の炭化水素基がより好ましく、炭素数1以上30以下の炭化水素基がさらに好ましい。 (terminal group)
As used herein, the terminal group refers to the structure of the terminal portion of the polymer compound formed by the end capping agent used at the end of polymerization of the polymer compound. In the composition of the present invention, the terminal group of the polymer compound containing the repeating unit represented by formula (1) is preferably a hydrocarbon group. From the viewpoint of charge transportability, 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.
本明細書において、末端基とは、高分子化合物の重合終了時に用いるエンドキャップ剤によって形成された、高分子化合物の末端部の構造のことを指す。本発明の組成物において、式(1)で表される繰り返し単位を含む高分子化合物の末端基は炭化水素基であることが好ましい。炭化水素基としては、電荷輸送性の観点から、炭素数1以上60以下の炭化水素基が好ましく、炭素数1以上40以下の炭化水素基がより好ましく、炭素数1以上30以下の炭化水素基がさらに好ましい。 (terminal group)
As used herein, the terminal group refers to the structure of the terminal portion of the polymer compound formed by the end capping agent used at the end of polymerization of the polymer compound. In the composition of the present invention, the terminal group of the polymer compound containing the repeating unit represented by formula (1) is preferably a hydrocarbon group. From the viewpoint of charge transportability, 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.
該炭化水素基としては、例えば、
メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、tert-ブチル基、n-ヘキシル基、シクロヘキシル基、ドデシル基等の、炭素数が通常1以上であり、好ましくは4以上であり、通常24以下であり、好ましくは12以下である、直鎖、分岐、又は環状のアルキル基;
ビニル基等の、炭素数が通常2以上、24以下であり、好ましくは12以下である、直鎖、分岐、又は環状のアルケニル基;
エチニル基等の、炭素数が通常2以上、24以下であり、好ましくは12以下である、直鎖又は分岐のアルキニル基;
フェニル基、ナフチル基等の、炭素数が通常6以上、36以下であり、好ましくは24以下である芳香族炭化水素基;
前記架橋基群Tの中の炭化水素基である架橋基;好ましくは前記式(X1)~前記式(X4)で表される架橋基;が挙げられる。 Examples of the hydrocarbon group include
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;
A linear, branched, or cyclic alkenyl group having usually 2 or more and 24 or less, preferably 12 or less carbon atoms, such as a vinyl group;
A linear or branched alkynyl group having usually 2 or more and 24 or less, preferably 12 or less carbon atoms, such as an ethynyl group;
an aromatic hydrocarbon group having usually 6 or more and 36 or less carbon atoms, preferably 24 or less, such as a phenyl group or a naphthyl group;
The cross-linking group which is a hydrocarbon group in the cross-linking group T; preferably the cross-linking groups represented by the above formulas (X1) to (X4);
メチル基、エチル基、n-プロピル基、i-プロピル基、n-ブチル基、i-ブチル基、sec-ブチル基、tert-ブチル基、n-ヘキシル基、シクロヘキシル基、ドデシル基等の、炭素数が通常1以上であり、好ましくは4以上であり、通常24以下であり、好ましくは12以下である、直鎖、分岐、又は環状のアルキル基;
ビニル基等の、炭素数が通常2以上、24以下であり、好ましくは12以下である、直鎖、分岐、又は環状のアルケニル基;
エチニル基等の、炭素数が通常2以上、24以下であり、好ましくは12以下である、直鎖又は分岐のアルキニル基;
フェニル基、ナフチル基等の、炭素数が通常6以上、36以下であり、好ましくは24以下である芳香族炭化水素基;
前記架橋基群Tの中の炭化水素基である架橋基;好ましくは前記式(X1)~前記式(X4)で表される架橋基;が挙げられる。 Examples of the hydrocarbon group include
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;
A linear, branched, or cyclic alkenyl group having usually 2 or more and 24 or less, preferably 12 or less carbon atoms, such as a vinyl group;
A linear or branched alkynyl group having usually 2 or more and 24 or less, preferably 12 or less carbon atoms, such as an ethynyl group;
an aromatic hydrocarbon group having usually 6 or more and 36 or less carbon atoms, preferably 24 or less, such as a phenyl group or a naphthyl group;
The cross-linking group which is a hydrocarbon group in the cross-linking group T; preferably the cross-linking groups represented by the above formulas (X1) to (X4);
これら炭化水素基はさらに置換基を有していてもよく、さらに有していてもよい置換基はアルキル基又は芳香族炭化水素基が好ましい。さらに有していてもよい置換基が複数ある場合は、互いに結合して環を形成していてもよい。これら炭化水素基が架橋基以外の基である場合、置換基はさらに前記架橋基群Tから選択される架橋基を有してもよい。
These hydrocarbon groups may further have a substituent, and the substituent that may further have is preferably an alkyl group or an aromatic hydrocarbon group. Further, when there are a plurality of substituents which may be possessed, they may be combined with each other to form a ring. When these hydrocarbon groups are groups other than cross-linking groups, the substituent may further have a cross-linking group selected from the above-described cross-linking group T.
末端基は、好ましくは、電荷輸送性及び耐久性の観点から、アルキル基、芳香族炭化水素基、又は前記架橋基群Tの中の炭化水素基である架橋基であり、より好ましくは芳香族炭化水素基であり、末端基が架橋基でない場合はさらに前記架橋基群Tから選択される架橋基を有することも好ましい。
From the viewpoint of charge transportability and durability, the terminal group is preferably an alkyl group, an aromatic hydrocarbon group, or a cross-linking group that is a hydrocarbon group in the cross-linking group group T, more preferably an aromatic When it is a hydrocarbon group and the terminal group is not a cross-linking group, it is also preferable to further have a cross-linking group selected from the above-mentioned cross-linking group group T.
[高分子化合物の分子量]
以下、本発明の組成物に含まれる高分子化合物の分子量について記す。 [Molecular Weight of Polymer Compound]
The molecular weights of the polymer compounds contained in the composition of the present invention are described below.
以下、本発明の組成物に含まれる高分子化合物の分子量について記す。 [Molecular Weight of Polymer Compound]
The molecular weights of the polymer compounds contained in the composition of the present invention are described below.
上述のフッ素を含むアリールアミン高分子化合物の重量平均分子量(Mw)は、通常1,000,000以下、好ましくは500,000以下、より好ましくは100,000以下、さらに好ましくは70,000以下、特に好ましくは50,000以下である。また、当該重量平均分子量は、通常5,000以上、好ましくは10,000以上、さらに好ましくは12,000以上、特に好ましくは15,000以上である。
The weight-average molecular weight (Mw) of the fluorine-containing arylamine polymer compound is usually 1,000,000 or less, preferably 500,000 or less, more preferably 100,000 or less, and still more preferably 70,000 or less. Particularly preferably, it is 50,000 or less. Moreover, the weight average molecular weight is usually 5,000 or more, preferably 10,000 or more, more preferably 12,000 or more, and particularly preferably 15,000 or more.
上述のフッ素を含むアリールアミン高分子化合物の重量平均分子量が上記上限値以下であることで、溶媒に対する溶解性が得られ、成膜性に優れる傾向にある。また、該高分子化合物の重量平均分子量が上記下限値以上であることで、高分子化合物のガラス転移温度、融点及び気化温度の低下が抑制され、耐熱性が向上する場合がある。加えて、架橋反応後の塗膜の有機溶媒に対する不溶性が十分である場合がある。
When the weight-average molecular weight of the fluorine-containing arylamine polymer compound is equal to or less than the above upper limit, solubility in a solvent is obtained, and film-forming properties tend to be excellent. Further, when the weight average molecular weight of the polymer compound is at least the above lower limit, the decrease in the glass transition temperature, melting point and vaporization temperature of the polymer compound may be suppressed and the heat resistance may be improved. In addition, in some cases, the coating film after the cross-linking reaction is sufficiently insoluble in organic solvents.
また、上述のフッ素を含むアリールアミン高分子化合物における数平均分子量(Mn)は、通常750,000以下、好ましくは250,000以下、より好ましくは100,000以下、特に好ましくは50,000以下である。また、当該数平均分子量は、通常2,000以上、好ましくは4,000以上、より好ましくは6,000以上、さらに好ましくは8,000以上である。
The number average molecular weight (Mn) of the fluorine-containing arylamine polymer compound is generally 750,000 or less, preferably 250,000 or less, more preferably 100,000 or less, and particularly preferably 50,000 or less. be. Moreover, 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.
さらに、上述のフッ素を含むアリールアミン高分子化合物における分散度(Mw/Mn)は、好ましくは3.5以下、さらに好ましくは2.5以下、特に好ましくは2.0以下である。なお、分散度は値が小さい程よいため、下限値は理想的には1である。当該高分子化合物の分散度が、上記上限値以下であると、精製が容易で、また溶媒に対する溶解性や電荷輸送能が良好である。
Further, the polydispersity (Mw/Mn) of the fluorine-containing arylamine polymer compound is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. Note that the lower limit value is ideally 1 because the smaller the value of the degree of dispersion, the better. When the degree of dispersion of the polymer compound is equal to or less than the above upper limit, purification is easy, and solubility in a solvent and charge transportability are good.
通常、高分子化合物の重量平均分子量及び数平均分子量はSEC(サイズ排除クロマトグラフィー)測定により決定される。SEC測定では高分子量成分ほど溶出時間が短く、低分子量成分ほど溶出時間が長くなるが、分子量既知のポリスチレン(標準試料)の溶出時間から算出した校正曲線を用いて、サンプルの溶出時間を分子量に換算することによって、重量平均分子量及び数平均分子量が算出される。
Usually, the weight average molecular weight and number average molecular weight of a polymer compound are 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.
(式(1)で表される繰り返し単位の含有量)
高分子化合物において、式(1)で表される繰り返し単位の含有量は特に制限されないが、式(1)で表される繰り返し単位は高分子化合物の全繰り返し単位100モル%中に通常10モル%以上含まれ、30モル%以上含まれることが好ましく、40モル%以上含まれることがより好ましく、50モル%以上含まれることがさらに好ましい。 (Content of repeating unit represented by formula (1))
In the polymer compound, the content of the repeating unit represented by formula (1) is not particularly limited, but the repeating unit represented by formula (1) is usually 10 mol per 100 mol% of all repeating units in the polymer compound. % or more, preferably 30 mol % or more, more preferably 40 mol % or more, even more preferably 50 mol % or more.
高分子化合物において、式(1)で表される繰り返し単位の含有量は特に制限されないが、式(1)で表される繰り返し単位は高分子化合物の全繰り返し単位100モル%中に通常10モル%以上含まれ、30モル%以上含まれることが好ましく、40モル%以上含まれることがより好ましく、50モル%以上含まれることがさらに好ましい。 (Content of repeating unit represented by formula (1))
In the polymer compound, the content of the repeating unit represented by formula (1) is not particularly limited, but the repeating unit represented by formula (1) is usually 10 mol per 100 mol% of all repeating units in the polymer compound. % or more, preferably 30 mol % or more, more preferably 40 mol % or more, even more preferably 50 mol % or more.
高分子化合物は、繰り返し単位が、式(1)で表される繰り返し単位のみから構成されていてもよいが、有機電界発光素子とした場合の諸性能をバランスさせる目的から、式(1)で表される繰り返し単位とは別の繰り返し単位を有していてもよい。その場合、重合体中の式(1)で表される繰り返し単位の含有量は、通常、99モル%以下、好ましくは95モル%以下である。
In the polymer compound, the repeating unit may be composed only of repeating units represented by formula (1). It may have a repeating unit other than the repeating unit shown. In that case, the content of the repeating unit represented by formula (1) in the polymer is usually 99 mol % or less, preferably 95 mol % or less.
[具体例]
前記の高分子化合物の具体例を以下に示すが、前記の高分子化合物はこれらに限定されるものではない。なお、化学式中の数字は繰返し単位のモル比を表す。 [Concrete example]
Specific examples of the polymer compound are shown below, but the polymer compound is not limited to these. The numbers in the chemical formulas represent the molar ratio of repeating units.
前記の高分子化合物の具体例を以下に示すが、前記の高分子化合物はこれらに限定されるものではない。なお、化学式中の数字は繰返し単位のモル比を表す。 [Concrete example]
Specific examples of the polymer compound are shown below, but the polymer compound is not limited to these. The numbers in the chemical formulas represent the molar ratio of repeating units.
これらの高分子化合物は、ランダム共重合体、交互共重合体、ブロック共重合体、又はグラフト共重合体等のいずれでもよく、単量体の配列順序には限定されない。
These polymer compounds may be random copolymers, alternating copolymers, block copolymers, graft copolymers, or the like, and the sequence of the monomers is not limited.
<重合体の製造方法>
本発明の組成物が含有する高分子化合物の製造方法は特には制限されず任意である。例えば、Suzuki反応による重合方法、Grignard反応による重合方法、Yamamoto反応による重合方法、Ullmann反応による重合方法、Buchwald-Hartwig反応による重合方法等などが挙げられる。また、国際公開第2019/177175号、国際公開第2020/171190号、国際公開第2021/125011号に記載の重合体の製造方法と同様の製造方法にて製造できる。 <Method for producing polymer>
The method for producing the polymer compound contained in the composition of the present invention 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. Moreover, it can be manufactured by the manufacturing method similar to the manufacturing method of the polymer as described in WO2019/177175, WO2020/171190, and WO2021/125011.
本発明の組成物が含有する高分子化合物の製造方法は特には制限されず任意である。例えば、Suzuki反応による重合方法、Grignard反応による重合方法、Yamamoto反応による重合方法、Ullmann反応による重合方法、Buchwald-Hartwig反応による重合方法等などが挙げられる。また、国際公開第2019/177175号、国際公開第2020/171190号、国際公開第2021/125011号に記載の重合体の製造方法と同様の製造方法にて製造できる。 <Method for producing polymer>
The method for producing the polymer compound contained in the composition of the present invention 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. Moreover, it can be manufactured by the manufacturing method similar to the manufacturing method of the polymer as described in WO2019/177175, WO2020/171190, and WO2021/125011.
Ullmann反応による重合方法及びBuchwald-Hartwig反応による重合方法の場合、例えば、下記式(2a)で表されるジハロゲン化アリール(ZはI、Br、Cl、F等のハロゲン原子を表す。)と下記式(2b)で表される1級アミノアリールとを反応させることにより、前記式(54)で表される繰り返し単位を含む重合体が合成される。
In the case of the polymerization method by the Ullmann reaction and the polymerization method by the Buchwald-Hartwig reaction, for example, an aryl dihalide represented by the following formula (2a) (Z represents a halogen atom such as I, Br, Cl, F) and the following A polymer containing a repeating unit represented by the formula (54) is synthesized by reacting it with a primary aminoaryl represented by the formula (2b).
(上記反応式中、Ar51、R201、R202、X、a~dは前記式(54)における定義と同義である。)
(In the above reaction scheme, Ar 51 , R 201 , R 202 , X, and a to d have the same definitions as in the above formula (54).)
また、Ullmann反応による重合方法及びBuchwald-Hartwig反応による重合方法の場合、例えば、式(3a)で表されるジハロゲン化アリール(ZはI、Br、Cl、F等のハロゲン原子を表す。)と式(3b)で表される1級アミノアリールとを反応させることにより、式(55)で表される繰り返し単位を含む重合体が合成される。
Further, in the case of the polymerization method by the Ullmann reaction and the polymerization method by the Buchwald-Hartwig reaction, for example, an aryl dihalide represented by the formula (3a) (Z represents a halogen atom such as I, Br, Cl, F) and A polymer containing a repeating unit represented by formula (55) is synthesized by reacting it with a primary aminoaryl represented by formula (3b).
(上記反応式中、Ar51、R303~R306、n、m、l、p、qは前記式(55)における定義と同義である。)
(In the above reaction scheme, Ar 51 , R 303 to R 306 , n, m, l, p, and q have the same definitions as in the above formula (55).)
なお、上記の重合方法において、通常、N-アリール結合を形成する反応は、例えば炭酸カリウム、tert-ブトキシナトリウム、トリエチルアミン等の塩基存在下で行う。また、例えば銅やパラジウム錯体等の遷移金属触媒存在下で行うこともできる。
In the polymerization method described above, 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.
<本発明のフッ素を含むアリールアミン高分子化合物の含有量>
本発明の組成物の固形分成分の組成比率において電荷輸送層に注入障壁を低減する観点から、本発明のフッ素を含むアリールアミン高分子化合物の含有量は10質量%以上が好ましく、25質量%以上がより好ましく、30質量%以上がさらに好ましい。一方、電荷輸送層内の電荷輸送性を維持する観点から、本発明の組成物中の本発明のフッ素を含むアリールアミン高分子化合物の含有量は、組成物の固形分成分の組成比率において99質量%以下であることが好ましく、90質量%以下であることがより好ましく、80質量%以下であることがさらに好ましい。 <Content of fluorine-containing arylamine polymer compound of the present invention>
From the viewpoint of reducing the injection barrier in the charge transport layer in the composition ratio of the solid components of the composition of the present invention, the content of the fluorine-containing arylamine polymer compound of the present invention is preferably 10% by mass or more, and preferably 25% by mass. The above is more preferable, and 30% by mass or more is even more preferable. On the other hand, from the viewpoint of maintaining the charge transport property in the charge transport layer, the content of the fluorine-containing arylamine polymer compound of the present invention in the composition of the present invention is 99% in terms of the composition ratio of the solid components of the composition. It is preferably 90% by mass or less, more preferably 80% by mass or less.
本発明の組成物の固形分成分の組成比率において電荷輸送層に注入障壁を低減する観点から、本発明のフッ素を含むアリールアミン高分子化合物の含有量は10質量%以上が好ましく、25質量%以上がより好ましく、30質量%以上がさらに好ましい。一方、電荷輸送層内の電荷輸送性を維持する観点から、本発明の組成物中の本発明のフッ素を含むアリールアミン高分子化合物の含有量は、組成物の固形分成分の組成比率において99質量%以下であることが好ましく、90質量%以下であることがより好ましく、80質量%以下であることがさらに好ましい。 <Content of fluorine-containing arylamine polymer compound of the present invention>
From the viewpoint of reducing the injection barrier in the charge transport layer in the composition ratio of the solid components of the composition of the present invention, the content of the fluorine-containing arylamine polymer compound of the present invention is preferably 10% by mass or more, and preferably 25% by mass. The above is more preferable, and 30% by mass or more is even more preferable. On the other hand, from the viewpoint of maintaining the charge transport property in the charge transport layer, the content of the fluorine-containing arylamine polymer compound of the present invention in the composition of the present invention is 99% in terms of the composition ratio of the solid components of the composition. It is preferably 90% by mass or less, more preferably 80% by mass or less.
[電子受容性化合物]
陽極から正孔注入層又は正孔輸送層への正孔注入性を向上させるため、若しくは正孔注入層又は正孔輸送層内での電荷輸送性を向上させるため、正孔注入層又は正孔輸送層に含まれる電荷輸送材料はカチオンラジカル部位を含むことが好ましい。電荷輸送材料をカチオンラジカル化させるため、正孔注入層又は正孔輸送層を形成する場合に電子受容性化合物を用いる。電子受容性化合物の母骨格としては、後述するイオン価1のアニオンであるテトラアリールホウ酸イオンと対カチオンからなるイオン化合物が高い安定性を有するため好ましい。 [Electron-accepting compound]
In order to improve the hole injection property from the anode to the hole injection layer or the hole transport layer, or to improve the charge transport property in the hole injection layer or the hole transport layer, a hole injection layer or a hole The charge transport material contained in the transport layer preferably contains cation radical sites. An electron-accepting compound is used when forming a hole-injecting layer or a hole-transporting layer in order to convert the charge-transporting material into cation radicals. As the base skeleton of the electron-accepting compound, an ionic compound composed of a tetraarylborate ion, which is an anion having an ion valence of 1, and a counter cation, which will be described later, is preferable because of its high stability.
陽極から正孔注入層又は正孔輸送層への正孔注入性を向上させるため、若しくは正孔注入層又は正孔輸送層内での電荷輸送性を向上させるため、正孔注入層又は正孔輸送層に含まれる電荷輸送材料はカチオンラジカル部位を含むことが好ましい。電荷輸送材料をカチオンラジカル化させるため、正孔注入層又は正孔輸送層を形成する場合に電子受容性化合物を用いる。電子受容性化合物の母骨格としては、後述するイオン価1のアニオンであるテトラアリールホウ酸イオンと対カチオンからなるイオン化合物が高い安定性を有するため好ましい。 [Electron-accepting compound]
In order to improve the hole injection property from the anode to the hole injection layer or the hole transport layer, or to improve the charge transport property in the hole injection layer or the hole transport layer, a hole injection layer or a hole The charge transport material contained in the transport layer preferably contains cation radical sites. An electron-accepting compound is used when forming a hole-injecting layer or a hole-transporting layer in order to convert the charge-transporting material into cation radicals. As the base skeleton of the electron-accepting compound, an ionic compound composed of a tetraarylborate ion, which is an anion having an ion valence of 1, and a counter cation, which will be described later, is preferable because of its high stability.
(電荷輸送材料のカチオンラジカル化)
電荷輸送材料のカチオンラジカル化は次のように行われる。
電荷輸送材料として本発明のフッ素を含むアリールアミン高分子化合物を用いた場合、ジアリールヨードニウムを対カチオンとするテトラアリールホウ酸塩を電子受容性化合物として用いると、正孔注入層又は正孔輸送層形成時に、下記式のように対カチオンはジアリールヨードニウムからアリールアミンカチオンに変わり得る。 (Cation radicalization of charge transport material)
Cation radicalization of the charge transport material is carried out as follows.
When the fluorine-containing arylamine polymer compound of the present invention is used as the charge-transporting material, a hole-injecting layer or a hole-transporting layer can be formed by using a tetraarylborate having a diaryliodonium as a counter cation as an electron-accepting compound. Upon formation, the counter cation can change from a diaryliodonium to an arylamine cation, as in the formula below.
電荷輸送材料のカチオンラジカル化は次のように行われる。
電荷輸送材料として本発明のフッ素を含むアリールアミン高分子化合物を用いた場合、ジアリールヨードニウムを対カチオンとするテトラアリールホウ酸塩を電子受容性化合物として用いると、正孔注入層又は正孔輸送層形成時に、下記式のように対カチオンはジアリールヨードニウムからアリールアミンカチオンに変わり得る。 (Cation radicalization of charge transport material)
Cation radicalization of the charge transport material is carried out as follows.
When the fluorine-containing arylamine polymer compound of the present invention is used as the charge-transporting material, a hole-injecting layer or a hole-transporting layer can be formed by using a tetraarylborate having a diaryliodonium as a counter cation as an electron-accepting compound. Upon formation, the counter cation can change from a diaryliodonium to an arylamine cation, as in the formula below.
(例えば、Ar、Ar1’~Ar4’は各々独立に、置換基を有してもよい芳香族炭化水素基、置換基を有していてもよい芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素環基及び置換基を有していてもよい芳香族複素環基から選択される構造が複数連結した1価の基である。)
(For example, Ar, Ar 1′ to Ar 4′ each independently represent an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, or a substituent It is a monovalent group in which a plurality of structures selected from an optionally substituted aromatic hydrocarbon ring group and an optionally substituted aromatic heterocyclic group are linked.)
上記反応で生成したアリールアミンカチオンは電子を受容し得る半占軌道(SOMO)を有しているため、アリールアミンイオン対カチオンとするテトラアリールホウ酸塩は、電子受容性化合物である。
Since the arylamine cation produced in the above reaction has a semi-occupied orbital (SOMO) that can accept electrons, the tetraarylborate used as the arylamine ion counter cation is an electron-accepting compound.
本発明においては、この電荷輸送材料のカチオンとアニオンであるテトラアリールホウ酸イオンからなる化合物を、電荷輸送性イオン化合物と称する。詳細は後述する。
In the present invention, a compound composed of tetraarylborate ions, which are cations and anions of the charge-transporting material, is referred to as a charge-transporting ionic compound. Details will be described later.
後述するように、本発明の有機電界発光素子の正孔注入層及び/又は正孔輸送層は、本発明の組成物を湿式成膜して得ることが好ましく、本発明の組成物は、後述するテトラアリールホウ酸イオン構造を有する電子受容性化合物及び後述する電荷輸送材料を有機溶剤に溶解又は分散させる工程を経て得られた組成物であることが好ましい。そして、本発明の有機電界発光素子の電荷輸送層中では、後述する本発明におけるテトラアリールホウ酸イオン構造をアニオンとし、本発明の電荷輸送材料のカチオンを対カチオンとする電荷輸送性イオン化合物を含むことが好ましい。
As will be described later, the hole injection layer and/or the hole transport layer of the organic electroluminescent device of the present invention is preferably obtained by wet film formation of the composition of the present invention. It is preferably a composition obtained through a step of dissolving or dispersing an electron-accepting compound having a tetraarylborate ion structure and a charge-transporting material described later in an organic solvent. In the charge transport layer of the organic electroluminescent device of the present invention, a charge-transporting ionic compound having the tetraarylborate ion structure of the present invention described later as an anion and the cation of the charge transport material of the present invention as a counter cation is used. preferably included.
(架橋反応物)
本発明の組成物は、架橋基を有する高分子化合物と架橋基を有する電子受容性化合物を含む。そのため、本発明の組成物を用いて湿式成膜法にて形成された有機層は、架橋基を有する高分子化合物と架橋基を有する電子受容性化合物の架橋反応物を含む。さらに、後述するように本発明の電子受容性化合物は、後述するテトラアリールホウ酸イオンと対カチオンからなるイオン化合物が好ましく、該テトラアリールホウ酸イオンが架橋基を有することが好ましい。そのため、該有機層には、以下の架橋構造を含む架橋反応物が含まれうる。
・高分子化合物と電子受容性化合物の架橋構造
・高分子化合物の架橋基同士の架橋構造
・電子受容性化合物同士の架橋構造
・電子受容性化合物とテトラアリールホウ酸イオンの架橋構造
・テトラアリールホウ酸イオン同士が架橋した化合物
・高分子化合物とテトラアリールホウ酸イオンの架橋構造 (Crosslinking reaction product)
The composition of the present invention contains a polymer compound having a cross-linking group and an electron-accepting compound having a cross-linking group. Therefore, the organic layer formed by the wet film-forming method using the composition of the present invention contains a cross-linked reaction product of a polymer compound having a cross-linking group and an electron-accepting compound having a cross-linking group. Furthermore, as will be described later, the electron-accepting compound of the present invention is preferably an ionic compound consisting of a tetraarylborate ion and a counter cation, and the tetraarylborate ion preferably has a cross-linking group. Therefore, the organic layer can contain a cross-linking reactant containing the following cross-linked structure.
・Crosslinked structure between polymer compound and electron-accepting compound ・Crosslinked structure between crosslinkable groups of polymer compound ・Crosslinked structure between electron-accepting compounds ・Crosslinked structure between electron-accepting compound and tetraarylborate ion ・Tetraarylborate Compounds in which acid ions are crosslinked ・Crosslinked structure of polymer compounds and tetraarylborate ions
本発明の組成物は、架橋基を有する高分子化合物と架橋基を有する電子受容性化合物を含む。そのため、本発明の組成物を用いて湿式成膜法にて形成された有機層は、架橋基を有する高分子化合物と架橋基を有する電子受容性化合物の架橋反応物を含む。さらに、後述するように本発明の電子受容性化合物は、後述するテトラアリールホウ酸イオンと対カチオンからなるイオン化合物が好ましく、該テトラアリールホウ酸イオンが架橋基を有することが好ましい。そのため、該有機層には、以下の架橋構造を含む架橋反応物が含まれうる。
・高分子化合物と電子受容性化合物の架橋構造
・高分子化合物の架橋基同士の架橋構造
・電子受容性化合物同士の架橋構造
・電子受容性化合物とテトラアリールホウ酸イオンの架橋構造
・テトラアリールホウ酸イオン同士が架橋した化合物
・高分子化合物とテトラアリールホウ酸イオンの架橋構造 (Crosslinking reaction product)
The composition of the present invention contains a polymer compound having a cross-linking group and an electron-accepting compound having a cross-linking group. Therefore, the organic layer formed by the wet film-forming method using the composition of the present invention contains a cross-linked reaction product of a polymer compound having a cross-linking group and an electron-accepting compound having a cross-linking group. Furthermore, as will be described later, the electron-accepting compound of the present invention is preferably an ionic compound consisting of a tetraarylborate ion and a counter cation, and the tetraarylborate ion preferably has a cross-linking group. Therefore, the organic layer can contain a cross-linking reactant containing the following cross-linked structure.
・Crosslinked structure between polymer compound and electron-accepting compound ・Crosslinked structure between crosslinkable groups of polymer compound ・Crosslinked structure between electron-accepting compounds ・Crosslinked structure between electron-accepting compound and tetraarylborate ion ・Tetraarylborate Compounds in which acid ions are crosslinked ・Crosslinked structure of polymer compounds and tetraarylborate ions
なお、該テトラアリールホウ酸イオンとは該電子受容性化合物を構成するアニオン構造部位のことである。前記架橋構造において、テトラアリールホウ酸イオンとは、高分子化合物のカチオンラジカルとイオン結合しているテトラアリールホウ酸イオンである。詳細は後述する。
The tetraarylborate ion is an anion structural site that constitutes the electron-accepting compound. In the crosslinked structure, the tetraarylborate ion is a tetraarylborate ion ionically bonded to the cation radical of the polymer compound. Details will be described later.
ここで、“本発明におけるテトラアリールホウ酸イオン”とは、後述するテトラアリールホウ酸イオンと対カチオンとからなるイオン化合物である電子受容性化合物として存在する場合、及び後述するテトラアリールホウ酸イオンと電荷輸送材料のカチオンとからなる電荷輸送性イオン化合物として存在する場合を含む。
Here, the “tetraarylborate ion in the present invention” refers to the case where it exists as an electron-accepting compound that is an ionic compound consisting of a tetraarylborate ion and a counter cation described later, and a tetraarylborate ion described later. and the cation of the charge-transporting material as a charge-transporting ionic compound.
架橋反応する2つの架橋基は、架橋反応可能であれば同じ架橋基であっても異なる架橋基であってもよい。
The two cross-linking groups that undergo a cross-linking reaction may be the same cross-linking group or different cross-linking groups as long as they are cross-linkable.
[電子受容性化合物]
テトラアリールホウ酸イオンと対カチオンからなるイオン化合物である電子受容性化合物は、下記式(81)で表わされる非配位性アニオンである対アニオンと対カチオンからなる電子受容性イオン化合物であって、架橋基を有する。下記式(81)で表わされる非配位性アニオンはアニオンとして後述する式(83)をテトラアリールホウ酸イオンとして有することが好ましい。尚、本発明で用いる電子受容性化合物は電子受容性イオン化合物と称することがある。 [Electron-accepting compound]
The electron-accepting compound, which is an ionic compound composed of a tetraarylborate ion and a counter cation, is an electron-accepting ionic compound composed of a counter anion, which is a non-coordinating anion represented by the following formula (81), and a counter cation, , has a bridging group. The non-coordinating anion represented by formula (81) below preferably has formula (83), which will be described later, as a tetraarylborate ion. Incidentally, the electron-accepting compound used in the present invention may be called an electron-accepting ion compound.
テトラアリールホウ酸イオンと対カチオンからなるイオン化合物である電子受容性化合物は、下記式(81)で表わされる非配位性アニオンである対アニオンと対カチオンからなる電子受容性イオン化合物であって、架橋基を有する。下記式(81)で表わされる非配位性アニオンはアニオンとして後述する式(83)をテトラアリールホウ酸イオンとして有することが好ましい。尚、本発明で用いる電子受容性化合物は電子受容性イオン化合物と称することがある。 [Electron-accepting compound]
The electron-accepting compound, which is an ionic compound composed of a tetraarylborate ion and a counter cation, is an electron-accepting ionic compound composed of a counter anion, which is a non-coordinating anion represented by the following formula (81), and a counter cation, , has a bridging group. The non-coordinating anion represented by formula (81) below preferably has formula (83), which will be described later, as a tetraarylborate ion. Incidentally, the electron-accepting compound used in the present invention may be called an electron-accepting ion compound.
(式(81)中、
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) (In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. )
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) (In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. )
前記式(81)で表される電子受容性化合物は架橋基を有し、架橋基は2以上であることが好ましい。架橋基は、前記式(81)で表される電子受容性化合物のアニオン部すなわち、テトラアリールホウ酸イオンである後述の式(82)で表される化合物に有することが好ましい。
The electron-accepting compound represented by formula (81) has a cross-linking group, and the number of cross-linking groups is preferably two or more. The bridging group is preferably provided in the anion portion of the electron-accepting compound represented by the formula (81), that is, the compound represented by the below-described formula (82), which is a tetraarylborate ion.
[テトラアリールホウ酸イオン]
上述の電子受容性化合物の母骨格としては、ホウ素原子に、4つの、置換基を有していてもよい芳香族炭化水素環又は置換基を有していてもよい芳香族複素環が置換した、イオン価1のアニオンであるテトラアリールホウ酸イオンと対カチオンからなるイオン化合物が、高い安定性を有するため好ましい。 [Tetraarylborate ion]
As the backbone of the above-described electron-accepting compound, the boron atom is substituted with four aromatic hydrocarbon rings optionally having substituents or aromatic heterocycles optionally having substituents , an ionic compound composed of a tetraarylborate ion, which is an anion with an ionic valence of 1, and a counter cation is preferable because of its high stability.
上述の電子受容性化合物の母骨格としては、ホウ素原子に、4つの、置換基を有していてもよい芳香族炭化水素環又は置換基を有していてもよい芳香族複素環が置換した、イオン価1のアニオンであるテトラアリールホウ酸イオンと対カチオンからなるイオン化合物が、高い安定性を有するため好ましい。 [Tetraarylborate ion]
As the backbone of the above-described electron-accepting compound, the boron atom is substituted with four aromatic hydrocarbon rings optionally having substituents or aromatic heterocycles optionally having substituents , an ionic compound composed of a tetraarylborate ion, which is an anion with an ionic valence of 1, and a counter cation is preferable because of its high stability.
テトラアリールホウ酸イオンは、下記式(82)で表される、前記式(81)のアニオン体である。
A tetraarylborate ion is an anion of the above formula (81) represented by the following formula (82).
(式(82)中、R81~R84はそれぞれ式(81)のR81~R84と同じである。
Ph1~Ph4はそれぞれ式(81)のPh1~Ph4と同じで4つのベンゼン環を指す符号である。) (In formula (82), R 81 to R 84 are the same as R 81 to R 84 in formula (81).
Ph 1 to Ph 4 are the same as Ph 1 to Ph 4 in formula (81), and are symbols indicating four benzene rings. )
Ph1~Ph4はそれぞれ式(81)のPh1~Ph4と同じで4つのベンゼン環を指す符号である。) (In formula (82), R 81 to R 84 are the same as R 81 to R 84 in formula (81).
Ph 1 to Ph 4 are the same as Ph 1 to Ph 4 in formula (81), and are symbols indicating four benzene rings. )
R81~R84に用いられる芳香族炭化水素基の炭素数は、6~50が好ましい。芳香族炭化水素環構造としては、単環又は2~6縮合環、及びこれらが2~8個連結した構造が好ましい。芳香族炭化水素基としては、具体的には、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環、ビフェニル構造、テルフェニル構造、又はクアテルフェニル構造の単独の1価の基、及び、これらが2~8個連結した1価の基が挙げられる。
The aromatic hydrocarbon group used for R 81 to R 84 preferably has 6 to 50 carbon atoms. As the aromatic hydrocarbon ring structure, a single ring, 2 to 6 condensed rings, and a structure in which 2 to 8 of these are linked are preferable. Specific examples of aromatic hydrocarbon groups 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 Single monovalent groups having a ring, biphenyl structure, terphenyl structure, or quaterphenyl structure, and monovalent groups in which 2 to 8 of these are linked are included.
R81~R84に用いられる芳香族複素環基の炭素数は3~50が好ましい。芳香族複素環構造としては、単環又は2~6縮合環、及びこれらが2~8個連結した構造が好ましい。芳香族複素環基としては、具体的には、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シンノリン環、キノキサリン環、フェナントリジン環、ペリミジン環、キナゾリン環、キナゾリノン環、又はアズレン環の単独の1価の基、及び、これらが2~8個連結した1価の基が挙げられる。さらに、ここで言う芳香族複素環基としては、これら単独の構造を少なくとも1つ含んでいればよく、連結する構造としては芳香族炭化水素環構造を含んでもよい。芳香族炭化水素環構造を含む場合は、前記芳香族複素環及び芳香族炭化水素環を合わせて、2~8個連結した構造で有り得る。ここで、芳香族炭化水素環としては、前記R81~R84に用いられる芳香族炭化水素環の単独の構造を用いることが出来る。
The aromatic heterocyclic group used for R 81 to R 84 preferably has 3 to 50 carbon atoms. As the aromatic heterocyclic ring structure, a single ring, 2 to 6 condensed rings, and a structure in which 2 to 8 of these are linked are preferable. Specific examples of aromatic heterocyclic groups include 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, pyridazine ring, pyrimidine ring, a single monovalent group of triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, perimidine ring, quinazoline ring, quinazolinone ring, or azulene ring, and 2 to 8 of these linked together A monovalent group is mentioned. Furthermore, the aromatic heterocyclic group referred to herein may contain at least one of these independent structures, and the connecting structure may contain an aromatic hydrocarbon ring structure. When it contains an aromatic hydrocarbon ring structure, it may have a structure in which 2 to 8 of the above aromatic heterocycles and aromatic hydrocarbon rings are combined. Here, as the aromatic hydrocarbon ring, a single structure of the aromatic hydrocarbon ring used for R 81 to R 84 can be used.
中でも、安定性、耐熱性に優れることから、ベンゼン環、ナフタレン環、フルオレン環、ピリジン環もしくはカルバゾール環の1価の基、又はこれらの基が2~5個連結したビフェニル基等の1価の基がより好ましい。特に好ましくはベンゼン環の1価の基又はベンゼン環が2~5個連結した基が好ましく、具体的にはフェニル基、ビフェニル基、ターフェニル基等である。
Among them, since they are excellent in stability and heat resistance, monovalent groups such as benzene, naphthalene, fluorene, pyridine or carbazole rings, or biphenyl groups in which 2 to 5 of these groups are linked. groups are more preferred. A monovalent group of a benzene ring or a group in which 2 to 5 benzene rings are linked is particularly preferred, and specific examples thereof include a phenyl group, a biphenyl group and a terphenyl group.
置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される構造が複数連結した1価の基に含まれる芳香族炭化水素基および芳香族複素環基の数は2以上であり、8以下が好ましく、4以下がさらに好ましく、3以下がより好ましい。ただし、芳香族炭化水素基がビフェニル基、ターフェニル基、クアテルフェニル基の場合は、それぞれフェニル基が2個連結した構造、3個連結した構造、4個連結した構造であるとみなす。
An aromatic hydrocarbon group contained in a monovalent group in which a plurality of structures selected from an optionally substituted aromatic hydrocarbon group and an optionally substituted aromatic heterocyclic group are linked and the number of aromatic heterocyclic groups is 2 or more, preferably 8 or less, more preferably 4 or less, and more preferably 3 or less. However, when the aromatic hydrocarbon group is a biphenyl group, a terphenyl group, or a quaterphenyl group, it is regarded as a structure in which two, three, or four phenyl groups are linked, respectively.
