KR20210113556A - Arylamine-fluorene alternating copolymer including silicone, and electroluminescence device material and electroluminescence device using the polymer - Google Patents

Abstract

The object of the present invention is to provide a technique capable of improving the durability (especially, luminescence lifetime) of an electroluminescent device. To this end, the present invention provides an arylamine-fluorene alternating copolymer having a structural unit (A) represented by formula (1).

Description

Arylamine-fluorene alternating copolymer and electroluminescent device material and electroluminescent device using same

The present invention relates to an arylamine-fluorene alternating copolymer, and an electroluminescent device material and an electroluminescent device using the same.

BACKGROUND ART Research and development of an electroluminescent device (EL device) is being actively conducted. In particular, the EL element is promising for use as an inexpensive, large-area full-color display element of a solid-state light-emitting type or a recording light source array. The EL element is a light emitting element having a thin film of several nanometers to several hundred nanometers between an anode and a cathode. Further, the EL element usually further includes a hole transport layer, a light emitting layer, an electron transport layer, and the like.

Among these, as a light emitting layer, there exist a fluorescent light emitting material and a phosphorescent light emitting material. A phosphorescent light emitting material is a material whose luminous efficiency is expected to be about 4 times greater than that of a fluorescent light emitting material. In addition, since it covers a wide color gamut, an emission spectrum with a narrow half-width is required as an RGB light source. In particular, although deep blue is required for blue, a device capable of satisfying the viewpoint of color purity while having a long life has not been found at present.

As a method for solving such a problem, there is a light emitting device using "quantum dots", which are inorganic light emitting materials, as a light emitting material (Patent Document 1). Quantum dots (QDs) are semiconductor materials having a crystal structure of several nanometers in size, and are composed of hundreds to thousands of atoms. Since quantum dots are very small in size, their surface area per unit volume is large. For this reason, most atoms exist on the surface of the nanocrystal, and exhibit a quantum confinement effect and the like. Due to such a quantum confinement effect, quantum dots are attracting much attention because they can control the emission wavelength only by adjusting their size, and have characteristics such as excellent color purity and high PL (photoluminescence) emission efficiency. A quantum dot electroluminescence device (QD LED) has a three-layer structure including a hole transport layer (HTL) and an electron transport layer (ETL) at both ends with a quantum dot light emitting layer interposed therebetween. The element is known as the basic element.

Japanese Laid-Open Patent Publication No. 2010-199067

However, in the electroluminescent device (especially a quantum dot electroluminescent device) using the hole transport material described in patent document 1, sufficient durability (especially light emission lifetime) could not be achieved.

Accordingly, the present invention has been made in view of the above circumstances, and an object of the present invention is to provide a technique capable of improving the durability (especially light emission lifetime) of an electroluminescent device (especially a quantum dot electroluminescent device). .

MEANS TO SOLVE THE PROBLEM The present inventors conducted research in order to solve the said subject. As a result, it was found that the above problems could be solved by using a polymer having a specific structure, and the present invention was completed.

That is, the said object can be achieved by the arylamine-fluorene alternating copolymer which has a structural unit (A) represented by following formula (1).

In formula (1), R ₁ to R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms,

L ₁ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent aromatic heterocyclic group,

x is 0, 1 or 2, and when x is 2, L ₁ may be the same or different,

L _{2 -} represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent aromatic heterocyclic group, wherein L ₂ may form a ring with _{Ar 1,}

Ar ₁ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent aromatic heterocyclic group, and forms a ring with _{Ar 2} or L _{2 ,}

Ar ₂ represents an aromatic hydrocarbon group or aromatic heterocyclic group having 6 to 25 carbon atoms or an aromatic heterocyclic group substituted with a straight chain or branched hydrocarbon group having 1 to 12 carbon atoms or less, and Ar ₂ is Ar ₁ and a ring may be formed.

1 is a schematic diagram showing an organic electroluminescence device according to the present embodiment.

In a first aspect, the present invention provides an arylamine-fluorene alternating copolymer having a structural unit (A) represented by the following formula (1):

In formula (1), R ₁ to R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms,

L ₁ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent aromatic heterocyclic group,

x is 0, 1 or 2, and when x is 2, L ₁ may be the same or different,

L ₂ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent aromatic heterocyclic group, in this case, L ₂ may form a ring with _{Ar 1,}

Ar ₁ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent aromatic heterocyclic group, and forms a ring with _{Ar 2} or L _{2 ,}

Ar ₂ represents an aromatic hydrocarbon group or aromatic heterocyclic group having 6 to 25 carbon atoms or an aromatic heterocyclic group substituted with a straight chain or branched hydrocarbon group having 1 to 12 carbon atoms or less, and Ar ₂ is Ar ₁ and a ring may be formed. In this specification, the structural unit (A) represented by Formula (1) is also called simply "structural unit (A)" or "structural unit (A) which concerns on this invention". In addition, the arylamine-fluorene alternating copolymer having the structural unit (A) represented by formula (1) is simply referred to as "arylamine-fluorene alternating copolymer" or "arylamine-fluorene alternating copolymer according to the present invention" It is also called "copolymer" or "alternating copolymer according to the present invention".

In a second aspect, the present invention provides an electroluminescent device material comprising the arylamine-fluorene alternating copolymer of the present invention.

In a third aspect, the present invention provides an electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers is provided. An electroluminescent device is provided, wherein the first layer contains the arylamine-fluorene alternating copolymer of the present invention. In this specification, the electroluminescent element is also simply called "LED". A quantum dot electroluminescence device is also simply referred to as "QLED". An organic electroluminescent element is also simply called "OLED".

As a material constituting a light emitting layer or a carrier transport layer of an electroluminescence device, various low molecular weight materials and high molecular weight materials are used. Among these, the low molecular material is favorable in terms of the effective lifetime of the device. However, when using a low molecular material, since it is necessary to manufacture an element by a vacuum process, there exists a subject that manufacturing cost is high. On the other hand, as a polymer material, TFB etc. are known as a hole transport material (for example, paragraph "0037" of patent document 1). However, it cannot be said that durability (luminescence lifetime) is sufficiently long in such a polymer material (refer to Comparative Example 1 below). For this reason, development of the polymer material which can improve durability (light emission lifetime) is calculated|required. The inventors of the present inventors have conducted research on the above problem (that is, durability (improvement of luminescence life) means. As a result, an alternating copolymer having the structural unit (A) of the above formula (1) is applied to an electroluminescent device. It has been found that by applying, the luminescence lifetime can be improved compared to the case of using a known material.In addition, by applying the alternating copolymer having the structural unit (A) of the formula (1) to the electroluminescence device, It was also discovered that sufficient luminous efficiency can be achieved while maintaining a somewhat low driving voltage.Mechanism of exerting the above-mentioned effect by the structure of the present invention is estimated as follows. In , a hydrocarbon group _{exists in the side chain (Ar 2} ) Thereby, in a quantum dot electroluminescence device having a hole transport layer including an arylamine-fluorene alternating copolymer and a light emitting layer including quantum dots, hole The hydrocarbon group of the side chain of the arylamine-fluorene alternating copolymer in the transport layer and the quantum dot included in the light emitting layer exist closer together, so that the hydrocarbon group of the side chain of the arylamine-fluorene alternating copolymer is closely related to the quantum dot. Accordingly, holes can be efficiently injected into the quantum dot (that is, the hole injection property is high), and durability (luminescence lifetime) can be improved.

In addition, in the structural unit (A) of the said Formula (1), the nitrogen atom cut|disconnects the conjugate|conjugation of a main chain. Thereby, the triplet energy level of the arylamine-fluorene alternating copolymer is increased, and the hole mobility (Bulk Nobility) by the main chain is high, so that high current efficiency can be achieved. Therefore, excellent luminous efficiency can be achieved by the polymer compound (main chain) having the structural unit (A). In addition, in the structural unit (A) of the said Formula (1), the principal chain is cut|disconnected with the nitrogen atom. For this reason, the arylamine-fluorene alternating copolymer of the present invention exhibits properties of a low molecular compound phase having a similar energy level to that of a quantum dot even when polymerized. For this reason, by using the arylamine-fluorene alternating copolymer of the present invention, it is possible to suppress the increase in the driving voltage and to reduce the driving voltage.

Therefore, an electroluminescent device (especially a quantum dot electroluminescent device) using an alternating copolymer having the structural unit (A) of the formula (1) can exhibit high durability (luminescence lifetime) and low Sufficient luminous efficiency can be achieved under the driving voltage.

In addition, since the arylamine-fluorene alternating copolymer of the present invention is excellent in film formability and solvent solubility, film formation by a wet (coating) method is possible. Therefore, by using the arylamine-fluorene alternating copolymer of the present invention, it becomes possible to increase the area of the electroluminescent device and to achieve high productivity. The above effect can be effectively exhibited when the arylamine-fluorene alternating copolymer of the present invention is applied to an EL device, particularly, a hole transport layer or a hole injection layer of a QLED.

On the other hand, the above-described mechanism is by guesswork, and the present invention is not limited by the above mechanism at all.

EMBODIMENT OF THE INVENTION Hereinafter, embodiment of this invention is described. In addition, this invention is not limited only to the following embodiment. In addition, each drawing is exaggerated for convenience of description, and the dimensional ratio of each component in each drawing may be different from the actual one. In addition, when embodiment of this invention is demonstrated, referring drawings, the same code|symbol is attached|subjected to the same element in description of drawing, and overlapping description is abbreviate|omitted.

In this specification, unless otherwise stated, operation and measurement of physical properties etc. are measured at room temperature (20 degreeC or more and 25 degrees C or less)/relative humidity 40%RH or more and 50%RH or less conditions.

[Arylamine-fluorene alternating copolymer]

The arylamine-fluorene alternating copolymer of the present invention has a structural unit (A) represented by the following formula (1). The arylamine-fluorene alternating copolymer having such a structural unit (A) has a high quantum dot hole injection property and can improve durability (luminescence lifetime). In addition, high current efficiency and low driving voltage can be achieved. The arylamine-fluorene alternating copolymer of the present invention may contain one structural unit (A), or may include two or more structural units (A).

In the formula (1), R ₁ to _{R 4} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms. Here, R ₁ to _{R 4} may be the same or different. Preferably, R ₁ and R ₂ are preferably the same. In addition, although two R<_3> in said Formula (1) may be the same or different, the same thing is preferable. Similarly, in the formula (1), two R ₄ may be the same or different, but preferably the same.

The hydrocarbon group having 1 to 16 carbon atoms as R ₁ to _{R 4} is not particularly limited, and examples thereof include linear or branched alkyl groups, alkenyl groups, alkynyl groups and cycloalkyl groups. On the other hand, when R ₁ to _{R 4} is an alkenyl group or an alkynyl group, _{the carbon number of R 1} to _{R 4} is 2 or more and 16 or less. Similarly, in the case where the R ₁ is a cycloalkyl group, the number of carbon atoms of R ₁ ~R ₄ is a three or more 16 or less.

Examples of the alkyl group having 1 to 16 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethyl Butyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methyl butyl group, n-octyl group, 2- Ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethyl hexyl group Sil group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group and the like.

Examples of the alkenyl group having 2 or more and 16 or less carbon atoms include a vinyl group, an allyl group, a 1-propenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, and an isopropenyl group. have.

As a C2-C16 alkynyl group, an ethynyl group, a propargyl group, etc. are mentioned, for example.