R81~R84が有してもよい置換基としては、前記置換基群Z又は架橋基群Tから選択される基が好ましい。
As the substituent that R 81 to R 84 may have, a group selected from the substituent group Z or the bridging group group T is preferable.
R81~R84は、アニオンの安定性が増し、カチオンを安定させる効果が向上する点から、各々独立して、フッ素原子又はフッ素置換されたアルキル基が好ましい。また、フッ素原子又はフッ素置換されたアルキル基は、2つ以上含むことが好ましく、3つ以上含むことがより好ましく、4つ含むことが最も好ましい。
R 81 to R 84 are each independently preferably a fluorine atom or a fluorine-substituted alkyl group from the viewpoint of increasing the stability of the anion and improving the effect of stabilizing the cation. Moreover, it preferably contains two or more fluorine atoms or fluorine-substituted alkyl groups, more preferably three or more, and most preferably four.
R81~R84に用いられるフッ素置換されたアルキル基としては、炭素数1~12の直鎖又は分岐のアルキル基であってフッ素原子が置換している基が好ましく、パーフルオロアルキル基がより好ましく、炭素数1~5の直鎖又は分岐のパーフルオロアルキル基がさらに好ましく、炭素数1~3の直鎖又は分岐のパーフルオロアルキル基が特に好ましく、パーフルオロメチル基が最も好ましい。この理由は、架橋基を有する電子受容性化合物の架橋反応物を含む電荷注入層や、その上層に積層される塗布膜が安定になるためである。フッ素置換されたアルキル基は、ホウ素原子のパラ位に結合することが好ましい。
The fluorine-substituted alkyl group used for R 81 to R 84 is preferably a linear or branched alkyl group having 1 to 12 carbon atoms and is substituted with a fluorine atom, more preferably a perfluoroalkyl group. A linear or branched perfluoroalkyl group having 1 to 5 carbon atoms is more preferable, a linear or branched perfluoroalkyl group having 1 to 3 carbon atoms is particularly preferable, and a perfluoromethyl group is most preferable. The reason for this is that the charge injection layer containing the cross-linking reaction product of the electron-accepting compound having a cross-linking group and the coating film laminated thereon are stabilized. The fluorine-substituted alkyl group is preferably attached to the para-position of the boron atom.
テトラアリールホウ酸イオンは、アニオンの安定性がさらに増し、カチオンを安定させる効果がさらに向上する点で、前記式(82)における、*-Ph1-(R81)5、*-Ph2-(R82)5、*-Ph3-(R83)5、*-Ph4-(R84)5、(*は式(82)のホウ素Bとの結合を表す)の内、少なくとも1つが4つのフッ素原子を有する下記式(84)で表される基であることが好ましく、アニオンの安定性が向上する点で、少なくとも2つが同一の式(84)で表される基であることがさらに好ましく、アニオンの安定性がさらに向上する点で、少なくとも3つが同一の下記式(84)で表される基であることが最も好ましい。
The tetraarylborate ion further increases the stability of the anion and further improves the effect of stabilizing the cation. At least one of (R 82 ) 5 , *-Ph 3 -(R 83 ) 5 , *-Ph 4 -(R 84 ) 5 (* represents a bond with boron B in formula (82)) It is preferably a group represented by the following formula (84) having four fluorine atoms, and in terms of improving the stability of the anion, it is preferable that at least two of them are groups represented by the same formula (84). More preferably, at least three of them are the same group represented by the following formula (84) from the viewpoint of further improving the stability of the anion.
(式(84)中、*は式(82)のホウ素Bとの結合を表し、F4はフッ素原子が4個置換していることを表し、
R85は、置換基を有してもよい芳香族炭化水素基、又は架橋基を表す。) (In formula (84), * represents a bond with boron B in formula (82), F4 represents that four fluorine atoms are substituted,
R85 represents an optionally substituted aromatic hydrocarbon group or a bridging group. )
R85は、置換基を有してもよい芳香族炭化水素基、又は架橋基を表す。) (In formula (84), * represents a bond with boron B in formula (82), F4 represents that four fluorine atoms are substituted,
R85 represents an optionally substituted aromatic hydrocarbon group or a bridging group. )
R85に用いることのできる芳香族炭化水素基の炭素数は3~40が好ましい。芳香族炭化水素環構造としては、単環又は2~6縮合環、及びこれらが2~5個連結した構造が好ましい。具体的には、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環、ビフェニル構造、テルフェニル構造、又はクアテルフェニル構造の単独の1価の基、及び、これらが2~6連結した1価の基が挙げられる。芳香族炭化水素基が有してよい架橋基は前記架橋基群Tから選択される架橋基が好ましい。
The aromatic hydrocarbon group that can be used for R 85 preferably has 3 to 40 carbon atoms. As the aromatic hydrocarbon ring structure, a single ring, 2 to 6 condensed rings, and a structure in which 2 to 5 of these are linked are preferable. Specifically, 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 structure, terphenyl structure , or a single monovalent group having a quaterphenyl structure, and a monovalent group in which 2 to 6 of these are linked. The cross-linking group which the aromatic hydrocarbon group may have is preferably a cross-linking group selected from the above-described cross-linking group T.
R85に用いることのできる架橋基は、前記架橋基群Tから選択される架橋基が好ましい。
前記芳香族炭化水素基及び前記芳香族炭化水素基が有してよい架橋基ではない置換基としては前記置換基群Zから選択される基が好ましく、中でも芳香族炭化水素基が安定性の観点から好ましく、アルキル基が溶解性の観点から好ましい。 The cross-linking group that can be used for R 85 is preferably a cross-linking group selected from the above-described cross-linking group T.
The aromatic hydrocarbon group and the substituent which is not a cross-linking group which the aromatic hydrocarbon group may have are preferably groups selected from the substituent group Z, among which the aromatic hydrocarbon group is preferred from the viewpoint of stability. from the viewpoint of solubility, and an alkyl group is preferred from the viewpoint of solubility.
前記芳香族炭化水素基及び前記芳香族炭化水素基が有してよい架橋基ではない置換基としては前記置換基群Zから選択される基が好ましく、中でも芳香族炭化水素基が安定性の観点から好ましく、アルキル基が溶解性の観点から好ましい。 The cross-linking group that can be used for R 85 is preferably a cross-linking group selected from the above-described cross-linking group T.
The aromatic hydrocarbon group and the substituent which is not a cross-linking group which the aromatic hydrocarbon group may have are preferably groups selected from the substituent group Z, among which the aromatic hydrocarbon group is preferred from the viewpoint of stability. from the viewpoint of solubility, and an alkyl group is preferred from the viewpoint of solubility.
<テトラアリールホウ酸イオンを含むイオン化合物>
テトラアリールホウ酸イオンは、テトラアリールホウ酸イオンを含む電子受容性イオン化合物として用いられる。 <Ionic compound containing tetraarylborate ion>
A tetraarylborate ion is used as an electron-accepting ion compound containing a tetraarylborate ion.
テトラアリールホウ酸イオンは、テトラアリールホウ酸イオンを含む電子受容性イオン化合物として用いられる。 <Ionic compound containing tetraarylborate ion>
A tetraarylborate ion is used as an electron-accepting ion compound containing a tetraarylborate ion.
(対カチオン)
対カチオンとしては、ヨードニウムカチオン、スルホニウムカチオン、カルボカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオンまたは遷移金属を有するフェロセニウムカチオンが好ましく、ヨードニウムカチオン、スルホニウムカチオン、カルボカチオン、アンモニウムカチオンがより好ましく、ヨードニウムカチオンが特に好ましい。 (counter cation)
The counter cation is preferably an iodonium cation, a sulfonium cation, a carbocation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a ferrocenium cation having a transition metal. Ammonium cations are more preferred, and iodonium cations are particularly preferred.
対カチオンとしては、ヨードニウムカチオン、スルホニウムカチオン、カルボカチオン、オキソニウムカチオン、アンモニウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオンまたは遷移金属を有するフェロセニウムカチオンが好ましく、ヨードニウムカチオン、スルホニウムカチオン、カルボカチオン、アンモニウムカチオンがより好ましく、ヨードニウムカチオンが特に好ましい。 (counter cation)
The counter cation is preferably an iodonium cation, a sulfonium cation, a carbocation, an oxonium cation, an ammonium cation, a phosphonium cation, a cycloheptyltrienyl cation or a ferrocenium cation having a transition metal. Ammonium cations are more preferred, and iodonium cations are particularly preferred.
ヨードニウムカチオンとして好ましくは、下記式(83)で表される構造であり、さらに好ましい構造も同様である。
The structure represented by the following formula (83) is preferable as the iodonium cation, and the more preferable structure is the same.
ヨードニウムカチオンとして具体的には、ジフェニルヨードニウムカチオン、ビス(4-tert-ブチルフェニル)ヨードニウムカチオン、4-tert-ブトキシフェニルフェニルヨードニウムカチオン、4-メトキシフェニルフェニルヨードニウムカチオン、4-イソプロピルフェニル-4-メチルフェニルヨードニウムカチオン等が好ましい。
Specific examples of iodonium cations include diphenyliodonium cation, bis(4-tert-butylphenyl)iodonium cation, 4-tert-butoxyphenylphenyliodonium cation, 4-methoxyphenylphenyliodonium cation, 4-isopropylphenyl-4-methyl Phenyliodonium cations and the like are preferred.
スルホニウムカチオンとして具体的には、トリフェニルスルホニウムカチオン、4-ヒドロキシフェニルジフェニルスルホニウムカチオン、4-シクロヘキシルフェニルジフェニルスルホニウムカチオン、4-メタンスルホニルフェニルジフェニルスルホニウムカチオン、(4-tert-ブトキシフェニル)ジフェニルスルホニウムカチオン、ビス(4-tert-ブトキシフェニル)フェニルスルホニウムカチオン、4-シクロヘキシルスルホニルフェニルジフェニルスルホニウムカチオン等が好ましい。
Specific examples of sulfonium cations include triphenylsulfonium cation, 4-hydroxyphenyldiphenylsulfonium cation, 4-cyclohexylphenyldiphenylsulfonium cation, 4-methanesulfonylphenyldiphenylsulfonium cation, (4-tert-butoxyphenyl)diphenylsulfonium cation, Bis(4-tert-butoxyphenyl)phenylsulfonium cation, 4-cyclohexylsulfonylphenyldiphenylsulfonium cation and the like are preferred.
カルボカチオンとして具体的には、トリフェニルカルボカチオン、トリ(メチルフェニル)カルボカチオン、トリ(ジメチルフェニル)カルボカチオンなどの三置換カルボカチオン等が好ましい。
Specifically, trisubstituted carbocations such as triphenyl carbocation, tri(methylphenyl) carbocation, and tri(dimethylphenyl) carbocation are preferred as carbocations.
アンモニウムカチオンとして具体的には、トリメチルアンモニウムカチオン、トリエチルアンモニウムカチオン、トリプロピルアンモニウムカチオン、トリブチルアンモニウムカチオン、トリ(n-ブチル)アンモニウムカチオンなどのトリアルキルアンモニウムカチオン;N,N-ジエチルアニリニウムカチオン、N,N-2,4,6-ペンタメチルアニリニウムカチオンなどのN,N-ジアルキルアニリニウムカチオン;ジ(イソプロピル)アンモニウムカチオン、ジシクロヘキシルアンモニウムカチオンなどのジアルキルアンモニウムカチオン等が好ましい。
Specific examples of ammonium cations include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, tri(n-butyl)ammonium cation; N,N-diethylanilinium cation, N , N-2,4,6-pentamethylanilinium cation; and dialkylammonium cations such as di(isopropyl)ammonium cation and dicyclohexylammonium cation.
ホスホニウムカチオンとして具体的には、テトラフェニルホスホニウムカチオン、テトラキス(メチルフェニル)ホスホニウムカチオン、テトラキス(ジメチルフェニル)ホスホニウムカチオンなどのテトラアリールホスホニウムカチオン;テトラブチルホスホニウムカチオン、テトラプロピルホスホニウムカチオンなどのテトラアルキルホスホニウムカチオン等が好ましい。
Specific examples of phosphonium cations include tetraarylphosphonium cations such as tetraphenylphosphonium cations, tetrakis(methylphenyl)phosphonium cations and tetrakis(dimethylphenyl)phosphonium cations; tetraalkylphosphonium cations such as tetrabutylphosphonium cations and tetrapropylphosphonium cations. etc. are preferred.
これらの中では、化合物の膜安定性の点でヨードニウムカチオン、カルボカチオン、スルホニウムカチオンが好ましく、ヨードニウムカチオンがより好ましい。
Among these, iodonium cations, carbocations, and sulfonium cations are preferred, and iodonium cations are more preferred, in terms of film stability of the compound.
(X+:ヨードニウムカチオン)
前記式(81)における対カチオンであるX+は下記式(83)の構造を有するヨードニウムカチオンであることが好ましい。 (X + : iodonium cation)
The counter cation X + in formula (81) is preferably an iodonium cation having the structure of formula (83) below.
前記式(81)における対カチオンであるX+は下記式(83)の構造を有するヨードニウムカチオンであることが好ましい。 (X + : iodonium cation)
The counter cation X + in formula (81) is preferably an iodonium cation having the structure of formula (83) below.
式(83)中、Ar81、Ar82は各々独立に、置換基を有していてもよい炭素数6~12の芳香族炭化水素基である。
In formula (83), Ar 81 and Ar 82 are each independently an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms.
芳香族炭化水素基としては炭素数6~18の芳香族炭化水素基が好ましく、さらに好ましくは炭素数6~12であり、最も好ましくはフェニル基である。有してよい置換基は前記置換基群Zから選択される基であり、その中で最も好ましくはアルキル基である。
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and most preferably a phenyl group. The substituent which may be present is a group selected from the above-described substituent group Z, most preferably an alkyl group.
芳香族炭化水素基として好ましくは、フェニル基、ビフェニル基、ターフェニル基、クアテルフェニル基、ナフチル基、フェナントレニル基、トリフェニレン基、ナフチルフェニル基等が挙げられ、フェニル基が化合物の安定性から最も好ましい。
Preferable aromatic hydrocarbon groups include phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthrenyl, triphenylene, and naphthylphenyl groups. preferable.
(分子量)
本発明の電子受容性化合物の分子量は、通常900以上、好ましくは1000以上、更に好ましくは1200以上、また、通常10000以下、好ましくは5000以下、更に好ましくは3000以下の範囲である。分子量が小さすぎると、正電荷及び負電荷の非局在化が不十分なため、電子受容能が低下するおそれがあり、分子量が大きすぎると、電荷輸送の妨げとなるおそれがある。 (molecular weight)
The molecular weight of the electron-accepting compound of the present invention is usually 900 or more, preferably 1000 or more, more preferably 1200 or more, and usually 10000 or less, preferably 5000 or less, more preferably 3000 or less. If the molecular weight is too small, the delocalization of the positive and negative charges is insufficient, which may reduce the electron-accepting ability. If the molecular weight is too large, the charge transport may be hindered.
本発明の電子受容性化合物の分子量は、通常900以上、好ましくは1000以上、更に好ましくは1200以上、また、通常10000以下、好ましくは5000以下、更に好ましくは3000以下の範囲である。分子量が小さすぎると、正電荷及び負電荷の非局在化が不十分なため、電子受容能が低下するおそれがあり、分子量が大きすぎると、電荷輸送の妨げとなるおそれがある。 (molecular weight)
The molecular weight of the electron-accepting compound of the present invention is usually 900 or more, preferably 1000 or more, more preferably 1200 or more, and usually 10000 or less, preferably 5000 or less, more preferably 3000 or less. If the molecular weight is too small, the delocalization of the positive and negative charges is insufficient, which may reduce the electron-accepting ability. If the molecular weight is too large, the charge transport may be hindered.
(具体例)
以下に式(81)で表される本発明の電子受容性化合物の具体例を挙げるが、本発明の電子受容性化合物はこれらに限定されるものではない。 (Concrete example)
Specific examples of the electron-accepting compound of the present invention represented by formula (81) are shown below, but the electron-accepting compound of the present invention is not limited thereto.
以下に式(81)で表される本発明の電子受容性化合物の具体例を挙げるが、本発明の電子受容性化合物はこれらに限定されるものではない。 (Concrete example)
Specific examples of the electron-accepting compound of the present invention represented by formula (81) are shown below, but the electron-accepting compound of the present invention is not limited thereto.
<組成物中のフッ素を含むアリールアミン高分子化合物と電子受容性化合物の組成比率・含有量>
本発明の組成物において、本発明のフッ素を含むアリールアミン高分子化合物と本発明の電子受容性化合物合計量に対して、本発明の高分子化合物の含有量は、99質量%以下であることが好ましく、97質量%以下であることがより好ましく、95質量%以下であることがさらに好ましい。また、50質量%以上であることが好ましく、70質量%以上であることがより好ましく、80質量%以上であることがさらに好ましい。これらの範囲であることで、本発明の組成物を用いて形成された膜が十分架橋して不溶化し、本発明の組成物を用いて形成された膜に直接湿式塗布成膜することが可能であり、かつ、本発明の組成物を用いて形成された膜を電荷注入膜として用いた場合、電荷輸送層に注入障壁が低減して電荷輸送性優れ、電荷輸送時の安定性が向上し、本発明の組成物を用いて形成された膜を含む素子の耐久性が向上すると考えられる。 <Composition ratio/content of fluorine-containing arylamine polymer compound and electron-accepting compound in composition>
In the composition of the present invention, the content of the polymer compound of the present invention is 99% by mass or less with respect to the total amount of the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention. is preferred, 97% by mass or less is more preferred, and 95% by mass or less is even more preferred. Moreover, it is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. Within these ranges, the film formed using the composition of the present invention is sufficiently crosslinked to be insolubilized, and the film formed using the composition of the present invention can be directly wet-coated to form a film. In addition, when the film formed using the composition of the present invention is used as a charge injection film, the injection barrier in the charge transport layer is reduced, the charge transport property is excellent, and the stability during charge transport is improved. It is believed that the durability of the device containing the film formed using the composition of the present invention is improved.
本発明の組成物において、本発明のフッ素を含むアリールアミン高分子化合物と本発明の電子受容性化合物合計量に対して、本発明の高分子化合物の含有量は、99質量%以下であることが好ましく、97質量%以下であることがより好ましく、95質量%以下であることがさらに好ましい。また、50質量%以上であることが好ましく、70質量%以上であることがより好ましく、80質量%以上であることがさらに好ましい。これらの範囲であることで、本発明の組成物を用いて形成された膜が十分架橋して不溶化し、本発明の組成物を用いて形成された膜に直接湿式塗布成膜することが可能であり、かつ、本発明の組成物を用いて形成された膜を電荷注入膜として用いた場合、電荷輸送層に注入障壁が低減して電荷輸送性優れ、電荷輸送時の安定性が向上し、本発明の組成物を用いて形成された膜を含む素子の耐久性が向上すると考えられる。 <Composition ratio/content of fluorine-containing arylamine polymer compound and electron-accepting compound in composition>
In the composition of the present invention, the content of the polymer compound of the present invention is 99% by mass or less with respect to the total amount of the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention. is preferred, 97% by mass or less is more preferred, and 95% by mass or less is even more preferred. Moreover, it is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more. Within these ranges, the film formed using the composition of the present invention is sufficiently crosslinked to be insolubilized, and the film formed using the composition of the present invention can be directly wet-coated to form a film. In addition, when the film formed using the composition of the present invention is used as a charge injection film, the injection barrier in the charge transport layer is reduced, the charge transport property is excellent, and the stability during charge transport is improved. It is believed that the durability of the device containing the film formed using the composition of the present invention is improved.
[組成物]
本発明の組成物は、更に、溶媒を含んでいてもよく、また、重合開始剤、添加剤等を含んでいてもよい。 [Composition]
The composition of the present invention may further contain a solvent, and may contain a polymerization initiator, additives and the like.
本発明の組成物は、更に、溶媒を含んでいてもよく、また、重合開始剤、添加剤等を含んでいてもよい。 [Composition]
The composition of the present invention may further contain a solvent, and may contain a polymerization initiator, additives and the like.
<溶媒>
本発明の組成物は、本発明のフッ素を含むアリールアミン高分子化合物と本発明の電子受容性化合物を含むことが好ましい。さらに溶媒を含むことが好ましい。特に、本発明の組成物を用いて、湿式成膜法により電荷輸送膜を形成する場合には、溶媒を用いて本発明のフッ素を含むアリールアミン高分子化合物と本発明の電子受容性化合物を溶解させた状態とすることが好ましい。 <Solvent>
The composition of the present invention preferably contains the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention. Furthermore, it is preferable that a solvent is included. In particular, when the composition of the present invention is used to form a charge transport film by a wet film-forming method, a solvent is used to combine the fluorine-containing arylamine polymer compound of the present invention with the electron-accepting compound of the present invention. It is preferably in a dissolved state.
本発明の組成物は、本発明のフッ素を含むアリールアミン高分子化合物と本発明の電子受容性化合物を含むことが好ましい。さらに溶媒を含むことが好ましい。特に、本発明の組成物を用いて、湿式成膜法により電荷輸送膜を形成する場合には、溶媒を用いて本発明のフッ素を含むアリールアミン高分子化合物と本発明の電子受容性化合物を溶解させた状態とすることが好ましい。 <Solvent>
The composition of the present invention preferably contains the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention. Furthermore, it is preferable that a solvent is included. In particular, when the composition of the present invention is used to form a charge transport film by a wet film-forming method, a solvent is used to combine the fluorine-containing arylamine polymer compound of the present invention with the electron-accepting compound of the present invention. It is preferably in a dissolved state.
本発明の組成物に含まれる溶媒としては、本発明のフッ素を含むアリールアミン高分子化合物と本発明の電子受容性化合物をともに溶解することが可能な溶媒であれば、その種類は特に限定されない。ここで、本発明のフッ素を含むアリールアミン高分子化合物と本発明の電子受容性化合物を溶解する溶媒とは、本発明のフッ素を含むアリールアミン高分子化合物を好ましくは0.005質量%以上、より好ましくは0.5質量%以上、更に好ましくは1質量%以上溶解する溶媒である。また、前記電子受容性化合物を好ましくは0.001質量%以上、より好ましくは0.1質量%以上、更に好ましくは0.2質量%以上溶解する溶媒である。
The type of solvent contained in the composition of the present invention is not particularly limited as long as it can dissolve both the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention. . Here, the fluorine-containing arylamine polymer compound of the present invention and the solvent for dissolving the electron-accepting compound of the present invention preferably contain 0.005% by mass or more of the fluorine-containing arylamine polymer compound of the present invention. More preferably 0.5% by mass or more, more preferably 1% by mass or more is a solvent that dissolves. The solvent preferably dissolves the electron-accepting compound in an amount of 0.001% by mass or more, more preferably 0.1% by mass or more, and still more preferably 0.2% by mass or more.
好ましい溶媒としては、例えば、芳香族炭化水素系溶媒、エーテル系溶媒及びエステル系溶媒が挙げられる。
Preferred solvents include, for example, aromatic hydrocarbon solvents, ether solvents and ester solvents.
具体的には、芳香族炭化水素系溶媒としては、トルエン、キシレン、メシチレン、テトラリン、シクロヘキシルベンゼンが挙げられる。
Specifically, aromatic hydrocarbon solvents include toluene, xylene, mesitylene, tetralin, and cyclohexylbenzene.
エーテル系溶媒としては、例えば、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコール-1-モノメチルエーテルアセタート(PGMEA)等の脂肪族エーテル;1,2-ジメトキシベンゼン、1,3-ジメトキシベンゼン、アニソール、フェネトール、2-メトキシトルエン、3-メトキシトルエン、4-メトキシトルエン、2,3-ジメチルアニソール、2,4-ジメチルアニソール等の芳香族エーテル等が挙げられる。
Examples of ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole , phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole.
エステル系溶媒としては、例えば、酢酸エチル、酢酸n-ブチル、乳酸エチル、乳酸n-ブチル等の脂肪族エステル;酢酸フェニル、プロピオン酸フェニル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸n-ブチル等の芳香族エステル等が挙げられる。
Examples of ester solvents include aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, benzoic acid; aromatic esters such as n-butyl;
これらは何れか1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で用いてもよい。
Any one of these may be used alone, or two or more may be used in any combination and ratio.
上述のエーテル系溶媒及びエステル系溶媒以外に使用可能な溶媒としては、例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等のアミド系溶媒、ジメチルスルホキシド等が挙げられる。これらは何れか1種を単独で用いてもよく、2種以上を任意の組み合わせ及び比率で用いてもよい。また、これらの溶媒のうち1種又は2種以上を、上述のエーテル系溶媒及びエステル系溶媒のうちの1種又は2種以上と組み合わせて用いてもよい。特に、ベンゼン、トルエン、キシレン等の芳香族炭化水素系溶媒は、電子受容性化合物、フリーキャリア(カチオンラジカル)を溶解する能力が低いため、エーテル系溶媒及びエステル系溶媒と混合して用いることが好ましい。
Examples of solvents that can be used in addition to the ether solvents and ester solvents described above include amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, and dimethyl sulfoxide. Any one of these may be used alone, or two or more thereof may be used in any combination and ratio. Also, one or more of these solvents may be used in combination with one or more of the ether solvents and ester solvents described above. In particular, aromatic hydrocarbon solvents such as benzene, toluene, and xylene have low ability to dissolve electron-accepting compounds and free carriers (cation radicals), so they can be used by mixing with ether solvents and ester solvents. preferable.
溶媒を使用する場合、本発明の組成物に対する溶媒の濃度は、好ましくは10質量%以上、より好ましくは30質量%以上、さらに好ましくは50%質量以上である。また、組成物に対する溶媒の濃度は、好ましくは99.999質量%以下、より好ましくは99.99質量%以下、更に好ましくは99.9質量%以下の範囲である。なお、2種以上の溶媒を混合して用いる場合には、これらの溶媒の合計がこの範囲を満たすようにする。
When a solvent is used, the solvent concentration relative to the composition of the present invention is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more. The concentration of the solvent in the composition is preferably 99.999% by mass or less, more preferably 99.99% by mass or less, and still more preferably 99.9% by mass or less. When two or more solvents are mixed and used, the total of these solvents should satisfy this range.
なお、本発明の組成物を有機電界発光素子に用いる場合、有機電界発光素子は多数の有機化合物からなる層を積層して形成するため、各層がいずれも均一な層であることが要求される。湿式成膜法で層形成する場合、薄膜形成用の溶液(組成物)に水分が存在すると、塗膜に水分が混入して膜の均一性が損なわれるため、溶液中の水分含有量はできるだけ少ない方が好ましい。また、一般に有機電界発光素子は、陰極等の水分により著しく劣化する材料が多く使用されているため、素子の劣化の観点からも水分の存在は好ましくない。
When the composition of the present invention is used in an organic electroluminescent element, each layer is required to be a uniform layer because the organic electroluminescent element is formed by laminating a large number of layers composed of organic compounds. . When a layer is formed by a wet film-forming method, if water is present in the solution (composition) for thin film formation, the water will be mixed in the coating film and the uniformity of the film will be impaired. Less is better. In addition, the presence of moisture is not preferable from the viewpoint of deterioration of the element, because organic electroluminescence elements generally use many materials, such as cathodes, that are significantly deteriorated by moisture.
具体的に、本発明の組成物に含まれる水分量は、好ましくは1質量%以下、中でも0.1質量%以下、更には0.05質量%以下に抑えることが好ましい。
Specifically, the amount of water contained in the composition of the present invention is preferably 1% by mass or less, more preferably 0.1% by mass or less, and more preferably 0.05% by mass or less.
組成物中の水分量を低減する方法としては、例えば、窒素ガスシール、乾燥剤の使用、溶媒を予め脱水する、水の溶解度が低い溶媒を使用する等が挙げられる。中でも、塗布工程中に溶液塗膜が大気中の水分を吸収して白化する現象を防ぐという観点からは、水の溶解度が低い溶媒を使用することが好ましい。
Examples of methods for reducing the amount of water in the composition include sealing with nitrogen gas, using a desiccant, dehydrating the solvent in advance, and using a solvent with low water solubility. Among them, it is preferable to use a solvent with low water solubility from the viewpoint of preventing the solution coating film from whitening due to absorption of moisture in the atmosphere during the coating process.
湿式成膜法により成膜する用途に用いる場合、本発明の組成物は、水の溶解度が低い溶媒、具体的には、25℃における水の溶解度が1質量%以下、好ましくは0.1質量%以下である溶媒を、組成物全体に対して好ましくは10質量%以上、中でも30質量%以上、特に50質量%以上の濃度で含有することが好ましい。
When used for film formation by a wet film-forming method, the composition of the present invention is a solvent having a low water solubility, specifically, a water solubility at 25° C. of 1% by mass or less, preferably 0.1% by mass. % or less, preferably 10% by mass or more, more preferably 30% by mass or more, particularly preferably 50% by mass or more, based on the total composition.
<電荷輸送膜用組成物>
架橋基を有する電子受容性化合物が前記の電子受容性イオン化合物である場合、該電子受容性イオン化合物と前記の式(1)のフッ素を含むアリールアミン高分子化合物とを含有する組成物(以下、適宜「電荷輸送膜用組成物(A)」という。)、又は、後記の架橋基を有するフッ素を含むアリールアミン高分子化合物のカチオンラジカルと該電子受容性イオン化合物の一部である対アニオンからなる電荷輸送性イオン化合物を含有する組成物(以下、適宜「電荷輸送膜用組成物(B)」という。)として用いることが好ましい。ここで、便宜上、電荷輸送膜用組成物(A)と電荷輸送膜用組成物(B)に分けて説明するが、電荷輸送膜用組成物は、前記の電子受容性イオン化合物、後記の架橋基を有するフッ素を含むアリールアミン高分子化合物及び、後記の架橋基を有するフッ素を含むアリールアミン高分子化合物のカチオンラジカルと前記の電子受容性イオン化合物の一部である対アニオンからなる電荷輸送性イオン化合物とを含む組成物も含む。 <Composition for charge transport film>
When the electron-accepting compound having a cross-linking group is the electron-accepting ionic compound, a composition containing the electron-accepting ionic compound and the fluorine-containing arylamine polymer compound of formula (1) (hereinafter referred to as , appropriately referred to as "charge-transporting film composition (A)"), or a cation radical of an arylamine polymer compound containing fluorine having a cross-linking group described later and a counter anion which is a part of the electron-accepting ion compound. is preferably used as a composition containing a charge-transporting ionic compound consisting of Here, for the sake of convenience, the charge transport film composition (A) and the charge transport film composition (B) will be described separately. A charge-transporting property comprising a cation radical of an arylamine polymer compound containing fluorine having a group and a cation radical of the arylamine polymer compound containing fluorine having a crosslinking group described later and a counter anion which is a part of the electron-accepting ion compound. Also included are compositions comprising ionic compounds.
架橋基を有する電子受容性化合物が前記の電子受容性イオン化合物である場合、該電子受容性イオン化合物と前記の式(1)のフッ素を含むアリールアミン高分子化合物とを含有する組成物(以下、適宜「電荷輸送膜用組成物(A)」という。)、又は、後記の架橋基を有するフッ素を含むアリールアミン高分子化合物のカチオンラジカルと該電子受容性イオン化合物の一部である対アニオンからなる電荷輸送性イオン化合物を含有する組成物(以下、適宜「電荷輸送膜用組成物(B)」という。)として用いることが好ましい。ここで、便宜上、電荷輸送膜用組成物(A)と電荷輸送膜用組成物(B)に分けて説明するが、電荷輸送膜用組成物は、前記の電子受容性イオン化合物、後記の架橋基を有するフッ素を含むアリールアミン高分子化合物及び、後記の架橋基を有するフッ素を含むアリールアミン高分子化合物のカチオンラジカルと前記の電子受容性イオン化合物の一部である対アニオンからなる電荷輸送性イオン化合物とを含む組成物も含む。 <Composition for charge transport film>
When the electron-accepting compound having a cross-linking group is the electron-accepting ionic compound, a composition containing the electron-accepting ionic compound and the fluorine-containing arylamine polymer compound of formula (1) (hereinafter referred to as , appropriately referred to as "charge-transporting film composition (A)"), or a cation radical of an arylamine polymer compound containing fluorine having a cross-linking group described later and a counter anion which is a part of the electron-accepting ion compound. is preferably used as a composition containing a charge-transporting ionic compound consisting of Here, for the sake of convenience, the charge transport film composition (A) and the charge transport film composition (B) will be described separately. A charge-transporting property comprising a cation radical of an arylamine polymer compound containing fluorine having a group and a cation radical of the arylamine polymer compound containing fluorine having a crosslinking group described later and a counter anion which is a part of the electron-accepting ion compound. Also included are compositions comprising ionic compounds.
なお、前記電荷輸送膜用組成物(A)及び(B)は、電荷輸送材料の用途に広く用いることが可能な組成物(電荷輸送材料用組成物)である。但し、通常はこれを成膜し、正孔注入層及び/又は正孔輸送層として、即ち電荷である正孔を輸送する「電荷輸送膜」として用いるため、本明細書では特に「電荷輸送膜用組成物」と呼ぶことにする。
The charge transport film compositions (A) and (B) are compositions (compositions for charge transport materials) that can be widely used as charge transport materials. However, since it is usually formed into a film and used as a hole injection layer and/or a hole transport layer, that is, as a "charge transport film" that transports holes, which are charges, in this specification, the term "charge transport film will be referred to as the "composition for
<電荷輸送膜用組成物(A)>
電荷輸送膜用組成物(A)は、前記架橋基を有するフッ素を含むアリールアミン高分子化合物、前記架橋基を有する電子受容性化合物、及び溶剤を含む。前記フッ素を含むアリールアミン高分子化合物は1種単独で含んでもよく2種以上の複数種含んでもよい。 <Composition for charge transport film (A)>
The charge-transporting film composition (A) comprises the fluorine-containing arylamine polymer compound having a cross-linking group, the electron-accepting compound having a cross-linking group, and a solvent. The fluorine-containing arylamine polymer compound may be contained singly or in combination of two or more kinds.
電荷輸送膜用組成物(A)は、前記架橋基を有するフッ素を含むアリールアミン高分子化合物、前記架橋基を有する電子受容性化合物、及び溶剤を含む。前記フッ素を含むアリールアミン高分子化合物は1種単独で含んでもよく2種以上の複数種含んでもよい。 <Composition for charge transport film (A)>
The charge-transporting film composition (A) comprises the fluorine-containing arylamine polymer compound having a cross-linking group, the electron-accepting compound having a cross-linking group, and a solvent. The fluorine-containing arylamine polymer compound may be contained singly or in combination of two or more kinds.
<電荷輸送膜用組成物(A)の調製方法>
電荷輸送膜用組成物(A)は、少なくとも、前記本発明のフッ素を含むアリールアミン高分子化合物と、前記架橋基を有する電子受容性化合物とを混合することで調製される。この時、電荷輸送膜用組成物(A)は溶剤を含み、前記本発明のフッ素を含むアリールアミン高分子化合物と、前記架橋基を有する電子受容性化合物とを溶剤に溶解して混合することが好ましい。 <Method for preparing composition (A) for charge transport film>
The charge-transporting film composition (A) is prepared by mixing at least the fluorine-containing arylamine polymer compound of the present invention with the electron-accepting compound having a cross-linking group. At this time, the charge-transporting film composition (A) contains a solvent, and the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound having a cross-linking group are dissolved in the solvent and mixed. is preferred.
電荷輸送膜用組成物(A)は、少なくとも、前記本発明のフッ素を含むアリールアミン高分子化合物と、前記架橋基を有する電子受容性化合物とを混合することで調製される。この時、電荷輸送膜用組成物(A)は溶剤を含み、前記本発明のフッ素を含むアリールアミン高分子化合物と、前記架橋基を有する電子受容性化合物とを溶剤に溶解して混合することが好ましい。 <Method for preparing composition (A) for charge transport film>
The charge-transporting film composition (A) is prepared by mixing at least the fluorine-containing arylamine polymer compound of the present invention with the electron-accepting compound having a cross-linking group. At this time, the charge-transporting film composition (A) contains a solvent, and the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound having a cross-linking group are dissolved in the solvent and mixed. is preferred.
電荷輸送膜用組成物(A)における前記本発明の架橋基を有する電子受容性化合物の含有量は、前記本発明のフッ素を含むアリールアミン高分子化合物に対する値で、通常0.1質量%以上、好ましくは1質量%以上、また、通常100質量%以下、好ましくは40質量%以下である。電子受容性化合物の含有量が上記下限以上であれば、フリーキャリア(前記本発明のフッ素を含むアリールアミン高分子化合物のカチオンラジカル)が十分に生成でき好ましく、上記上限以下であれば、十分な電荷輸送能が確保でき好ましい。2種以上の電子受容性化合物を併用する場合には、これらの合計の含有量が上記範囲に含まれるようにする。電荷輸送性化合物についても同様である。
The content of the electron-accepting compound having a crosslinkable group of the present invention in the composition (A) for a charge transport film is usually 0.1% by mass or more in terms of the fluorine-containing arylamine polymer compound of the present invention. , preferably 1% by mass or more, and usually 100% by mass or less, preferably 40% by mass or less. If the content of the electron-accepting compound is at least the above lower limit, free carriers (cation radicals of the fluorine-containing arylamine polymer compound of the present invention) can be sufficiently generated, and if it is at most the above upper limit, it is sufficient. It is preferable because the charge transport ability can be ensured. When two or more electron-accepting compounds are used in combination, the total content of these should be within the above range. The same applies to charge-transporting compounds.
<電荷輸送膜用組成物(B)>
電荷輸送膜用組成物(B)は、前記の通り、前記本発明のフッ素を含むアリールアミン高分子化合物のカチオンラジカルと前記の電子受容性イオン化合物の対アニオンからなる電荷輸送性イオン化合物を含有する組成物である。 <Composition for charge transport film (B)>
The charge-transporting film composition (B) contains, as described above, a charge-transporting ionic compound comprising a cation radical of the fluorine-containing arylamine polymer compound of the present invention and a counter anion of the electron-accepting ionic compound. It is a composition that
電荷輸送膜用組成物(B)は、前記の通り、前記本発明のフッ素を含むアリールアミン高分子化合物のカチオンラジカルと前記の電子受容性イオン化合物の対アニオンからなる電荷輸送性イオン化合物を含有する組成物である。 <Composition for charge transport film (B)>
The charge-transporting film composition (B) contains, as described above, a charge-transporting ionic compound comprising a cation radical of the fluorine-containing arylamine polymer compound of the present invention and a counter anion of the electron-accepting ionic compound. It is a composition that
電荷輸送性イオン化合物のカチオンである前記本発明のフッ素を含むアリールアミン高分子化合物のカチオンラジカルは、前記の本発明のフッ素を含むアリールアミン高分子化合物に示す電気的に中性の化合物から、一電子取り除いた化学種である。
The cation radical of the fluorine-containing arylamine polymer compound of the present invention, which is the cation of the charge-transporting ionic compound, is obtained from the electrically neutral compound shown in the fluorine-containing arylamine polymer compound of the present invention. It is a chemical species with one electron removed.
前記本発明のフッ素を含むアリールアミン高分子化合物のカチオンラジカルとしては、下記式(110)で表される構造を有するフッ素を含むアリールアミン高分子化合物である。
The cation radical of the fluorine-containing arylamine polymer compound of the present invention is a fluorine-containing arylamine polymer compound having a structure represented by the following formula (110).