Examples of the cycloalkyl group having 3 to 16 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Among them, from the viewpoint of higher hole injection property, higher triplet energy level and lower driving voltage and film forming property, and a balance of any two or more of these (particularly the balance between hole injection property and film forming property), R ₁ to R ₂ are each independently a linear or branched alkyl group having 4 to 15 carbon atoms or a branched alkyl group having 4 to 15 carbon atoms, straight chain having 5 to 12 carbon atoms or a branched alkyl group having 5 to 12 carbon atoms More preferably, it is still more preferable that it is a C6-C10 linear alkyl group, and it is especially preferable that it is a C6-C8 linear alkyl group. In addition, from the viewpoint of higher hole injection property, higher triplet energy level and lower driving voltage and film forming property, and a balance of any two or more of these (especially the balance between hole injection property and film forming property), R ₃ to R ₄ is each independently a hydrogen atom (unsubstituted) or a linear or branched alkyl group having 1 to 8 carbon atoms or a hydrogen atom (unsubstituted) or 3 to 6 carbon atoms It is more preferable that it is a linear alkyl group, and it is especially preferable that it is a hydrogen atom (unsubstituted).

In the formula (1), L ₁ represents a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent aromatic heterocyclic group. Here, the aromatic hydrocarbon group is not particularly limited, but may be an aromatic hydrocarbon group having 6 or more and 25 or less carbon atoms. Specifically, benzene (phenylene group), pentalene, indene, naphthalene, anthracene, azulene, heptalene, acenaphthene, phenalene, fluorene, phenanthrine, biphenyl, terphenyl, quaterphenyl, quinquephenyl and divalent groups derived from aromatic hydrocarbons such as , sexyphenyl, pyrene, 9,9-diphenylfluorene, 9,9'-spirobi[fluorene], and 9,9-dialkyl fluorene. The aromatic heterocyclic group is not particularly limited, but may be an aromatic heterocyclic group having 12 or more and 25 or less carbon atoms. Specifically, acridine, phenazine, benzoquinoline, benzoisoquinoline, phenanthridine, phenanthroline, anthraquinone, fluorenone, dibenzofuran, dibenzothiophene, carbazole, imidazophenanthridine , benzimidazophenanthridine, azadibenzofuran, 9-phenylcarbazole, azacarbazole, azadibenzothiophene, diazadibenzofuran, diazacarbazole, diazadibenzothiophene, xanthone, di and divalent groups derived from heterocyclic aromatic compounds such as oxanthone, pyridine, quinoline and anthraquinoline. Of these, L ₁ is preferably a divalent group derived from a compound selected from benzene, fluorene, dibenzofuran, dibenzothiophene, and biphenyl. More preferably, L ₁ is a divalent group derived from a compound selected from benzene (o,m,p-phenylene group), dibenzofuran, and fluorene. Particularly preferably, L ₁ is a phenylene group (particularly a p-phenylene group). If it is such L _{1 ,} it is possible to achieve a higher hole injection property, a higher triplet energy level, a lower driving voltage, and a balance of any two or more of these (especially a balance between hole injection properties and film forming properties). have. In addition, in the said preferable aspect, _{unsubstituted may be sufficient as L<1>} , or any hydrogen atom may be substituted by the substituent.

Here, the _{number of substituents introduced when any one of the hydrogen atoms in L 1} is substituted is not particularly limited, but is preferably 1 or more and 3 or less, more preferably 1 or more and 2 or less, and particularly preferably 1 am. When L ₁ owns a substituent, the bonding position of the substituent is not particularly limited. The substituent is preferably located as far as possible from the nitrogen atom of the main chain to which _{L 1 connects.} By the presence of a substituent at such a position, a higher hole injection property, a higher triplet energy level, a lower driving voltage, and a balance of any two or more of these (especially the balance between hole injection and film forming performance) are obtained. can be achieved

In addition, the _{substituents that may be present when any one of the hydrogen atoms in L 1} are substituted are not particularly limited, and an alkyl group, a cycloalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, a cycloalkoxy group, an alkenyl group, an alkynyl group, Amino group, aryl group, aryloxy group, alkylthio group, cycloalkylthio group, arylthio group, alkoxycarbonyl group, aryloxycarbonyl group, hydroxyl group (-OH), carboxyl group (-COOH), thiol group (-SH), cyano group No group (-CN), etc. are mentioned.

Here, the alkyl group may be either linear or branched, but preferably a linear or branched alkyl group having 1 or more and 18 or less carbon atoms or a branched alkyl group having 1 or more and 18 or less carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, Neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1 ,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylbutyl group, 1-ethyl-3-methyl butyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1 -Isopropylbutyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isode Sil group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n- An octadecyl group etc. are mentioned.

Examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

As the hydroxyalkyl group, for example, the alkyl group is substituted with 1 or more and 3 or less (preferably 1 or more and 2 or less, particularly preferably 1) hydroxyl group (for example, hydroxymethyl group, hydroxyethyl group) This is exemplified.

Examples of the alkoxyalkyl group include those in which the alkyl group is substituted by 1 or more and 3 or less (preferably 1 or more and 2 or less, particularly preferably 1) of the alkoxy group.

Examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, Undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, 2-ethylhexyloxy group, 3-ethylphen A tyloxy group etc. are mentioned.

Examples of the cycloalkoxy group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the alkenyl group include vinyl group, allyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3- Pentenyl group, 1-hexenyl group, 2-hexenyl group, 3-hexenyl group, 1-heptenyl group, 2-heptenyl group, 5-heptenyl group, 1-octenyl group, 3-octenyl group, 5-octenyl group and the like.

As the alkynyl group, for example, acetylenyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-pentetyl group, 2-pentetyl group, 3-pentetyl group tyl group, 1-hexynyl group, 2-hexynyl group, 3-hexynyl group, 1-heptynyl group, 2-heptynyl group, 5-heptynyl group, 1-octynyl group, 3-octynyl group, 5-octynyl group, etc. are mentioned. have.

Examples of the aryl group include a phenyl group, a naphthyl group, a biphenyl group, a fluorenyl group, an anthryl group, a pyrenyl group, an azurenyl group, an acenaphthylenyl group, a terphenyl group, and a phenanthryl group.