[上記式(110)中、
Ar1a、Ar2a、G1aは、それぞれ前記式(1)におけるAr1、Ar2、Gと同様である。] [In the above formula (110),
Ar 1a , Ar 2a and G 1a are respectively the same as Ar 1 , Ar 2 and G in the formula (1). ]
Ar1a、Ar2a、G1aは、それぞれ前記式(1)におけるAr1、Ar2、Gと同様である。] [In the above formula (110),
Ar 1a , Ar 2a and G 1a are respectively the same as Ar 1 , Ar 2 and G in the formula (1). ]
式(110)としては特に、下記式(110-1)で表れる構造を有するフッ素を含むアリールアミン高分子化合物であることが、適度な酸化還元電位を有する点、安定な電荷輸送性イオンが得られる点から好ましい。
Formula (110) is particularly a fluorine-containing arylamine polymer compound having a structure represented by the following formula (110-1). It is preferable because it is
[上記式(110-1)中、
Ar1bは、芳香族炭化水素基であり、当該芳香族炭化水素基の炭素数は、好ましくは6~30、より好ましくは6~24、さらに好ましくは6~18である。芳香族炭化水素基としては、具体的には、ベンゼン環、ナフタレン環、フルオレン環、テトラフェニレン環等の、炭素数が通常6以上、通常30以下、好ましくは18以下、さらに好ましくは14以下である芳香族炭化水素環構造の2価の基、又は、これらの構造から選択された複数の構造が鎖状に又は分岐して結合した構造の2価の基が挙げられる。芳香族炭化水素環が複数個連結する場合は、通常、2~7個連結した構造が挙げられ、2~5個連結した構造であることが好ましい。芳香族炭化水素環が複数個連結する場合、同一の構造が連結してもよく、異なる構造が連結してもよい。
Ar2a、G1aは、それぞれ前記式(1)におけるAr2、Gと同様である。] [In the above formula (110-1),
Ar 1b is an aromatic hydrocarbon group, and the number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-24, still more preferably 6-18. Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a fluorene ring, a tetraphenylene ring, and the like, having usually 6 or more and usually 30 or less, preferably 18 or less, more preferably 14 or less carbon atoms. A bivalent group having a certain aromatic hydrocarbon ring structure, or a bivalent group having a structure in which a plurality of structures selected from these structures are bonded in a chain or branched manner is exemplified. When a plurality of aromatic hydrocarbon rings are linked, a structure in which 2 to 7 rings are linked is usually mentioned, and a structure in which 2 to 5 rings are linked is preferable. When a plurality of aromatic hydrocarbon rings are linked, the same structure may be linked, or different structures may be linked.
Ar 2a and G 1a are the same as Ar 2 and G in formula (1) above, respectively. ]
Ar1bは、芳香族炭化水素基であり、当該芳香族炭化水素基の炭素数は、好ましくは6~30、より好ましくは6~24、さらに好ましくは6~18である。芳香族炭化水素基としては、具体的には、ベンゼン環、ナフタレン環、フルオレン環、テトラフェニレン環等の、炭素数が通常6以上、通常30以下、好ましくは18以下、さらに好ましくは14以下である芳香族炭化水素環構造の2価の基、又は、これらの構造から選択された複数の構造が鎖状に又は分岐して結合した構造の2価の基が挙げられる。芳香族炭化水素環が複数個連結する場合は、通常、2~7個連結した構造が挙げられ、2~5個連結した構造であることが好ましい。芳香族炭化水素環が複数個連結する場合、同一の構造が連結してもよく、異なる構造が連結してもよい。
Ar2a、G1aは、それぞれ前記式(1)におけるAr2、Gと同様である。] [In the above formula (110-1),
Ar 1b is an aromatic hydrocarbon group, and the number of carbon atoms in the aromatic hydrocarbon group is preferably 6-30, more preferably 6-24, still more preferably 6-18. Specific examples of the aromatic hydrocarbon group include a benzene ring, a naphthalene ring, a fluorene ring, a tetraphenylene ring, and the like, having usually 6 or more and usually 30 or less, preferably 18 or less, more preferably 14 or less carbon atoms. A bivalent group having a certain aromatic hydrocarbon ring structure, or a bivalent group having a structure in which a plurality of structures selected from these structures are bonded in a chain or branched manner is exemplified. When a plurality of aromatic hydrocarbon rings are linked, a structure in which 2 to 7 rings are linked is usually mentioned, and a structure in which 2 to 5 rings are linked is preferable. When a plurality of aromatic hydrocarbon rings are linked, the same structure may be linked, or different structures may be linked.
Ar 2a and G 1a are the same as Ar 2 and G in formula (1) above, respectively. ]
Ar1bは好ましくは置換基を有する芳香族炭化水素基であり、その具体例、好ましい基、有していてもよい置換基の例及び好ましい置換基の例は、前記置換基群Zから選択される基が好ましい。特に好ましくは置換基を有していてもよい炭素数6~14の芳香族炭化水素基である。
Ar 1b is preferably an aromatic hydrocarbon group having a substituent, and specific examples thereof, preferred groups, examples of optionally substituted substituents and examples of preferred substituents are selected from the substituent group Z is preferred. Particularly preferred is an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.
式(110-1)で表される部分構造がカチオンラジカルになりやすいおよび電荷輸送の観点から、Ar1bは好ましくはフェニレン基、ビフェニレン基、フェニルフルオレン基であり、さらに好ましくはフェニレン基、ビフェニレン基であり、フェニレン基が特に好ましい。
Ar 1b is preferably a phenylene group, a biphenylene group, or a phenylfluorene group, more preferably a phenylene group or a biphenylene group, from the viewpoints of charge transport and that the partial structure represented by formula (110-1) tends to become a cation radical. and a phenylene group is particularly preferred.
<電荷輸送性イオン化合物>
電荷輸送性イオン化合物は、前記の前記本発明のフッ素を含むアリールアミン高分子化合物のカチオンラジカルと、電子受容性イオン化合物の一部である対アニオンとがイオン結合した化合物である。 <Charge-transporting ionic compound>
The charge-transporting ionic compound is a compound in which the cation radical of the fluorine-containing arylamine polymer compound of the present invention is ionically bonded to a counter anion that is a part of the electron-accepting ionic compound.
電荷輸送性イオン化合物は、前記の前記本発明のフッ素を含むアリールアミン高分子化合物のカチオンラジカルと、電子受容性イオン化合物の一部である対アニオンとがイオン結合した化合物である。 <Charge-transporting ionic compound>
The charge-transporting ionic compound is a compound in which the cation radical of the fluorine-containing arylamine polymer compound of the present invention is ionically bonded to a counter anion that is a part of the electron-accepting ionic compound.
電荷輸送性イオン化合物は、フッ素を含むアリールアミン高分子化合物と、電子受容性イオン化合物とを混合することによって得ることができ、種々の溶媒に容易に溶解する。具体的には、後述の、<電荷輸送膜用組成物(B)の調製方法>にて記した方法で得ることが出来る。
A charge-transporting ionic compound can be obtained by mixing an arylamine polymer compound containing fluorine and an electron-accepting ionic compound, and is easily dissolved in various solvents. Specifically, it can be obtained by the method described in <Method for preparing composition (B) for charge transport film> described below.
電荷輸送性イオン化合物の重量平均分子量(Mw)は、通常1,000,000以下、好ましくは500,000以下、より好ましくは100,000以下、さらに好ましくは70,000以下、特に好ましくは50,000以下である。また、当該重量平均分子量は、通常5,000以上、好ましくは10,000以上、さらに好ましくは12,000以上、特に好ましくは15,000以上である。
The weight average molecular weight (Mw) of the charge-transporting ionic compound is usually 1,000,000 or less, preferably 500,000 or less, more preferably 100,000 or less, still more preferably 70,000 or less, particularly preferably 50,000 or less. 000 or less. Moreover, the weight average molecular weight is usually 5,000 or more, preferably 10,000 or more, more preferably 12,000 or more, and particularly preferably 15,000 or more.
<電荷輸送膜用組成物(B)の調製方法>
電荷輸送性イオン化合物(B)は、前記本発明のフッ素を含むアリールアミン高分子化合物と、電子受容性イオン化合物とを溶媒に溶解して混合して調製して得ることが好ましい。この溶液中で、電子受容性イオン化合物によって前記本発明のフッ素を含むアリールアミン高分子化合物が酸化されてカチオンラジカル化し、電子受容性イオン化合物の対アニオンと、前記本発明のフッ素を含むアリールアミン高分子化合物のカチオンラジカルとのイオン化合物である、電荷輸送性イオン化合物が生成する。 <Method for preparing composition (B) for charge transport film>
The charge-transporting ionic compound (B) is preferably prepared by dissolving and mixing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting ionic compound in a solvent. In this solution, the fluorine-containing arylamine polymer compound of the present invention is oxidized by the electron-accepting ion compound to form a cation radical, and the counter anion of the electron-accepting ion compound and the fluorine-containing arylamine of the present invention are converted into cation radicals. A charge-transporting ionic compound, which is an ionic compound with the cation radical of the polymer compound, is produced.
電荷輸送性イオン化合物(B)は、前記本発明のフッ素を含むアリールアミン高分子化合物と、電子受容性イオン化合物とを溶媒に溶解して混合して調製して得ることが好ましい。この溶液中で、電子受容性イオン化合物によって前記本発明のフッ素を含むアリールアミン高分子化合物が酸化されてカチオンラジカル化し、電子受容性イオン化合物の対アニオンと、前記本発明のフッ素を含むアリールアミン高分子化合物のカチオンラジカルとのイオン化合物である、電荷輸送性イオン化合物が生成する。 <Method for preparing composition (B) for charge transport film>
The charge-transporting ionic compound (B) is preferably prepared by dissolving and mixing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting ionic compound in a solvent. In this solution, the fluorine-containing arylamine polymer compound of the present invention is oxidized by the electron-accepting ion compound to form a cation radical, and the counter anion of the electron-accepting ion compound and the fluorine-containing arylamine of the present invention are converted into cation radicals. A charge-transporting ionic compound, which is an ionic compound with the cation radical of the polymer compound, is produced.
これは下記理由のためである。すなわち、このとき、前記本発明のフッ素を含むアリールアミン高分子化合物と電子受容性イオン化合物とを溶液中で混合することにより、前記本発明のフッ素を含むアリールアミン高分子化合物の酸化されやすい部位であるアリールアミン窒素原子近傍に電子受容性イオン化合物が存在する確率が高くなる。そして、電子受容性イオン化合物によって前記本発明のフッ素を含む高分子化合物のアリールアミン窒素原子が酸化されてカチオンラジカル化し、電子受容性イオン化合物の対アニオンと、前記本発明のフッ素を含む高分子化合物のカチオンラジカルとのイオン化合物が生成しやすい。このとき、溶液を加熱することが、前記反応を促進する観点で好ましい。
This is for the following reasons. That is, at this time, by mixing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting ion compound in a solution, the easily oxidizable site of the fluorine-containing arylamine polymer compound of the present invention The probability that the electron-accepting ion compound exists in the vicinity of the arylamine nitrogen atom is increased. Then, the electron-accepting ionic compound oxidizes the arylamine nitrogen atom of the fluorine-containing polymer compound of the present invention to form a cation radical, forming a counter anion of the electron-accepting ion compound and the fluorine-containing polymer of the present invention. An ionic compound is likely to form with the cation radical of the compound. At this time, it is preferable to heat the solution from the viewpoint of promoting the reaction.
また、電子受容性イオン化合物と、前記本発明のフッ素を含む高分子化合物との混合物を加熱して調製することも好ましい。この混合物は、電子受容性イオン化合物と、前記本発明のフッ素を含む高分子化合物との混合物を溶媒に溶解した溶液を塗布乾燥して成膜した膜であることが好ましい。
It is also preferable to prepare by heating a mixture of the electron-accepting ionic compound and the fluorine-containing polymer compound of the present invention. This mixture is preferably a film formed by coating and drying a solution obtained by dissolving a mixture of an electron-accepting ionic compound and the fluorine-containing polymer compound of the present invention in a solvent.
これは下記理由のためである。すなわち、混合物を加熱することにより、混合物中で電子受容性イオン化合物と前記本発明のフッ素を含む高分子化合物とが互いに拡散し、前記本発明のフッ素を含む高分子化合物の酸化されやすい部位であるアリールアミンの窒素原子近傍に電子受容性化合物が存在する確率が高くなる。そして、電子受容性イオン化合物の対アニオンと、前記本発明のフッ素を含む高分子化合物のカチオンラジカルとのイオン化合物が生成しやすい。この時の加熱温度は、組成物の架橋基が架橋反応しない温度が好ましいが、架橋基が架橋反応する温度であっても、架橋反応も拡散しながら起こるため、電子受容性イオン化合物は問題なく形成される。
This is for the following reasons. That is, by heating the mixture, the electron-accepting ion compound and the fluorine-containing polymer compound of the present invention mutually diffuse in the mixture, and at the easily oxidizable sites of the fluorine-containing polymer compound of the present invention. The probability that an electron-accepting compound exists in the vicinity of the nitrogen atom of a certain arylamine increases. Then, an ionic compound of the counter anion of the electron-accepting ionic compound and the cation radical of the fluorine-containing polymer compound of the present invention is likely to be generated. The heating temperature at this time is preferably a temperature at which the cross-linking groups of the composition do not undergo a cross-linking reaction. It is formed.
電荷輸送膜用組成物(B)は、前記した電荷輸送性イオン化合物1種を単独で含有していてもよく、2種以上を含有していてもよい。電荷輸送性イオン化合物は1種又は2種含有することが好ましく、1種を単独で含有することがより好ましい。電荷輸送性イオン化合物のイオン化ポテンシャルのばらつきが少なく、正孔輸送性が優れるためである。
The charge-transporting film composition (B) may contain one type of charge-transporting ionic compound described above, or may contain two or more types. It is preferable to contain one or two types of charge-transporting ionic compounds, and it is more preferable to contain one type alone. This is because the ionization potential of the charge-transporting ionic compound has little variation and the hole-transporting property is excellent.
電荷輸送性イオン化合物1種を単独で、又は2種含有する組成物とは、電子受容性イオン化合物と前記本発明のフッ素を含む高分子化合物を合計で2種のみ又は3種のみ用いて調製された組成物であって、少なくとも1つの電子受容性イオン化合物と少なくとも1つの前記本発明のフッ素を含む高分子化合物とを用いて調製された組成物である。
A composition containing one type of charge-transporting ionic compound alone or two types is defined as a composition prepared by using only two or three types in total of the electron-accepting ionic compound and the fluorine-containing polymer compound of the present invention. The composition is prepared using at least one electron-accepting ion compound and at least one fluorine-containing polymer compound of the present invention.
電荷輸送膜用組成物(B)から形成される電荷輸送膜は、電荷輸送性イオン化合物から近傍の中性の電荷輸送性化合物に正電荷が移動することにより、高い正孔注入・輸送能を発揮する。このことから、電荷輸送性イオン化合物と中性の前記本発明のフッ素を含む高分子化合物の質量比が、1:100~100:1程度であることが好ましく、1:20~20:1程度の割合であることが更に好ましい。
The charge-transporting film formed from the charge-transporting-film composition (B) exhibits a high hole injection/transport capability due to positive charge transfer from the charge-transporting ionic compound to a nearby neutral charge-transporting compound. Demonstrate. For this reason, the mass ratio of the charge-transporting ionic compound and the neutral fluorine-containing polymer compound of the present invention is preferably about 1:100 to 100:1, more preferably about 1:20 to 20:1. is more preferable.
<電荷輸送膜用組成物(A)と(B)の関係>
電荷輸送膜用組成物(A)により形成される電荷輸送膜は、耐熱性に優れるとともに、高い正孔注入・輸送能を有する。この様な優れた特性が得られる理由を以下に説明する。 <Relationship between composition for charge transport film (A) and (B)>
The charge transport film formed from the charge transport film composition (A) has excellent heat resistance and high hole injection/transport capability. The reason why such excellent properties are obtained will be explained below.
電荷輸送膜用組成物(A)により形成される電荷輸送膜は、耐熱性に優れるとともに、高い正孔注入・輸送能を有する。この様な優れた特性が得られる理由を以下に説明する。 <Relationship between composition for charge transport film (A) and (B)>
The charge transport film formed from the charge transport film composition (A) has excellent heat resistance and high hole injection/transport capability. The reason why such excellent properties are obtained will be explained below.
電荷輸送膜用組成物(A)は、前述した電子受容性化合物と電荷輸送性化合物とを含有している。電子受容性イオン化合物中のカチオンは、超原子価の中心原子を有し、その正電荷が広く非局在化しているため、高い電子受容性を有している。これによって、電荷輸送性化合物から電子受容性イオン化合物のカチオンへと電子移動が起こり、電荷輸送性化合物のカチオンラジカルと対アニオンとからなる電荷輸送性イオン化合物が生成する。この電荷輸送性化合物のカチオンラジカルが電荷のキャリアとなるため、電荷輸送膜の電気伝導度を高めることができる。すなわち、電荷輸送膜用組成物(A)を調製すると、少なくとも一部は電荷輸送性化合物のカチオンラジカルと電子受容性イオン化合物の対アニオンとからなる電荷輸送性イオン化合物が生成すると考えられる。
The charge-transporting film composition (A) contains the electron-accepting compound and the charge-transporting compound described above. The cation in the electron-accepting ionic compound has a hypervalent central atom and its positive charge is widely delocalized, so it has a high electron-accepting property. As a result, electron transfer occurs from the charge-transporting compound to the cation of the electron-accepting ionic compound, and a charge-transporting ionic compound composed of the cation radical of the charge-transporting compound and the counter anion is generated. Since the cation radicals of the charge-transporting compound serve as charge carriers, the electrical conductivity of the charge-transporting film can be increased. That is, it is considered that when the charge transport film composition (A) is prepared, a charge transporting ionic compound at least partially composed of the cation radical of the charge transporting compound and the counter anion of the electron accepting ion compound is produced.
例えば、下記の式(7)で表される電荷輸送性化合物から式(6)で表される電子受容性化合物へ電子移動が起きる場合、式(9)で表される、電荷輸送性化合物のカチオンラジカルと対アニオンからなる電荷輸送性イオン化合物が生成する。
For example, when electron transfer occurs from the charge-transporting compound represented by the following formula (7) to the electron-accepting compound represented by the formula (6), the charge-transporting compound represented by the formula (9) A charge-transporting ionic compound consisting of a cation radical and a counter-anion is produced.
[組成物の調製]
本発明における組成物は、本発明のフッ素を含むアリールアミン高分子化合物、本発明の電子受容性化合物、好ましくは更に前述の電子受容性化合物を含む機能性材料と溶媒を混合させ、一定時間加温して溶解または分散させることで調製することができる。機能性材料を溶媒内に均一に溶解または分散させるためには、加温する温度は80℃以上が好ましく、90℃以上がより好ましく、100℃以上、例えば100~120℃がさらに好ましい。また、加温時間は30分以上が好ましく、45分以上がより好ましく、60分以上、例えば60~180分がさらに好ましい。 [Preparation of composition]
The composition of the present invention is prepared by mixing a functional material containing the fluorine-containing arylamine polymer compound of the present invention, the electron-accepting compound of the present invention, preferably the above-mentioned electron-accepting compound, with a solvent, followed by heating for a certain period of time. It can be prepared by heating to dissolve or disperse. In order to uniformly dissolve or disperse the functional material in the solvent, the heating temperature is preferably 80.degree. C. or higher, more preferably 90.degree. The heating time is preferably 30 minutes or longer, more preferably 45 minutes or longer, and even more preferably 60 minutes or longer, for example 60 to 180 minutes.
本発明における組成物は、本発明のフッ素を含むアリールアミン高分子化合物、本発明の電子受容性化合物、好ましくは更に前述の電子受容性化合物を含む機能性材料と溶媒を混合させ、一定時間加温して溶解または分散させることで調製することができる。機能性材料を溶媒内に均一に溶解または分散させるためには、加温する温度は80℃以上が好ましく、90℃以上がより好ましく、100℃以上、例えば100~120℃がさらに好ましい。また、加温時間は30分以上が好ましく、45分以上がより好ましく、60分以上、例えば60~180分がさらに好ましい。 [Preparation of composition]
The composition of the present invention is prepared by mixing a functional material containing the fluorine-containing arylamine polymer compound of the present invention, the electron-accepting compound of the present invention, preferably the above-mentioned electron-accepting compound, with a solvent, followed by heating for a certain period of time. It can be prepared by heating to dissolve or disperse. In order to uniformly dissolve or disperse the functional material in the solvent, the heating temperature is preferably 80.degree. C. or higher, more preferably 90.degree. The heating time is preferably 30 minutes or longer, more preferably 45 minutes or longer, and even more preferably 60 minutes or longer, for example 60 to 180 minutes.
加温後の組成物は、メンブレンフィルタやデプスフィルタ等を用いて濾過し、粗大な粒子を取り除いてから使用できる。インクジェットヘッドのノズルから吐出して組成物を塗布することを考慮すると、フィルタの孔径は0.5μm以下が好ましく、0.2μm以下がより好ましく、0.1μm以下がさらに好ましい。
The composition after heating can be filtered using a membrane filter, depth filter, etc. to remove coarse particles before use. Considering that the composition is applied by ejecting from the nozzle of an inkjet head, the pore size of the filter is preferably 0.5 μm or less, more preferably 0.2 μm or less, and even more preferably 0.1 μm or less.
[組成物を用いた成膜方法]
本発明の組成物を用いて膜を形成する場合、本発明の組成物は溶媒を含む溶液であることが好ましく、本発明の組成物を湿式成膜することが好ましい。 [Method of forming a film using the composition]
When forming a film using the composition of the present invention, the composition of the present invention is preferably a solution containing a solvent, and the composition of the present invention is preferably used for wet film formation.
本発明の組成物を用いて膜を形成する場合、本発明の組成物は溶媒を含む溶液であることが好ましく、本発明の組成物を湿式成膜することが好ましい。 [Method of forming a film using the composition]
When forming a film using the composition of the present invention, the composition of the present invention is preferably a solution containing a solvent, and the composition of the present invention is preferably used for wet film formation.
湿式成膜法とは、基板上に溶媒を含む組成物を塗布し、溶媒を乾燥除去して膜を形成する方法をいう。塗布方法としては、特に限定はされないが、例えばスピンコート法、ディップコート法、ダイコート法、バーコート法、ブレードコート法、ロールコート法、スプレーコート法、キャピラリーコート法、インクジェット法、スクリーン印刷法、グラビア印刷法、フレキソ印刷法等が挙げられる。
The wet film formation method is a method in which a composition containing a solvent is applied onto a substrate and the solvent is removed by drying to form a film. The coating method is not particularly limited, but for example, spin coating, dip coating, die coating, bar coating, blade coating, roll coating, spray coating, capillary coating, inkjet, screen printing, A gravure printing method, a flexographic printing method, and the like can be mentioned.
溶媒を乾燥除去する方法としては、通常、加熱乾燥を行う。加熱工程において使用する加熱手段の例としては、クリーンオーブン、ホットプレート、赤外線加熱が挙げられる。赤外線加熱としては、ハロゲンヒーターやセラミックコートしたハロゲンヒーター、セラミックヒーター等が使用できる。
Heat drying is usually used to remove the solvent by drying. Examples of heating means used in the heating step include clean ovens, hot plates, and infrared heating. As infrared heating, a halogen heater, a ceramic-coated halogen heater, a ceramic heater, or the like can be used.
赤外線による加熱は基板あるいは膜に直接熱エネルギーを与えるため、オーブンやホットプレートを用いた加熱と比べて短時間での乾燥が可能となる。そのため加熱雰囲気のガス(水分や酸素)の影響や、微小なごみの影響を最小限に抑えることができ、生産性が向上し、好ましい。
Since infrared heating gives heat energy directly to the substrate or film, drying can be done in a short time compared to heating using an oven or hot plate. Therefore, the influence of gases (moisture and oxygen) in the heating atmosphere and the influence of fine dust can be minimized, and productivity is improved, which is preferable.
加熱温度は、通常80℃以上、好ましくは100℃以上、より好ましくは150℃以上である。また、加熱温度は、通常300℃以下、好ましくは280℃以下、より好ましくは260℃以下である。
The heating temperature is usually 80°C or higher, preferably 100°C or higher, more preferably 150°C or higher. Also, the heating temperature is usually 300° C. or lower, preferably 280° C. or lower, more preferably 260° C. or lower.
加熱時間は、通常10秒以上、好ましくは60秒以上、より好ましくは90秒以上であり、通常120分以下、好ましくは60分以下、より好ましくは30分以下である。
また、加熱乾燥の前に真空乾燥を行うことも好ましい。 The heating time is usually 10 seconds or more, preferably 60 seconds or more, more preferably 90 seconds or more, and usually 120 minutes or less, preferably 60 minutes or less, more preferably 30 minutes or less.
It is also preferable to perform vacuum drying before heat drying.
また、加熱乾燥の前に真空乾燥を行うことも好ましい。 The heating time is usually 10 seconds or more, preferably 60 seconds or more, more preferably 90 seconds or more, and usually 120 minutes or less, preferably 60 minutes or less, more preferably 30 minutes or less.
It is also preferable to perform vacuum drying before heat drying.
本発明の組成物を湿式成膜法にて成膜した有機層の膜厚は、通常5nm以上、好ましくは10nm以上、さらに好ましくは20nm以上である。また、膜厚は、通常1000nm以下、好ましくは500nm以下、さらに好ましくは300nm以下である。
The film thickness of the organic layer formed by forming the composition of the present invention by a wet film-forming method is usually 5 nm or more, preferably 10 nm or more, and more preferably 20 nm or more. Also, the film thickness is usually 1000 nm or less, preferably 500 nm or less, more preferably 300 nm or less.
[有機電界発光素子]
本発明の組成物を用いた膜及び本発明の組成物を用いて形成された膜は、電荷輸送層として好適に用いることができる。この電荷輸送層は、特に好ましくは、有機電界発光素子の電荷輸送膜として用いられる。 [Organic electroluminescent device]
A film using the composition of the present invention and a film formed using the composition of the present invention can be suitably used as a charge transport layer. This charge transport layer is particularly preferably used as a charge transport film of an organic electroluminescence device.
本発明の組成物を用いた膜及び本発明の組成物を用いて形成された膜は、電荷輸送層として好適に用いることができる。この電荷輸送層は、特に好ましくは、有機電界発光素子の電荷輸送膜として用いられる。 [Organic electroluminescent device]
A film using the composition of the present invention and a film formed using the composition of the present invention can be suitably used as a charge transport layer. This charge transport layer is particularly preferably used as a charge transport film of an organic electroluminescence device.
有機電界発光素子は、例えば、基板上に、陽極及び陰極を有し、該陽極と該陰極の間に有機層を有する有機電界発光素子であり、該有機層を、本発明の組成物を用いて湿式成膜法にて形成することが好ましい。前記有機層は、陽極と発光層の間にある有機層であることが好ましい。該有機電界発光素子の発光層に無機発光物質である「量子ドット」を用いた素子は、量子ドット発光素子とも言う。
The organic electroluminescent device is, for example, an organic electroluminescent device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode, and the organic layer is formed using the composition of the present invention. It is preferably formed by a wet film-forming method. The organic layer is preferably an organic layer between the anode and the light-emitting layer. A device using "quantum dots", which are inorganic light-emitting substances, in the light-emitting layer of the organic electroluminescent device is also called a quantum dot light-emitting device.
また、該有機層が、前記式(1)で表される繰り返し単位を有し、主鎖及び側鎖の少なくとも1つに置換基を有していてもよいフルオレンを有し、架橋基を有する高分子化合物と、前記式(81)で表される、架橋基を有する電子受容性化合物との架橋反応物を含有することが好ましい。
Further, the organic layer has a repeating unit represented by the formula (1), has a fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group. It preferably contains a crosslinked reaction product of a polymer compound and an electron-accepting compound having a crosslinkable group represented by the above formula (81).
本発明の有機電界発光素子の構造の一例として、図1に有機電界発光素子8の構造例の模式図(断面)を示す。図1において、1は基板、2は陽極、3は正孔注入層、4は正孔輸送層、5は発光層、6は電子輸送層、7は陰極を各々表す。
As an example of the structure of the organic electroluminescence device of the present invention, FIG. 1 shows a schematic diagram (cross section) of a structural example of the organic electroluminescence device 8 . In FIG. 1, 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 an electron transport layer, and 7 is a cathode.
[基板]
基板1は、有機電界発光素子の支持体となるものであり、通常、石英やガラスの板、金属板や金属箔、プラスチックフィルムやシート等が用いられる。これらのうち、ガラス板や、ポリエステル、ポリメタクリレート、ポリカーボネート、ポリスルホン等の透明な合成樹脂の板が好ましい。基板は、外気による有機電界発光素子の劣化が起こり難いことからガスバリア性の高い材質とするのが好ましい。このため、特に合成樹脂製の基板等のようにガスバリア性の低い材質を用いる場合は、基板の少なくとも片面に緻密なシリコン酸化膜等を設けてガスバリア性を上げるのが好ましい。 [substrate]
Thesubstrate 1 serves as a support for the organic electroluminescence element, and is usually made of a quartz or glass plate, a metal plate or metal foil, a plastic film or sheet, or the like. Among these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate and polysulfone are preferred. The substrate is preferably made of a material having a high gas barrier property because deterioration of the organic electroluminescence element due to outside air is unlikely to occur. Therefore, especially when using a material having low gas barrier properties such as a synthetic resin substrate, it is preferable to provide a dense silicon oxide film or the like on at least one side of the substrate to improve the gas barrier properties.
基板1は、有機電界発光素子の支持体となるものであり、通常、石英やガラスの板、金属板や金属箔、プラスチックフィルムやシート等が用いられる。これらのうち、ガラス板や、ポリエステル、ポリメタクリレート、ポリカーボネート、ポリスルホン等の透明な合成樹脂の板が好ましい。基板は、外気による有機電界発光素子の劣化が起こり難いことからガスバリア性の高い材質とするのが好ましい。このため、特に合成樹脂製の基板等のようにガスバリア性の低い材質を用いる場合は、基板の少なくとも片面に緻密なシリコン酸化膜等を設けてガスバリア性を上げるのが好ましい。 [substrate]
The
[陽極]
陽極2は、発光層5側の層に正孔を注入する機能を担う。 [anode]
Theanode 2 has the function of injecting holes into the layer on the light-emitting layer 5 side.
陽極2は、発光層5側の層に正孔を注入する機能を担う。 [anode]
The
陽極2は、通常、アルミニウム、金、銀、ニッケル、パラジウム、白金等の金属;インジウム及び/又はスズの酸化物等の金属酸化物;ヨウ化銅等のハロゲン化金属;カーボンブラック及びポリ(3-メチルチオフェン)、ポリピロール、ポリアニリン等の導電性高分子等により構成される。
Anode 2 is typically made of metals such as aluminum, gold, silver, nickel, palladium, platinum; metal oxides such as indium and/or tin oxide; metal halides such as copper iodide; carbon black and poly(3 -methylthiophene), polypyrrole, and polyaniline.
陽極2の形成は、通常、スパッタリング法、真空蒸着法等の乾式法により行われることが多い。また、銀等の金属微粒子、ヨウ化銅等の微粒子、カーボンブラック、導電性の金属酸化物微粒子、導電性高分子微粉末等を用いて陽極を形成する場合には、適当なバインダー樹脂溶液に分散させて、基板上に塗布することにより形成することもできる。また、導電性高分子の場合は、電解重合により直接基板上に薄膜を形成したり、基板上に導電性高分子を塗布して陽極を形成することもできる(Appl.Phys.Lett.,60巻,2711頁,1992年)。
The formation of the anode 2 is usually carried out by dry methods such as sputtering and vacuum deposition. In addition, when the anode is formed using metal fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc., an appropriate binder resin solution may be used. It can also be formed by dispersing and coating on a substrate. In the case of a conductive polymer, a thin film can be formed directly on a substrate by electrolytic polymerization, or an anode can be formed by coating a conductive polymer on a substrate (Appl. Phys. Lett., 60 2711, 1992).
陽極2は、通常、単層構造であるが、適宜、積層構造としてもよい。陽極2が積層構造である場合、1層目の陽極上に異なる導電材料を積層してもよい。
The anode 2 usually has a single-layer structure, but may have a laminated structure as appropriate. When the anode 2 has a laminated structure, different conductive materials may be laminated on the first layer of the anode.
陽極2の厚みは、必要とされる透明性と材質等に応じて決めればよい。特に高い透明性が必要とされる場合は、可視光の透過率が60%以上となる厚みが好ましく、可視光の透過率が80%以上となる厚みが更に好ましい。陽極2の厚みは、通常5nm以上、好ましくは10nm以上であり、また、通常1000nm以下、好ましくは500nm以下である。一方、透明性が不要な場合は、陽極2の厚みは必要な強度等に応じて任意に厚みとすればよく、この場合、陽極2は基板と同一の厚みでもよい。
The thickness of the anode 2 may be determined according to the required transparency and material. When particularly high transparency is required, the thickness is preferably such that the visible light transmittance is 60% or more, and more preferably the thickness is such that the visible light transmittance is 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. On the other hand, when transparency is not required, the thickness of the anode 2 may be arbitrarily set according to the required strength, etc. In this case, the thickness of the anode 2 may be the same as that of the substrate.
陽極2の表面に他の層を成膜する場合は、成膜前に、紫外線/オゾン、酸素プラズマ、アルゴンプラズマ等の処理を施すことにより、陽極2上の不純物を除去すると共に、そのイオン化ポテンシャルを調整して正孔注入性を向上させておくことが好ましい。
When another layer is formed on the surface of the anode 2, the impurity on the anode 2 is removed and its ionization potential is changed by treating with ultraviolet rays/ozone, oxygen plasma, argon plasma, etc. before the film formation. is preferably adjusted to improve the hole injection property.
[正孔注入層]
陽極2側から発光層5側に正孔を輸送する機能を担う層は、通常、正孔注入輸送層又は正孔輸送層と呼ばれる。そして、陽極2側から発光層5側に正孔を輸送する機能を担う層が2層以上ある場合に、より陽極側に近い方の層を正孔注入層3と呼ぶことがある。正孔注入層3は、陽極2から発光層5側に正孔を輸送する機能を強化する点で、形成されることが好ましい。正孔注入層3を形成する場合、通常、正孔注入層3は、陽極2上に形成される。 [Hole injection layer]
A layer that functions to transport holes from theanode 2 side to the light emitting layer 5 side is usually called a hole injection transport layer or a hole transport layer. When there are two or more layers that function to transport holes from the anode 2 side to the light emitting layer 5 side, the layer closer to the anode side may be called the hole injection layer 3 . The hole injection layer 3 is preferably formed in order to enhance the function of transporting holes from the anode 2 to the light emitting layer 5 side. When forming the hole injection layer 3 , the hole injection layer 3 is usually formed on the anode 2 .
陽極2側から発光層5側に正孔を輸送する機能を担う層は、通常、正孔注入輸送層又は正孔輸送層と呼ばれる。そして、陽極2側から発光層5側に正孔を輸送する機能を担う層が2層以上ある場合に、より陽極側に近い方の層を正孔注入層3と呼ぶことがある。正孔注入層3は、陽極2から発光層5側に正孔を輸送する機能を強化する点で、形成されることが好ましい。正孔注入層3を形成する場合、通常、正孔注入層3は、陽極2上に形成される。 [Hole injection layer]
A layer that functions to transport holes from the
本発明の組成物を用いて成膜された正孔注入層3は、本発明のフッ素を含むアリールアミン高分子化合物と本発明の電子受容性化合物との架橋反応物を含む。
The hole injection layer 3 formed using the composition of the present invention contains a crosslinked reaction product of the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention.
正孔注入層3の形成方法は特に制限されず、真空蒸着法、湿式成膜法等が挙げられる。湿式成膜法による層形成の場合は、本発明の組成物を調製し、スピンコート法やディップコート法等の湿式成膜法により陽極2上に塗布し、乾燥して、正孔注入層3を形成させる。
The method for forming the hole injection layer 3 is not particularly limited, and examples thereof include a vacuum deposition method and a wet film formation method. In the case of layer formation by a wet film-forming method, the composition of the present invention is prepared, applied onto the anode 2 by a wet film-forming method such as a spin coating method or a dip coating method, and dried to form a hole injection layer 3. form.
特に好ましくは、本発明の前記本発明のフッ素を含むアリールアミン高分子化合物と前記本発明の電子受容性化合物とを含む組成物を用いること、及び本発明の前記本発明のフッ素を含むアリールアミン高分子化合物と前記本発明の電子受容性化合物とを含む組成物を用いて形成された膜を用いることである。
このようにして形成される正孔注入層3の膜厚は、通常5nm以上、好ましくは10nm以上、また、通常1000nm以下、好ましくは500nm以下の範囲である。 It is particularly preferable to use a composition containing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention, and to use the fluorine-containing arylamine of the present invention. It is to use a film formed using a composition containing a polymer compound and the electron-accepting compound of the present invention.
The film thickness of the hole injection layer 3 thus formed is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
このようにして形成される正孔注入層3の膜厚は、通常5nm以上、好ましくは10nm以上、また、通常1000nm以下、好ましくは500nm以下の範囲である。 It is particularly preferable to use a composition containing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention, and to use the fluorine-containing arylamine of the present invention. It is to use a film formed using a composition containing a polymer compound and the electron-accepting compound of the present invention.
The film thickness of the hole injection layer 3 thus formed is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
正孔注入層の形成方法は、真空蒸着法でも、湿式成膜法でもよい。成膜性が優れる点では、湿式成膜法により形成することが好ましい。
溶剤としては、例えば、エーテル系溶剤、エステル系溶剤、芳香族炭化水素系溶剤、アミド系溶剤等が挙げられる。 A method for forming the hole injection layer may be a vacuum deposition method or a wet film formation method. From the viewpoint of excellent film-forming properties, it is preferable to form the film by a wet film-forming method.
Examples of the solvent include ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, amide-based solvents, and the like.
溶剤としては、例えば、エーテル系溶剤、エステル系溶剤、芳香族炭化水素系溶剤、アミド系溶剤等が挙げられる。 A method for forming the hole injection layer may be a vacuum deposition method or a wet film formation method. From the viewpoint of excellent film-forming properties, it is preferable to form the film by a wet film-forming method.
Examples of the solvent include ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, amide-based solvents, and the like.
エーテル系溶剤としては、例えば、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコール-1-モノメチルエーテルアセタート(PGMEA)等の脂肪族エーテル及び1,2-ジメトキシベンゼン、1,3-ジメトキシベンゼン、アニソール、フェネトール、2-メトキシトルエン、3-メトキシトルエン、4-メトキシトルエン、2,3-ジメチルアニソール、2,4-ジメチルアニソール等の芳香族エーテル等が挙げられる。
Examples of ether-based solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and anisole. , phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole.
エステル系溶剤としては、例えば、酢酸フェニル、プロピオン酸フェニル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸n-ブチル等の芳香族エステル等が挙げられる。
Examples of ester-based solvents include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.
芳香族炭化水素系溶剤としては、例えば、トルエン、キシレン、シクロヘキシルベンゼン、3-イソプロピルビフェニル、1,2,3,4-テトラメチルベンゼン、1,4-ジイソプロピルベンゼン、シクロヘキシルベンゼン、メチルナフタレン等が挙げられる。
Examples of aromatic hydrocarbon solvents include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, and methylnaphthalene. be done.
アミド系溶剤としては、例えば、N,N-ジメチルホルムアミド、N,N-ジメチルアセトアミド等が挙げられる。
Examples of amide-based solvents include N,N-dimethylformamide and N,N-dimethylacetamide.
これらの他、ジメチルスルホキシド等も用いることができる。
In addition to these, dimethyl sulfoxide and the like can also be used.
正孔注入層3の湿式成膜法による形成は、通常、正孔注入層形成用組成物を調製後に、これを、正孔注入層3の下層に該当する層(通常は、陽極2)上に塗布成膜し、乾燥することにより行われる。
Formation of the hole injection layer 3 by a wet film-forming method is usually carried out by preparing a composition for forming a hole injection layer and then applying it on a layer corresponding to the lower layer of the hole injection layer 3 (usually the anode 2). It is carried out by coating and forming a film on the surface and drying it.
正孔注入層3は、通常、成膜後に、加熱や減圧乾燥等により塗布膜を乾燥させる。
After forming the hole injection layer 3, the coating film is usually dried by heating, drying under reduced pressure, or the like.
[正孔輸送層]
正孔輸送層4は、陽極2側から発光層5側に正孔を輸送する機能を担う層である。正孔輸送層4は、本発明の有機電界発光素子では、必須の層では無いが、陽極2から発光層5に正孔を輸送する機能を強化する点では、この層を形成することが好ましい。正孔輸送層4を形成する場合、通常、正孔輸送層4は、陽極2と発光層5の間に形成される。また、上述の正孔注入層3がある場合は、正孔注入層3と発光層5の間に形成される。 [Hole transport layer]
The hole transport layer 4 is a layer that functions to transport holes from theanode 2 side to the light emitting layer 5 side. The hole transport layer 4 is not an essential layer in the organic electroluminescent device of the present invention, but it is preferable to form this layer in terms of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5. . When forming the hole transport layer 4 , the hole transport layer 4 is usually formed between the anode 2 and the light emitting layer 5 . Further, when the hole injection layer 3 described above is present, it is formed between the hole injection layer 3 and the light emitting layer 5 .
正孔輸送層4は、陽極2側から発光層5側に正孔を輸送する機能を担う層である。正孔輸送層4は、本発明の有機電界発光素子では、必須の層では無いが、陽極2から発光層5に正孔を輸送する機能を強化する点では、この層を形成することが好ましい。正孔輸送層4を形成する場合、通常、正孔輸送層4は、陽極2と発光層5の間に形成される。また、上述の正孔注入層3がある場合は、正孔注入層3と発光層5の間に形成される。 [Hole transport layer]
The hole transport layer 4 is a layer that functions to transport holes from the
正孔輸送層4の膜厚は、通常5nm以上、好ましくは10nm以上であり、また、一方、通常300nm以下、好ましくは100nm以下である。
The film thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and is usually 300 nm or less, preferably 100 nm or less.
正孔輸送層4を形成する材料としては、正孔輸送性が高く、かつ、注入された正孔を効率よく輸送することができる材料であることが好ましい。さらに正孔注入層から正孔輸送層に注入障壁が低いことが好ましい。そのために、イオン化ポテンシャルが適切的、可視光の光に対して透明性が高く、正孔移動度が大きく、安定性に優れ、トラップとなる不純物が製造時や使用時に発生しにくいことが好ましい。また、多くの場合、正孔輸送層4は、発光層5に接するため、発光層5からの発光を消光したり、発光層5との間でエキサイプレックスを形成して効率を低下させたりしないことが好ましい。
A material that forms the hole transport layer 4 is preferably a material that has a high hole transport property and can efficiently transport the injected holes. Furthermore, it is preferable that the injection barrier from the hole injection layer to the hole transport layer is low. Therefore, it is preferable that the ionization potential is appropriate, the transparency to visible light is high, the hole mobility is large, the stability is excellent, and impurities that become traps are less likely to occur during manufacture and use. In many cases, since the hole transport layer 4 is in contact with the light emitting layer 5, it does not quench the light emitted from the light emitting layer 5 or form an exciplex with the light emitting layer 5 to reduce the efficiency. is preferred.
このような正孔輸送層4の材料としては、従来、正孔輸送層の構成材料として用いられている材料であればよく、例えば、前記の正孔注入層3に使用される正孔輸送性化合物として例示したものが挙げられる。また、アリールアミン誘導体、フルオレン誘導体、スピロ誘導体、カルバゾール誘導体、ピリジン誘導体、ピラジン誘導体、ピリミジン誘導体、トリアジン誘導体、キノリン誘導体、フェナントロリン誘導体、フタロシアニン誘導体、ポルフィリン誘導体、シロール誘導体、オリゴチオフェン誘導体、縮合多環芳香族誘導体、金属錯体などが挙げられる。
As the material for such a hole transport layer 4, any material can be used as long as it is a material conventionally used as a constituent material for a hole transport layer. Examples of compounds include those exemplified. Also, arylamine derivatives, fluorene derivatives, spiro derivatives, carbazole derivatives, pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline derivatives, phthalocyanine derivatives, porphyrin derivatives, silole derivatives, oligothiophene derivatives, condensed polycyclic aromatic group derivatives, metal complexes, and the like.
また、例えば、ポリビニルカルバゾール誘導体、ポリアリールアミン誘導体、ポリビニルトリフェニルアミン誘導体、ポリフルオレン誘導体、ポリアリーレン誘導体、テトラフェニルベンジジンを含有するポリアリーレンエーテルサルホン誘導体、ポリアリーレンビニレン誘導体、ポリシロキサン誘導体、ポリチオフェン誘導体、ポリ(p-フェニレンビニレン)誘導体等が挙げられる。これらは、交互共重合体、ランダム重合体、ブロック重合体又はグラフト共重合体のいずれであってもよい。また、主鎖に枝分かれがあり末端部が3つ以上ある高分子や、所謂デンドリマーであってもよい。
Also, for example, polyvinylcarbazole derivatives, polyarylamine derivatives, polyvinyltriphenylamine derivatives, polyfluorene derivatives, polyarylene derivatives, polyarylene ether sulfone derivatives containing tetraphenylbenzidine, polyarylene vinylene derivatives, polysiloxane derivatives, polythiophenes. derivatives, poly(p-phenylene vinylene) derivatives and the like. These may be alternating copolymers, random polymers, block polymers or graft copolymers. Also, a polymer having a branched main chain and three or more terminal portions, or a so-called dendrimer may be used.
中でも、ポリアリールアミン誘導体やポリアリーレン誘導体が好ましい。
ポリアリールアミン誘導体としては、下記式(I)で表される繰り返し単位を含む重合体が好ましい。特に、下記式(I)で表される繰り返し単位からなる重合体が好ましく、この場合、繰り返し単位それぞれにおいて、Ara’又はArb’が異なっているものであってもよい。 Among them, polyarylamine derivatives and polyarylene derivatives are preferred.
As the polyarylamine derivative, a polymer containing a repeating unit represented by the following formula (I) is preferred. In particular, a polymer composed of repeating units represented by the following formula (I) is preferable, and in this case, Ar a ' or Ar b ' may be different in each repeating unit.
ポリアリールアミン誘導体としては、下記式(I)で表される繰り返し単位を含む重合体が好ましい。特に、下記式(I)で表される繰り返し単位からなる重合体が好ましく、この場合、繰り返し単位それぞれにおいて、Ara’又はArb’が異なっているものであってもよい。 Among them, polyarylamine derivatives and polyarylene derivatives are preferred.
As the polyarylamine derivative, a polymer containing a repeating unit represented by the following formula (I) is preferred. In particular, a polymer composed of repeating units represented by the following formula (I) is preferable, and in this case, Ar a ' or Ar b ' may be different in each repeating unit.
(式(I)中、Ara’及びArb’は、それぞれ独立して、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表す。)
(In formula (I), Ar a ' and Ar b ' are each independently an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group represents.)
ポリアリーレン誘導体としては、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基などのアリーレン基をその繰り返し単位に有する高分子化合物が挙げられる。
Examples of polyarylene derivatives include polymer compounds having an arylene group such as an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group as a repeating unit. be done.
ポリアリーレン誘導体としては、下記式(II-1)及び/又は下記式(II-2)からなる繰り返し単位を有する高分子化合物が好ましい。
As the polyarylene derivative, a polymer compound having a repeating unit represented by the following formula (II-1) and/or the following formula (II-2) is preferable.
(式(II-1)中、Ra、Rb、Rc及びRdは、それぞれ独立に、アルキル基、アルコキシ基、フェニルアルキル基、フェニルアルコキシ基、フェニル基、フェノキシ基、アルキルフェニル基、アルコキシフェニル基、アルキルカルボニル基、アルコキシカルボニル基又はカルボキシ基を表す。x11及びx12は、それぞれ独立に、0~3の整数を表す。x11又はx12が2以上の場合、一分子中に含まれる複数のRa又はRbは同一であっても異なっていてもよく、隣接するRa又はRb同士で環を形成していてもよい。)
(In formula (II-1), R a , R b , R c and R d are each independently an alkyl group, an alkoxy group, a phenylalkyl group, a phenylalkoxy group, a phenyl group, a phenoxy group, an alkylphenyl group, represents an alkoxyphenyl group, an alkylcarbonyl group, an alkoxycarbonyl group or a carboxy group, x11 and x12 each independently represent an integer of 0 to 3. When x11 or x12 is 2 or more, a plurality of groups contained in one molecule may be the same or different, and adjacent Ra or Rb may form a ring. )
(式(II-2)中、Re及びRfは、それぞれ独立に、上記式(II-1)におけるRa、Rb、Rc又はRdと同義である。x13及びx14は、それぞれ独立に、0~3の整数を表す。x13又はx14が2以上の場合、一分子中に含まれる複数のRe及びRfは同一であっても異なっていてもよく、隣接するRe又はRf同士で環を形成していてもよい。Lは、5員環又は6員環を構成する原子又は原子群を表す。)
(In formula (II-2), R e and R f are each independently synonymous with R a , R b , R c or R d in formula (II-1) above. x13 and x14 are each independently represents an integer of 0 to 3. When x13 or x14 is 2 or more, a plurality of R e and R f contained in one molecule may be the same or different, and adjacent R e or R f may form a ring together, and L represents an atom or a group of atoms constituting a 5- or 6-membered ring.)
Lの具体例としては、酸素原子、置換基を有していてもよいホウ素原子、置換基を有していてもよい窒素原子、置換基を有していてもよいケイ素原子、置換基を有していてもよいリン原子、置換基を有していてもよいイオウ原子、置換基を有していてもよい炭素原子又はこれらが結合してなる基である。
Specific examples of L include an oxygen atom, an optionally substituted boron atom, an optionally substituted nitrogen atom, an optionally substituted silicon atom, and an optionally substituted an optionally substituted phosphorus atom, an optionally substituted sulfur atom, an optionally substituted carbon atom, or a group formed by combining these atoms.
また、ポリアリーレン誘導体としては、上記式(II-1)及び/又は上記式(II-2)からなる繰り返し単位に加えて、さらに下記式(III-3)で表される繰り返し単位を有することが好ましい。
Further, the polyarylene derivative has a repeating unit represented by the following formula (III-3) in addition to the repeating unit represented by the above formula (II-1) and/or the above formula (II-2). is preferred.
(式(III-3)中、Arc~Ariは、それぞれ独立に、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表す。x15及びx16は、それぞれ独立に0又は1を表す。)
(In formula (III-3), Ar c to Ar i each independently represent an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group; x15 and x16 each independently represent 0 or 1.)
上記式(III-1)~(III-3)の具体例及びポリアリーレン誘導体の具体例等は、特開2008-98619号公報に記載のものなどが挙げられる。
Specific examples of the above formulas (III-1) to (III-3) and specific examples of the polyarylene derivative include those described in JP-A-2008-98619.
湿式成膜法で正孔輸送層4を形成する場合は、上記正孔注入層3の形成と同様にして、正孔輸送層形成用組成物を調製した後、湿式成膜後、加熱乾燥させる。
When the hole transport layer 4 is formed by a wet film formation method, a composition for forming a hole transport layer is prepared in the same manner as in the formation of the hole injection layer 3, and after wet film formation, heat drying is performed. .
正孔輸送層形成用組成物は、上述の正孔輸送性化合物の他、溶剤を含有する。用いる溶剤は上記正孔注入層形成用組成物に用いたものと同様である。また、成膜条件、加熱乾燥条件等も正孔注入層3の形成の場合と同様である。
The hole-transporting layer-forming composition contains a solvent in addition to the hole-transporting compound described above. The solvent to be used is the same as that used for the composition for forming the hole injection layer. Further, the film formation conditions, heat drying conditions, etc. are the same as in the case of forming the hole injection layer 3 .
真空蒸着法により正孔輸送層を形成する場合もまた、その成膜条件等は上記正孔注入層3の形成の場合と同様である。
In the case of forming the hole transport layer by vacuum evaporation, the film forming conditions and the like are the same as in the case of forming the hole injection layer 3 described above.
正孔輸送層4は、上記正孔輸送性化合物の他、各種の発光材料、電子輸送性化合物、バインダー樹脂、塗布性改良剤などを含有していてもよい。
The hole-transporting layer 4 may contain various light-emitting materials, electron-transporting compounds, binder resins, coatability improvers, etc., in addition to the above hole-transporting compounds.
また、正孔輸送層4は、架橋性化合物を架橋して形成される層であってもよい。架橋性化合物は、架橋性基を有する化合物であって、架橋することにより網目状高分子化合物を形成する。
Further, the hole transport layer 4 may be a layer formed by cross-linking a cross-linking compound. The crosslinkable compound is a compound having a crosslinkable group, and forms a network polymer compound by crosslinking.
この架橋性基の例を挙げると、オキセタン、エポキシなどの環状エーテル由来の基;ビニル基、トリフルオロビニル基、スチリル基、アクリル基、メタクリロイル、シンナモイル等の不飽和二重結合由来の基;ベンゾシクロブテン由来の基などが挙げられる。
Examples of crosslinkable groups include groups derived from cyclic ethers such as oxetane and epoxy; groups derived from unsaturated double bonds such as vinyl, trifluorovinyl, styryl, acryl, methacryloyl, and cinnamoyl; Examples thereof include groups derived from cyclobutene.
架橋性化合物は、モノマー、オリゴマー、ポリマーのいずれであってもよい。架橋性化合物は1種のみを有していてもよく、2種以上を任意の組み合わせ及び比率で有していてもよい。
The crosslinkable compound may be a monomer, oligomer, or polymer. The crosslinkable compound may have only one type, or may have two or more types in any combination and ratio.
架橋性化合物としては、架橋性基を有する正孔輸送性化合物を用いることが好ましい。正孔輸送性化合物としては、上記の例示したものが挙げられ、架橋性化合物としては、これら正孔輸送性化合物に対して、架橋性基が主鎖又は側鎖に結合しているものが挙げられる。特に架橋性基は、アルキレン基等の連結基を介して、主鎖に結合していることが好ましい。また、特に正孔輸送性化合物としては、架橋性基を有する繰り返し単位を含む重合体であることが好ましく、上記式(I)や式(II-1)~(III-3)に架橋性基が直接又は連結基を介して結合した繰り返し単位を有する高分子化合物であることが好ましい。
A hole-transporting compound having a crosslinkable group is preferably used as the crosslinkable compound. Examples of the hole-transporting compound include those exemplified above, and examples of the cross-linking compound include those in which a cross-linking group is bonded to the main chain or side chain of these hole-transporting compounds. be done. In particular, the crosslinkable group is preferably bonded to the main chain via a linking group such as an alkylene group. In particular, the hole-transporting compound is preferably a polymer containing a repeating unit having a crosslinkable group. is preferably a polymer compound having repeating units linked directly or via a linking group.
架橋性化合物を架橋して正孔輸送層4を形成するには、通常、架橋性化合物を溶剤に溶解又は分散した正孔輸送層形成用組成物を調製して、湿式成膜により成膜して架橋させる。
In order to form the hole transport layer 4 by cross-linking the cross-linking compound, a composition for forming a hole transport layer is usually prepared by dissolving or dispersing the cross-linking compound in a solvent, and the film is formed by wet film formation. to cross-link.
このようにして形成される正孔輸送層4の膜厚は、通常5nm以上、好ましくは10nm以上であり、また、通常300nm以下、好ましくは150nm以下である。
The film thickness of the hole transport layer 4 thus formed is usually 5 nm or more, preferably 10 nm or more, and usually 300 nm or less, preferably 150 nm or less.
[発光層]
発光層5は、一対の電極間に電界が与えられた時に、陽極2から注入される正孔と陰極7から注入される電子が再結合することにより励起され、発光する機能を担う層である。発光層5は、陽極2と陰極7の間に形成される層であり、発光層は、陽極の上に正孔注入層がある場合は、正孔注入層と陰極の間に形成され、陽極の上に正孔輸送層がある場合は、正孔輸送層と陰極の間に形成される。
本発明における有機電界発光素子は、前記の通り、発光層として好適な発光層形成材料を含むことが好ましい。 [Light emitting layer]
The light-emitting layer 5 is a layer that functions to emit light by being excited by recombination of holes injected from theanode 2 and electrons injected from the cathode 7 when an electric field is applied between a pair of electrodes. . The light-emitting layer 5 is a layer formed between the anode 2 and the cathode 7, and the light-emitting layer is formed between the hole-injection layer and the cathode, if there is a hole-injection layer on the anode, and the anode If there is a hole-transport layer on top, it is formed between the hole-transport layer and the cathode.
As described above, the organic electroluminescent element in the present invention preferably contains a light-emitting layer-forming material suitable for the light-emitting layer.
発光層5は、一対の電極間に電界が与えられた時に、陽極2から注入される正孔と陰極7から注入される電子が再結合することにより励起され、発光する機能を担う層である。発光層5は、陽極2と陰極7の間に形成される層であり、発光層は、陽極の上に正孔注入層がある場合は、正孔注入層と陰極の間に形成され、陽極の上に正孔輸送層がある場合は、正孔輸送層と陰極の間に形成される。
本発明における有機電界発光素子は、前記の通り、発光層として好適な発光層形成材料を含むことが好ましい。 [Light emitting layer]
The light-emitting layer 5 is a layer that functions to emit light by being excited by recombination of holes injected from the
As described above, the organic electroluminescent element in the present invention preferably contains a light-emitting layer-forming material suitable for the light-emitting layer.
発光層5の膜厚は、本発明の効果を著しく損なわない限り任意であるが、膜に欠陥が生じ難い点では厚い方が好ましく、また、一方、薄い方が低駆動電圧としやすい点で好ましい。このため、3nm以上であるのが好ましく、5nm以上であるのが更に好ましく、また、一方、通常200nm以下であるのが好ましく、100nm以下であるのが更に好ましい。
The film thickness of the light-emitting layer 5 is arbitrary as long as it does not significantly impair the effects of the present invention, but a thicker film is preferable because defects are less likely to occur in the film, and a thinner film is preferable because a low driving voltage can be easily achieved. . Therefore, it is preferably 3 nm or more, more preferably 5 nm or more, and on the other hand, it is usually preferably 200 nm or less, more preferably 100 nm or less.
発光層5は、少なくとも、発光の性質を有する材料(発光材料)を含み、好ましくは、1つまたは複数のホスト材料を含む。
The light-emitting layer 5 contains at least a material having light-emitting properties (light-emitting material), and preferably contains one or more host materials.
[好適な発光層形成材料]
本発明における発光層は、発光材料と電荷輸送材料を含む。発光材料は燐光発光材料でもよいし、蛍光発光材料でもよい。電荷輸送膜好ましくは、赤発光材料と緑発光材料は燐光発光材料であり、青発光材料は蛍光発光材料である。 [Suitable material for forming light-emitting layer]
The light-emitting layer in the present invention contains a light-emitting material and a charge transport material. The luminescent material may be a phosphorescent luminescent material or a fluorescent luminescent material. Charge Transport Film Preferably, the red-emitting material and the green-emitting material are phosphorescent materials, and the blue-emitting material is a fluorescent material.
本発明における発光層は、発光材料と電荷輸送材料を含む。発光材料は燐光発光材料でもよいし、蛍光発光材料でもよい。電荷輸送膜好ましくは、赤発光材料と緑発光材料は燐光発光材料であり、青発光材料は蛍光発光材料である。 [Suitable material for forming light-emitting layer]
The light-emitting layer in the present invention contains a light-emitting material and a charge transport material. The luminescent material may be a phosphorescent luminescent material or a fluorescent luminescent material. Charge Transport Film Preferably, the red-emitting material and the green-emitting material are phosphorescent materials, and the blue-emitting material is a fluorescent material.
<燐光発光材料>
燐光発光材料とは、励起三重項状態から発光を示す材料をいう。例えば、Ir、Pt、Euなどを有する金属錯体化合物がその代表例であり、材料の構造として、金属錯体を含むものが好ましい。 <Phosphorescent material>
A phosphorescent material is a material that emits light from an excited triplet state. For example, metal complex compounds containing Ir, Pt, Eu, etc. are typical examples, and materials containing metal complexes are preferable as the structure of the material.
燐光発光材料とは、励起三重項状態から発光を示す材料をいう。例えば、Ir、Pt、Euなどを有する金属錯体化合物がその代表例であり、材料の構造として、金属錯体を含むものが好ましい。 <Phosphorescent material>
A phosphorescent material is a material that emits light from an excited triplet state. For example, metal complex compounds containing Ir, Pt, Eu, etc. are typical examples, and materials containing metal complexes are preferable as the structure of the material.
金属錯体の中でも、三重項状態を経由して発光する燐光発光性有機金属錯体として、長周期型周期表(以下、特に断り書きの無い限り「周期表」という場合には、長周期型周期表を指すものとする。)第7~11族から選ばれる金属を中心金属として含むウェルナー型錯体又は有機金属錯体化合物が挙げられる。このような燐光発光材料としては、例えば、国際公開第2014/024889号、国際公開第2015-087961号、国際公開第2016/194784、特開2014-074000号に記載の燐光発光材料が挙げられる。好ましくは、下記式(201)で表される化合物、又は下記式(205)で表される化合物が好ましく、より好ましくは下記式(201)で表される化合物である。
Among metal complexes, 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. Examples of such phosphorescent materials include those described in International Publication No. 2014/024889, International Publication No. 2015-087961, International Publication No. 2016/194784, and JP-A-2014-074000. 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.
式(201)において、環A1は置換基を有していてもよい芳香族炭化水素環構造又は置換基を有していてもよい芳香族複素環構造を表す。
環A2は置換基を有していてもよい芳香族複素環構造を表す。
R101、R102は各々独立に式(202)で表される構造であり、“*”は環A1又は環A2との結合位置を表す。R101、R102は同じであっても異なっていてもよく、R101、R102がそれぞれ複数存在する場合、それらは同じであっても異なっていてもよい。 In formula (201), 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 which may have a substituent.
R 101 and R 102 each independently represent a structure represented by formula (202), and "*" represents the bonding position with ring A1 or ring A2. R 101 and R 102 may be the same or different, and when multiple R 101 and R 102 are present, they may be the same or different.
環A2は置換基を有していてもよい芳香族複素環構造を表す。
R101、R102は各々独立に式(202)で表される構造であり、“*”は環A1又は環A2との結合位置を表す。R101、R102は同じであっても異なっていてもよく、R101、R102がそれぞれ複数存在する場合、それらは同じであっても異なっていてもよい。 In formula (201), 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 which may have a substituent.
R 101 and R 102 each independently represent a structure represented by formula (202), and "*" represents the bonding position with ring A1 or ring A2. R 101 and R 102 may be the same or different, and when multiple R 101 and R 102 are present, they may be the same or different.
Ar201、Ar203は、各々独立に、置換基を有していてもよい芳香族炭化水素環構造、又は置換基を有していてもよい芳香族複素環構造を表す。
Ar202は、置換基を有していてもよい芳香族炭化水素環構造、置換基を有していてもよい芳香族複素環構造、又は置換基を有していてもよい脂肪族炭化水素構造を表す。
環A1に結合する置換基同士、環A2に結合する置換基同士、又は環A1に結合する置換基と環A2に結合する置換基同士は、互いに結合して環を形成してもよい。 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
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 may be bonded to each other to form a ring.
Ar202は、置換基を有していてもよい芳香族炭化水素環構造、置換基を有していてもよい芳香族複素環構造、又は置換基を有していてもよい脂肪族炭化水素構造を表す。
環A1に結合する置換基同士、環A2に結合する置換基同士、又は環A1に結合する置換基と環A2に結合する置換基同士は、互いに結合して環を形成してもよい。 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
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 may be bonded to each other to form a ring.
B201-L200-B202は、アニオン性の2座配位子を表す。B201及びB202は、それぞれ独立に、炭素原子、酸素原子又は窒素原子を表し、これらの原子は環を構成する原子であってもよい。L200は、単結合、又は、B201及びB202とともに2座配位子を構成する原子団を表す。B201-L200-B202が複数存在する場合、それらは同一でも異なっていてもよい。
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 . When there are multiple groups of B 201 -L 200 -B 202 , they may be the same or different.
なお、式(201)、(202)において、
i1、i2はそれぞれ独立に、0以上12以下の整数を表し、
i3は、Ar202に置換可能な数を上限とする0以上の整数を表し、
i4は、Ar201に置換可能な数を上限とする0以上の整数を表し、
k1及びk2はそれぞれ独立に、環A1、環A2に置換可能な数を上限とする0以上の整数を表し、
zは1~3の整数を表す。 Note that in formulas (201) and (202),
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;
i1、i2はそれぞれ独立に、0以上12以下の整数を表し、
i3は、Ar202に置換可能な数を上限とする0以上の整数を表し、
i4は、Ar201に置換可能な数を上限とする0以上の整数を表し、
k1及びk2はそれぞれ独立に、環A1、環A2に置換可能な数を上限とする0以上の整数を表し、
zは1~3の整数を表す。 Note that in formulas (201) and (202),
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;
(置換基)
特に断りのない場合、発光層形成材料における置換基としては、次の置換基群Sから選ばれる基が好ましい。 (substituent)
Unless otherwise specified, a group selected from the following Substituent Group S is preferable as the substituent in the material for forming the light-emitting layer.
特に断りのない場合、発光層形成材料における置換基としては、次の置換基群Sから選ばれる基が好ましい。 (substituent)
Unless otherwise specified, a group selected from the following Substituent Group S is preferable as the substituent in the material for forming the light-emitting layer.
<置換基群S>
・アルキル基、好ましくは炭素数1~20のアルキル基、より好ましくは炭素数1~12のアルキル基、さらに好ましくは炭素数1~8のアルキル基、特に好ましくは炭素数1~6のアルキル基。
・アルコキシ基、好ましくは炭素数1~20のアルコキシ基、より好ましくは炭素数1~12のアルコキシ基、さらに好ましくは炭素数1~6のアルコキシ基。
・アリールオキシ基、好ましくは炭素数6~20のアリールオキシ基、より好ましくは炭素数6~14のアリールオキシ基、さらに好ましくは炭素数6~12のアリールオキシ基、特に好ましくは炭素数6のアリールオキシ基。
・ヘテロアリールオキシ基、好ましくは炭素数3~20のヘテロアリールオキシ基、より好ましくは炭素数3~12のヘテロアリールオキシ基。
・アルキルアミノ基、好ましくは炭素数1~20のアルキルアミノ基、より好ましくは炭素数1~12のアルキルアミノ基。
・アリールアミノ基、好ましくは炭素数6~36のアリールアミノ基、より好ましくは炭素数6~24のアリールアミノ基。
・アラルキル基、好ましくは炭素数7~40のアラルキル基、より好ましくは炭素数7~18のアラルキル基、さらに好ましくは炭素数7~12のアラルキル基。
・ヘテロアラルキル基、好ましくは炭素数7~40のヘテロアラルキル基、より好ましくは炭素数7~18のヘテロアラルキル基、
・アルケニル基、好ましくは炭素数2~20のアルケニル基、より好ましくは炭素数2~12のアルケニル基、さらに好ましくは炭素数2~8のアルケニル基、特に好ましくは炭素数2~6のアルケニル基。
・アルキニル基、好ましくは炭素数2~20のアルキニル基、より好ましくは炭素数2~12のアルキニル基。
・アリール基、好ましくは炭素数6~30のアリール基、より好ましくは炭素数6~24のアリール基、さらに好ましくは炭素数6~18のアリール基、特に好ましくは炭素数6~14のアリール基。
・ヘテロアリール基、好ましくは炭素数3~30のヘテロアリール基、より好ましくは炭素数3~24のヘテロアリール基、さらに好ましくは炭素数3~18のヘテロアリール基、特に好ましくは炭素数3~14のヘテロアリール基。
・アルキルシリル基、好ましくはアルキル基の炭素数が1~20であるアルキルシリル基、より好ましくはアルキル基の炭素数が1~12であるアルキルシリル基。
・アリールシリル基、好ましくはアリール基の炭素数が6~20であるアリールシリル基、より好ましくはアリール基の炭素数が6~14であるアリールシリル基。
・アルキルカルボニル基、好ましくは炭素数2~20のアルキルカルボニル基。
・アリールカルボニル基、好ましくは炭素数7~20のアリールカルボニル基。 <Substituent group S>
- an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms .
- An alkoxy group, preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and 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;
・アルキル基、好ましくは炭素数1~20のアルキル基、より好ましくは炭素数1~12のアルキル基、さらに好ましくは炭素数1~8のアルキル基、特に好ましくは炭素数1~6のアルキル基。
・アルコキシ基、好ましくは炭素数1~20のアルコキシ基、より好ましくは炭素数1~12のアルコキシ基、さらに好ましくは炭素数1~6のアルコキシ基。
・アリールオキシ基、好ましくは炭素数6~20のアリールオキシ基、より好ましくは炭素数6~14のアリールオキシ基、さらに好ましくは炭素数6~12のアリールオキシ基、特に好ましくは炭素数6のアリールオキシ基。
・ヘテロアリールオキシ基、好ましくは炭素数3~20のヘテロアリールオキシ基、より好ましくは炭素数3~12のヘテロアリールオキシ基。
・アルキルアミノ基、好ましくは炭素数1~20のアルキルアミノ基、より好ましくは炭素数1~12のアルキルアミノ基。
・アリールアミノ基、好ましくは炭素数6~36のアリールアミノ基、より好ましくは炭素数6~24のアリールアミノ基。
・アラルキル基、好ましくは炭素数7~40のアラルキル基、より好ましくは炭素数7~18のアラルキル基、さらに好ましくは炭素数7~12のアラルキル基。
・ヘテロアラルキル基、好ましくは炭素数7~40のヘテロアラルキル基、より好ましくは炭素数7~18のヘテロアラルキル基、
・アルケニル基、好ましくは炭素数2~20のアルケニル基、より好ましくは炭素数2~12のアルケニル基、さらに好ましくは炭素数2~8のアルケニル基、特に好ましくは炭素数2~6のアルケニル基。
・アルキニル基、好ましくは炭素数2~20のアルキニル基、より好ましくは炭素数2~12のアルキニル基。
・アリール基、好ましくは炭素数6~30のアリール基、より好ましくは炭素数6~24のアリール基、さらに好ましくは炭素数6~18のアリール基、特に好ましくは炭素数6~14のアリール基。
・ヘテロアリール基、好ましくは炭素数3~30のヘテロアリール基、より好ましくは炭素数3~24のヘテロアリール基、さらに好ましくは炭素数3~18のヘテロアリール基、特に好ましくは炭素数3~14のヘテロアリール基。
・アルキルシリル基、好ましくはアルキル基の炭素数が1~20であるアルキルシリル基、より好ましくはアルキル基の炭素数が1~12であるアルキルシリル基。
・アリールシリル基、好ましくはアリール基の炭素数が6~20であるアリールシリル基、より好ましくはアリール基の炭素数が6~14であるアリールシリル基。
・アルキルカルボニル基、好ましくは炭素数2~20のアルキルカルボニル基。
・アリールカルボニル基、好ましくは炭素数7~20のアリールカルボニル基。 <Substituent group S>
- an alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms .
- An alkoxy group, preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, and 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;
以上の基は1つ以上の水素原子がフッ素原子で置き換えられているか、若しくは1つ以上の水素原子が重水素原子で置き換えらえられていてもよい。
特に断りのない限り、アリールは芳香族炭化水素環であり、ヘテロアリールは芳香族複素環である。
・水素原子、重水素原子、フッ素原子、シアノ基、又は、-SF5。 In the above groups, one or more hydrogen atoms may be replaced with fluorine atoms, or one or more hydrogen atoms may be replaced with deuterium atoms.
Unless otherwise specified, aryl is an aromatic hydrocarbon ring and heteroaryl is a heteroaromatic ring.
- A hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, or -SF 5 .
特に断りのない限り、アリールは芳香族炭化水素環であり、ヘテロアリールは芳香族複素環である。
・水素原子、重水素原子、フッ素原子、シアノ基、又は、-SF5。 In the above groups, one or more hydrogen atoms may be replaced with fluorine atoms, or one or more hydrogen atoms may be replaced with deuterium atoms.
Unless otherwise specified, aryl is an aromatic hydrocarbon ring and heteroaryl is a heteroaromatic ring.
- A hydrogen atom, a deuterium atom, a fluorine atom, a cyano group, or -SF 5 .
上記置換基群Sのうち、好ましくは、アルキル基、アルコキシ基、アリールオキシ基、アリールアミノ基、アラルキル基、アルケニル基、アリール基、ヘテロアリール基、アルキルシリル基、アリールシリル基、及びこれらの基の1つ以上の水素原子がフッ素原子で置き換えられている基、フッ素原子、シアノ基、又は-SF5であり、
より好ましくはアルキル基、アリールアミノ基、アラルキル基、アルケニル基、アリール基、ヘテロアリール基であり、及びこれらの基の1つ以上の水素原子がフッ素原子で置き換えられている基、フッ素原子、シアノ基、又は-SF5であり、
さらに好ましくは、アルキル基、アルコキシ基、アリールオキシ基、アリールアミノ基、アラルキル基、アルケニル基、アリール基、ヘテロアリール基、アルキルシリル基、アリールシリル基であり、
特に好ましくはアルキル基、アリールアミノ基、アラルキル基、アルケニル基、アリール基、ヘテロアリール基であり、
最も好ましくはアルキル基、アリールアミノ基、アラルキル基、アリール基、ヘテロアリール基である。 Of the 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 preferred are alkyl groups, arylamino groups, aralkyl groups, alkenyl groups, aryl groups, heteroaryl groups, and groups in which one or more hydrogen atoms of these groups are replaced with fluorine atoms, fluorine atoms, cyano a group, or —SF 5 ,
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,
Particularly preferred are alkyl groups, arylamino groups, aralkyl groups, alkenyl groups, aryl groups and heteroaryl groups,
Most preferred are alkyl groups, arylamino groups, aralkyl groups, aryl groups and heteroaryl groups.
より好ましくはアルキル基、アリールアミノ基、アラルキル基、アルケニル基、アリール基、ヘテロアリール基であり、及びこれらの基の1つ以上の水素原子がフッ素原子で置き換えられている基、フッ素原子、シアノ基、又は-SF5であり、
さらに好ましくは、アルキル基、アルコキシ基、アリールオキシ基、アリールアミノ基、アラルキル基、アルケニル基、アリール基、ヘテロアリール基、アルキルシリル基、アリールシリル基であり、
特に好ましくはアルキル基、アリールアミノ基、アラルキル基、アルケニル基、アリール基、ヘテロアリール基であり、
最も好ましくはアルキル基、アリールアミノ基、アラルキル基、アリール基、ヘテロアリール基である。 Of the 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 preferred are alkyl groups, arylamino groups, aralkyl groups, alkenyl groups, aryl groups, heteroaryl groups, and groups in which one or more hydrogen atoms of these groups are replaced with fluorine atoms, fluorine atoms, cyano a group, or —SF 5 ,
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,
Particularly preferred are alkyl groups, arylamino groups, aralkyl groups, alkenyl groups, aryl groups and heteroaryl groups,
Most preferred are alkyl groups, arylamino groups, aralkyl groups, aryl groups and heteroaryl groups.
これら置換基群Sにはさらに置換基群Sから選ばれる置換基を置換基として有していてもよい。有していてもよい置換基の好ましい基、より好ましい基、さらに好ましい基、特に好ましい基、最も好ましい基は置換基群Sの中の好ましい基と同様である。
These 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.
(環A1)
環A1は置換基を有していてもよい芳香族炭化水素環構造又は置換基を有していてもよい芳香族複素環構造を表す。 (Ring A1)
Ring A1 represents an optionally substituted aromatic hydrocarbon ring structure or an optionally substituted aromatic heterocyclic ring structure.
環A1は置換基を有していてもよい芳香族炭化水素環構造又は置換基を有していてもよい芳香族複素環構造を表す。 (Ring A1)
Ring A1 represents an optionally substituted aromatic hydrocarbon ring structure or an optionally substituted aromatic heterocyclic ring structure.
芳香族炭化水素環としては、好ましくは炭素数6~30の芳香族炭化水素環である。具体的には、ベンゼン環、ナフタレン環、アントラセン環、トリフェニリル環、アセナフテン環、フルオランテン環、フルオレン環が好ましい。
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.
芳香族複素環としては、ヘテロ原子として窒素原子、酸素原子、又は硫黄原子のいずれかを含む、炭素数3~30の芳香族複素環が好ましい。さらに好ましくは、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環である。
環A1としてより好ましくは、ベンゼン環、ナフタレン環、フルオレン環であり、特に好ましくはベンゼン環又はフルオレン環であり、最も好ましくはベンゼン環である。 As the aromatic heterocyclic ring, 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. Further preferred are 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.
環A1としてより好ましくは、ベンゼン環、ナフタレン環、フルオレン環であり、特に好ましくはベンゼン環又はフルオレン環であり、最も好ましくはベンゼン環である。 As the aromatic heterocyclic ring, 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. Further preferred are 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.
(環A2)
環A2は置換基を有していてもよい芳香族複素環構造を表す。
芳香族複素環としては、好ましくはヘテロ原子として窒素原子、酸素原子、又は硫黄原子のいずれかを含む、炭素数3~30の芳香族複素環である。具体的には、ピリジン環、ピリミジン環、ピラジン環、トリアジン環、イミダゾール環、オキサゾール環、チアゾール環、ベンゾチアゾール環、ベンゾオキサゾール環、ベンゾイミダゾール環、キノリン環、イソキノリン環、キノキサリン環、キナゾリン環、ナフチリジン環、フェナントリジン環が挙げられ、好ましくは、ピリジン環、ピラジン環、ピリミジン環、イミダゾール環、ベンゾチアゾール環、ベンゾオキサゾール環、キノリン環、イソキノリン環、キノキサリン環、キナゾリン環であり、より好ましくは、ピリジン環、イミダゾール環、ベンゾチアゾール環、キノリン環、イソキノリン環、キノキサリン環、キナゾリン環であり、最も好ましくは、ピリジン環、イミダゾール環、ベンゾチアゾール環、キノリン環、キノキサリン環、キナゾリン環である。 (Ring A2)
Ring A2 represents an aromatic heterocyclic structure which may have 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. Specifically, pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, oxazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, naphthyridine ring and phenanthridine ring, preferably pyridine ring, pyrazine ring, pyrimidine ring, imidazole ring, benzothiazole ring, benzoxazole ring, quinoline ring, isoquinoline ring, quinoxaline ring and quinazoline ring, more preferably is pyridine ring, imidazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, most preferably pyridine ring, imidazole ring, benzothiazole ring, quinoline ring, quinoxaline ring, quinazoline ring .