As an aryloxy group, a phenoxy group, a naphthyloxy group, etc. are mentioned, for example.

Examples of the alkylthio group include a methylthio group, an ethylthio group, a propylthio group, a pentylthio group, a hexylthio group, an octylthio group, and a dodecylthio group.

As a cycloalkylthio group, a cyclopentylthio group, a cyclohexylthio group, etc. are mentioned, for example.

As an arylthio group, a phenylthio group, a naphthylthio group, etc. are mentioned, for example.

Examples of the alkoxycarbonyl group include a methyloxycarbonyl group, an ethyloxycarbonyl group, a butyloxycarbonyl group, an octyloxycarbonyl group, and a dodecyloxycarbonyl group.

Examples of the aryloxycarbonyl group include a phenyloxycarbonyl group and a naphthyloxycarbonyl group.

Among the above _{, it is more preferable that L 1} is a divalent group selected from the following group. In other words, in a preferred embodiment of the present invention, in the formula (1), x is 1 or 2 (particularly preferably 1), and L ₁ is each independently a divalent group selected from the following group. On the other hand, in the following structure, R ₁₁₁ to _{R 125} each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 16 carbon atoms (particularly preferably R ₁₁₁ to R ) ₁₂₅ is a hydrogen atom).

In the formula (1), x is 0, 1 or 2. Meanwhile, when x is 2, L ₁ may be the same or different. From the viewpoint of a higher hole injection property, a higher triplet energy level and a lower driving voltage and film forming property, and a balance of any two or more thereof (especially a balance between hole injection property and film forming property), x is 0 or It is preferable that it is 1, and it is more preferable that it is 1.

In the formula (1), L ₂ represents a substituted or unsubstituted divalent or trivalent aromatic hydrocarbon group having 6 to 25 carbon atoms or a substituted or unsubstituted divalent or trivalent aromatic heterocyclic group. At this time, L ₂ may form a ring with Ar _{1 .} On the other hand, when L ₂ forms a ring with Ar _{1 , L 2} is a trivalent group. When L ₂ does not form a ring with Ar _{1 , L 2} is a divalent group.

Here, the aromatic hydrocarbon group and aromatic heterocyclic group having 6 to 25 carbon atoms as _{L 2 are not particularly limited.} When L ₂ does not form a ring with Ar ₁ , a divalent group derived from an aromatic hydrocarbon having 6 to 25 carbon atoms as defined for _{L 1 can be exemplified.} Similarly, in the above case, the _{aromatic heterocyclic group as L 2} is not particularly limited, and examples of the divalent group derived from the heterocyclic cyclic aromatic compound defined for _{L 1 are exemplified.} Further, when L ₂ forms a ring with Ar ₁ , it can be exemplified by converting a divalent group derived from an aromatic hydrocarbon having 6 to 25 carbon atoms as defined in _{L 1 above to a trivalent group.} Similarly, in the above case, the _{aromatic heterocyclic group as L 2} is not particularly limited, and can be exemplified by converting a divalent group derived from the heterocyclic cyclic aromatic compound defined for _{L 1 to a trivalent group.} Among these, a divalent or trivalent group derived from a compound selected from benzene, fluorene, dibenzofuran, dibenzothiophene and biphenyl is preferable. More preferably, L ₂ is a divalent group (eg, o,m,p-phenylene group) or a trivalent group (eg, 1,3,4-phenylylene group). Particularly preferably, L ₂ is a benzene-derived divalent (phenylene group, particularly p-phenylene group) or trivalent group (particularly 1,3,4-phenylylene group). If it is such L ₂ , a higher hole injection property, a higher triplet energy level, and a lower driving voltage and film forming property, and a balance of any two or more of these (particularly a balance between hole injection property and film forming property) can be achieved. have. In addition, in the said preferable aspect, L<_2> may be unsubstituted, or any hydrogen atom may be substituted by the substituent. The substituents present on L to obtain the case ₂ be substituted any of the hydrogen atoms of which may be not particularly limited, and applies to an example such as the L _1. Preferably, L ₂ is unsubstituted.

In the formula (1), Ar ₁ represents a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 25 carbon atoms or a substituted or unsubstituted divalent aromatic heterocyclic group.

Here, the aromatic hydrocarbon group having 6 or more and 25 or less carbon atoms as _{Ar 1} is not particularly limited, and examples of the divalent group derived from the aromatic hydrocarbon having 6 or more and 25 or less carbon atoms specified for _{L 1 are exemplified.} Similarly, the _{aromatic heterocyclic group as Ar 1} is not particularly limited, and examples of the divalent group derived from the heterocyclic cyclic aromatic compound defined for _{L 1 are exemplified.} Among these, those selected from a phenylene group, a biphenylene group, a dibenzofuranyl group and a fluorenyl group are preferable. More preferably, Ar ₁ is a phenylene group (o,m,p-phenylene group). Particularly preferably, Ar ₁ is an o-phenylene group. If it is Ar ₁ , a higher hole injection property, a higher triplet energy level, a lower driving voltage, and a balance of any two or more of these (particularly, a balance between hole injection properties and film forming properties) can be achieved. have. In addition, Ar ₁ may be unsubstituted, or any hydrogen atom may be substituted with a substituent. On the other hand, _{when any one hydrogen atom of Ar 1} is substituted, the substituents that may be present are not particularly limited, and examples such as _{L 1 above may be applied.} Ar ₁ is preferably unsubstituted or substituted with a linear or branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms, unsubstituted or straight chain having 3 to 10 carbon atoms or 3 or more carbon atoms Bivalent derived from a compound selected from a biphenylene group substituted with a branched alkyl group of 10 or less, and a fluorenyl group substituted with an unsubstituted or straight-chain or branched alkyl group having 3 or more and 10 or less carbon atoms it's gi More preferably, Ar ₁ is an o, m, p-phenylene group which is unsubstituted or substituted with a straight chain or branched alkyl group having 3 to 10 carbon atoms, particularly preferably unsubstituted. or an o-phenylene group substituted with a straight-chain alkyl group having 5 or more and 8 or less carbon atoms. On the other hand, when Ar ₁ owns a substituent (that is, a substituted divalent aromatic hydrocarbon group or a substituted divalent aromatic heterocyclic group having 6 to 25 carbon atoms), the position of the substituent is not particularly limited, but Ar ₁ With respect to the nitrogen atom that is bound to the , it is preferable to be located as far away as possible. For example, when Ar ₁ is an o-phenylene group, the substituent is preferably present at a para position with respect to the nitrogen atom. With this arrangement, the distance between the alternating copolymer and the quantum dot becomes closer, and the interaction between the alternating arylamine-fluorene copolymer in the hole transport layer and the quantum dot in the light emitting layer becomes stronger, so the hole injection property (i.e., , durability (luminescence lifetime)) can be further improved.