環A2は置換基を有していてもよい芳香族複素環構造を表す。
芳香族複素環としては、好ましくはヘテロ原子として窒素原子、酸素原子、又は硫黄原子のいずれかを含む、炭素数3~30の芳香族複素環である。具体的には、ピリジン環、ピリミジン環、ピラジン環、トリアジン環、イミダゾール環、オキサゾール環、チアゾール環、ベンゾチアゾール環、ベンゾオキサゾール環、ベンゾイミダゾール環、キノリン環、イソキノリン環、キノキサリン環、キナゾリン環、ナフチリジン環、フェナントリジン環が挙げられ、好ましくは、ピリジン環、ピラジン環、ピリミジン環、イミダゾール環、ベンゾチアゾール環、ベンゾオキサゾール環、キノリン環、イソキノリン環、キノキサリン環、キナゾリン環であり、より好ましくは、ピリジン環、イミダゾール環、ベンゾチアゾール環、キノリン環、イソキノリン環、キノキサリン環、キナゾリン環であり、最も好ましくは、ピリジン環、イミダゾール環、ベンゾチアゾール環、キノリン環、キノキサリン環、キナゾリン環である。 (Ring A2)
Ring A2 represents an aromatic heterocyclic structure which may have 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. Specifically, pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, oxazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, naphthyridine ring and phenanthridine ring, preferably pyridine ring, pyrazine ring, pyrimidine ring, imidazole ring, benzothiazole ring, benzoxazole ring, quinoline ring, isoquinoline ring, quinoxaline ring and quinazoline ring, more preferably is pyridine ring, imidazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, most preferably pyridine ring, imidazole ring, benzothiazole ring, quinoline ring, quinoxaline ring, quinazoline ring .
(環A1と環A2との組み合わせ)
環A1と環A2の好ましい組み合せとしては、(環A1-環A2)と表記すると、(ベンゼン環-ピリジン環)、(ベンゼン環-キノリン環)、(ベンゼン環-キノキサリン環)、(ベンゼン環-キナゾリン環)、(ベンゼン環-ベンゾチアゾール環)、(ベンゼン環-イミダゾール環)、(ベンゼン環-ピロール環)、(ベンゼン環-ジアゾール環)、及び(ベンゼン環-チオフェン環)である。 (Combination of 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).
環A1と環A2の好ましい組み合せとしては、(環A1-環A2)と表記すると、(ベンゼン環-ピリジン環)、(ベンゼン環-キノリン環)、(ベンゼン環-キノキサリン環)、(ベンゼン環-キナゾリン環)、(ベンゼン環-ベンゾチアゾール環)、(ベンゼン環-イミダゾール環)、(ベンゼン環-ピロール環)、(ベンゼン環-ジアゾール環)、及び(ベンゼン環-チオフェン環)である。 (Combination of 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).
(環A1、環A2の置換基)
環A1、環A2が有していてもよい置換基は任意に選択できるが、好ましくは前記置換基群Sから選ばれる1種又は複数種の置換基である。 (Ring A1, substituent of ring A2)
The substituents that the 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.
環A1、環A2が有していてもよい置換基は任意に選択できるが、好ましくは前記置換基群Sから選ばれる1種又は複数種の置換基である。 (Ring A1, substituent of ring A2)
The substituents that the 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、Ar202、Ar203)
Ar201、Ar203は、各々独立に、置換基を有していてもよい芳香族炭化水素環構造、又は置換基を有していてもよい芳香族複素環構造を表す。
Ar202は、置換基を有していてもよい芳香族炭化水素環構造、置換基を有していてもよい芳香族複素環構造、又は置換基を有していてもよい脂肪族炭化水素構造を表す。 ( Ar201 , Ar202 , Ar203 )
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
Ar201、Ar203は、各々独立に、置換基を有していてもよい芳香族炭化水素環構造、又は置換基を有していてもよい芳香族複素環構造を表す。
Ar202は、置換基を有していてもよい芳香族炭化水素環構造、置換基を有していてもよい芳香族複素環構造、又は置換基を有していてもよい脂肪族炭化水素構造を表す。 ( Ar201 , Ar202 , Ar203 )
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
Ar201、Ar202、Ar203のいずれかが置換基を有していてもよい芳香族炭化水素環構造である場合、該芳香族炭化水素環構造としては、好ましくは炭素数6~30の芳香族炭化水素環である。具体的には、ベンゼン環、ナフタレン環、アントラセン環、トリフェニリル環、アセナフテン環、フルオランテン環、フルオレン環が好ましく、より好ましくはベンゼン環、ナフタレン環、フルオレン環が好ましく、最も好ましくはベンゼン環である。
When any of Ar 201 , Ar 202 and Ar 203 is an optionally substituted aromatic hydrocarbon ring structure, 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.
Ar201、Ar202のいずれかが置換基を有していてもよいベンゼン環である場合、少なくとも1つのベンゼン環がオルト位又はメタ位で隣接する構造と結合していることが好ましく、少なくとも1つのベンゼン環がメタ位で隣接する構造と結合していることがより好ましい。
When either 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. More preferably, one benzene ring is attached to the adjacent structure at the meta position.
Ar201、Ar202、Ar203のいずれかが置換基を有していてもよいフルオレン環である場合、フルオレン環の9位及び9’位は、置換基を有するか又は隣接する構造と結合していることが好ましい。
When any of 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.
Ar201、Ar202、Ar203のいずれかが置換基を有していてもよい芳香族複素環構造である場合、芳香族複素環構造としては、好ましくはヘテロ原子として窒素原子、酸素原子、又は硫黄原子のいずれかを含む、炭素数3~30の芳香族複素環であり、具体的には、ピリジン環、ピリミジン環、ピラジン環、トリアジン環、イミダゾール環、オキサゾール環、チアゾール環、ベンゾチアゾール環、ベンゾオキサゾール環、ベンゾイミダゾール環、キノリン環、イソキノリン環、キノキサリン環、キナゾリン環、ナフチリジン環、フェナントリジン環、カルバゾール環、ジベンゾフラン環、ジベンゾチオフェン環が挙げられ、好ましくは、ピリジン環、ピリミジン環、トリアジン環、カルバゾール環、ジベンゾフラン環、ジベンゾチオフェン環である。
When any one of 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 An aromatic heterocyclic ring having 3 to 30 carbon atoms containing any of a sulfur atom, specifically, a pyridine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a benzothiazole ring. , benzoxazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, naphthyridine ring, phenanthridine ring, carbazole ring, dibenzofuran ring, and dibenzothiophene ring, preferably pyridine ring and pyrimidine ring. , triazine ring, carbazole ring, dibenzofuran ring, and dibenzothiophene ring.
Ar201、Ar202、Ar203のいずれかが置換基を有していてもよいカルバゾール環である場合、カルバゾール環のN位は、置換基を有するか又は隣接する構造と結合していることが好ましい。
When any of 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.
Ar202が置換基を有していてもよい脂肪族炭化水素構造である場合、直鎖、分岐鎖、又は環状構造を有する脂肪族炭化水素構造であり、好ましくは炭素数が1以上24以下であり、さらに好ましくは炭素数が1以上12以下であり、より好ましくは炭素数が1以上8以下である。
When 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、i2、i3、i4、k1、k2)
i1、i2はそれぞれ独立に、0~12の整数を表し、好ましくは1~12、さらに好ましくは1~8、より好ましくは1~6である。この範囲であることにより、溶解性向上や電荷輸送性向上が見込まれる。
i3は好ましくは0~5の整数を表し、さらに好ましくは0~2、より好ましくは0又は1である。
i4は好ましくは0~2の整数を表し、さらに好ましくは0又は1である。
k1、k2はそれぞれ独立に、好ましくは0~3の整数を表し、さらに好ましくは1~3であり、より好ましくは1又は2であり、特に好ましくは1である。 (i1, i2, i3, i4, k1, k2)
i1 and i2 each independently represent an integer of 0-12, preferably 1-12, more preferably 1-8, more preferably 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 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 1 to 3, more preferably 1 or 2, and particularly preferably 1.
i1、i2はそれぞれ独立に、0~12の整数を表し、好ましくは1~12、さらに好ましくは1~8、より好ましくは1~6である。この範囲であることにより、溶解性向上や電荷輸送性向上が見込まれる。
i3は好ましくは0~5の整数を表し、さらに好ましくは0~2、より好ましくは0又は1である。
i4は好ましくは0~2の整数を表し、さらに好ましくは0又は1である。
k1、k2はそれぞれ独立に、好ましくは0~3の整数を表し、さらに好ましくは1~3であり、より好ましくは1又は2であり、特に好ましくは1である。 (i1, i2, i3, i4, k1, k2)
i1 and i2 each independently represent an integer of 0-12, preferably 1-12, more preferably 1-8, more preferably 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 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 1 to 3, more preferably 1 or 2, and particularly preferably 1.
(Ar201、Ar202、Ar203の好ましい置換基)
Ar201、Ar202、Ar203が有していてもよい置換基は任意に選択できるが、好ましくは前記置換基群Sから選ばれる1種又は複数種の置換基であり、好ましい基も前記置換基群Sの通りであるが、より好ましくは無置換(水素原子)、アルキル基、アリール基であり、特に好ましくは無置換(水素原子)、アルキル基であり、最も好ましくは無置換(水素原子)またはターシャリーブチル基であり、ターシャリーブチル基はAr203が存在する場合はAr203に、Ar203が存在しない場合はAr202に、Ar202とAr203が存在しない場合はAr201に置換していることが好ましい。 (Preferred substituents of Ar 201 , Ar 202 and Ar 203 )
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 substituents. Group S, but 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, where the tertiary butyl group is substituted for Ar 203 if Ar 203 is present, Ar 202 if Ar 203 is absent, or Ar 201 if Ar 202 and Ar 203 are absent. preferably.
Ar201、Ar202、Ar203が有していてもよい置換基は任意に選択できるが、好ましくは前記置換基群Sから選ばれる1種又は複数種の置換基であり、好ましい基も前記置換基群Sの通りであるが、より好ましくは無置換(水素原子)、アルキル基、アリール基であり、特に好ましくは無置換(水素原子)、アルキル基であり、最も好ましくは無置換(水素原子)またはターシャリーブチル基であり、ターシャリーブチル基はAr203が存在する場合はAr203に、Ar203が存在しない場合はAr202に、Ar202とAr203が存在しない場合はAr201に置換していることが好ましい。 (Preferred substituents of Ar 201 , Ar 202 and Ar 203 )
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 substituents. Group S, but 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, where the tertiary butyl group is substituted for Ar 203 if Ar 203 is present, Ar 202 if Ar 203 is absent, or Ar 201 if Ar 202 and Ar 203 are absent. preferably.
(式(201)で表される化合物の好ましい態様)
前記式(201)で表される化合物は、下記(I)~(IV)のうちのいずれか1以上を満たす化合物であることが好ましい。 (Preferred Embodiment of Compound Represented by Formula (201))
The compound represented by the formula (201) is preferably a compound satisfying any one or more of the following (I) to (IV).
前記式(201)で表される化合物は、下記(I)~(IV)のうちのいずれか1以上を満たす化合物であることが好ましい。 (Preferred Embodiment of Compound Represented by Formula (201))
The compound represented by the formula (201) is preferably a compound satisfying any one or more of the following (I) to (IV).
(I)フェニレン連結式
式(202)で表される構造はベンゼン環が連結した基を有する構造、すなわち、ベンゼン環構造、i1が1~6で、少なくとも1つの前記ベンゼン環がオルト位又はメタ位で隣接する構造と結合していることが好ましい。
このような構造であることによって、溶解性が向上し、かつ電荷輸送性が向上することが期待される。 (I) Phenylene linking formula 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 1 to 6, and at least one of the benzene rings is in the ortho or meta position. It is preferred that the sites are linked to adjacent structures.
Such a structure is expected to improve the solubility and the charge transport property.
式(202)で表される構造はベンゼン環が連結した基を有する構造、すなわち、ベンゼン環構造、i1が1~6で、少なくとも1つの前記ベンゼン環がオルト位又はメタ位で隣接する構造と結合していることが好ましい。
このような構造であることによって、溶解性が向上し、かつ電荷輸送性が向上することが期待される。 (I) Phenylene linking formula 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 1 to 6, and at least one of the benzene rings is in the ortho or meta position. It is preferred that the sites are linked to adjacent structures.
Such a structure is expected to improve the solubility and the charge transport property.
(II)(フェニレン)-アラルキル(アルキル)
環A1又は環A2に、アルキル基若しくはアラルキル基が結合した芳香族炭化水素基若しくは芳香族複素環基を有する構造、すなわち、Ar201が芳香族炭化水素構造又は芳香族複素環構造、i1が1~6、Ar202が脂肪族炭化水素構造、i2が1~12、好ましくは3~8、Ar203がベンゼン環構造、i3が0又は1である構造、好ましくは、Ar201は前記芳香族炭化水素構造であり、さらに好ましくはベンゼン環が1~5連結した構造であり、より好ましくはベンゼン環1つである。
このような構造であることによって、溶解性が向上し、かつ電荷輸送性が向上することが期待される。 (II) (phenylene)-aralkyl (alkyl)
A structure having an aromatic hydrocarbon group or aromatic heterocyclic group to which an alkyl group or an aralkyl group is bonded to ring A1 or ring A2, that is, Ar 201 is an aromatic hydrocarbon structure or an aromatic heterocyclic structure, i1 is 1 ~6, Ar 202 is an aliphatic hydrocarbon structure, i2 is 1 to 12, preferably 3 to 8, Ar 203 is a benzene ring structure, i3 is 0 or 1, preferably Ar 201 is the aromatic hydrocarbon structure It is a hydrogen 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.
環A1又は環A2に、アルキル基若しくはアラルキル基が結合した芳香族炭化水素基若しくは芳香族複素環基を有する構造、すなわち、Ar201が芳香族炭化水素構造又は芳香族複素環構造、i1が1~6、Ar202が脂肪族炭化水素構造、i2が1~12、好ましくは3~8、Ar203がベンゼン環構造、i3が0又は1である構造、好ましくは、Ar201は前記芳香族炭化水素構造であり、さらに好ましくはベンゼン環が1~5連結した構造であり、より好ましくはベンゼン環1つである。
このような構造であることによって、溶解性が向上し、かつ電荷輸送性が向上することが期待される。 (II) (phenylene)-aralkyl (alkyl)
A structure having an aromatic hydrocarbon group or aromatic heterocyclic group to which an alkyl group or an aralkyl group is bonded to ring A1 or ring A2, that is, Ar 201 is an aromatic hydrocarbon structure or an aromatic heterocyclic structure, i1 is 1 ~6, Ar 202 is an aliphatic hydrocarbon structure, i2 is 1 to 12, preferably 3 to 8, Ar 203 is a benzene ring structure, i3 is 0 or 1, preferably Ar 201 is the aromatic hydrocarbon structure It is a hydrogen 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.
(III)デンドロン
環A1又は環A2に、デンドロンが結合した構造、例えば、Ar201、Ar202がベンゼン環構造、Ar203がビフェニル又はターフェニル構造、i1、i2が1~6、i3が2、jが2である。
このような構造であることによって、溶解性が向上し、かつ電荷輸送性が向上することが期待される。 (III) Dendron A structure in which a dendron is bound to ring A1 or ring A2, for example, Ar 201 and Ar 202 are benzene ring structures, Ar 203 is a biphenyl or terphenyl structure, i1 and i2 are 1 to 6, i3 is 2, j is 2.
Such a structure is expected to improve the solubility and the charge transport property.
環A1又は環A2に、デンドロンが結合した構造、例えば、Ar201、Ar202がベンゼン環構造、Ar203がビフェニル又はターフェニル構造、i1、i2が1~6、i3が2、jが2である。
このような構造であることによって、溶解性が向上し、かつ電荷輸送性が向上することが期待される。 (III) Dendron A structure in which a dendron is bound to ring A1 or ring A2, for example, Ar 201 and Ar 202 are benzene ring structures, Ar 203 is a biphenyl or terphenyl structure, i1 and i2 are 1 to 6, i3 is 2, j is 2.
Such a structure is expected to improve the solubility and the charge transport property.
(IV)B201-L200-B202
B201-L200-B202で表される構造は下記式(203)又は下記式(204)で表される構造であることが好ましい。 (IV) 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).
B201-L200-B202で表される構造は下記式(203)又は下記式(204)で表される構造であることが好ましい。 (IV) 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).
式(203)中、R211、R212、R213はそれぞれ独立に置換基を表す。
式(204)中、環B3は、置換基を有していてもよい、窒素原子を含む芳香族複素環構造を表す。環B3は好ましくはピリジン環である。 In formula (203), R 211 , R 212 and R 213 each independently represent a substituent.
In formula (204), ring B3 represents an aromatic heterocyclic structure containing a nitrogen atom, which may have a substituent. Ring B3 is preferably a pyridine ring.
式(204)中、環B3は、置換基を有していてもよい、窒素原子を含む芳香族複素環構造を表す。環B3は好ましくはピリジン環である。 In formula (203), R 211 , R 212 and R 213 each independently represent a substituent.
In formula (204), ring B3 represents an aromatic heterocyclic structure containing a nitrogen atom, which may have a substituent. Ring B3 is preferably a pyridine ring.
(好ましい燐光発光材料)
前記式(201)で表される燐光発光材料としては特に限定はされないが、好ましいものとして以下のものが挙げられる。 (Preferred phosphorescent material)
Although the phosphorescent material represented by the formula (201) is not particularly limited, the following are preferred.
前記式(201)で表される燐光発光材料としては特に限定はされないが、好ましいものとして以下のものが挙げられる。 (Preferred phosphorescent material)
Although the phosphorescent material represented by the formula (201) is not particularly limited, the following are preferred.
また、下記式(205)で表される燐光発光材料も好ましい。
A phosphorescent material represented by the following formula (205) is also preferable.
[式(205)中、M2は金属を表し、Tは炭素原子又は窒素原子を表す。R92~R95は、それぞれ独立に置換基を表す。但し、Tが窒素原子の場合は、R94及びR95は無い。]
[In formula (205), M2 represents a metal, and T represents a carbon atom or a nitrogen atom. R 92 to R 95 each independently represent a substituent. However, when T is a nitrogen atom, there are no R94 and R95 . ]
式(205)中、M2の具体例としては、周期表第7~11族から選ばれる金属が挙げられる。中でも好ましくは、ルテニウム、ロジウム、パラジウム、銀、レニウム、オスミウム、イリジウム、白金又は金が挙げられ、特に好ましくは、白金、パラジウム等の2価の金属が挙げられる。
Specific examples of 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.
また、式(205)において、R92及びR93は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アラルキル基、アルケニル基、シアノ基、アミノ基、アシル基、アルコキシカルボニル基、カルボキシル基、アルコキシ基、アルキルアミノ基、アラルキルアミノ基、ハロアルキル基、水酸基、アリールオキシ基、芳香族炭化水素基又は芳香族複素環基を表す。
In formula (205), 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;
更に、Tが炭素原子の場合、R94及びR95は、それぞれ独立に、R92及びR93と同様の例示物で表される置換基を表す。また、Tが窒素原子の場合は該Tに直接結合するR94又はR95は存在しない。また、R92~R95は、更に置換基を有していてもよい。置換基としては、前記の置換基とすることができる。更に、R92~R95のうち任意の2つ以上の基が互いに連結して環を形成してもよい。
Furthermore, when T is a carbon atom, R94 and R95 each independently represent a substituent represented by the same examples as R92 and R93 . Also, when T is a nitrogen atom, there is no R94 or R95 directly bonded to said T. In addition, R 92 to R 95 may further have a substituent. The substituents may be the substituents described above. Furthermore, any two or more groups selected from R 92 to R 95 may be linked together to form a ring.
(分子量)
燐光発光材料の分子量は、好ましくは5000以下、更に好ましくは4000以下、特に好ましくは3000以下である。また、燐光発光材料の分子量は、好ましくは800以上、より好ましくは1000以上、更に好ましくは1200以上である。この分子量範囲であることによって、燐光発光材料同士が凝集せず電荷輸送材料と均一に混合し、発光効率の高い発光層を得ることができると考えられる。 (molecular weight)
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.
燐光発光材料の分子量は、好ましくは5000以下、更に好ましくは4000以下、特に好ましくは3000以下である。また、燐光発光材料の分子量は、好ましくは800以上、より好ましくは1000以上、更に好ましくは1200以上である。この分子量範囲であることによって、燐光発光材料同士が凝集せず電荷輸送材料と均一に混合し、発光効率の高い発光層を得ることができると考えられる。 (molecular weight)
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.
燐光発光材料の分子量は、Tgや融点、分解温度等が高く、燐光発光材料及び形成された発光層の耐熱性に優れる点、及び、ガス発生、再結晶化及び分子のマイグレーション等に起因する膜質の低下や材料の熱分解に伴う不純物濃度の上昇等が起こり難い点では大きいことが好ましい。一方、燐光発光材料の分子量は、有機化合物の精製が容易である点では小さいことが好ましい。
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. On the other hand, the molecular weight of the phosphorescent light-emitting material is preferably small in terms of facilitating purification of the organic compound.
<電荷輸送材料>
発光層に用いる電荷輸送材料は、電荷輸送性に優れる骨格を有する材料であり、電子輸送性材料、正孔輸送性材料及び電子と正孔の両方を輸送可能な両極性材料から選ばれることが好ましい。 <Charge transport material>
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.
発光層に用いる電荷輸送材料は、電荷輸送性に優れる骨格を有する材料であり、電子輸送性材料、正孔輸送性材料及び電子と正孔の両方を輸送可能な両極性材料から選ばれることが好ましい。 <Charge transport material>
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.
電荷輸送性に優れる骨格としては、具体的には、芳香族構造、芳香族アミン構造、トリアリールアミン構造、ジベンゾフラン構造、ナフタレン構造、フェナントレン構造、フタロシアニン構造、ポルフィリン構造、チオフェン構造、ベンジルフェニル構造、フルオレン構造、キナクリドン構造、トリフェニレン構造、カルバゾール構造、ピレン構造、アントラセン構造、フェナントロリン構造、キノリン構造、ピリジン構造、ピリミジン構造、トリアジン構造、オキサジアゾール構造又はイミダゾール構造等が挙げられる。
Specific examples of 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.
電子輸送性材料としては、電子輸送性に優れ構造が比較的安定な材料である観点から、ピリジン構造、ピリミジン構造、トリアジン構造を有する化合物がより好ましく、ピリミジン構造、トリアジン構造を有する化合物であることがさらに好ましい。
As the electron-transporting material, 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 a relatively stable structure. is more preferred.
正孔輸送性材料は、正孔輸送性に優れた構造を有する化合物であり、前記電荷輸送性に優れた中心骨格の中でも、カルバゾール構造、ジベンゾフラン構造、トリアリールアミン構造、ナフタレン構造、フェナントレン構造又はピレン構造が正孔輸送性に優れた構造として好ましく、カルバゾール構造、ジベンゾフラン構造又はトリアリールアミン構造がさらに好ましい。
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.
発光層に用いる電荷輸送材料は、3環以上の縮合環構造を有することが好ましく、3環以上の縮合環構造を2以上有する化合物又は5環以上の縮合環を少なくとも1つ有する化合物であることがさらに好ましい。これらの化合物であることで、分子の剛直性が増し、熱に応答する分子運動の程度を抑制する効果が得られ易くなる。さらに、3環以上の縮合環及び5環以上の縮合環は、芳香族炭化水素環又は芳香族複素環を有することが電荷輸送性及び材料の耐久性の点で好ましい。
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. Furthermore, 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.
3環以上の縮合環構造としては、具体的には、アントラセン構造、フェナントレン構造、ピレン構造、クリセン構造、ナフタセン構造、トリフェニレン構造、フルオレン構造、ベンゾフルオレン構造、インデノフルオレン構造、インドロフルオレン構造、カルバゾール構造、インデノカルバゾール構造、インドロカルバゾール構造、ジベンゾフラン構造、ジベンゾチオフェン構造等が挙げられる。電荷輸送性ならびに溶解性の観点から、フェナントレン構造、フルオレン構造、インデノフルオレン構造、カルバゾール構造、インデノカルバゾール構造、インドロカルバゾール構造、ジベンゾフラン構造及びジベンゾチオフェン構造からなる群より選択される少なくとも1つが好ましく、電荷に対する耐久性の観点からカルバゾール構造又はインドロカルバゾール構造がさらに好ましい。
Specific examples of 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. At least one selected from the group consisting of a phenanthrene structure, a fluorene structure, an indenofluorene structure, a carbazole structure, an indenocarbazole structure, an indolocarbazole structure, a dibenzofuran structure, and a dibenzothiophene structure, from the viewpoints of charge transportability and solubility. A carbazole structure or an indolocarbazole structure is more preferred from the viewpoint of durability against electric charges.
本発明においては、有機電界発光素子の電荷に対する耐久性の観点から、発光層の電荷輸送材料の内、少なくとも1つはピリミジン骨格又はトリアジン骨格を有する材料であることが好ましい。
In the present invention, 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.
発光層の電荷輸送材料は、可撓性に優れる観点では高分子材料であることが好ましい。可撓性に優れる材料を用いて形成された発光層は、フレキシブル基板上に形成された有機電界発光素子の発光層として好ましい。発光層に含まれる電荷輸送材料が高分子材料である場合、分子量は、好ましくは5,000以上1,000,000以下、より好ましくは10,000以上、500,000以下、さらに好ましくは10,000以上100,000以下である。
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. When the charge-transporting material contained in the light-emitting layer is a polymeric material, the molecular weight is preferably 5,000 or more and 1,000,000 or less, more preferably 10,000 or more and 500,000 or less, and still more preferably 10,000 or less. 000 or more and 100,000 or less.
また、発光層の電荷輸送材料は、合成及び精製のしやすさ、電子輸送性能及び正孔輸送性能の設計のしやすさ、溶媒に溶解した時の粘度調整のしやすさの観点からは、低分子であることが好ましい。発光層に含まれる電荷輸送材料が低分子材料である場合、分子量は、5,000以下が好ましく、さらに好ましくは4,000以下であり、特に好ましくは3,000以下であり、最も好ましくは2,000以下であり、好ましくは300以上、より好ましくは350以上、さらに好ましくは400以上である。
From the viewpoints of ease of synthesis and purification, ease of designing electron-transporting performance and hole-transporting performance, and ease of viscosity adjustment when dissolved in a solvent, the charge-transporting material for the light-emitting layer is A low molecular weight is preferred. When the charge-transporting material contained in the light-emitting layer is a low-molecular-weight material, 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.
<蛍光発光材料>
蛍光発光材料としては特に限定されないが、下記式(211)で表される化合物が好ましい。 <Fluorescent material>
The fluorescent light-emitting material is not particularly limited, but a compound represented by the following formula (211) is preferable.
蛍光発光材料としては特に限定されないが、下記式(211)で表される化合物が好ましい。 <Fluorescent material>
The fluorescent light-emitting material is not particularly limited, but a compound represented by the following formula (211) is preferable.
上記式(211)において、Ar241は置換基を有していてもよい芳香族炭化水素縮合環構造を表し、Ar242、Ar243は各々独立に置換基を有していてもよいアルキル基、芳香族炭化水素基、芳香族複素基又はこれらが結合した基を表す。n41は1~4の整数である。
In the above formula (211), Ar 241 represents an optionally substituted aromatic hydrocarbon condensed ring structure, Ar 242 and Ar 243 are each independently an optionally substituted alkyl group, represents an aromatic hydrocarbon group, a heteroaromatic group, or a group in which these are bonded. n41 is an integer of 1-4.
Ar241は好ましくは炭素数10~30の芳香族炭化水素縮合環構造を表し、具体的な環構造としては、ナフタレン、アセナフテン、フルオレン、アントラセン、フェナトレン、フルオランテン、ピレン、テトラセン、クリセン、ペリレン等が挙げられる。
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.
Ar241はより好ましくは炭素数12~20の芳香族炭化水素縮合環構造であり、具体的な環構造としては、アセナフテン、フルオレン、アントラセン、フェナトレン、フルオランテン、ピレン、テトラセン、クリセン、ペリレンが挙げられる。
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. .
Ar241はさらに好ましくは炭素数16~18の芳香族炭化水素縮合環構造であり、具体的な環構造としては、フルオランテン、ピレン、クリセンが挙げられる。
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は1~4であり、好ましくは1~3、さらに好ましくは1~2、最も好ましくは2である。
n41 is 1-4, preferably 1-3, more preferably 1-2, most preferably 2.
Ar242、Ar243のアルキル基としては、炭素数1~12のアルキル基が好ましく、より好ましくは炭素数1~6のアルキル基である。
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.
Ar242、Ar243の芳香族炭化水素基としては、炭素数6~30の芳香族炭化水素基が好ましく、より好ましくは炭素数6~24の芳香族炭化水素基であり、最も好ましくはフェニル基、ナフチル基である。
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.
Ar242、Ar243の芳香族複素基としては、炭素数3~30の芳香族複素基が好ましく、より好ましくは炭素数5~24の芳香族炭化水素基であり、具体的にはカルバゾリル基、ジベンゾフラニル基、ジベンゾチオフェニル基が好ましく、ジベンゾフラニル基がより好ましい。
The heteroaromatic group for Ar 242 and Ar 243 is preferably a heteroaromatic group having 3 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 5 to 24 carbon atoms, specifically a carbazolyl group, A dibenzofuranyl group and a dibenzothiophenyl group are preferred, and a dibenzofuranyl group is more preferred.
Ar241、Ar242、Ar243が有していてもよい置換基は、前記置換基群Sから選ばれる基が好ましく、より好ましくは置換基群Sに含まれる、炭化水素基であり、さらに好ましくは置換基群Sとして好ましい基の中の炭化水素基である。
The substituent that Ar 241 , Ar 242 , and Ar 243 may have is preferably a group selected from the substituent group S, more preferably a hydrocarbon group included in the substituent group S, and still more preferably is a hydrocarbon group among preferred groups for the group S of substituents.
上記蛍光発光材料と共に用いる電荷輸送材料としては特に限定されないが、下記式(212)で表されるものが好ましい。
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).
上記式(212)において、R251、R252はそれぞれ独立に式(213)で表される構造であり、R253は置換基を表し、R253が複数ある場合、同一であっても異なっていてもよく、n43は0~8の整数である。
In formula (212) above, R 251 and R 252 each independently represent a structure represented by formula (213), R 253 represents a substituent, and when there are multiple R 253 , they may be the same or different. and n43 is an integer from 0 to 8.
上記式(213)において、*は式(212)のアントラセン環との結合手を表し、Ar254、Ar255はそれぞれ独立に、置換基を有していてもよい芳香族炭化水素構造、又は置換基を有していてもよい複素芳香環構造を表し、Ar254、Ar255はそれぞれ複数存在する場合、同一であっても異なっていてもよく、n44は1~5の整数、n45は0~5の整数である。
In the above formula (213), * represents a bond to the anthracene ring of formula (212), Ar 254 and Ar 255 are each independently an aromatic hydrocarbon structure optionally having a substituent, or a substituted represents a heteroaromatic ring structure which may have 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 0 to An integer of 5.
Ar254は好ましくは、置換基を有していてもよい、炭素数6~30の単環又は縮合環である芳香族炭化水素構造であり、より好ましくは、置換基を有していてもよい、炭素数6~12の単環又は縮合環である芳香族炭化水素構造である。
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.
Ar255は好ましくは、置換基を有していてもよい、炭素数6~30の単環もしくは縮合環である芳香族炭化水素構造、又は置換基を有していてもよい炭素数6~30の縮合環である芳香族複素環構造である。Ar255はより好ましくは、置換基を有していてもよい、炭素数6~12の単環もしくは縮合環である芳香族炭化水素構造、又は置換基を有していてもよい炭素数12の縮合環である芳香族複素環構造である。
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 C 12 It is an aromatic heterocyclic ring structure that is a condensed ring.
n44は好ましくは1~3の整数であり、より好ましくは1又は2である。
n45は好ましくは0~3の整数であり、より好ましくは0~2の整数である。 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.
n45は好ましくは0~3の整数であり、より好ましくは0~2の整数である。 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.
置換基であるR253、Ar254及びAr255が有していてもよい置換基は、前記置換基群Sから選ばれる基が好ましい。より好ましくは置換基群Sに含まれる炭化水素基であり、さらに好ましくは置換基群Sとして好ましい基の中の炭化水素基である。
The substituent that the substituents R 253 , Ar 254 and Ar 255 may have is preferably a group selected from the substituent group S described above. 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.
蛍光発光材料及び電荷輸送材料の分子量は5,000以下が好ましく、さらに好ましくは4,000以下であり、特に好ましくは3,000以下であり、最も好ましくは2,000以下である。また、好ましくは300以上であり、より好ましくは350以上、さらに好ましくは400以上である。
<量子ドット>
発光層は、発光物質として量子ドットを含むことが好ましい。量子ドットは、発光性の半導体ナノ粒子で、通常、直径の範囲は1~20nmである。 The molecular weights of the fluorescence-emitting material and charge-transporting material are 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.
<Quantum dots>
The light-emitting layer preferably contains quantum dots as light-emitting substances. Quantum dots are luminescent semiconductor nanoparticles, typically ranging in diameter from 1 to 20 nm.
<量子ドット>
発光層は、発光物質として量子ドットを含むことが好ましい。量子ドットは、発光性の半導体ナノ粒子で、通常、直径の範囲は1~20nmである。 The molecular weights of the fluorescence-emitting material and charge-transporting material are 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.
<Quantum dots>
The light-emitting layer preferably contains quantum dots as light-emitting substances. Quantum dots are luminescent semiconductor nanoparticles, typically ranging in diameter from 1 to 20 nm.
量子ドットは、II-VI族化合物、III-V族化合物、IV-VI族化合物、IV族元素、IV族化合物、又はこれらの組み合わせからなることが好ましい。
The quantum dots are preferably composed of II-VI group compounds, III-V group compounds, IV-VI group compounds, IV group elements, IV group compounds, or combinations thereof.
II-VI族化合物としては、CdSe、CdTe、CdS、ZnS、ZnSe、ZnTe、ZnO、HgS、HgSe、HgTe、MgSe、MgS、AgInS、CuInS、CdSeS、CdSeTe、CdSTe、ZnSeS、ZnSeTe、ZnSTe、HgSeS、HgSeTe、HeSTe、CdZnS、CdZnSe、CdZnTe、CdHgS、CdHgSe、CdHgTe、HgZnS、HeZnSe、HeZnTe、MgZnSe、MgZnS、HgZnTeS、CdZnSeS、CdZnSeTe、CdZnSTe、CdHgSeS、CdHgSeTe、CdHgSTe、HgZnSeS、HgZnSeTe、HgZnSTeが挙げられる。
II-VI group compounds include CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, AgInS, CuInS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HeSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HeZnSe, HeZnTe, MgZnSe, MgZnS, HgZnTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHg SeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe.
III-V族化合物としては、GaN、GaP、GaAs、GaSb、AlN、AlP、AlAs、AlSb、InN、InP、InAs、InSb、GaNP、GaNAs、GaNSb、GaPAs、GaPSb、AlNP、AlNAs、AlNSb、AlPAs、AlPSb、InGaP、InNP、InNAs、InNSb、InPAs、InPSb、GaAlNP、GaAlNAs、GaAlNSb、GaAlPAs、GaAlPSb、GaInNP、GaInNAs、GaInNSb、GaInPAs、GaInPSb、InAlNP、InAlNAs、InAlNSb、InAlPAs、InAlPSbが挙げられる。
III-V compounds include GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, ALPSB, INGAP, Innp, Innas, Innsb, Inpasb, INPSB, GAALNAS, GAALNAS, GAALNSB, GAALPAS, GAALPSB, GAINNP, GAINNAS, GAINNSB, GAINNSB, GAINSB. Pas, GAINPSB, Inalnp, Inalnasb, Inalpasb, and Inalpsb are listed.
IV-VI族化合物としては、SnS、SnSe、SnTe、PbS、PbSe、PbTe、SnSeS、SnSeTe、SnSTe、PbSeS、PbSeTe、PbSTe、SnPbS、SnPbSe、SnPbTe、SnPbSSe、SnPbSeTe、SnPbSTeが挙げられる。
SNS, Sns, Snse, Snte, PBS, PBS, PBSE, PBSE, SnSes, Snset, SnSETE, SNSETE, PBSETE, PBSETE, SNPBSETE, SNPBSE, SNPBTE, SNPBSSE, SNPBSSE, SNPBSSE, SNPBSSE. , SnpbSete and Snpbste are listed.
IV族元素としてはSi、Geが、IV族化合物としてはSiC、SiGeが挙げられる。
Group IV elements include Si and Ge, and Group IV compounds include SiC and SiGe.
量子ドットは、均質な単一構造であってもよく、コア/シェルの二重構造であってもよい。また、コア/シェル/シェルのように三重または四重以上の構造であってもよい。コアとシェルとを構成する物質は、異なる化合物からなる。その際、シェルの化合物のエネルギーバンドギャップは、コアの化合物のエネルギーバンドギャップより大きいことが好ましい。具体的には、ZnTeSe/ZnSe/ZnS、CdSe/ZnS、InP/ZnSなどの構造が好ましい。
A quantum dot may have a homogeneous single structure or a core/shell dual structure. It may also have a triple or quadruple or more structure such as core/shell/shell. The materials that make up the core and shell consist of different compounds. In this case, the energy bandgap of the shell compound is preferably larger than the energy bandgap of the core compound. Specifically, structures such as ZnTeSe/ZnSe/ZnS, CdSe/ZnS, and InP/ZnS are preferred.
[量子ドットを含有する発光層形成用組成物]
量子ドットを含有する発光層の形成方法は、真空蒸着法及び湿式成膜法のいずれでもよいが、好ましくは湿式成膜法である。湿式成膜法の場合、発光層は有機溶剤を含む発光層形成用組成物を塗布、乾燥して成膜する。
量子ドットを含有する発光層形成用組成物は、量子ドット及び有機溶剤を含む。 [Composition for forming a light-emitting layer containing quantum dots]
The method for forming the light-emitting layer containing quantum dots may be either a vacuum deposition method or a wet film formation method, but the wet film formation method is preferred. In the case of the wet film-forming method, the light-emitting layer is formed by coating and drying a composition for forming a light-emitting layer containing an organic solvent.
The composition for forming a light-emitting layer containing quantum dots contains quantum dots and an organic solvent.
量子ドットを含有する発光層の形成方法は、真空蒸着法及び湿式成膜法のいずれでもよいが、好ましくは湿式成膜法である。湿式成膜法の場合、発光層は有機溶剤を含む発光層形成用組成物を塗布、乾燥して成膜する。
量子ドットを含有する発光層形成用組成物は、量子ドット及び有機溶剤を含む。 [Composition for forming a light-emitting layer containing quantum dots]
The method for forming the light-emitting layer containing quantum dots may be either a vacuum deposition method or a wet film formation method, but the wet film formation method is preferred. In the case of the wet film-forming method, the light-emitting layer is formed by coating and drying a composition for forming a light-emitting layer containing an organic solvent.
The composition for forming a light-emitting layer containing quantum dots contains quantum dots and an organic solvent.
(有機溶剤)
量子ドットを含有する発光層形成用組成物に含有される有機溶剤は、湿式成膜により量子ドットを含む層を形成するために用いる、揮発性を有する液体成分である。 (Organic solvent)
The organic solvent contained in the composition for forming a light-emitting layer containing quantum dots is a volatile liquid component used for forming a layer containing quantum dots by wet film formation.