Moreover, Ar ₁ forms a ring with Ar ₂ or L _{2 .} As such, _{by forming a ring with Ar 1} and Ar ₂ or L ₂ , a higher triplet energy level can be imparted. _{Among these, Ar 1} from the viewpoint of higher hole injection property, higher triplet energy level and lower driving voltage and film forming property, and a balance of any two or more of these (particularly the balance between hole injection property and film forming property) it is preferable to form the L ₂ and the ring. The Ar ₁ and L ₂ at the time of forming the ring, a ring structure formed by Ar ₁ and L ₂ is not particularly limited, as Ar ₁ and L _2, it is preferable to form a carbazole ring. In other words, in a preferred embodiment of the present invention, -L ₂ -N(Ar ₁ )(Ar ₂ ) in the formula (1) has a structure selected from the following group.

However, R ₂₁₁ to _{R 214} are each independently a hydrogen atom or a linear or branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms.

More preferably, a carbazole ring of the following structure is formed _{with Ar 1} and L _{2 .}

However, R ₂₁₁ to _{R 214} are each independently a hydrogen atom or a linear or branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. Preferably, R ₂₁₁ and R ₂₁₃ are a hydrogen atom, and R ₂₁₂ and R ₂₁₄ are a hydrogen atom or a straight-chain alkyl group having 5 to 8 carbon atoms.

In the formula (1), Ar ₂ is a monovalent or divalent aromatic hydrocarbon group having 6 or more and 25 or less carbon atoms substituted with a straight chain or branched hydrocarbon group having 1 to 12 carbon atoms or monovalent or a divalent aromatic heterocyclic group. In this case, Ar ₂ may form a ring with _{Ar 1 .} On the other hand, when Ar ₂ forms a ring with Ar _{1 , Ar 2} is a divalent group. When Ar ₂ does not form a ring with Ar _{1 , Ar 2} is a monovalent group.

Here, the aromatic hydrocarbon group and aromatic heterocyclic ring group having 6 or more and 25 or less carbon atoms as _{Ar 2 are not particularly limited.} When Ar ₂ does not form a ring with Ar ₁ , it can be exemplified by converting a divalent group derived from an aromatic hydrocarbon having 6 to 25 carbon atoms as defined in _{L 1 above to a monovalent group.} Similarly, in the above case, the _{aromatic heterocyclic group as Ar 2} is not particularly limited, and can be exemplified by converting a divalent group derived from a heterocyclic cyclic aromatic compound defined for _{L 1 to a monovalent group.} Further, when Ar ₂ forms a ring with Ar ₁ , a divalent group derived from an aromatic hydrocarbon having 6 or more and 25 or less carbon atoms as defined for _{L 1 can be exemplified.} Similarly, in the above case, the _{aromatic heterocyclic group as Ar 2} is not particularly limited, and examples of the divalent group derived from the heterocyclic aromatic compound defined for _{L 1 are exemplified.} Among them, Ar ₂ is preferably a divalent group derived from a compound selected from benzene, biphenyl, dibenzofuranyl group and fluorenyl group. More preferably, Ar ₂ is a benzene-derived divalent group (phenyl group or o,m,p-phenylene group). Most preferably, Ar is _2, Ar ₂ is a phenylene group include o- If said phenyl group is, if not form a ring and Ar _1, or Ar ₂ is Ar ₁ and forming a ring. In the case of such Ar ₂ (unsubstituted form), a higher hole injection property, a higher triplet energy level, a lower driving voltage, and a balance of any two or more of these (especially the balance between hole injection and film forming performance) ) can be achieved. On the other hand, in the above preferred aspect, Ar ₂ may be unsubstituted, or any hydrogen atom may be substituted with a substituent.

In addition, Ar ₂ is a group having a branched hydrocarbon group of a carbon number of 1 or more and or a straight chain of 1 or less carbon atoms as a substituent at least 12 12. By disposing such a hydrocarbon group at the terminal of the arylamine-fluorene alternating copolymer, the alternating copolymer according to the present invention in the hole transport layer can interact closely with the quantum dots in the light emitting layer, so that holes can be efficiently injected into the quantum dots. (high hole injection property), and can improve durability (luminescence lifetime). Here, the hydrocarbon group having 1 or more and 12 or less carbon atoms is not particularly limited, and examples thereof include straight-chain or branched alkyl groups, alkenyl groups, alkynyl groups and cycloalkyl groups. On the other hand, when Ar ₂ is an alkenyl group or an alkynyl group, _{the carbon number of Ar 2} is 2 or more and 16 or less. Similarly, when Ar ₂ is a cycloalkyl group, _{the carbon number of Ar 2} is 3 or more and 6 or less.

Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, Isopentyl group, tert-pentyl group, neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropyl propyl group, 1,2-dimethyl Butyl group, n-heptyl group, 1,4-dimethyl pentyl group, 3-ethyl pentyl group, 2-methyl-1-isopropylbutyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2- Ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2-methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group Sil group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group, etc. are mentioned.

Examples of the alkenyl group having 2 or more and 16 or less carbon atoms include a vinyl group, an allyl group, a 1-propenyl group, a 2-butenyl group, a 1,3-butadienyl group, a 2-pentenyl group, and an isopropenyl group. have.

As a C2-C16 alkynyl group, an ethynyl group, a propargyl group, etc. are mentioned, for example.

Examples of the cycloalkyl group having 3 to 6 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

_{Among these, Ar 2} from the viewpoint of higher hole injection property, higher triplet energy level and lower driving voltage and film forming property, and a balance of any two or more of these (particularly the balance between hole injection property and film forming property) It is preferable that the hydrocarbon group present in a C4 or more and 10 or less linear or branched alkyl group having 4 or more and 10 or less carbon atoms. In this way _{, by increasing the carbon number of the hydrocarbon group present in Ar 2} (longer chain), the distance between the alternating copolymer and the quantum dot becomes closer, and the arylamine-fluorene alternating copolymer in the hole transport layer and the quantum dot in the light emitting layer are Since the interaction becomes stronger, the hole injection property (ie, durability (luminescence lifetime)) can be further improved. In other words, in a preferred embodiment of the present invention, Ar ₂ is a group derived from a compound selected from the group consisting of benzene, biphenyl, dibenzofuran and fluorene, and at the same time is a straight chain having 4 or more and 10 or less or 4 or more carbon atoms. substituted with up to 10 branched alkyl groups. More preferably, Ar ₂ is a linear alkyl group having 5 or more and 8 or less carbon atoms. In other words, in a more preferred embodiment of the present invention, Ar ₂ is a benzene-derived group (phenyl group, o, m, p-phenylene group) substituted with a straight-chain alkyl group having 5 or more and 8 or less carbon atoms. Particularly preferably, Ar ₂ is a straight-chain alkyl group having 6 or more and 8 or less carbon atoms. In other words, in a preferred embodiment of the present invention, Ar ₂ is a phenyl group substituted with a straight-chain alkyl group having 6 to 8 carbon atoms (when Ar ₂ does not form a ring with Ar ₁ ) or an o-phenylene group (Ar ₂ is when forming a ring with Ar _{1 ).}

On the other hand, the position of the hydrocarbon group present in _{Ar 2} is not particularly limited, but is preferably located as far away as possible from the nitrogen atom of _{-L 2} -N(Ar ₁ )(Ar _{2 ).} For example, when Ar ₁ forms a ring with L _{2 and Ar 2} is a phenyl group, the hydrocarbon group is preferably present in the para position with respect to the nitrogen atom. With this arrangement, the distance between the alternating copolymer and the quantum dot becomes closer, and the interaction between the alternating arylamine-fluorene copolymer in the hole transport layer and the quantum dot in the light emitting layer becomes stronger, so the hole injection property (i.e., , durability (luminescence lifetime)) can be further improved.

Ar ₂ may form a ring with Ar _{1 .} When Ar ₂ and Ar ₁ to form a ring, the ring structure formed by Ar ₂ and Ar ₁ is not particularly limited, it is preferable that Ar ₂ and Ar _1, to form a carbazole ring. In other words, in a more preferred aspect of the present invention, in the formula (1), Ar ₁ forms a ring with Ar _{2 , and —N(Ar 1} )(Ar ₂ ) is a group selected from the following group.

However, R ₃₁₁ to _{R 323} each independently represent a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms, _{and at least one of R 311} to _{R 323} is a straight chain having 1 to 12 carbon atoms or 1 to 12 carbon atoms. A branched hydrocarbon group of (more preferably a straight-chain or branched alkyl group having 4 or more and 10 or less carbon atoms, more preferably a straight-chain alkyl group having 5 or more and 8 or less carbon atoms, particularly preferably 6 carbon atoms 8 or less linear alkyl group).

More preferably, a carbazole ring of the following structure is formed _{with Ar 2} and Ar _{1 .} In other words, in a more preferable aspect of the present invention, -N(Ar ₁ )(Ar ₂ ) in the formula (1) has the following structure.

However, R ₃₁₁ represents a hydrogen atom or a linear or branched alkyl group having 4 to 10 carbon atoms (more preferably a hydrogen atom or a straight chain alkyl group having 5 to 8 carbon atoms) having 4 or more and 10 or less carbon atoms, R ₃₁₂ Silver is a linear or branched alkyl group having 4 to 10 carbon atoms or a branched alkyl group having 4 to 10 carbon atoms (more preferably a straight chain alkyl group having 5 to 8 carbon atoms, particularly preferably a straight chain alkyl group having 6 to 8 carbon atoms) indicates.

Accordingly, the structural unit (A) according to the present invention is preferably selected from the following group.

However, R ₄₁₁ to _{R 431} each independently represent a linear or branched alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms, and R ₅₁₁ to _{R 543} are each independently a hydrogen atom or 1 or more carbon atoms. 16 or less hydrocarbon groups are shown.

The composition of the structural unit (A) in the arylamine-fluorene alternating copolymer of the present invention is not particularly limited. Considering the durability (luminescence lifetime) of the layer (for example, hole injection layer, hole transport layer) formed using the resulting arylamine-fluorene alternating copolymer and the further improved effect of hole transport ability, the structural unit (A) is , with respect to the precursor unit constituting the arylamine-fluorene alternating copolymer, preferably 10 mol% or more and 100 mol% or less, more preferably more than 50 mol% and 100 mol% or less, particularly preferably 100 mol% %am. In other words, in a preferred embodiment of the present invention, the structural unit (A) is contained in a ratio of 10 mol% or more and 100 mol% or less with respect to the precursor unit. In a more preferable aspect of this invention, a structural unit (A) is contained in the ratio of more than 50 mol% and 100 mol% or less with respect to a precursor unit. In a particularly preferred embodiment of the present invention, the arylamine-fluorene alternating copolymer is composed of only the structural unit (A) (that is, the ratio of the structural unit (A) to the precursor unit = 100 mol%). On the other hand, when the arylamine-fluorene alternating copolymer contains two or more types of structural units (A), the content of the structural units (A) means the total amount of the structural units (A).