量子ドットを含有する発光層形成用組成物に含有される有機溶剤は、湿式成膜により量子ドットを含む層を形成するために用いる、揮発性を有する液体成分である。 (Organic solvent)
The organic solvent contained in the composition for forming a light-emitting layer containing quantum dots is a volatile liquid component used for forming a layer containing quantum dots by wet film formation.
該有機溶剤は、溶質である量子ドットが良好に溶解する有機溶剤であれば特に限定されない。
The organic solvent is not particularly limited as long as it is an organic solvent in which the solute quantum dots are well dissolved.
好ましい有機溶剤としては、例えば、n-デカン、シクロヘキサン、エチルシクロヘキサン、デカリン、ビシクロヘキサン等のアルカン類;トルエン、キシレン、メシチレン、フェニルシクロヘキサン、テトラリン、メチルナフタレン等の芳香族炭化水素類;クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン等のハロゲン化芳香族炭化水素類;1,2-ジメトキシベンゼン、1,3-ジメトキシベンゼン、アニソール、フェネトール、2-メトキシトルエン、3-メトキシトルエン、4-メトキシトルエン、2,3-ジメチルアニソール、2,4-ジメチルアニソール、ジフェニルエーテル等の芳香族エーテル類;酢酸フェニル、プロピオン酸フェニル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸n-ブチル等の芳香族エステル類;シクロヘキサノン、シクロオクタノン、フェンコン等の脂環族ケトン類;シクロヘキサノール、シクロオクタノール等の脂環族アルコール類;メチルエチルケトン、ジブチルケトン等の脂肪族ケトン類;ブタノール、ヘキサノール等の脂肪族アルコール類;エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコール-1-モノメチルエーテルアセタート(PGMEA)等の脂肪族エーテル類;等が挙げられる。
Preferred organic solvents include, for example, alkanes such as n-decane, cyclohexane, ethylcyclohexane, decalin and bicyclohexane; aromatic hydrocarbons such as toluene, xylene, mesitylene, phenylcyclohexane, tetralin and methylnaphthalene; Halogenated aromatic hydrocarbons such as chlorobenzene and trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3 - aromatic ethers such as dimethylanisole, 2,4-dimethylanisole and diphenyl ether; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate and n-butyl benzoate; Alicyclic ketones such as cyclohexanone, cyclooctanone and fenchone; Alicyclic alcohols such as cyclohexanol and cyclooctanol; Aliphatic ketones such as methyl ethyl ketone and dibutyl ketone; Aliphatic alcohols such as butanol and hexanol; aliphatic ethers such as glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA);
これらの中でも、粘度と沸点の観点から、アルカン類、芳香族炭化水素類、芳香族エステル類が好ましい。
Among these, alkanes, aromatic hydrocarbons, and aromatic esters are preferable from the viewpoint of viscosity and boiling point.
これらの有機溶剤は1種類を単独で用いてもよく、また2種類以上を任意の組み合わせ、及び比率で用いてもよい。
One type of these organic solvents may be used alone, or two or more types may be used in any combination and ratio.
用いる有機溶剤の沸点は通常80℃以上、好ましくは100℃以上、より好ましくは120℃以上、また、通常350℃以下、好ましくは330℃以下、より好ましくは300℃以下である。有機溶剤の沸点がこの範囲を下回ると、湿式成膜時において、発光層形成用組成物からの溶剤蒸発により、成膜安定性が低下する可能性がある。有機溶剤の沸点がこの範囲を上回ると、湿式成膜時において、成膜後の溶剤残留により、成膜安定性が低下する可能性がある。
The boiling point of the organic solvent used is usually 80°C or higher, preferably 100°C or higher, more preferably 120°C or higher, and usually 350°C or lower, preferably 330°C or lower, more preferably 300°C or lower. If the boiling point of the organic solvent is below this range, the film formation stability may decrease due to evaporation of the solvent from the composition for forming the light-emitting layer during wet film formation. If the boiling point of the organic solvent exceeds this range, there is a possibility that the film formation stability will decrease due to the solvent remaining after film formation during wet film formation.
(含有量)
量子ドットを含有する発光層形成用組成物における量子ドットの含有量は、通常0.001質量%以上、好ましくは0.01質量%以上、通常30.0質量%以下、好ましくは20.0質量%以下である。当該含有量をこの範囲とすることにより、隣接する層(例えば、正孔輸送層や正孔阻止層)から発光層へ効率良く、正孔や電子の注入が行われ、駆動電圧を低減することができる。なお、量子ドットは発光層形成用組成物中に、1種のみ含まれていてもよく、2種以上が組み合わされて含まれていてもよい。 (Content)
The content of quantum dots in the composition for forming a light-emitting layer containing quantum dots is usually 0.001% by mass or more, preferably 0.01% by mass or more, usually 30.0% by mass or less, preferably 20.0% by mass. % or less. By setting the content in this range, holes and electrons are efficiently injected from adjacent layers (for example, a hole-transporting layer and a hole-blocking layer) to the light-emitting layer, thereby reducing the driving voltage. can be done. In addition, 1 type of quantum dots may be contained in the composition for light emitting layer formation, and 2 or more types may be combined and contained.
量子ドットを含有する発光層形成用組成物における量子ドットの含有量は、通常0.001質量%以上、好ましくは0.01質量%以上、通常30.0質量%以下、好ましくは20.0質量%以下である。当該含有量をこの範囲とすることにより、隣接する層(例えば、正孔輸送層や正孔阻止層)から発光層へ効率良く、正孔や電子の注入が行われ、駆動電圧を低減することができる。なお、量子ドットは発光層形成用組成物中に、1種のみ含まれていてもよく、2種以上が組み合わされて含まれていてもよい。 (Content)
The content of quantum dots in the composition for forming a light-emitting layer containing quantum dots is usually 0.001% by mass or more, preferably 0.01% by mass or more, usually 30.0% by mass or less, preferably 20.0% by mass. % or less. By setting the content in this range, holes and electrons are efficiently injected from adjacent layers (for example, a hole-transporting layer and a hole-blocking layer) to the light-emitting layer, thereby reducing the driving voltage. can be done. In addition, 1 type of quantum dots may be contained in the composition for light emitting layer formation, and 2 or more types may be combined and contained.
量子ドットを含有する発光層形成用組成物に含まれる有機溶媒の含有量は、通常10質量%以上、好ましくは50質量%以上、特に好ましくは80質量%以上で、通常99.95質量%以下、好ましくは99.9質量%以下、特に好ましくは99.8質量%以下である。有機溶媒の含有量が上記下限以上であれば適度な粘度を有して塗布性が向上し、上記上限以下であれば均一な膜が得られやすく成膜性が良好となる。
The content of the organic solvent contained in the light-emitting layer-forming composition containing quantum dots is usually 10% by mass or more, preferably 50% by mass or more, particularly preferably 80% by mass or more, and usually 99.95% by mass or less. , preferably 99.9% by mass or less, particularly preferably 99.8% by mass or less. If the content of the organic solvent is at least the above lower limit, the composition will have an appropriate viscosity and coatability will be improved.
(その他の成分)
量子ドットを含有する発光層形成用組成物は、必要に応じて、上記の化合物の他に、更に他の化合物を含有してもよい。他の化合物としては、好ましくは、酸化防止剤として知られているジブチルヒドロキシトルエンや、ジブチルフェノール等のフェノール類、及び、公知の電荷輸送性化合物が挙げられる。 (other ingredients)
The composition for forming a light-emitting layer containing quantum dots may contain other compounds in addition to the above compounds, if necessary. Other compounds preferably include dibutylhydroxytoluene, which is known as an antioxidant, phenols such as dibutylphenol, and known charge-transporting compounds.
量子ドットを含有する発光層形成用組成物は、必要に応じて、上記の化合物の他に、更に他の化合物を含有してもよい。他の化合物としては、好ましくは、酸化防止剤として知られているジブチルヒドロキシトルエンや、ジブチルフェノール等のフェノール類、及び、公知の電荷輸送性化合物が挙げられる。 (other ingredients)
The composition for forming a light-emitting layer containing quantum dots may contain other compounds in addition to the above compounds, if necessary. Other compounds preferably include dibutylhydroxytoluene, which is known as an antioxidant, phenols such as dibutylphenol, and known charge-transporting compounds.
(成膜方法)
量子ドットを含有する発光層の形成方法は、好ましくは湿式成膜法である。湿式成膜法とは、組成物を塗布して液膜を形成し、乾燥して有機溶媒を除去し、発光層の膜を形成する方法である。塗布方法としては、例えば、スピンコート法、ディップコート法、ダイコート法、バーコート法、ブレードコート法、ロールコート法、スプレーコート法、キャピラリーコート法、インクジェット法、ノズルプリンティング法、スクリーン印刷法、グラビア印刷法、フレキソ印刷法等の湿式で成膜させる方法を採用し、塗布膜を乾燥させて膜形成を行う。これらの塗布方法の中でも、スピンコート法、スプレーコート法、インクジェット法、ノズルプリンティング法等が好ましい。量子ドット発光素子を備えた量子ドット表示装置を製造する場合は、インクジェット法又はノズルプリンティング法が好ましく、インクジェット法が特に好ましい。 (Film formation method)
The method for forming the light-emitting layer containing quantum dots is preferably a wet film-forming method. The wet film-forming method is a method of applying a composition to form a liquid film, drying it to remove the organic solvent, and forming a light-emitting layer film. Examples of coating methods include spin coating, dip coating, die coating, bar coating, blade coating, roll coating, spray coating, capillary coating, inkjet, nozzle printing, screen printing, and gravure. A wet film-forming method such as a printing method or a flexographic printing method is employed, and the coating film is dried to form a film. Among these coating methods, the spin coating method, the spray coating method, the inkjet method, the nozzle printing method, and the like are preferable. When manufacturing a quantum dot display device equipped with a quantum dot light-emitting element, an inkjet method or a nozzle printing method is preferable, and an inkjet method is particularly preferable.
量子ドットを含有する発光層の形成方法は、好ましくは湿式成膜法である。湿式成膜法とは、組成物を塗布して液膜を形成し、乾燥して有機溶媒を除去し、発光層の膜を形成する方法である。塗布方法としては、例えば、スピンコート法、ディップコート法、ダイコート法、バーコート法、ブレードコート法、ロールコート法、スプレーコート法、キャピラリーコート法、インクジェット法、ノズルプリンティング法、スクリーン印刷法、グラビア印刷法、フレキソ印刷法等の湿式で成膜させる方法を採用し、塗布膜を乾燥させて膜形成を行う。これらの塗布方法の中でも、スピンコート法、スプレーコート法、インクジェット法、ノズルプリンティング法等が好ましい。量子ドット発光素子を備えた量子ドット表示装置を製造する場合は、インクジェット法又はノズルプリンティング法が好ましく、インクジェット法が特に好ましい。 (Film formation method)
The method for forming the light-emitting layer containing quantum dots is preferably a wet film-forming method. The wet film-forming method is a method of applying a composition to form a liquid film, drying it to remove the organic solvent, and forming a light-emitting layer film. Examples of coating methods include spin coating, dip coating, die coating, bar coating, blade coating, roll coating, spray coating, capillary coating, inkjet, nozzle printing, screen printing, and gravure. A wet film-forming method such as a printing method or a flexographic printing method is employed, and the coating film is dried to form a film. Among these coating methods, the spin coating method, the spray coating method, the inkjet method, the nozzle printing method, and the like are preferable. When manufacturing a quantum dot display device equipped with a quantum dot light-emitting element, an inkjet method or a nozzle printing method is preferable, and an inkjet method is particularly preferable.
乾燥方法は特に限定されないが、自然乾燥、減圧乾燥、加熱乾燥、又は、加熱しながらの減圧乾燥を適宜用いることができる。加熱乾燥は、自然乾燥又は減圧乾燥の後、更に残留有機溶媒を除去するために実施してもよい。
Although the drying method is not particularly limited, natural drying, reduced pressure drying, heat drying, or reduced pressure drying while heating can be used as appropriate. Heat drying may be carried out in order to further remove residual organic solvent after natural drying or vacuum drying.
減圧乾燥では、量子ドットを含有する発光層形成用組成物に含まれる有機溶媒の蒸気圧以下に減圧することが好ましい。
In the vacuum drying, it is preferable to reduce the pressure below the vapor pressure of the organic solvent contained in the composition for forming a light-emitting layer containing quantum dots.
加熱する場合は、加熱方法は特に限定されないが、ホットプレートによる加熱、オーブン内での加熱、赤外線加熱等を用いることができる。加熱温度は通常80℃以上、100℃以上が好ましく、110℃以上がさらに好ましく、また、200℃以下が好ましく、150℃以下がさらに好ましい。
When heating, the heating method is not particularly limited, but heating with a hot plate, heating in an oven, infrared heating, etc. can be used. The heating temperature is usually 80° C. or higher, preferably 100° C. or higher, more preferably 110° C. or higher, and preferably 200° C. or lower, more preferably 150° C. or lower.
加熱時間は、通常1分以上、2分以上が好ましく、通常60分以下、30分以下が好ましく、20分以下がさらに好ましい。
The heating time is usually 1 minute or more, preferably 2 minutes or more, usually 60 minutes or less, preferably 30 minutes or less, and more preferably 20 minutes or less.
[正孔阻止層]
発光層5と後述の電子注入層との間に、正孔阻止層を設けてもよい。正孔阻止層は、発光層5の上に、発光層5の陰極7側の界面に接するように積層される層である。 [Hole blocking layer]
A hole-blocking layer may be provided between the light-emitting layer 5 and an electron-injecting layer, which will be described later. The hole-blocking layer 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 thecathode 7 side.
発光層5と後述の電子注入層との間に、正孔阻止層を設けてもよい。正孔阻止層は、発光層5の上に、発光層5の陰極7側の界面に接するように積層される層である。 [Hole blocking layer]
A hole-blocking layer may be provided between the light-emitting layer 5 and an electron-injecting layer, which will be described later. The hole-blocking layer 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
この正孔阻止層は、陽極2から移動してくる正孔を陰極7に到達するのを阻止する役割と、陰極7から注入された電子を効率よく発光層5の方向に輸送する役割とを有する。正孔阻止層を構成する材料に求められる物性としては、電子移動度が高く正孔移動度が低いこと、エネルギーギャップ(HOMO、LUMOの差)が大きいこと、励起三重項準位(T1)が高いことが挙げられる。
This hole-blocking layer has the role of blocking holes moving from the anode 2 from reaching the cathode 7 and the role of efficiently transporting electrons injected from the cathode 7 toward the light-emitting layer 5. have. Physical properties required for the material constituting the hole blocking layer include high electron mobility and low hole mobility, a large energy gap (difference between HOMO and LUMO), and an excited triplet level (T 1 ). is high.
このような条件を満たす正孔阻止層の材料としては、例えば、ビス(2-メチル-8-キノリノラト)(フェノラト)アルミニウム、ビス(2-メチル-8-キノリノラト)(トリフェニルシラノラト)アルミニウム等の混合配位子錯体、ビス(2-メチル-8-キノラト)アルミニウム-μ-オキソ-ビス-(2-メチル-8-キノリラト)アルミニウム二核金属錯体等の金属錯体、ジスチリルビフェニル誘導体等のスチリル化合物(日本国特開平11-242996号公報)、3-(4-ビフェニルイル)-4-フェニル-5-(4-tert-ブチルフェニル)-1,2,4-トリアゾール等のトリアゾール誘導体(日本国特開平7-41759号公報)、バソクプロイン等のフェナントロリン誘導体(日本国特開平10-79297号公報)等が挙げられる。更に、国際公開第2005/022962号に記載の2,4,6位が置換されたピリジン環を少なくとも1個有する化合物も、正孔阻止層の材料として好ましい。
Examples of materials for the hole blocking layer that satisfy these conditions include bis(2-methyl-8-quinolinolato)(phenolato)aluminum, bis(2-methyl-8-quinolinolato)(triphenylsilanolate)aluminum, and the like. mixed ligand complexes, bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolato) aluminum binuclear metal complexes such as metal complexes, distyrylbiphenyl derivatives and the like Styryl compounds (JP-A-11-242996), triazole derivatives such as 3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole ( JP-A-7-41759), phenanthroline derivatives such as bathocuproine (JP-A-10-79297), and the like. Furthermore, the compound having at least one pyridine ring substituted at the 2,4,6 positions described in WO 2005/022962 is also preferable as a material for the hole blocking layer.
正孔阻止層の形成方法に制限はない。従って、湿式成膜法、蒸着法や、その他の方法で形成できる。
There are no restrictions on the method of forming the hole blocking layer. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.
正孔阻止層の膜厚は、本発明の効果を著しく損なわない限り任意であるが、通常0.3nm以上、好ましくは0.5nm以上であり、また、通常100nm以下、好ましくは50nm以下である。
The thickness of the hole-blocking layer is arbitrary as long as it does not significantly impair the effects of the present invention. .
[電子輸送層]
電子輸送層6は素子の電流効率をさらに向上させることを目的として、発光層5と陰極7との間に設けられる。 [Electron transport layer]
The electron transport layer 6 is provided between the light emitting layer 5 and thecathode 7 for the purpose of further improving the current efficiency of the device.
電子輸送層6は素子の電流効率をさらに向上させることを目的として、発光層5と陰極7との間に設けられる。 [Electron transport layer]
The electron transport layer 6 is provided between the light emitting layer 5 and the
電子輸送層6は、電界を与えられた電極間において陰極7から注入された電子を効率よく発光層5の方向に輸送することができる化合物より形成される。電子輸送層6に用いられる電子輸送性化合物としては、陰極7からの電子注入効率が高く、かつ、高い電子移動度を有し、注入された電子を効率よく輸送することができる化合物であることが必要である。
The electron transport layer 6 is made of a compound that can efficiently transport electrons injected from the cathode 7 toward the light emitting layer 5 between electrodes to which an electric field is applied. The electron-transporting compound used in the electron-transporting layer 6 is a compound that has high electron injection efficiency from the cathode 7, high electron mobility, and can efficiently transport the injected electrons. is necessary.
電子輸送層に用いる電子輸送性化合物としては、具体的には、例えば、8-ヒドロキシキノリンのアルミニウム錯体等の金属錯体(日本国特開昭59-194393号公報)、10-ヒドロキシベンゾ[h]キノリンの金属錯体、オキサジアゾール誘導体、ジスチリルビフェニル誘導体、シロール誘導体、3-ヒドロキシフラボン金属錯体、5-ヒドロキシフラボン金属錯体、ベンズオキサゾール金属錯体、ベンゾチアゾール金属錯体、トリスベンズイミダゾリルベンゼン(米国特許第5645948号明細書)、キノキサリン化合物(日本国特開平6-207169号公報)、フェナントロリン誘導体(日本国特開平5-331459号公報)、2-tert-ブチル-9,10-N,N’-ジシアノアントラキノンジイミン、n型水素化非晶質炭化シリコン、n型硫化亜鉛、n型セレン化亜鉛等が挙げられる。
Specific examples of the electron-transporting compound used in the electron-transporting layer include, for example, a metal complex such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), 10-hydroxybenzo[h] quinoline metal complexes, oxadiazole derivatives, distyrylbiphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Patent No. 5645948), quinoxaline compounds (Japanese Patent Laid-Open No. 6-207169), phenanthroline derivatives (Japanese Patent Laid-Open No. 5-331459), 2-tert-butyl-9,10-N,N'-dicyano Anthraquinonediimine, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide, and the like.
電子輸送層6の膜厚は、通常1nm以上、好ましくは5nm以上であり、また、通常300nm以下、好ましくは100nm以下である。
The film thickness of the electron transport layer 6 is usually 1 nm or more, preferably 5 nm or more, and is usually 300 nm or less, preferably 100 nm or less.
電子輸送層6は、前記と同様にして湿式成膜法、或いは真空蒸着法により正孔阻止層上に積層することにより形成される。通常は、真空蒸着法が用いられる。
本発明においては、前記のように、好適な発光層形成材料を含む発光層上に、湿式成膜法にて電子輸送層を形成することが出来る。 The electron transport layer 6 is formed on the hole blocking layer by a wet film forming method or a vacuum vapor deposition method in the same manner as described above. A vacuum deposition method is usually used.
In the present invention, as described above, the electron-transporting layer can be formed on the light-emitting layer containing a suitable material for forming the light-emitting layer by a wet film-forming method.
本発明においては、前記のように、好適な発光層形成材料を含む発光層上に、湿式成膜法にて電子輸送層を形成することが出来る。 The electron transport layer 6 is formed on the hole blocking layer by a wet film forming method or a vacuum vapor deposition method in the same manner as described above. A vacuum deposition method is usually used.
In the present invention, as described above, the electron-transporting layer can be formed on the light-emitting layer containing a suitable material for forming the light-emitting layer by a wet film-forming method.
[電子注入層]
電子注入層は、陰極7から注入された電子を効率よく、電子輸送層6又は発光層5へ注入するために設けられてもよい。 [Electron injection layer]
The electron injection layer may be provided to efficiently inject electrons injected from thecathode 7 into the electron transport layer 6 or the light emitting layer 5 .
電子注入層は、陰極7から注入された電子を効率よく、電子輸送層6又は発光層5へ注入するために設けられてもよい。 [Electron injection layer]
The electron injection layer may be provided to efficiently inject electrons injected from the
電子注入を効率よく行うには、電子注入層を形成する材料は、仕事関数の低い金属が好ましい。例としては、ナトリウムやセシウム等のアルカリ金属、バリウムやカルシウム等のアルカリ土類金属等が用いられる。その膜厚は通常0.1nm以上、5nm以下が好ましい。
In order to perform electron injection efficiently, it is preferable that the material forming the electron injection layer be a metal with a low work function. Examples thereof include alkali metals such as sodium and cesium, alkaline earth metals such as barium and calcium, and the like. The film thickness is preferably 0.1 nm or more and 5 nm or less.
更に、バソフェナントロリン等の含窒素複素環化合物や8-ヒドロキシキノリンのアルミニウム錯体等の金属錯体に代表される有機電子輸送材料に、ナトリウム、カリウム、セシウム、リチウム、ルビジウム等のアルカリ金属をドープする(日本国特開平10-270171号公報、日本国特開2002-100478号公報、日本国特開2002-100482号公報等に記載)ことも、電子注入・輸送性が向上し優れた膜質を両立させることが可能となるため好ましい。
Furthermore, an organic electron-transporting material typified by a nitrogen-containing heterocyclic compound such as bathophenanthroline or a metal complex such as an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium or rubidium ( JP-A-10-270171, JP-A-2002-100478, JP-A-2002-100482, etc.) also improves electron injection and transport properties and achieves excellent film quality. It is preferable because it enables
電子注入層の膜厚は、通常5nm以上、好ましくは10nm以上であり、また通常200nm以下、好ましくは100nm以下の範囲である。
The thickness of the electron injection layer is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.
電子注入層は、湿式成膜法或いは真空蒸着法により、発光層5又はその上の正孔阻止層や電子輸送層6上に積層することにより形成される。
湿式成膜法の場合の詳細は、前述の発光層の場合と同様である。 The electron injection layer is formed by laminating the light emitting layer 5 or the hole blocking layer or the electron transport layer 6 thereon by a wet film forming method or a vacuum deposition method.
The details of the wet film formation method are the same as those of the light-emitting layer described above.
湿式成膜法の場合の詳細は、前述の発光層の場合と同様である。 The electron injection layer is formed by laminating the light emitting layer 5 or the hole blocking layer or the electron transport layer 6 thereon by a wet film forming method or a vacuum deposition method.
The details of the wet film formation method are the same as those of the light-emitting layer described above.
正孔阻止層、電子輸送層、電子注入層を電子輸送材料とリチウム錯体共ドープの操作で一層にする場合にもある。
In some cases, the hole-blocking layer, electron-transporting layer, and electron-injecting layer are formed into a single layer by co-doping the electron-transporting material and the lithium complex.
[陰極]
陰極7は、発光層5側の層(電子注入層又は発光層など)に電子を注入する役割を果たす。 [cathode]
Thecathode 7 plays a role of injecting electrons into a layer (an electron injection layer, a light-emitting layer, or the like) on the light-emitting layer 5 side.
陰極7は、発光層5側の層(電子注入層又は発光層など)に電子を注入する役割を果たす。 [cathode]
The
陰極7の材料としては、前記の陽極2に使用される材料を用いることが可能であるが、効率良く電子注入を行なう上では、仕事関数の低い金属を用いることが好ましく、例えば、スズ、マグネシウム、インジウム、カルシウム、アルミニウム、銀等の金属又はそれらの合金等が用いられる。具体例としては、例えば、マグネシウム-銀合金、マグネシウム-インジウム合金、アルミニウム-リチウム合金等の低仕事関数の合金電極等が挙げられる。
As the material of the cathode 7, it is possible to use the material used for the anode 2, but in terms of efficient electron injection, it is preferable to use a metal with a low work function, such as tin or magnesium. , indium, calcium, aluminum, and silver, or alloys thereof. Specific examples include low work function alloy electrodes such as magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys.
有機電界発光素子の安定性の点では、陰極の上に、仕事関数が高く、大気に対して安定な金属層を積層して、低仕事関数の金属からなる陰極を保護することが好ましい。積層する金属としては、例えば、アルミニウム、銀、銅、ニッケル、クロム、金、白金等の金属が挙げられる。
From the viewpoint of the stability of the organic electroluminescent device, it is preferable to protect the cathode made of a metal with a low work function by stacking a metal layer that has a high work function and is stable against the atmosphere on the cathode. Metals to be laminated include, for example, metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum.
陰極の膜厚は通常、陽極と同様である。
The film thickness of the cathode is usually the same as that of the anode.
[その他の層]
本発明の有機電界発光素子は、本発明の効果を著しく損なわなければ、更に他の層を有していてもよい。すなわち、陽極と陰極との間に、上述の他の任意の層を有していてもよい。 [Other layers]
The organic electroluminescence device of the present invention may further have other layers as long as they do not significantly impair the effects of the present invention. That is, it may have any of the other layers described above between the anode and cathode.
本発明の有機電界発光素子は、本発明の効果を著しく損なわなければ、更に他の層を有していてもよい。すなわち、陽極と陰極との間に、上述の他の任意の層を有していてもよい。 [Other layers]
The organic electroluminescence device of the present invention may further have other layers as long as they do not significantly impair the effects of the present invention. That is, it may have any of the other layers described above between the anode and cathode.
[その他の素子構成]
本発明の有機電界発光素子は、上述の説明とは逆の構造、即ち、例えば、基板上に陰極、電子注入層、電子輸送層、正孔阻止層、発光層、正孔輸送層、正孔注入層、陽極の順に積層することも可能である。 [Other device configurations]
The organic electroluminescence device of the present invention has a structure opposite to that described above. It is also possible to laminate the injection layer and the anode in this order.
本発明の有機電界発光素子は、上述の説明とは逆の構造、即ち、例えば、基板上に陰極、電子注入層、電子輸送層、正孔阻止層、発光層、正孔輸送層、正孔注入層、陽極の順に積層することも可能である。 [Other device configurations]
The organic electroluminescence device of the present invention has a structure opposite to that described above. It is also possible to laminate the injection layer and the anode in this order.
本発明の有機電界発光素子を有機電界発光装置に適用する場合は、単一の有機電界発光素子として用いても、複数の有機電界発光素子がアレイ状に配置された構成にして用いても、陽極と陰極がX-Yマトリックス状に配置された構成にして用いてもよい。
When the organic electroluminescent element of the present invention is applied to an organic electroluminescent device, it may be used as a single organic electroluminescent element or may be used in a configuration in which a plurality of organic electroluminescent elements are arranged in an array. A configuration in which anodes and cathodes are arranged in an XY matrix may be used.
[表示装置]
本発明の表示装置(有機電界発光素子表示装置)は、本発明の有機電界発光素子を備える。本発明の表示装置の型式や構造については特に制限はなく、本発明の有機電界発光素子を用いて常法に従って組み立てることができる。 [Display device]
The display device (organic electroluminescent element display device) of the present invention comprises the organic electroluminescent element of the present invention. There are no particular restrictions on the type and structure of the display device of the present invention, and the device can be assembled according to a conventional method using the organic electroluminescence device of the present invention.
本発明の表示装置(有機電界発光素子表示装置)は、本発明の有機電界発光素子を備える。本発明の表示装置の型式や構造については特に制限はなく、本発明の有機電界発光素子を用いて常法に従って組み立てることができる。 [Display device]
The display device (organic electroluminescent element display device) of the present invention comprises the organic electroluminescent element of the present invention. There are no particular restrictions on the type and structure of the display device of the present invention, and the device can be assembled according to a conventional method using the organic electroluminescence device of the present invention.
例えば、「有機ELディスプレイ」(オーム社、平成16年8月20日発行、時任静士、安達千波矢、村田英幸著)に記載されているような方法で、本発明の有機EL表示装置を形成することができる。
For example, the organic EL display device of the present invention can be manufactured by the method described in "Organic EL Display" (Ohmsha, August 20, 2004, by Shizuo Tokito, Chihaya Adachi, and Hideyuki Murata). can be formed.
[照明装置]
本発明の照明装置(有機電界発光素子照明装置)は、本発明の有機電界発光素子を備える。本発明の照明装置の型式や構造については特に制限はなく、本発明の有機電界発光素子を用いて常法に従って組み立てることができる。 [Lighting device]
The lighting device (organic electroluminescent element lighting device) of the present invention comprises the organic electroluminescent element of the present invention. There are no particular restrictions on the type and structure of the lighting device of the present invention, and the device can be assembled using the organic electroluminescence device of the present invention in a conventional manner.
本発明の照明装置(有機電界発光素子照明装置)は、本発明の有機電界発光素子を備える。本発明の照明装置の型式や構造については特に制限はなく、本発明の有機電界発光素子を用いて常法に従って組み立てることができる。 [Lighting device]
The lighting device (organic electroluminescent element lighting device) of the present invention comprises the organic electroluminescent element of the present invention. There are no particular restrictions on the type and structure of the lighting device of the present invention, and the device can be assembled using the organic electroluminescence device of the present invention in a conventional manner.
<量子ドット表示装置>
本発明の量子ドット表示装置(量子ドット発光素子表示装置)は、本発明の量子ドット発光素子を備える。本発明の量子ドット表示装置の型式や構造については特に制限はなく、本発明の量子ドット発光素子を用いて常法に従って組み立てることができる。 <Quantum dot display device>
The quantum dot display device (quantum dot light emitting device display device) of the present invention comprises the quantum dot light emitting device of the present invention. The type and structure of the quantum dot display device of the present invention are not particularly limited, and the quantum dot light emitting device of the present invention can be assembled according to a conventional method.
本発明の量子ドット表示装置(量子ドット発光素子表示装置)は、本発明の量子ドット発光素子を備える。本発明の量子ドット表示装置の型式や構造については特に制限はなく、本発明の量子ドット発光素子を用いて常法に従って組み立てることができる。 <Quantum dot display device>
The quantum dot display device (quantum dot light emitting device display device) of the present invention comprises the quantum dot light emitting device of the present invention. The type and structure of the quantum dot display device of the present invention are not particularly limited, and the quantum dot light emitting device of the present invention can be assembled according to a conventional method.
例えば、「有機ELディスプレイ」(オーム社、平成16年8月20日発行、時任静士、安達千波矢、村田英幸著)に記載されているような方法を参考に、有機発光層を、量子ドットを含む発光層に置き換えることで、本発明の量子ドット表示装置を形成することができる。
For example, referring to the method described in "Organic EL Display" (Ohmsha, August 20, 2004, Shizuo Tokito, Chihaya Adachi, Hideyuki Murata), the organic light-emitting layer is The quantum dot display device of the present invention can be formed by replacing with a light-emitting layer containing dots.
<量子ドット照明装置>
本発明の量子ドット照明装置(量子ドット発光素子照明装置)は、本発明の量子ドット発光素子を備える。本発明の量子ドット照明装置の型式や構造については特に制限はなく、本発明の量子ドット発光素子を用いて常法に従って組み立てることができる。 <Quantum dot illumination device>
The quantum dot lighting device (quantum dot light emitting element lighting device) of the present invention comprises the quantum dot light emitting device of the present invention. There are no particular restrictions on the type and structure of the quantum dot lighting device of the present invention, and it can be assembled using the quantum dot light emitting device of the present invention in accordance with conventional methods.
本発明の量子ドット照明装置(量子ドット発光素子照明装置)は、本発明の量子ドット発光素子を備える。本発明の量子ドット照明装置の型式や構造については特に制限はなく、本発明の量子ドット発光素子を用いて常法に従って組み立てることができる。 <Quantum dot illumination device>
The quantum dot lighting device (quantum dot light emitting element lighting device) of the present invention comprises the quantum dot light emitting device of the present invention. There are no particular restrictions on the type and structure of the quantum dot lighting device of the present invention, and it can be assembled using the quantum dot light emitting device of the present invention in accordance with conventional methods.
以下、実施例を示して本発明について更に具体的に説明する。ただし、本発明は以下の実施例に限定されるものではなく、本発明はその要旨を逸脱しない限り任意に変更して実施できる。
Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and the present invention can be arbitrarily modified without departing from the scope of the invention.
<中間体の合成>
[化合物1の合成] <Synthesis of intermediates>
[Synthesis of compound 1]
[化合物1の合成] <Synthesis of intermediates>
[Synthesis of compound 1]
1Lフラスコにトルエンを270mL、エタノールを135mL、2,7-ビス(4,4,5,5-テトラメチル-1,3,2-ジオキサボロラン-2-イル)-9,9-ジヘキシルフルオレン(20.0g、34.1mmol)、5-ブロモ-2-ヨードトルエンを50.72g(136.5mmol)、りん酸カリウム水溶液(2M、すなわち2モル/リットル濃度)102mLを入れた溶液を真空脱気後に窒素置換した。窒素気流下に加熱し、30分間攪拌した。その後ビス(トリフェニルホスフィン)パラジウム(II)ジクロリド0.48g(0.68mmol)を加え、65℃で6時間反応した。反応液に水を入れ、トルエンで抽出し、MgSO4および活性白土で処理した。トルエン溶液を加熱還流したのち不溶物をろ過し、再結晶して無色固体の化合物1を得た(収量16.5g、収率72.1%)。
270 mL of toluene, 135 mL of ethanol, 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9,9-dihexylfluorene (20. 0 g, 34.1 mmol), 50.72 g (136.5 mmol) of 5-bromo-2-iodotoluene, and 102 mL of an aqueous potassium phosphate solution (2 M, that is, 2 mol/liter concentration). replaced. Heated under a stream of nitrogen and stirred for 30 minutes. After that, 0.48 g (0.68 mmol) of bis(triphenylphosphine) palladium (II) dichloride was added and reacted at 65°C for 6 hours. Water was added to the reaction solution, extracted with toluene, and treated with MgSO 4 and activated clay. After the toluene solution was heated under reflux, the insoluble matter was filtered and recrystallized to obtain compound 1 as a colorless solid (yield: 16.5 g, yield: 72.1%).
[化合物3の合成]
[Synthesis of compound 3]
次いで、3-ブロモ-3’-イオド-1,1-ビフェニル(29.4g、81.9mmol)、市販の化合物2(20.0g、81.9mmol)、リン酸カリウム(2M水溶液、103g、205mmol)、トルエン(200mL)、及びエタノール(100mL)をフラスコに仕込み、系内を十分に窒素置換して60℃まで加温した。テトラキス(トリフェニルホスフィン)パラジウム(0)(2.37g、2.05mmol)を加え、85℃で6時間攪拌した。反応液に水を加え、トルエンで抽出を行った。有機層を無水硫酸マグネシウムで乾燥して活性白土より粗精製した。粗精製品をカラムクロマトグラフィー(展開液:ヘキサン/塩化メチレン=950/50)により精製し、化合物3(23.1g、収率81%)を得た。
Then 3-bromo-3′-iodo-1,1-biphenyl (29.4 g, 81.9 mmol), commercially available compound 2 (20.0 g, 81.9 mmol), potassium phosphate (2 M aqueous solution, 103 g, 205 mmol) ), toluene (200 mL), and ethanol (100 mL) were charged into a flask, the system was sufficiently purged with nitrogen, and heated to 60°C. Tetrakis(triphenylphosphine)palladium(0) (2.37 g, 2.05 mmol) was added and stirred at 85° C. for 6 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified using activated clay. The crude product was purified by column chromatography (developer: hexane/methylene chloride=950/50) to obtain compound 3 (23.1 g, yield 81%).
[化合物4の合成]
[Synthesis of Compound 4]
化合物3(23.1g、66.1mmol)、市販の3-アミノフェニルボロン酸(9.8g、63.0mmol)、リン酸カリウム(2M水溶液、79g、158mmol)、及びトルエン(160mL)、エタノール(80mL)をフラスコに仕込み、系内を十分に窒素置換して60℃まで加温した。テトラキス(トリフェニルホスフィン)パラジウム(0)(1.85g、1.6mmol)を加え、85℃で4時間攪拌した。反応液に水を加え、トルエンで抽出を行った。有機層を無水硫酸マグネシウムで乾燥して活性白土より粗精製した。粗精製品をカラムクロマトグラフィー(展開液:ヘキサン/酢酸エチル=8/2)により精製し、化合物4(22.2g、収率92.9%)を得た。
Compound 3 (23.1 g, 66.1 mmol), commercially available 3-aminophenylboronic acid (9.8 g, 63.0 mmol), potassium phosphate (2 M aqueous solution, 79 g, 158 mmol), and toluene (160 mL), ethanol ( 80 mL) was placed in a flask, the system was sufficiently purged with nitrogen, and heated to 60°C. Tetrakis(triphenylphosphine)palladium(0) (1.85 g, 1.6 mmol) was added and stirred at 85° C. for 4 hours. Water was added to the reaction solution, and extraction was performed with toluene. The organic layer was dried over anhydrous magnesium sulfate and crudely purified using activated clay. The crude product was purified by column chromatography (developer: hexane/ethyl acetate=8/2) to obtain compound 4 (22.2 g, yield 92.9%).
[化合物5の合成]
化合物5は、国際公開第2020/171190号に記載された方法で合成した。 [Synthesis of compound 5]
Compound 5 was synthesized by the method described in WO2020/171190.
化合物5は、国際公開第2020/171190号に記載された方法で合成した。 [Synthesis of compound 5]
Compound 5 was synthesized by the method described in WO2020/171190.
<高分子化合物の合成>
[高分子化合物P-1の合成]
以下の反応式に従い、高分子化合物P-1を合成した。 <Synthesis of polymer compound>
[Synthesis of polymer compound P-1]
A polymer compound P-1 was synthesized according to the following reaction formula.
[高分子化合物P-1の合成]
以下の反応式に従い、高分子化合物P-1を合成した。 <Synthesis of polymer compound>
[Synthesis of polymer compound P-1]
A polymer compound P-1 was synthesized according to the following reaction formula.
化合物1(2.0g、2.97mmol)、化合物4(1.1179g、3.09mmol)、2,4-ジフロロアニリン(0.3686g、2.85mmol)、tert-ブトキシナトリウム(2.2g、22.89mmol)及びトルエン(40g、46mL)を仕込み、系内を十分に窒素置換して、60℃まで加温した(溶液A1)。
Compound 1 (2.0 g, 2.97 mmol), Compound 4 (1.1179 g, 3.09 mmol), 2,4-difluoroaniline (0.3686 g, 2.85 mmol), sodium tert-butoxy (2.2 g, 22.89 mmol) and toluene (40 g, 46 mL) were charged, the system was sufficiently purged with nitrogen, and heated to 60° C. (solution A1).
トリス(ジベンジリデンアセトン)ジパラジウム錯体(0.055g、0.06mmol)のトルエン9.5mL溶液に、[4-(N,N-ジメチルアミノ)フェニル]ジ-tert-ブチルホスフィン(Amphos)(0.126g、0.47mmol)を加え、60℃まで加温した(溶液B1)。
[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0 .126 g, 0.47 mmol) was added and warmed to 60° C. (solution B1).
窒素気流中、溶液A1に溶液B1を添加し、1.0時間、加熱還流反応した。化合物1が消失したことを確認し、4,4′-ジブロモビフェニル(0.668g、2.14mmol)を添加した。2時間加熱還流後、ブロモベンゼン(1.3g、8.2mmol)を添加し、2時間加熱還流反応した。反応液を放冷してエタノール/水(210mL/30mL)溶液に滴下し、エンドキャップした粗ポリマーを得た。
Solution B1 was added to solution A1 in a nitrogen stream, and the mixture was heated under reflux for 1.0 hour. After confirming that compound 1 had disappeared, 4,4'-dibromobiphenyl (0.668 g, 2.14 mmol) was added. After heating under reflux for 2 hours, bromobenzene (1.3 g, 8.2 mmol) was added and the reaction was carried out under heating under reflux for 2 hours. The reaction solution was allowed to cool and added dropwise to an ethanol/water (210 mL/30 mL) solution to obtain an end-capped crude polymer.
このエンドキャップした粗ポリマーをトルエンに溶解し、アセトンに再沈殿し、析出したポリマーを濾別した。得られたポリマーをトルエンに溶解させ、希塩酸にて洗浄し、アンモニア含有エタノールにて再沈殿した。濾取したポリマーをカラムクロマトグラフィーにより精製し、目的物である高分子化合物P-1を得た(1.6g)。得られた高分子化合物P-1の分子量等は以下の通りであった。
This end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was separated by filtration. The resulting polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer compound P-1 (1.6 g). The molecular weight and the like of the obtained polymer compound P-1 were as follows.
重量平均分子量(Mw)=16360
数平均分子量(Mn)=11680
分散度(Mw/Mn)=1.40 Weight average molecular weight (Mw) = 16360
Number average molecular weight (Mn) = 11680
Dispersity (Mw/Mn) = 1.40
数平均分子量(Mn)=11680
分散度(Mw/Mn)=1.40 Weight average molecular weight (Mw) = 16360
Number average molecular weight (Mn) = 11680
Dispersity (Mw/Mn) = 1.40
[高分子化合物P-2の合成]
以下の反応式に従い、高分子化合物P-2を合成した。 [Synthesis of polymer compound P-2]
A polymer compound P-2 was synthesized according to the following reaction formula.
以下の反応式に従い、高分子化合物P-2を合成した。 [Synthesis of polymer compound P-2]
A polymer compound P-2 was synthesized according to the following reaction formula.
化合物1(2.0g、2.97mmol)、化合物4(1.1179g、3.09mmol)、3,5-ジフロロアニリン(0.3686g、2.85mmol)、tert-ブトキシナトリウム(2.2g、22.89mmol)及びトルエン(40g、46mL)を仕込み、系内を十分に窒素置換して、60℃まで加温した(溶液A2)。
Compound 1 (2.0 g, 2.97 mmol), Compound 4 (1.1179 g, 3.09 mmol), 3,5-difluoroaniline (0.3686 g, 2.85 mmol), sodium tert-butoxy (2.2 g, 22.89 mmol) and toluene (40 g, 46 mL) were charged, the system was sufficiently purged with nitrogen, and heated to 60° C. (solution A2).
トリス(ジベンジリデンアセトン)ジパラジウム錯体(0.055g、0.06mmol)のトルエン9.5mL溶液に、[4-(N,N-ジメチルアミノ)フェニル]ジ-tert-ブチルホスフィン(Amphos)(0.126g、0.47mmol)を加え、60℃まで加温した(溶液B2)。
[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0 .126 g, 0.47 mmol) was added and warmed to 60° C. (solution B2).
窒素気流中、溶液A2に溶液B2を添加し、1.0時間、加熱還流反応した。化合物1が消失したことを確認し、4,4′-ジブロモビフェニル(0.668g、2.14mmol)を添加した。2時間加熱還流後、ブロモベンゼン(1.3g、8.2mmol)を添加し、2時間加熱還流反応した。反応液を放冷してエタノール/水(210mL/30mL)溶液に滴下し、エンドキャップした粗ポリマーを得た。
Solution B2 was added to solution A2 in a nitrogen stream, and the mixture was heated under reflux for 1.0 hour. After confirming that compound 1 had disappeared, 4,4'-dibromobiphenyl (0.668 g, 2.14 mmol) was added. After heating under reflux for 2 hours, bromobenzene (1.3 g, 8.2 mmol) was added and the reaction was carried out under heating under reflux for 2 hours. The reaction solution was allowed to cool and added dropwise to an ethanol/water (210 mL/30 mL) solution to obtain an end-capped crude polymer.
このエンドキャップした粗ポリマーをトルエンに溶解し、アセトンに再沈殿し、析出したポリマーを濾別した。得られたポリマーをトルエンに溶解させ、希塩酸にて洗浄し、アンモニア含有エタノールにて再沈殿した。濾取したポリマーをカラムクロマトグラフィーにより精製し、目的物である高分子化合物P-2を得た(1.5g)。得られた高分子化合物P-2の分子量等は以下の通りであった。
This end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was separated by filtration. The resulting polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer compound P-2 (1.5 g). The molecular weight and the like of the obtained polymer compound P-2 were as follows.
重量平均分子量(Mw)=13610
数平均分子量(Mn)=10230
分散度(Mw/Mn)=1.33 Weight average molecular weight (Mw) = 13610
Number average molecular weight (Mn) = 10230
Dispersity (Mw/Mn) = 1.33
数平均分子量(Mn)=10230
分散度(Mw/Mn)=1.33 Weight average molecular weight (Mw) = 13610
Number average molecular weight (Mn) = 10230
Dispersity (Mw/Mn) = 1.33
[高分子化合物P-3の合成]
以下の反応式に従い、高分子化合物P-3を合成した。 [Synthesis of polymer compound P-3]
A polymer compound P-3 was synthesized according to the following reaction formula.
以下の反応式に従い、高分子化合物P-3を合成した。 [Synthesis of polymer compound P-3]
A polymer compound P-3 was synthesized according to the following reaction formula.
4,4′-ジブロモビフェニル(2.56g、8.21mmol)、化合物4(1.9465g、5.38mmol)、3,5-ジフロロアニリン(0.96g、7.44mmol)、tert-ブトキシナトリウム(4.75g、49.43mmol)及びトルエン(40g、46mL)を仕込み、系内を十分に窒素置換して、60℃まで加温した(溶液A3)。
4,4′-dibromobiphenyl (2.56 g, 8.21 mmol), compound 4 (1.9465 g, 5.38 mmol), 3,5-difluoroaniline (0.96 g, 7.44 mmol), sodium tert-butoxy (4.75 g, 49.43 mmol) and toluene (40 g, 46 mL) were charged, the system was sufficiently purged with nitrogen, and heated to 60° C. (solution A3).
トリス(ジベンジリデンアセトン)ジパラジウム錯体(0.1174g、0.13mmol)のトルエン20mL溶液に、[4-(N,N-ジメチルアミノ)フェニル]ジ-tert-ブチルホスフィン(Amphos)(0.272g、1.02mmol)を加え、60℃まで加温した(溶液B3)。
[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0.272 g) was added to a toluene 20 mL solution of tris(dibenzylideneacetone) dipalladium complex (0.1174 g, 0.13 mmol). , 1.02 mmol) and warmed to 60° C. (solution B3).
窒素気流中、溶液A3に溶液B3を添加し、2.0時間、加熱還流反応した。4,4′-ジブロモビフェニルが消失したことを確認し、化合物1(1.811g、2.69mmol)を添加した。2時間加熱還流後、ブロモベンゼン(3.0g、19.11mmol)を添加し、2時間加熱還流反応した。反応液を放冷してエタノール/水(255mL/60mL)溶液に滴下し、エンドキャップした粗ポリマーを得た。
Solution B3 was added to solution A3 in a nitrogen stream, and the mixture was heated under reflux for 2.0 hours. After confirming that 4,4′-dibromobiphenyl had disappeared, compound 1 (1.811 g, 2.69 mmol) was added. After heating under reflux for 2 hours, bromobenzene (3.0 g, 19.11 mmol) was added, and the reaction was carried out under heating under reflux for 2 hours. The reaction solution was allowed to cool and added dropwise to an ethanol/water (255 mL/60 mL) solution to obtain an end-capped crude polymer.
このエンドキャップした粗ポリマーをトルエンに溶解し、アセトンに再沈殿し、析出したポリマーを濾別した。得られたポリマーをトルエンに溶解させ、希塩酸にて洗浄し、アンモニア含有エタノールにて再沈殿した。濾取したポリマーをカラムクロマトグラフィーにより精製し、目的物である高分子化合物P-3を得た(2.1g)。得られた高分子化合物P-3の分子量等は以下の通りであった。
This end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was separated by filtration. The resulting polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The filtered polymer was purified by column chromatography to obtain the target polymer compound P-3 (2.1 g). The molecular weight and the like of the obtained polymer compound P-3 were as follows.
重量平均分子量(Mw)=11250
数平均分子量(Mn)=8272
分散度(Mw/Mn)=1.36 Weight average molecular weight (Mw) = 11250
Number average molecular weight (Mn) = 8272
Dispersity (Mw/Mn) = 1.36
数平均分子量(Mn)=8272
分散度(Mw/Mn)=1.36 Weight average molecular weight (Mw) = 11250
Number average molecular weight (Mn) = 8272
Dispersity (Mw/Mn) = 1.36
[高分子化合物P-4の合成]
以下の反応式に従い、高分子化合物P-4を合成した。 [Synthesis of polymer compound P-4]
A polymer compound P-4 was synthesized according to the following reaction formula.
以下の反応式に従い、高分子化合物P-4を合成した。 [Synthesis of polymer compound P-4]
A polymer compound P-4 was synthesized according to the following reaction formula.
4,4′-ジブロモビフェニル(3.0g、9.62mmol)、化合物4(1.5294g、4.23mmol)、3,5-ジフロロアニリン(1.5642g、12.12mmol)、2-アミノ-9,9′-ジヘキシルフルオレン(1.0083g、2.88mmol)、tert-ブトキシナトリウム(7.12g、74.09mmol)及びトルエン(45g、52mL)を仕込み、系内を十分に窒素置換して、60℃まで加温した
(溶液A4)。 4,4′-dibromobiphenyl (3.0 g, 9.62 mmol), compound 4 (1.5294 g, 4.23 mmol), 3,5-difluoroaniline (1.5642 g, 12.12 mmol), 2-amino- 9,9′-Dihexylfluorene (1.0083 g, 2.88 mmol), tert-butoxysodium (7.12 g, 74.09 mmol) and toluene (45 g, 52 mL) were charged, and the inside of the system was sufficiently replaced with nitrogen, Warmed to 60° C. (solution A4).
(溶液A4)。 4,4′-dibromobiphenyl (3.0 g, 9.62 mmol), compound 4 (1.5294 g, 4.23 mmol), 3,5-difluoroaniline (1.5642 g, 12.12 mmol), 2-amino- 9,9′-Dihexylfluorene (1.0083 g, 2.88 mmol), tert-butoxysodium (7.12 g, 74.09 mmol) and toluene (45 g, 52 mL) were charged, and the inside of the system was sufficiently replaced with nitrogen, Warmed to 60° C. (solution A4).
トリス(ジベンジリデンアセトン)ジパラジウム錯体(0.1761g、0.192mmol)のトルエン30mL溶液に、[4-(N,N-ジメチルアミノ)フェニル]ジ-tert-ブチルホスフィン(Amphos)(0.408g、1.54mmol)を加え、60℃まで加温した(溶液B4)。
[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0.408 g) was added to a solution of tris(dibenzylideneacetone) dipalladium complex (0.1761 g, 0.192 mmol) in 30 mL of toluene. , 1.54 mmol) and warmed to 60° C. (solution B4).
窒素気流中、溶液A4に溶液B4を添加し、1.0時間、加熱還流反応した。4,4′-ジブロモビフェニルが消失したことを確認し、4,4′-ジブロモビフェニル(2.415g、7.74mmol)を添加した。2時間加熱還流後、ブロモベンゼン(2.94g、18.7mmol)を添加し、2時間加熱還流反応した。反応液を放冷してエタノール/水(315mL/50mL)溶液に滴下し、エンドキャップした粗ポリマーを得た。
Solution B4 was added to solution A4 in a nitrogen stream, and the mixture was heated under reflux for 1.0 hour. After confirming that 4,4'-dibromobiphenyl had disappeared, 4,4'-dibromobiphenyl (2.415 g, 7.74 mmol) was added. After heating under reflux for 2 hours, bromobenzene (2.94 g, 18.7 mmol) was added and the reaction was carried out under heating under reflux for 2 hours. The reaction solution was allowed to cool and added dropwise to an ethanol/water (315 mL/50 mL) solution to obtain an end-capped crude polymer.
このエンドキャップした粗ポリマーをトルエンに溶解し、アセトンに再沈殿し、析出したポリマーを濾別した。得られたポリマーをトルエンに溶解させ、希塩酸にて洗浄し、アンモニア含有エタノールにて再沈殿した。濾取したポリマーをカラムクロマトグラフィーにより精製し、目的物である高分子化合物P-4を得た(2.1g)。得られた高分子化合物P-4の分子量等は以下の通りであった。
This end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was separated by filtration. The resulting polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer compound P-4 (2.1 g). The molecular weight and the like of the obtained polymer compound P-4 were as follows.
重量平均分子量(Mw)=13500
数平均分子量(Mn)=9854
分散度(Mw/Mn)=1.37 Weight average molecular weight (Mw) = 13500
Number average molecular weight (Mn) = 9854
Dispersity (Mw/Mn) = 1.37
数平均分子量(Mn)=9854
分散度(Mw/Mn)=1.37 Weight average molecular weight (Mw) = 13500
Number average molecular weight (Mn) = 9854
Dispersity (Mw/Mn) = 1.37
[高分子化合物P-aの合成]
以下の反応式に従い、高分子化合物P-aを合成した。 [Synthesis of polymer compound Pa]
Polymer compound Pa was synthesized according to the following reaction scheme.
以下の反応式に従い、高分子化合物P-aを合成した。 [Synthesis of polymer compound Pa]
Polymer compound Pa was synthesized according to the following reaction scheme.
4,4‘-ジブロモ-p-タ-フェニル(3.0g、7.73mmol)、2-アミノ-9,9-ジヘキシルフルオレン(2.205g、6.31mmol)、化合物5(0.565g、1.42mmol)、3,5-ジフロロアニリン(0.998g、7.73mmol)、tert-ブトキシナトリウム(5.73g、59.63mmol)及びトルエン(83ml)を仕込み、系内を十分に窒素置換して、60℃まで加温した(溶液A5)。
4,4′-dibromo-p-terphenyl (3.0 g, 7.73 mmol), 2-amino-9,9-dihexylfluorene (2.205 g, 6.31 mmol), compound 5 (0.565 g, 1 .42 mmol), 3,5-difluoroaniline (0.998 g, 7.73 mmol), tert-butoxysodium (5.73 g, 59.63 mmol) and toluene (83 ml) were charged, and the system was sufficiently replaced with nitrogen. and heated to 60° C. (solution A5).
トリス(ジベンジリデンアセトン)ジパラジウム錯体(0.142g、0.155mmol)のトルエン9.5ml溶液に、[4-(N,N-ジメチルアミノ)フェニル]ジ-tert-ブチルホスフィン(Amphos)(0.328g、1.24mmol)を加え、60℃まで加温した(溶液B5)。
[4-(N,N-dimethylamino)phenyl]di-tert-butylphosphine (Amphos) (0 .328 g, 1.24 mmol) was added and warmed to 60° C. (solution B5).
窒素気流中、溶液A5に溶液B5を添加し、1.0時間、加熱還流反応した。化合物5が消失したことを確認し、2,7-ビス(4-ブロモフエニル)9,9-ジヘキシルフルオレン(3.54g、5.49mmol)を添加した。2時間加熱還流後、ブロモベンゼン(3.52g、22.42mmol)を添加し、2時間加熱還流反応した。反応液を放冷してエタノール/水(275ml/50ml)溶液に滴下し、エンドキャップした粗ポリマーを得た。
Solution B5 was added to solution A5 in a nitrogen stream, and the mixture was heated under reflux for 1.0 hour. After confirming that compound 5 had disappeared, 2,7-bis(4-bromophenyl)9,9-dihexylfluorene (3.54 g, 5.49 mmol) was added. After heating under reflux for 2 hours, bromobenzene (3.52 g, 22.42 mmol) was added, and the reaction was heated under reflux for 2 hours. The reaction mixture was allowed to cool and added dropwise to an ethanol/water (275 ml/50 ml) solution to obtain an end-capped crude polymer.
このエンドキャップした粗ポリマーをトルエンに溶解し、アセトンに再沈殿し、析出したポリマーを濾別した。得られたポリマーをトルエンに溶解させ、希塩酸にて洗浄し、アンモニア含有エタノールにて再沈殿した。濾取したポリマーをカラムクロマトグラフィーにより精製し、目的物である高分子化合物P-aを得た(2.0g)。得られた高分子化合物P-aの分子量等は以下の通りであった。
重量平均分子量(Mw)=18320
数平均分子量(Mn)=14774
分散度(Mw/Mn)=1.24 This end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was separated by filtration. The resulting polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The filtered polymer was purified by column chromatography to obtain the target polymer compound Pa (2.0 g). The molecular weight and the like of the obtained polymer compound Pa were as follows.
Weight average molecular weight (Mw) = 18320
Number average molecular weight (Mn) = 14774
Dispersity (Mw/Mn) = 1.24
重量平均分子量(Mw)=18320
数平均分子量(Mn)=14774
分散度(Mw/Mn)=1.24 This end-capped crude polymer was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was separated by filtration. The resulting polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The filtered polymer was purified by column chromatography to obtain the target polymer compound Pa (2.0 g). The molecular weight and the like of the obtained polymer compound Pa were as follows.
Weight average molecular weight (Mw) = 18320
Number average molecular weight (Mn) = 14774
Dispersity (Mw/Mn) = 1.24
[高分子化合物P-5の合成]
[Synthesis of polymer compound P-5]
前記高分子化合物P-1と同じ様に高分子化合物P-5を合成した。
A polymer compound P-5 was synthesized in the same manner as the polymer compound P-1.
〔有機電界発光素子の製造〕
[実施例1]
ガラス基板上にインジウム・スズ酸化物(ITO)透明導電膜を50nmの厚さに堆積したもの(ジオマテック社製、スパッタ成膜品)を通常のフォトリソグラフィー技術と塩酸エッチングを用いて2mm幅のストライプにパターニングして陽極を形成した。このようにITOをパターン形成した基板を、界面活性剤水溶液による超音波洗浄、超純水による水洗、超純水による超音波洗浄、超純水による水洗の順で洗浄後、圧縮空気で乾燥させ、最後に紫外線オゾン洗浄を行った。 [Production of organic electroluminescent device]
[Example 1]
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate to a thickness of 50 nm (manufactured by Geomatec, a sputter-deposited product) was subjected to a 2 mm-wide stripe using ordinary photolithography and etching with hydrochloric acid. was patterned to form an anode. The substrate on which the ITO pattern is formed in this manner is washed with ultrasonic waves using an aqueous solution of surfactant, washed with ultrapure water, ultrasonically washed with ultrapure water, and washed with ultrapure water in this order, and then dried with compressed air. , and finally performed ultraviolet ozone cleaning.
[実施例1]
ガラス基板上にインジウム・スズ酸化物(ITO)透明導電膜を50nmの厚さに堆積したもの(ジオマテック社製、スパッタ成膜品)を通常のフォトリソグラフィー技術と塩酸エッチングを用いて2mm幅のストライプにパターニングして陽極を形成した。このようにITOをパターン形成した基板を、界面活性剤水溶液による超音波洗浄、超純水による水洗、超純水による超音波洗浄、超純水による水洗の順で洗浄後、圧縮空気で乾燥させ、最後に紫外線オゾン洗浄を行った。 [Production of organic electroluminescent device]
[Example 1]
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate to a thickness of 50 nm (manufactured by Geomatec, a sputter-deposited product) was subjected to a 2 mm-wide stripe using ordinary photolithography and etching with hydrochloric acid. was patterned to form an anode. The substrate on which the ITO pattern is formed in this manner is washed with ultrasonic waves using an aqueous solution of surfactant, washed with ultrapure water, ultrasonically washed with ultrapure water, and washed with ultrapure water in this order, and then dried with compressed air. , and finally performed ultraviolet ozone cleaning.
正孔注入層形成用組成物として、下記式(P-1)の構造を有する正孔輸送性高分子化合物3.1質量%と下記電子受容性化合物(HI-1)0.6質量%とを、安息香酸エチルに溶解させた組成物を調製した。
As a composition for forming a hole injection layer, 3.1% by mass of a hole-transporting polymer compound having a structure of the following formula (P-1) and 0.6% by mass of an electron-accepting compound (HI-1) below. was dissolved in ethyl benzoate to prepare a composition.
この組成物を、大気中で上記基板上にスピンコートし、大気中ホットプレートで230℃、30分乾燥させ、膜厚40nmの均一な薄膜を形成し、正孔注入層とした。
This composition was spin-coated on the substrate in the atmosphere and dried on a hot plate in the atmosphere at 230° C. for 30 minutes to form a uniform thin film with a thickness of 40 nm, which was used as a hole injection layer.
次に、下記の構造式(HT-1)を有する電荷輸送性高分子化合物100質量部を、1,3,5-トリメチルベンゼンに溶解させ、2.0質量%の溶液を調製した。
Next, 100 parts by mass of a charge-transporting polymer compound having the following structural formula (HT-1) was dissolved in 1,3,5-trimethylbenzene to prepare a 2.0% by mass solution.
この溶液を、上記正孔注入層を塗布成膜した基板上に窒素グローブボックス中でスピンコートし、窒素グローブボックス中のホットプレートで230℃、30分間乾燥させ、膜厚40nmの均一な薄膜を形成し、正孔輸送層とした。
This solution was spin-coated on the substrate on which the hole injection layer was coated in a nitrogen glove box, and dried on a hot plate in the nitrogen glove box at 230° C. for 30 minutes to form a uniform thin film with a thickness of 40 nm. was formed to form a hole transport layer.
次に、下記構造式(BH-1)を有するホスト化合物と下記構造式(BD-1)を有するドーパント化合物を100:10となるような質量部でシクロヘキシルベンゼンに溶解させ、4.4質量%の溶液を調製した。
Next, a host compound having the following structural formula (BH-1) and a dopant compound having the following structural formula (BD-1) were dissolved in cyclohexylbenzene in parts by weight of 100:10 to give 4.4% by weight. was prepared.
上記正孔輸送層までを塗布成膜した基板上に、窒素グローブボックス中でスピンコートし40nmの均一な薄膜を形成し、発光層とした。窒素グローブボックス中のホットプレートで120℃、20分間乾燥させて発光層とした。
A uniform thin film of 40 nm was formed by spin coating in a nitrogen glove box on the substrate on which the film up to the hole transport layer had been applied and formed as a light-emitting layer. It was dried on a hot plate in a nitrogen glove box at 120° C. for 20 minutes to form a light-emitting layer.
発光層までを成膜した基板を真空蒸着装置に設置し、装置内を2×10-4Pa以下になるまで排気した。
The substrate on which up to the light-emitting layer was formed was placed in a vacuum deposition apparatus, and the inside of the apparatus was evacuated to 2×10 −4 Pa or less.
次に、下記の構造式(ET-1)で表される化合物および8-ヒドロキシキノリノラトリチウムを2:3の膜厚比で、発光層上に真空蒸着法にて共蒸着し、膜厚30nmの電子輸送層を形成した。
Next, a compound represented by the following structural formula (ET-1) and 8-hydroxyquinolinolatritium are co-deposited on the light-emitting layer at a film thickness ratio of 2:3 by a vacuum vapor deposition method to obtain a film thickness. A 30 nm electron transport layer was formed.
続いて、陰極蒸着用のマスクとして2mm幅のストライプ状シャドーマスクを、陽極のITOストライプとは直交するように基板に密着させて、真空蒸着法によりアルミニウムをモリブデンボートにより加熱して、膜厚80nmのアルミニウム層を形成して陰極を形成した。以上の様にして、2mm×2mmのサイズの発光面積部分を有する有機電界発光素子が得られた。
Subsequently, a striped shadow mask with a width of 2 mm was adhered to the substrate so as to be orthogonal to the ITO stripes of the anode as a mask for cathode evaporation, and aluminum was heated by a molybdenum boat by vacuum evaporation to obtain a film thickness of 80 nm. was formed to form a cathode. As described above, an organic electroluminescence device having a light-emitting area of 2 mm×2 mm was obtained.
窒素で充填された空間内で、中空構造を有するガラス基板の内側に、水分および酸素吸着剤を貼り合わせ、ガラス基板の有機電界発光素子を有する面と、中空ガラスの水分・酸素吸着剤を有する面を対向させ、有機電界発光素子部の外周を囲うように紫外線硬化樹脂を塗布して、互いの面を接着した。さらに、紫外線硬化樹脂部に紫外線を照射し、有機電界発光素子部を外部空間と隔離する構造を形成した。これにより、直接有機電界発光素子面にはどのような構造物も触れない形で、水分や酸素から隔離することができ、水分や酸素の影響を除外して有機電界発光素子の性能を評価することができる。
In a space filled with nitrogen, a moisture and oxygen adsorbent is attached to the inside of a glass substrate having a hollow structure, and the surface of the glass substrate having the organic electroluminescent element and the moisture and oxygen adsorbent of the hollow glass are provided. The surfaces were made to face each other, and an ultraviolet curable resin was applied so as to surround the outer periphery of the organic electroluminescence element portion, and the surfaces were bonded to each other. Further, a structure was formed in which the ultraviolet curable resin portion was irradiated with ultraviolet rays to isolate the organic electroluminescence element portion from the external space. As a result, the surface of the organic electroluminescent device can be isolated from moisture and oxygen without any structure directly touching it, and the performance of the organic electroluminescent device can be evaluated by excluding the influence of moisture and oxygen. be able to.
[実施例2]
正孔注入層形成用組成物として、前記式(P-2)の構造を有する正孔輸送性高分子化合物3.1質量%と電子受容性化合物(HI-1)0.6質量%のみを、安息香酸エチルに溶解させた組成物を調製して用いたほかは、実施例1と同様にして有機電界発光素子を作製した。 [Example 2]
As the composition for forming a hole injection layer, 3.1% by mass of the hole-transporting polymer compound having the structure of the formula (P-2) and 0.6% by mass of the electron-accepting compound (HI-1) alone. An organic electroluminescence device was produced in the same manner as in Example 1, except that a composition dissolved in ethyl benzoate was prepared and used.
正孔注入層形成用組成物として、前記式(P-2)の構造を有する正孔輸送性高分子化合物3.1質量%と電子受容性化合物(HI-1)0.6質量%のみを、安息香酸エチルに溶解させた組成物を調製して用いたほかは、実施例1と同様にして有機電界発光素子を作製した。 [Example 2]
As the composition for forming a hole injection layer, 3.1% by mass of the hole-transporting polymer compound having the structure of the formula (P-2) and 0.6% by mass of the electron-accepting compound (HI-1) alone. An organic electroluminescence device was produced in the same manner as in Example 1, except that a composition dissolved in ethyl benzoate was prepared and used.
[実施例3]
正孔注入層形成用組成物として、前記式(P-4)の構造を有する正孔輸送性高分子化合物3.1質量%と電子受容性化合物(HI-1)0.6質量%とを、安息香酸エチルに溶解させた組成物を調製して用いたほかは、実施例1と同様にして有機電界発光素子を作製した。 [Example 3]
As a composition for forming a hole injection layer, 3.1% by mass of a hole-transporting polymer compound having the structure of formula (P-4) and 0.6% by mass of an electron-accepting compound (HI-1) are mixed. An organic electroluminescence device was produced in the same manner as in Example 1, except that a composition dissolved in ethyl benzoate was prepared and used.
正孔注入層形成用組成物として、前記式(P-4)の構造を有する正孔輸送性高分子化合物3.1質量%と電子受容性化合物(HI-1)0.6質量%とを、安息香酸エチルに溶解させた組成物を調製して用いたほかは、実施例1と同様にして有機電界発光素子を作製した。 [Example 3]
As a composition for forming a hole injection layer, 3.1% by mass of a hole-transporting polymer compound having the structure of formula (P-4) and 0.6% by mass of an electron-accepting compound (HI-1) are mixed. An organic electroluminescence device was produced in the same manner as in Example 1, except that a composition dissolved in ethyl benzoate was prepared and used.
[比較例1]
正孔注入層形成用組成物として、前記式P-5の構造を有する正孔輸送性高分子化合物3.1質量%と電子受容性化合物(HI-1)0.6質量%とを、安息香酸エチルに溶解させた組成物を調製して用いたほかは、実施例1と同様にして有機電界発光素子を作製した。 [Comparative Example 1]
As a composition for forming a hole injection layer, 3.1% by mass of a hole-transporting polymer compound having a structure of the above formula P-5 and 0.6% by mass of an electron-accepting compound (HI-1) are combined with benzoin. An organic electroluminescence device was produced in the same manner as in Example 1, except that a composition dissolved in ethyl acetate was prepared and used.
正孔注入層形成用組成物として、前記式P-5の構造を有する正孔輸送性高分子化合物3.1質量%と電子受容性化合物(HI-1)0.6質量%とを、安息香酸エチルに溶解させた組成物を調製して用いたほかは、実施例1と同様にして有機電界発光素子を作製した。 [Comparative Example 1]
As a composition for forming a hole injection layer, 3.1% by mass of a hole-transporting polymer compound having a structure of the above formula P-5 and 0.6% by mass of an electron-accepting compound (HI-1) are combined with benzoin. An organic electroluminescence device was produced in the same manner as in Example 1, except that a composition dissolved in ethyl acetate was prepared and used.
[蛍光素子の評価]
実施例1~3および比較例1で得られた有機電界発光素子を発光させると、ピーク波長468nmの青色発光が得られた。有機電界発光素子を1,000cd/m2で発光させた際の駆動電圧(V)及び電流効率(cd/A)を測定した。また、有機電界発光素子に15mA/cm2の電流密度で通電し続けた際の輝度低下寿命(輝度低下95%)を測定した。 [Evaluation of fluorescent element]
When the organic electroluminescent devices obtained in Examples 1 to 3 and Comparative Example 1 were caused to emit light, blue light emission with a peak wavelength of 468 nm was obtained. Driving voltage (V) and current efficiency (cd/A) were measured when the organic electroluminescence device was caused to emit light at 1,000 cd/m 2 . In addition, the luminance reduction lifetime (luminance reduction of 95%) was measured when the organic electroluminescence device was continuously energized at a current density of 15 mA/cm 2 .
実施例1~3および比較例1で得られた有機電界発光素子を発光させると、ピーク波長468nmの青色発光が得られた。有機電界発光素子を1,000cd/m2で発光させた際の駆動電圧(V)及び電流効率(cd/A)を測定した。また、有機電界発光素子に15mA/cm2の電流密度で通電し続けた際の輝度低下寿命(輝度低下95%)を測定した。 [Evaluation of fluorescent element]
When the organic electroluminescent devices obtained in Examples 1 to 3 and Comparative Example 1 were caused to emit light, blue light emission with a peak wavelength of 468 nm was obtained. Driving voltage (V) and current efficiency (cd/A) were measured when the organic electroluminescence device was caused to emit light at 1,000 cd/m 2 . In addition, the luminance reduction lifetime (luminance reduction of 95%) was measured when the organic electroluminescence device was continuously energized at a current density of 15 mA/cm 2 .
比較例1の有機電界発光素子の駆動電圧(V)を0.00Vとしたときの、他の実施例の及び比較例1の有機電界発光素子の駆動電圧の差(以下「相対電圧」と称す)を表1に記した。
When the driving voltage (V) of the organic electroluminescent device of Comparative Example 1 was set to 0.00 V, the difference in the driving voltages of the organic electroluminescent devices of the other examples and of Comparative Example 1 (hereinafter referred to as "relative voltage" ) are listed in Table 1.
比較例1の有機電界発光素子の電流発光効率(cd/A)を1.00としたときの、他の実施例及び比較例の有機電界発光素子の電流発光効率の比、すなわち、「比較例1以外の各有機電界発光素子の電流発光効率/比較例1の有機電界発光素子の電流発光効率」(以下「相対電流発光効率」と称す)を表1に記した。
When the current luminous efficiency (cd/A) of the organic electroluminescence device of Comparative Example 1 is 1.00, the ratio of the current luminous efficiencies of the organic electroluminescence devices of other examples and comparative examples, that is, “comparative example Table 1 shows the current luminescence efficiency of each organic electroluminescence device other than No. 1/current luminescence efficiency of the organic electroluminescence device of Comparative Example 1 (hereinafter referred to as "relative current luminescence efficiency").
また、これらの有機電界発光素子に15mA/cm2の電流密度で通電し続けた際に、素子の輝度が初期輝度の95%まで低下する時間(hr)を測定した。この値をLT95とする。比較例1の有機電界発光素子のLT95を1.00とした場合の、他の実施例及び比較例の有機電界発光素子のLT95の比、すなわち、「比較例1以外の各有機電界発光素子のLT95/比較例1の有機電界発光素子のLT95」(以下「相対寿命」と称す)を求め、表1に記した。
In addition, the time (hr) for the brightness of the device to decrease to 95% of the initial brightness was measured when a current density of 15 mA/cm 2 was continuously applied to these organic electroluminescence devices. Let this value be LT95. When the LT95 of the organic electroluminescent device of Comparative Example 1 is set to 1.00, the ratio of LT95 of the organic electroluminescent devices of other examples and comparative examples, that is, “of each organic electroluminescent device other than Comparative Example 1 LT95/LT95 of the organic electroluminescence device of Comparative Example 1 (hereinafter referred to as “relative life”) was determined and shown in Table 1.
表1の結果から、本発明のフッ素を含むアリールアミン高分子化合物と架橋基を有する電子受容性化合物を含む本発明の組成物を用いて形成した青蛍光有機電界発光素子は、電圧が低くなる傾向にあり、電流発光効率及び寿命が良好であることが判った。
From the results in Table 1, the voltage of the blue fluorescent organic electroluminescent device formed using the composition of the present invention containing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound having a cross-linking group is low. It was found that the current luminous efficiency and life were good.
[実施例4]
前記の実施例1の発光層の構成から以下のような発光層5に変えたこと以外に実施例1と同じように電界発光素子を作製した。 [Example 4]
An electroluminescence device was produced in the same manner as in Example 1, except that the structure of the light emitting layer in Example 1 was changed to the light emitting layer 5 as described below.
前記の実施例1の発光層の構成から以下のような発光層5に変えたこと以外に実施例1と同じように電界発光素子を作製した。 [Example 4]
An electroluminescence device was produced in the same manner as in Example 1, except that the structure of the light emitting layer in Example 1 was changed to the light emitting layer 5 as described below.
発光層5を形成するにあたり、下記の構造式で表される化合物(GH-1)を25質量部、下記の構造式で表される化合物(GH-2)を25質量部、下記の構造式で表される化合物(GH-3)を50質量部、および下記の構造式で表される化合物(GD-1)を30質量部秤量し、シクロヘキシルベンゼンに溶解させ7.02質量%の溶液を調製した。
In forming the light-emitting layer 5, 25 parts by mass of the compound (GH-1) represented by the following structural formula, 25 parts by mass of the compound (GH-2) represented by the following structural formula, and the following structural formula 50 parts by mass of the compound (GH-3) represented by and 30 parts by mass of the compound (GD-1) represented by the following structural formula were weighed and dissolved in cyclohexylbenzene to obtain a 7.02% by mass solution. prepared.
この溶液を、上記正孔輸送層を塗布成膜した基板上に窒素グローブボックス中でスピンコートし、窒素グローブボックス中のホットプレートで120℃、20分間乾燥させ、膜厚70nmの均一な薄膜を形成し、発光層5とした。
This solution was spin-coated in a nitrogen glove box onto the substrate on which the hole transport layer had been applied and dried on a hot plate in the nitrogen glove box at 120° C. for 20 minutes to form a uniform thin film with a thickness of 70 nm. A light-emitting layer 5 was formed.
[実施例5]
上記式(P-1)で表される化合物を上記式(P-2)で表される化合物に変えたこと以外は実施例4と同じように有機電界発光素子を作製した。 [Example 5]
An organic electroluminescence device was produced in the same manner as in Example 4 except that the compound represented by the above formula (P-1) was changed to the compound represented by the above formula (P-2).
上記式(P-1)で表される化合物を上記式(P-2)で表される化合物に変えたこと以外は実施例4と同じように有機電界発光素子を作製した。 [Example 5]
An organic electroluminescence device was produced in the same manner as in Example 4 except that the compound represented by the above formula (P-1) was changed to the compound represented by the above formula (P-2).
[実施例6]
上記式(P-1)で表される化合物を上記式(P-4)で表される化合物に変えたこと以外は実施例4と同じように有機電界発光素子を作製した。 [Example 6]
An organic electroluminescence device was produced in the same manner as in Example 4, except that the compound represented by the above formula (P-1) was changed to the compound represented by the above formula (P-4).
上記式(P-1)で表される化合物を上記式(P-4)で表される化合物に変えたこと以外は実施例4と同じように有機電界発光素子を作製した。 [Example 6]
An organic electroluminescence device was produced in the same manner as in Example 4, except that the compound represented by the above formula (P-1) was changed to the compound represented by the above formula (P-4).
[比較例2]
上記式(P-1)で表される化合物を上記式(P-5)で表される化合物に変えたこと以外は実施例4と同じように有機電界発光素子を作製した。 [Comparative Example 2]
An organic electroluminescence device was produced in the same manner as in Example 4, except that the compound represented by the above formula (P-1) was changed to the compound represented by the above formula (P-5).
上記式(P-1)で表される化合物を上記式(P-5)で表される化合物に変えたこと以外は実施例4と同じように有機電界発光素子を作製した。 [Comparative Example 2]
An organic electroluminescence device was produced in the same manner as in Example 4, except that the compound represented by the above formula (P-1) was changed to the compound represented by the above formula (P-5).
[燐光素子の評価]
実施例4~6および比較例2で得られた有機電界発光素子を発光させると、ピーク波長524nmの緑燐光発光が得られた。有機電界発光素子を1,000cd/m2で発光させた際の駆動電圧(V)及び電流効率(cd/A)を測定した。また、有機電界発光素子に15mA/cm2の電流密度で通電し続けた際の輝度低下寿命(輝度低下95%)を測定した。 [Evaluation of phosphorescent element]
When the organic electroluminescence devices obtained in Examples 4 to 6 and Comparative Example 2 were caused to emit light, green phosphorescence emission with a peak wavelength of 524 nm was obtained. Driving voltage (V) and current efficiency (cd/A) were measured when the organic electroluminescence device was caused to emit light at 1,000 cd/m 2 . In addition, the luminance reduction lifetime (luminance reduction of 95%) was measured when the organic electroluminescence device was continuously energized at a current density of 15 mA/cm 2 .