As described above, the arylamine-fluorene alternating copolymer of the present invention may be composed of only the structural unit (A). Alternatively, the arylamine-fluorene alternating copolymer of the present invention may further contain structural units other than the structural unit (A). In the case of including other structural units, other structural units are not particularly limited as long as the effect of the arylamine-fluorene alternating copolymer (particularly high triplet energy level, low driving voltage) is not impaired. Specific examples thereof include structural units selected from the following groups. In addition, below, the structural unit shown in the following group is also called "structural unit (B)."

The composition of the structural unit (B) in the arylamine-fluorene alternating copolymer of the present embodiment is not particularly limited. In consideration of the effect of further improving the film-forming ability and film strength of the resulting polymer compound, the structural unit (B) is preferably 1 mol%, based on the precursor units constituting the arylamine-fluorene alternating copolymer. or more and 10 mol% or less. On the other hand, when the arylamine-fluorene alternating copolymer contains two or more types of structural units (B), the content of the structural units (B) means the total amount of the structural units (B).

The weight average molecular weight (Mw) of the arylamine-fluorene alternating copolymer is not particularly limited as long as the objects and effects of the present invention are obtained. It is preferable that they are, for example, 12,000 or more and 1,000,000 or less, and, as for a weight average molecular weight (Mw), it is more preferable that they are 50,000 or more and 500,000 or less. If it is such a weight average molecular weight, the viscosity of the coating solution for forming a layer (for example, a hole injection layer, a hole transport layer) using an arylamine-fluorene alternating copolymer is appropriately adjusted, and the layer has a uniform film thickness. It is possible to form

In addition, the number average molecular weight (Mn) of the arylamine-fluorene alternating copolymer is not particularly limited as long as the objects and effects of the present invention are obtained. It is preferable that the number average molecular weights (Mn) are 10,000 or more and 250,000 or less, for example, More preferably, they are 30,000 or more and 100,000 or less. If it is such a number average molecular weight, the viscosity of the coating solution for forming a layer (for example, a hole injection layer, a hole transport layer) is appropriately adjusted using an arylamine-fluorene alternating copolymer, and a layer having a uniform film thickness It is possible to form Further, the polydispersity (weight average molecular weight/number average molecular weight) of the alternating arylamine-fluorene copolymer of the present embodiment is, for example, 1.2 or more and 4.0 or less, preferably 1.5 or more and 3.5 or less.

In this specification, the measurement of a number average molecular weight (Mn) and a weight average molecular weight (Mw) is not restrict|limited in particular, A well-known method can be used, or a well-known method can be modified and applied suitably. In this specification, the value measured by the following method is employ|adopted for a number average molecular weight (Mn) and a weight average molecular weight (Mw). On the other hand, the polydispersity (Mw/Mn) of the polymer is calculated by dividing the weight average molecular weight (Mw) from the number average molecular weight (Mn) measured by the following method.

(Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw))

The number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer material are measured by SEC (Size Exclusion Chromatography) using polystyrene as a standard material under the following conditions.

(SEC measurement conditions)

Analysis device (SEC): manufactured by Shimadzu Corporation, Prominence

Column: Polymer Laboratories, PLgel MIXED-B

Column temperature: 40°C

Flow rate: 1.0 mL/min

Injection volume of sample solution: 20 μL (polymer concentration: about 0.05 mass %)

Eluent: Tetrahydrofuran (THF)

Detector (UV-VIS detector): Shimadzu Corporation, SPD-10AV

Standard sample: polystyrene.

The terminal of the main chain of the alternating arylamine-fluorene copolymer of the present embodiment is not particularly limited and is appropriately defined depending on the kind of raw material used, but is usually a hydrogen atom.

The arylamine-fluorene alternating copolymer of the present embodiment can be synthesized by using a known organic synthesis method. The specific method of synthesizing the arylamine-fluorene alternating copolymer of the present embodiment can be easily understood by those skilled in the art with reference to the Examples to be described later. Specifically, the arylamine-fluorene alternating copolymer of the present embodiment can be prepared by polymerization using one or more monomers (1) represented by the following formula (1') or 1 represented by the following formula (1') It can manufacture by copolymerization reaction using the monomer (1) of more than types and the other monomer corresponded to the said other structural unit.

Alternatively, one or more monomers (2) represented by the following formula (2') and one or more monomers (3) represented by the following formula (3'), or one or more monomers represented by the following formula (2') ( 2) and one or more types of monomers (3) represented by the following formula (3') and other monomers corresponding to the above other structural units.

In the present invention, the monomer that can be used for polymerization of the arylamine-fluorene alternating copolymer can be synthesized by appropriately combining known synthetic reactions, and its structure is also known by a known method (eg, NMR, LC-MS, etc.).

In Formulas (1') to (3'), R ₁ to _{R 4} , L ₁ , L ₂ , Ar ₁ , Ar ₂ and x are defined as in Formula (1) above. X ₁ and X ₂ are each independently a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, a urea atom, particularly a bromine atom) or a group having the following structure. On the other hand, in the following structure, R _A to _{R D} are each independently an alkyl group having 1 or more and 3 or less carbon atoms. Preferably, R _A to _{R D} are methyl groups. _{In addition, X 1} and X ₂ in the formulas (1') to (3') may be the same or different, respectively. Preferably, in the formula (1'), X ₁ and X ₂ are different. In the above formula (2'), X ₁ ' and X ₂ ′ are preferably the same. In the formula (3'), X ₁ “and X ₂ ” are preferably the same.