実施例4~6および比較例2で得られた有機電界発光素子を発光させると、ピーク波長524nmの緑燐光発光が得られた。有機電界発光素子を1,000cd/m2で発光させた際の駆動電圧(V)及び電流効率(cd/A)を測定した。また、有機電界発光素子に15mA/cm2の電流密度で通電し続けた際の輝度低下寿命(輝度低下95%)を測定した。 [Evaluation of phosphorescent element]
When the organic electroluminescence devices obtained in Examples 4 to 6 and Comparative Example 2 were caused to emit light, green phosphorescence emission with a peak wavelength of 524 nm was obtained. Driving voltage (V) and current efficiency (cd/A) were measured when the organic electroluminescence device was caused to emit light at 1,000 cd/m 2 . In addition, the luminance reduction lifetime (luminance reduction of 95%) was measured when the organic electroluminescence device was continuously energized at a current density of 15 mA/cm 2 .
比較例2の有機電界発光素子の駆動電圧(V)を0.00Vとしたときの、他の実施例の及び比較例2の有機電界発光素子の駆動電圧の差(以下「相対電圧」と称す)を表2に記した。
When the driving voltage (V) of the organic electroluminescent device of Comparative Example 2 was set to 0.00 V, the difference in the driving voltages of the organic electroluminescent devices of the other examples and of Comparative Example 2 (hereinafter referred to as "relative voltage" ) are listed in Table 2.
比較例2の有機電界発光素子の電流発光効率(cd/A)を1.00としたときの、他の実施例及び比較例の有機電界発光素子の電流発光効率の比、すなわち、「比較例2以外の各有機電界発光素子の電流発光効率/比較例2の有機電界発光素子の電流発光効率」(以下「相対電流発光効率」と称す)を表2に記した。
When the current luminous efficiency (cd/A) of the organic electroluminescent device of Comparative Example 2 is 1.00, the ratio of the current luminous efficiency of the organic electroluminescent devices of other examples and comparative examples, i.e., "comparative example Table 2 shows the current luminescence efficiency of each organic electroluminescence device other than Example 2/current luminescence efficiency of the organic electroluminescence device of Comparative Example 2 (hereinafter referred to as "relative current luminescence efficiency").
また、これらの有機電界発光素子に15mA/cm2の電流密度で通電し続けた際に、素子の輝度が初期輝度の95%まで低下する時間(hr)を測定した。この値をLT95とする。比較例2の有機電界発光素子のLT95を1.00とした場合の、他の実施例及び比較例の有機電界発光素子のLT95の比、すなわち、「比較例2以外の各有機電界発光素子のLT95/比較例1の有機電界発光素子のLT95」(以下「相対寿命」と称す)を求め、表2に記した。
In addition, the time (hr) for the brightness of the device to decrease to 95% of the initial brightness was measured when a current density of 15 mA/cm 2 was continuously applied to these organic electroluminescence devices. Let this value be LT95. When the LT95 of the organic electroluminescent device of Comparative Example 2 is set to 1.00, the ratio of LT95 of the organic electroluminescent devices of other examples and comparative examples, that is, “of each organic electroluminescent device other than Comparative Example 2 LT95/LT95 of the organic electroluminescence device of Comparative Example 1 (hereinafter referred to as “relative life”) was obtained and shown in Table 2.
表2の結果から、本発明のフッ素を含むアリールアミン高分子化合物と架橋基を有する電子受容性化合物を含む本発明の組成物を用いて形成した緑燐光有機電界発光素子にも、電圧が低くなる傾向にあり、電流発光効率及び寿命が良好であることが判った。
From the results in Table 2, the green phosphorescent organic electroluminescent device formed using the composition of the present invention containing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound having a cross-linking group exhibited a low voltage. It was found that the current luminous efficiency and life were good.
[実施例7]
正孔注入層形成用組成物に含まれる電子受容性化合物として、上記式(HI-1)で表される化合物の代わりに下記式(HI-2)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例4と同様にして有機電界発光素子を作製した。 [Example 7]
As an electron-accepting compound contained in the composition for forming a hole injection layer, a compound represented by the following formula (HI-2) instead of the compound represented by the above formula (HI-1) is used for hole injection. A layer-forming composition was prepared, and an organic electroluminescence device was produced in the same manner as in Example 4, except that this composition was used.
正孔注入層形成用組成物に含まれる電子受容性化合物として、上記式(HI-1)で表される化合物の代わりに下記式(HI-2)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例4と同様にして有機電界発光素子を作製した。 [Example 7]
As an electron-accepting compound contained in the composition for forming a hole injection layer, a compound represented by the following formula (HI-2) instead of the compound represented by the above formula (HI-1) is used for hole injection. A layer-forming composition was prepared, and an organic electroluminescence device was produced in the same manner as in Example 4, except that this composition was used.
[比較例3]
正孔注入層形成用組成物に含まれる電子受容性化合物として、上記式(HI-2)で表される化合物の代わりに下記式(HI-3)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例7と同様にして有機電界発光素子を作製した。 [Comparative Example 3]
As an electron-accepting compound contained in the composition for forming a hole injection layer, a compound represented by the following formula (HI-3) instead of the compound represented by the above formula (HI-2) is used for hole injection. A layer-forming composition was prepared, and an organic electroluminescence device was produced in the same manner as in Example 7, except that this composition was used.
正孔注入層形成用組成物に含まれる電子受容性化合物として、上記式(HI-2)で表される化合物の代わりに下記式(HI-3)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例7と同様にして有機電界発光素子を作製した。 [Comparative Example 3]
As an electron-accepting compound contained in the composition for forming a hole injection layer, a compound represented by the following formula (HI-3) instead of the compound represented by the above formula (HI-2) is used for hole injection. A layer-forming composition was prepared, and an organic electroluminescence device was produced in the same manner as in Example 7, except that this composition was used.
[実施例8]
正孔注入層形成用組成物に含まれる正孔輸送性高分子化合物として、上記式(P-1)で表される化合物の代わりに上記式(P-2)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例7と同様にして有機電界発光素子を作製した。 [Example 8]
Using the compound represented by the above formula (P-2) instead of the compound represented by the above formula (P-1) as the hole-transporting polymer compound contained in the composition for forming a hole injection layer A composition for forming a hole injection layer was prepared, and an organic electroluminescence device was produced in the same manner as in Example 7, except that this composition was used.
正孔注入層形成用組成物に含まれる正孔輸送性高分子化合物として、上記式(P-1)で表される化合物の代わりに上記式(P-2)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例7と同様にして有機電界発光素子を作製した。 [Example 8]
Using the compound represented by the above formula (P-2) instead of the compound represented by the above formula (P-1) as the hole-transporting polymer compound contained in the composition for forming a hole injection layer A composition for forming a hole injection layer was prepared, and an organic electroluminescence device was produced in the same manner as in Example 7, except that this composition was used.
[比較例4]
正孔注入層形成用組成物に含まれる電子受容性化合物として、上記式(HI-2)で表される化合物の代わりに上記式(HI-3)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例8と同様にして有機電界発光素子を作製した。 [Comparative Example 4]
Hole injection using the compound represented by the above formula (HI-3) instead of the compound represented by the above formula (HI-2) as the electron-accepting compound contained in the composition for forming a hole injection layer A layer-forming composition was prepared, and an organic electroluminescence device was produced in the same manner as in Example 8, except that this composition was used.
正孔注入層形成用組成物に含まれる電子受容性化合物として、上記式(HI-2)で表される化合物の代わりに上記式(HI-3)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例8と同様にして有機電界発光素子を作製した。 [Comparative Example 4]
Hole injection using the compound represented by the above formula (HI-3) instead of the compound represented by the above formula (HI-2) as the electron-accepting compound contained in the composition for forming a hole injection layer A layer-forming composition was prepared, and an organic electroluminescence device was produced in the same manner as in Example 8, except that this composition was used.
[実施例9]
正孔注入層形成用組成物に含まれる正孔輸送性高分子化合物として、上記式(P-1)で表される化合物の代わりに上記式(P-4)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例7と同様にして有機電界発光素子を作製した。 [Example 9]
Using the compound represented by the above formula (P-4) instead of the compound represented by the above formula (P-1) as the hole-transporting polymer compound contained in the composition for forming a hole injection layer A composition for forming a hole injection layer was prepared, and an organic electroluminescence device was produced in the same manner as in Example 7, except that this composition was used.
正孔注入層形成用組成物に含まれる正孔輸送性高分子化合物として、上記式(P-1)で表される化合物の代わりに上記式(P-4)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例7と同様にして有機電界発光素子を作製した。 [Example 9]
Using the compound represented by the above formula (P-4) instead of the compound represented by the above formula (P-1) as the hole-transporting polymer compound contained in the composition for forming a hole injection layer A composition for forming a hole injection layer was prepared, and an organic electroluminescence device was produced in the same manner as in Example 7, except that this composition was used.
[比較例5]
正孔注入層形成用組成物に含まれる電子受容性化合物として、上記式(HI-2)で表される化合物の代わりに上記式(HI-3)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例9と同様にして有機電界発光素子を作製した。 [Comparative Example 5]
Hole injection using the compound represented by the above formula (HI-3) instead of the compound represented by the above formula (HI-2) as the electron-accepting compound contained in the composition for forming a hole injection layer A layer-forming composition was prepared, and an organic electroluminescence device was produced in the same manner as in Example 9, except that this composition was used.
正孔注入層形成用組成物に含まれる電子受容性化合物として、上記式(HI-2)で表される化合物の代わりに上記式(HI-3)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例9と同様にして有機電界発光素子を作製した。 [Comparative Example 5]
Hole injection using the compound represented by the above formula (HI-3) instead of the compound represented by the above formula (HI-2) as the electron-accepting compound contained in the composition for forming a hole injection layer A layer-forming composition was prepared, and an organic electroluminescence device was produced in the same manner as in Example 9, except that this composition was used.
[実施例10]
正孔注入層形成用組成物に含まれる正孔輸送性高分子化合物として、上記式(P-1)で表される化合物の代わりに下記式(P-a)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例4と同様にして有機電界発光素子を作製した。 [Example 10]
As a hole-transporting polymer compound contained in the composition for forming a hole injection layer, a compound represented by the following formula (Pa) is used instead of the compound represented by the above formula (P-1). A composition for forming a hole injection layer was prepared, and an organic electroluminescence device was produced in the same manner as in Example 4, except that this composition was used.
正孔注入層形成用組成物に含まれる正孔輸送性高分子化合物として、上記式(P-1)で表される化合物の代わりに下記式(P-a)で表される化合物を用いて正孔注入層形成用組成物を調製し、これを用いた他は実施例4と同様にして有機電界発光素子を作製した。 [Example 10]
As a hole-transporting polymer compound contained in the composition for forming a hole injection layer, a compound represented by the following formula (Pa) is used instead of the compound represented by the above formula (P-1). A composition for forming a hole injection layer was prepared, and an organic electroluminescence device was produced in the same manner as in Example 4, except that this composition was used.
[素子の評価]
実施例7、実施例8、実施例9、実施例10、比較例2、比較例3、比較例4および比較例5で得られた有機電界発光素子を1,000cd/m2で発光させた際の電流効率(cd/A)を測定した。また、有機電界発光素子に15mA/cm2の電流密度で通電し続けた際、素子の輝度が初期輝度の95%まで低下する時間(hr)を測定した。この値をLT95とする。
比較例4の有機電界発光素子の電流発光効率(cd/A)を1.00としたときの、実施例および比較例の有機電界発光素子の電流発光効率の比、すなわち、それぞれ「実施例又は比較例の有機電界発光素子の電流発光効率/比較例4の有機電界発光素子の電流発光効率」(以下「相対電流発光効率」と称す)を表3に記した。
比較例4の有機電界発光素子のLT95を1.00とした場合の、実施例および比較例の有機電界発光素子のLT95の比、すなわち、それぞれ「実施例又は比較例の有機電界発光素子のLT95/比較例の有機電界発光素子のLT95」(以下「相対寿命」と称す)を求め、表3に記した。 [Evaluation of element]
The organic electroluminescence devices obtained in Examples 7, 8, 9, 10, Comparative Example 2, Comparative Example 3, Comparative Example 4 and Comparative Example 5 were caused to emit light at 1,000 cd/m 2 . The actual current efficiency (cd/A) was measured. Further, the time (hr) for the brightness of the device to decrease to 95% of the initial brightness was measured when the organic electroluminescence device was continuously energized at a current density of 15 mA/cm 2 . Let this value be LT95.
When the current luminous efficiency (cd/A) of the organic electroluminescent device of Comparative Example 4 is 1.00, the ratio of the current luminous efficiencies of the organic electroluminescent devices of Examples and Comparative Examples, that is, “Example or Table 3 shows the current luminous efficiency of the organic electroluminescent device of Comparative Example/current luminous efficiency of the organic electroluminescent device of Comparative Example 4 (hereinafter referred to as "relative current luminous efficiency").
When the LT95 of the organic electroluminescent device of Comparative Example 4 is set to 1.00, the ratio of the LT95 of the organic electroluminescent devices of Examples and Comparative Examples, that is, the LT95 of the organic electroluminescent devices of Examples and Comparative Examples, respectively / LT95 of the organic electroluminescence device of the comparative example (hereinafter referred to as "relative life") was determined and shown in Table 3.
実施例7、実施例8、実施例9、実施例10、比較例2、比較例3、比較例4および比較例5で得られた有機電界発光素子を1,000cd/m2で発光させた際の電流効率(cd/A)を測定した。また、有機電界発光素子に15mA/cm2の電流密度で通電し続けた際、素子の輝度が初期輝度の95%まで低下する時間(hr)を測定した。この値をLT95とする。
比較例4の有機電界発光素子の電流発光効率(cd/A)を1.00としたときの、実施例および比較例の有機電界発光素子の電流発光効率の比、すなわち、それぞれ「実施例又は比較例の有機電界発光素子の電流発光効率/比較例4の有機電界発光素子の電流発光効率」(以下「相対電流発光効率」と称す)を表3に記した。
比較例4の有機電界発光素子のLT95を1.00とした場合の、実施例および比較例の有機電界発光素子のLT95の比、すなわち、それぞれ「実施例又は比較例の有機電界発光素子のLT95/比較例の有機電界発光素子のLT95」(以下「相対寿命」と称す)を求め、表3に記した。 [Evaluation of element]
The organic electroluminescence devices obtained in Examples 7, 8, 9, 10, Comparative Example 2, Comparative Example 3, Comparative Example 4 and Comparative Example 5 were caused to emit light at 1,000 cd/m 2 . The actual current efficiency (cd/A) was measured. Further, the time (hr) for the brightness of the device to decrease to 95% of the initial brightness was measured when the organic electroluminescence device was continuously energized at a current density of 15 mA/cm 2 . Let this value be LT95.
When the current luminous efficiency (cd/A) of the organic electroluminescent device of Comparative Example 4 is 1.00, the ratio of the current luminous efficiencies of the organic electroluminescent devices of Examples and Comparative Examples, that is, “Example or Table 3 shows the current luminous efficiency of the organic electroluminescent device of Comparative Example/current luminous efficiency of the organic electroluminescent device of Comparative Example 4 (hereinafter referred to as "relative current luminous efficiency").
When the LT95 of the organic electroluminescent device of Comparative Example 4 is set to 1.00, the ratio of the LT95 of the organic electroluminescent devices of Examples and Comparative Examples, that is, the LT95 of the organic electroluminescent devices of Examples and Comparative Examples, respectively / LT95 of the organic electroluminescence device of the comparative example (hereinafter referred to as "relative life") was determined and shown in Table 3.
表3の結果から、フッ素を含まない高分子化合物、架橋基を含まない電子受容性化合物を用いた燐光有機電界発光素子に対し、本発明のフッ素を含むアリールアミン高分子化合物と架橋基を有する電子受容性化合物を含む本発明の組成物を用いて形成した燐光有機電界発光素子は、良好な電流発光効率及び寿命を示すことが判った。
From the results in Table 3, it was found that the phosphorescent organic electroluminescent device using the fluorine-free polymer compound and the electron-accepting compound not containing the cross-linking group has the fluorine-containing arylamine polymer compound of the present invention and the cross-linking group. It was found that the phosphorescent organic electroluminescent device formed using the composition of the present invention containing an electron-accepting compound exhibits good current luminescence efficiency and lifetime.
<イオン化ポテンシャルの測定方法>
光電子収量分光法(PYS)によりイオン化ポテンシャル(IP)の測定を行う。該測定は、Optel社製PCR-101を用いて行うことが好ましいが、同等の測定を行えるものであれば限定されるものではない。
具体的には、ホスト材料を適当な溶剤に溶解してサンプル用塗布液を調製する。溶剤は限定されるものではなく、上記発光層形成用組成物に用いる溶剤として例示したものが使用できるが、好ましくは、実際に発光層を形成する際に用いる溶剤である。 <Method for measuring ionization potential>
Ionization potential (IP) measurements are performed by photoelectron yield spectroscopy (PYS). The measurement is preferably performed using PCR-101 manufactured by Optel, but is not limited as long as equivalent measurement can be performed.
Specifically, a sample coating liquid is prepared by dissolving the host material in a suitable solvent. The solvent is not limited, and those exemplified as the solvent used for the composition for forming the light-emitting layer can be used, but the solvent used when actually forming the light-emitting layer is preferable.
光電子収量分光法(PYS)によりイオン化ポテンシャル(IP)の測定を行う。該測定は、Optel社製PCR-101を用いて行うことが好ましいが、同等の測定を行えるものであれば限定されるものではない。
具体的には、ホスト材料を適当な溶剤に溶解してサンプル用塗布液を調製する。溶剤は限定されるものではなく、上記発光層形成用組成物に用いる溶剤として例示したものが使用できるが、好ましくは、実際に発光層を形成する際に用いる溶剤である。 <Method for measuring ionization potential>
Ionization potential (IP) measurements are performed by photoelectron yield spectroscopy (PYS). The measurement is preferably performed using PCR-101 manufactured by Optel, but is not limited as long as equivalent measurement can be performed.
Specifically, a sample coating liquid is prepared by dissolving the host material in a suitable solvent. The solvent is not limited, and those exemplified as the solvent used for the composition for forming the light-emitting layer can be used, but the solvent used when actually forming the light-emitting layer is preferable.
サンプル用塗布液の濃度は、特に限定されるものではないが、成膜および乾燥後、50nmの膜厚が形成される濃度であればよい。
調製されたサンプル用塗布液を、石英基板上に成膜する。成膜は、発光層の成膜工程に記載した方法と同様に行うことが好ましい。 Although the concentration of the sample coating liquid is not particularly limited, it may be a concentration at which a film thickness of 50 nm is formed after film formation and drying.
A film is formed on a quartz substrate from the prepared sample coating liquid. The film formation is preferably performed in the same manner as the method described in the film formation process of the light-emitting layer.
調製されたサンプル用塗布液を、石英基板上に成膜する。成膜は、発光層の成膜工程に記載した方法と同様に行うことが好ましい。 Although the concentration of the sample coating liquid is not particularly limited, it may be a concentration at which a film thickness of 50 nm is formed after film formation and drying.
A film is formed on a quartz substrate from the prepared sample coating liquid. The film formation is preferably performed in the same manner as the method described in the film formation process of the light-emitting layer.
成膜後、乾燥させることにより、50nmの膜厚の測定用サンプルを得る。乾燥もまた、発光層の乾燥工程に記載した方法と同様に行うことが好ましい。
この測定用サンプルを測定装置(Optel社製PCR-101)の測定室内の基板ホルダーにセットし、測定室の扉を閉じる。ターボ分子ポンプによって測定室を10-1Pa以下まで排気する。サンプルには、-50Vの電圧を与え、重水素ランプからの励起光を単色化してサンプルへ入射し、微少電流計によって励起によってサンプルから放出される光電子を検出する。単色化された励起光のエネルギーと光電子の検出量のプロットからイオン化ポテンシャルを決定する。 After the film is formed, it is dried to obtain a sample for measurement with a film thickness of 50 nm. Drying is also preferably carried out in the same manner as described in the step of drying the light-emitting layer.
This measurement sample is set on a substrate holder in the measurement chamber of the measurement device (Optel PCR-101), and the door of the measurement chamber is closed. The measuring chamber is evacuated to below 10 −1 Pa by a turbomolecular pump. A voltage of −50 V is applied to the sample, the excitation light from the deuterium lamp is made monochromatic and is incident on the sample, and the photoelectrons emitted from the sample due to the excitation are detected by a microammeter. The ionization potential is determined from a plot of monochromatic excitation light energy versus photoelectron detection.
この測定用サンプルを測定装置(Optel社製PCR-101)の測定室内の基板ホルダーにセットし、測定室の扉を閉じる。ターボ分子ポンプによって測定室を10-1Pa以下まで排気する。サンプルには、-50Vの電圧を与え、重水素ランプからの励起光を単色化してサンプルへ入射し、微少電流計によって励起によってサンプルから放出される光電子を検出する。単色化された励起光のエネルギーと光電子の検出量のプロットからイオン化ポテンシャルを決定する。 After the film is formed, it is dried to obtain a sample for measurement with a film thickness of 50 nm. Drying is also preferably carried out in the same manner as described in the step of drying the light-emitting layer.
This measurement sample is set on a substrate holder in the measurement chamber of the measurement device (Optel PCR-101), and the door of the measurement chamber is closed. The measuring chamber is evacuated to below 10 −1 Pa by a turbomolecular pump. A voltage of −50 V is applied to the sample, the excitation light from the deuterium lamp is made monochromatic and is incident on the sample, and the photoelectrons emitted from the sample due to the excitation are detected by a microammeter. The ionization potential is determined from a plot of monochromatic excitation light energy versus photoelectron detection.
エネルギーギャップ(Eg)については、上記した<イオン化ポテンシャルの測定方法>のように、作成された試料を使用して紫外-可視吸光度計で薄膜の吸収曲線を測定する。その薄膜の短波長側の立ち上がりの所に接線を引き、求まった交点の波長(λ)nmを次の式に代入し目的の値を求める。それによって得た値がEg(eV)になる。
Eg=1240/λ
例えば接線を引いて求めたλ値が450nmである場合、この時のEgの値は
Eg=1240/450=2.76(eV)
と言うことになる。
Ea(電子親和力)は、IpからEgを引いた値である。
HOMOのエネルギー準位の絶対値は電子軌道分子から外部(真空中)電子を取り出すためのエネルギーはイオン化ポテンシャルに相当し、LUMOのエネルギー準位の絶対値は電子親和力に相当するので、P-1、P-2、P-3、P-4、P-aおよびP-5のHOMO及びLUMOを表4に示す。 As for the energy gap (Eg), the prepared sample is used to measure the absorption curve of the thin film with an ultraviolet-visible spectrophotometer as described in <Method for Measuring Ionization Potential>. A tangent line is drawn at the short-wavelength side rise of the thin film, and the obtained wavelength (λ) nm at the crossing point is substituted into the following equation to obtain the target value. The value thus obtained is Eg (eV).
Eg=1240/λ
For example, if the λ value obtained by drawing the tangent line is 450 nm, the Eg value at this time is Eg=1240/450=2.76 (eV)
I will say.
Ea (electron affinity) is Ip minus Eg.
The absolute value of the HOMO energy level corresponds to the ionization potential, and the absolute value of the LUMO energy level corresponds to the electron affinity. , P-2, P-3, P-4, Pa and P-5 are shown in Table 4.
Eg=1240/λ
例えば接線を引いて求めたλ値が450nmである場合、この時のEgの値は
Eg=1240/450=2.76(eV)
と言うことになる。
Ea(電子親和力)は、IpからEgを引いた値である。
HOMOのエネルギー準位の絶対値は電子軌道分子から外部(真空中)電子を取り出すためのエネルギーはイオン化ポテンシャルに相当し、LUMOのエネルギー準位の絶対値は電子親和力に相当するので、P-1、P-2、P-3、P-4、P-aおよびP-5のHOMO及びLUMOを表4に示す。 As for the energy gap (Eg), the prepared sample is used to measure the absorption curve of the thin film with an ultraviolet-visible spectrophotometer as described in <Method for Measuring Ionization Potential>. A tangent line is drawn at the short-wavelength side rise of the thin film, and the obtained wavelength (λ) nm at the crossing point is substituted into the following equation to obtain the target value. The value thus obtained is Eg (eV).
Eg=1240/λ
For example, if the λ value obtained by drawing the tangent line is 450 nm, the Eg value at this time is Eg=1240/450=2.76 (eV)
I will say.
Ea (electron affinity) is Ip minus Eg.
The absolute value of the HOMO energy level corresponds to the ionization potential, and the absolute value of the LUMO energy level corresponds to the electron affinity. , P-2, P-3, P-4, Pa and P-5 are shown in Table 4.
表4の結果から、フッ素を含まない重合体P-5に対し、本発明のフッ素を含むアリールアミン高分子化合物のHOMOが深くなり、量子ドットを含有する発光層を有する電界発光素子に、良好な電流発光効率及び寿命を期待できる。
From the results in Table 4, the HOMO of the fluorine-containing arylamine polymer compound of the present invention is deeper than that of the fluorine-free polymer P-5. A high current luminous efficiency and lifetime can be expected.
本発明を特定の態様を用いて詳細に説明したが、本発明の意図と範囲を離れることなく様々な変更が可能であることは当業者に明らかである。
Although the present invention has been described in detail using specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the present invention.
以上、本発明を詳細にまた特定の実施態様を参照して説明したが、本発明の精神と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。本出願は、2022年2月24日出願の日本特許出願(特願2022-027242)に基づくものであり、その内容はここに参照として取り込まれる。
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2022-027242) filed on February 24, 2022, the contents of which are incorporated herein by reference.
1 基板
2 陽極
3 正孔注入層
4 正孔輸送層
5 発光層
6 電子輸送層
7 陰極
8 有機電界発光素子 REFERENCE SIGNSLIST 1 substrate 2 anode 3 hole injection layer 4 hole transport layer 5 light emitting layer 6 electron transport layer 7 cathode 8 organic electroluminescence device
2 陽極
3 正孔注入層
4 正孔輸送層
5 発光層
6 電子輸送層
7 陰極
8 有機電界発光素子 REFERENCE SIGNS
Claims (19)
- 下記式(1)で表される繰り返し単位を有し、主鎖及び側鎖の少なくとも1つに置換基を有していてもよいフルオレンを有し、架橋基を有する高分子化合物、および下記式(81)で表される、架橋基を有する電子受容性化合物を含む、組成物。
(式(1)中、
Ar1は、置換基を有していてもよい炭素数6~60の2価の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Gは、式(1-1)~式(1-3)のいずれかで表される2価の基を表し、
“*”は隣接する構造との結合位置を表し、
置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
Ar2は、水素原子、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表し、
mは、1~4の整数であり、
nは、1~6の整数である。)
(式(81)中、
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) A polymer compound having a repeating unit represented by the following formula (1), having a fluorene which may have a substituent in at least one of the main chain and the side chain, and having a cross-linking group; and A composition comprising an electron-accepting compound having a cross-linking group represented by (81).
(In formula (1),
Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group ,
G represents a divalent group represented by any one of formulas (1-1) to (1-3),
"*" represents the bonding position with the adjacent structure,
Each substituent A is independently a fluorine atom, CF3 , or SF5 .
Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms. A plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group,
m is an integer from 1 to 4,
n is an integer of 1-6. )
(In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. ) - 少なくとも2つの架橋基を有する前記式(81)で表される電子受容性化合物を含む、請求項1に記載の組成物。 The composition according to claim 1, comprising an electron-accepting compound represented by the formula (81) having at least two cross-linking groups.
- 前記式(1)で表される化合物及び前記式(81)で表される化合物が、各々独立に、下記架橋基群Tから選択される架橋基を有する、請求項1又は2に記載の組成物。
<架橋基群T>
(上記式中、
Qは直接結合又は連結基を表す。
“*”は結合位置を表す。
式(X4)、式(X5)、式(X6)及び式(X10)中のR110は、水素原子又は置換基を有していてもよいアルキル基を表す。
式(X1)~(X4)中、ベンゼン環及びナフタレン環は、置換基を有していてもよい。また、置換基は互いに結合して環を形成してもよい。
式(X1)、(X2)中、シクロブテン環は置換基を有していてもよい。) The composition according to claim 1 or 2, wherein the compound represented by the formula (1) and the compound represented by the formula (81) each independently have a cross-linking group selected from the following cross-linking group group T thing.
<Crosslinking Group T>
(In the above formula,
Q represents a direct bond or a linking group.
"*" represents the binding position.
R 110 in formula (X4), formula (X5), formula (X6) and formula (X10) represents a hydrogen atom or an optionally substituted alkyl group.
In formulas (X1) to (X4), the benzene ring and naphthalene ring may have a substituent. Also, the substituents may be combined with each other to form a ring.
In formulas (X1) and (X2), the cyclobutene ring may have a substituent. ) - 前記Ar1が、下記式(2-1)~(2-3)から選択される1つの部分構造を有するか、または、下記式(2-1)~(2-3)から選択される2以上が互いに結合してなる結合構造を有し、前記結合構造が下記式(2-1)~(2-3)から選択される少なくとも1種の構造を2以上結合した構造を含有してもよい、請求項1~5のいずれか1項に記載の組成物。
(上記式(2-1)~(2-3)それぞれにおいて、R1およびR2は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~18の芳香族炭化水素基、置換基を有していてもよい炭素数3~12の芳香族複素環基、炭素数1~12のアルキル基であり、“*”は隣接する構造との結合位置を表す。) Ar 1 has one partial structure selected from the following formulas (2-1) to (2-3), or 2 selected from the following formulas (2-1) to (2-3) or more bonded to each other, and the bonded structure contains a structure in which two or more of at least one structure selected from the following formulas (2-1) to (2-3) are bonded. Good, the composition according to any one of claims 1-5.
(In each of the above formulas (2-1) to (2-3), R 1 and R 2 each independently represent a hydrogen atom, a deuterium atom, a halogen atom, or an optionally substituted carbon number of 6 ~18 aromatic hydrocarbon groups, optionally substituted C3-C12 aromatic heterocyclic groups, C1-C12 alkyl groups, and "*" with the adjacent structure represents the binding position.) - 前記高分子化合物が、さらに、下記式(3)で表される繰り返し単位を有する、請求項1~6のいずれか1項に記載の組成物。
(上記式(3)中、Ar3は、置換基を有していてもよい2-フルオレニル基である。Ar4は、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は前記置換基を有していてもよい2価の芳香族炭化水素基及び前記置換基を有していてもよい2価の芳香族複素環基からなる群から選択される少なくとも2つの基が直接若しくは連結基を介して複数個連結した2価の基を表す。) The composition according to any one of claims 1 to 6, wherein the polymer compound further has a repeating unit represented by the following formula (3).
(In the above formula (3), Ar 3 is an optionally substituted 2-fluorenyl group. Ar 4 is an optionally substituted divalent aromatic hydrocarbon group, A divalent aromatic heterocyclic group which may have a substituent, or a divalent aromatic hydrocarbon group which may have a substituent and a divalent which may have a substituent represents a divalent group in which at least two groups selected from the group consisting of aromatic heterocyclic groups are linked directly or via a linking group.) - 更に溶媒を含有する、請求項1~7のいずれか1項に記載の組成物。 The composition according to any one of claims 1 to 7, further comprising a solvent.
- 基板上に、陽極及び陰極を有し、該陽極と該陰極の間に有機層を有する有機電界発光素子の製造方法であって、
該有機層を、請求項8に記載の組成物を用いて湿式成膜法にて形成する工程を有する、有機電界発光素子の製造方法。 A method for producing an organic electroluminescence device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode, comprising:
A method for producing an organic electroluminescence device, comprising the step of forming the organic layer by a wet film-forming method using the composition according to claim 8 . - 前記有機層が前記陽極と発光層の間にある有機層である、請求項9に記載の有機電界発光素子の製造方法。 The method for manufacturing an organic electroluminescence device according to claim 9, wherein the organic layer is an organic layer between the anode and the light-emitting layer.
- 基板上に、陽極及び陰極を有し、該陽極と該陰極の間に有機層を有する有機電界発光素子であって、
該有機層が、下記式(1)で表される繰り返し単位を有し、主鎖及び側鎖の少なくとも1つに置換基を有していてもよいフルオレンを有し、架橋基を有する高分子化合物と、下記式(81)で表される、架橋基を有する電子受容性化合物との架橋反応物を含有する、有機電界発光素子。
(式(1)中、
Ar1は、置換基を有していてもよい炭素数6~60の2価の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の2価の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基若しくは置換基を有していてもよい芳香族複素環基が直接若しくは連結基を介して複数個連結した2価の基を表し、
Gは、式(1-1)~式(1-3)のいずれかで表される2価の基を表し、
“*”は隣接する構造との結合部位を表し、
置換基Aは、各々独立に、フッ素原子、CF3、又はSF5である。
Ar2は、水素原子、置換基A、置換基を有していてもよい炭素数6~60の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、又は置換基を有していてもよい芳香族炭化水素基及び置換基を有していてもよい芳香族複素環基から選択される基が直接若しくは連結基を介して複数個連結した1価の基を表し、
mは、1~4の整数であり、
nは、1~6の整数である。)
(式(81)中、
5つのR81、5つのR82、5つのR83、5つのR84は、それぞれにおいて独立であり、かつ、R81~R84は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~50の芳香族炭化水素基、置換基を有していてもよい炭素数3~50の芳香族複素環基、フッ素置換された炭素数1~12のアルキル基、又は架橋基である。
Ph1、Ph2、Ph3、Ph4は、それぞれのベンゼン環を指す符号である。
X+は対カチオンを表す。) An organic electroluminescence device having an anode and a cathode on a substrate and an organic layer between the anode and the cathode,
The organic layer has a repeating unit represented by the following formula (1), has fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group. An organic electroluminescence device containing a cross-linking reaction product of a compound and an electron-accepting compound having a cross-linking group represented by the following formula (81).
(In formula (1),
Ar 1 is an optionally substituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or an optionally substituted divalent aromatic heterocyclic ring having 3 to 50 carbon atoms. or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are linked directly or via a linking group ,
G represents a divalent group represented by any one of formulas (1-1) to (1-3),
"*" represents the binding site with the adjacent structure,
Each substituent A is independently a fluorine atom, CF3 , or SF5 .
Ar 2 is a hydrogen atom, a substituent A, an optionally substituted aromatic hydrocarbon group having 6 to 60 carbon atoms, an optionally substituted aromatic heteroaromatic group having 3 to 50 carbon atoms. A plurality of groups selected from a cyclic group, an optionally substituted aromatic hydrocarbon group, and an optionally substituted aromatic heterocyclic group are linked directly or via a linking group. represents a monovalent group,
m is an integer from 1 to 4,
n is an integer of 1-6. )
(In formula (81),
5 R 81 , 5 R 82 , 5 R 83 and 5 R 84 are each independently, and R 81 to R 84 are each independently hydrogen atom, deuterium atom, halogen atom, optionally substituted aromatic hydrocarbon group having 6 to 50 carbon atoms, aromatic heterocyclic group having 3 to 50 carbon atoms optionally having substituent(s), fluorine-substituted 1 to 1 carbon atoms 12 alkyl groups or bridging groups.
Ph 1 , Ph 2 , Ph 3 and Ph 4 are symbols indicating respective benzene rings.
X + represents a counter cation. ) - 前記Ar1が、下記式(2-1)~(2-3)から選択される1つの部分構造を有するか、または、下記式(2-1)~(2-3)から選択される2以上が互いに結合してなる結合構造を有し、前記結合構造が下記式(2-1)~(2-3)から選択される少なくとも1種の構造を2以上結合した構造を含有してもよい、請求項11~13のいずれか1項に記載の有機電界発光素子。
(上記式(2-1)~式(2-3)それぞれにおいて、R1およびR2は、それぞれ独立に、水素原子、重水素原子、ハロゲン原子、置換基を有していてもよい炭素数6~18の芳香族炭化水素基、置換基を有していてもよい炭素数3~12の芳香族複素環基、炭素数1~12のアルキル基であり、*は隣接する構造との結合位置を表す。) Ar 1 has one partial structure selected from the following formulas (2-1) to (2-3), or 2 selected from the following formulas (2-1) to (2-3) or more bonded to each other, and the bonded structure contains a structure in which two or more of at least one structure selected from the following formulas (2-1) to (2-3) are bonded. The organic electroluminescence device according to any one of claims 11 to 13.
(In each of the above formulas (2-1) to (2-3), R 1 and R 2 are each independently a hydrogen atom, a deuterium atom, a halogen atom, or the number of carbon atoms which may have a substituent. an aromatic hydrocarbon group of 6 to 18, an aromatic heterocyclic group of 3 to 12 carbon atoms which may have a substituent, an alkyl group of 1 to 12 carbon atoms, and * is a bond with an adjacent structure position.) - 前記高分子化合物が、さらに、下記式(3)で表される繰り返し単位を有する、請求項11~14のいずれか1項に記載の有機電界発光素子。
(式(3)中、Ar3が、置換基を有していてもよい2-フルオレニル基である。Ar4は、置換基を有していてもよい2価の芳香族炭化水素基、置換基を有していてもよい2価の芳香族複素環基、又は前記置換基を有していてもよい2価の芳香族炭化水素基及び前記置換基を有していてもよい2価の芳香族複素環基からなる群から選択される少なくとも2つの基が直接若しくは連結基を介して複数個連結した2価の基を表す。) The organic electroluminescence device according to any one of claims 11 to 14, wherein the polymer compound further has a repeating unit represented by the following formula (3).
(In formula (3), Ar 3 is an optionally substituted 2-fluorenyl group. Ar 4 is an optionally substituted divalent aromatic hydrocarbon group, a substituted a divalent aromatic heterocyclic group optionally having a group, or a divalent aromatic hydrocarbon group optionally having a substituent and a divalent It represents a divalent group in which at least two groups selected from the group consisting of aromatic heterocyclic groups are linked directly or via a linking group.) - 請求項9又は10に記載の有機電界発光素子の製造方法で製造された、有機電界発光素子。 An organic electroluminescent device manufactured by the method for manufacturing an organic electroluminescent device according to claim 9 or 10.
- 発光層に量子ドットを含有する、請求項11~16のいずれか1項に記載の有機電界発光素子。 The organic electroluminescence device according to any one of claims 11 to 16, which contains quantum dots in the light-emitting layer.
- 請求項11~17のいずれか1項に記載の有機電界発光素子を有する、表示装置。 A display device comprising the organic electroluminescence device according to any one of claims 11 to 17.
- 請求項11~17のいずれか1項に記載の有機電界発光素子を有する、照明装置。 A lighting device comprising the organic electroluminescence device according to any one of claims 11 to 17.
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WO2017164268A1 (en) * | 2016-03-24 | 2017-09-28 | 三菱化学株式会社 | Electron-accepting compound, composition for charge transport film, and light-emitting element using same |
WO2018070460A1 (en) * | 2016-10-13 | 2018-04-19 | 日立化成株式会社 | Organic electronics material, ink composition, and organic electronics element |
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WO2017164268A1 (en) * | 2016-03-24 | 2017-09-28 | 三菱化学株式会社 | Electron-accepting compound, composition for charge transport film, and light-emitting element using same |
WO2018070460A1 (en) * | 2016-10-13 | 2018-04-19 | 日立化成株式会社 | Organic electronics material, ink composition, and organic electronics element |
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