The arylamine-fluorene alternating copolymer of the present embodiment has a structural unit (A). For this reason, the arylamine-fluorene alternating copolymer has a high hole injection property. Therefore, when the arylamine-fluorene alternating copolymer according to the present embodiment is used as a hole injection material or a hole transport material (especially a hole transport material), high durability (luminescence lifetime) can be achieved. Further, the alternating arylamine-fluorene copolymer of the present embodiment has a high triplet energy level and a low driving voltage at the same time. Therefore, when the arylamine-fluorene alternating copolymer according to the present embodiment is used as a hole injection material or a hole transport material (particularly a hole transport material), high hole mobility is achieved with a low driving voltage. Therefore, the electroluminescent device using the arylamine-fluorene alternating copolymer according to the present embodiment is excellent in durability (luminescence lifetime) and luminous efficiency.

[Electroluminescence device material]

The arylamine-fluorene alternating copolymer according to the present embodiment can be suitably used as an electroluminescent device material. According to the arylamine-fluorene alternating copolymer according to the present embodiment, an electroluminescent device material having excellent durability (luminescence lifetime) and high hole mobility is provided. Further, according to the arylamine-fluorene alternating copolymer according to the present embodiment, an electroluminescent device material having a high triplet energy level (current efficiency) and a low driving voltage is also provided. In addition, the main chain (structural unit of formula (1)) of the arylamine-fluorene alternating copolymer has appropriate flexibility. For this reason, the arylamine-fluorene alternating copolymer according to the present embodiment exhibits high solubility in solvents and high heat resistance. Therefore, it is possible to easily form a film (thin film) by the wet (coating) method. Accordingly, in a second aspect, an electroluminescent device material comprising the aryl amine-fluorene alternating copolymer of the present invention is provided. Alternatively, the use of an aryl amine-fluorene alternating copolymer as an electroluminescent device material is provided.

In addition, the aryl amine-fluorene alternating copolymer according to the present embodiment has a HOMO level of more than 5.20 eV, in particular, more than 5.33 eV. For this reason, the arylamine-fluorene alternating copolymer according to the present embodiment can be suitably used also for a quantum dot electroluminescence device (especially a hole transport layer).

[Electroluminescence device]

As described above, the arylamine-fluorene alternating copolymer according to the present embodiment can be preferably used for an electroluminescent device. In other words, an electroluminescence comprising a pair of electrodes and at least one organic film disposed between the electrodes and comprising the arylamine-fluorene alternating copolymer or the electroluminescent device material of the present embodiment. provide the element. Such an electroluminescent device can exhibit excellent luminous efficiency with a low driving voltage. Accordingly, in a third aspect, the present invention provides an electroluminescence device comprising a first electrode, a second electrode, and at least one organic film disposed between the first electrode and the second electrode, An electroluminescent device is provided, wherein at least one layer of the organic film contains the aryl amine-fluorene alternating copolymer of the present invention. The object (or effect) of the present invention can also be achieved in the electroluminescence device according to this embodiment. As a preferable aspect of the above aspect, the electroluminescent device further includes a light emitting layer disposed between the electrodes and made of a light emitting material capable of emitting light from triplet excitons. In addition, the electroluminescent element of this embodiment is an example of the electroluminescent element which concerns on this invention.

In addition, the present embodiment relates to the manufacture of an electroluminescent device comprising a pair of electrodes and at least one organic film disposed between the electrodes and comprising the arylamine-fluorene alternating copolymer of the present embodiment. As a method, there is provided a method in which at least one layer of the organic film is formed by a coating method. In addition, by such a method, the present embodiment provides an electroluminescence device in which at least one layer of the organic film is formed by a coating method.

Alternating arylamine-fluorene copolymer of the present embodiment, and electroluminescence device material (EL device material) according to the present embodiment (hereinafter collectively referred to as “arylamine-fluorene alternating copolymer/EL device material”) ) is excellent in solubility in organic solvents. For this reason, the arylamine-fluorene alternating copolymer/EL device material according to the present embodiment is particularly preferably used for manufacturing devices (especially thin films) by a coating method (wet process). Accordingly, the present embodiment provides a liquid composition containing the alternating arylamine-fluorene copolymer of the present embodiment and a solvent or dispersion medium. Such a liquid composition is an example of the liquid composition according to the present invention.

Moreover, as mentioned above, the electroluminescent element material which concerns on embodiment is used suitably for manufacture of the element (especially thin film) by the application|coating method (wet process). In view of the above, the present embodiment provides a thin film containing the arylamine-fluorene alternating copolymer of the present embodiment. Such a thin film is an example of the thin film which concerns on this invention.

Further, the EL device material according to the present embodiment is excellent in hole injection properties and hole mobility. For this reason, it can be suitably used also in formation of any organic film, such as a hole injection material, a hole transport material, or a light emitting material (host). Among them, from the viewpoint of hole transportability, it can be preferably used as a hole injection material or a hole transport material, and can be particularly preferably used as a hole transport material.

That is, the present embodiment provides a composition containing an arylamine-fluorene alternating copolymer and at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light emitting material. Here, the light emitting material contained in the composition is not particularly limited, and may contain an organometallic complex (luminescent organometallic complex compound) or semiconductor nanoparticles (semiconductor inorganic nanoparticles).

[Electroluminescence device]

Hereinafter, with reference to FIG. 1, the electroluminescent element which concerns on this embodiment is demonstrated in detail. 1 is a schematic diagram showing an electroluminescence device according to the present embodiment. In addition, in this specification, "electroluminescence element" may be abbreviated as "EL element" in some cases.

As shown in FIG. 1 , an EL element 100 according to the present embodiment is disposed on a substrate 110 , a first electrode 120 disposed on the substrate 110 , and the first electrode 120 . electrons disposed on the hole injection layer 130 , the hole transport layer 140 disposed on the hole injection layer 130 , the light emitting layer 150 disposed on the hole transport layer 140 , and the light emitting layer 150 . It includes a transport layer 160 , an electron injection layer 170 disposed on the electron transport layer 160 , and a second electrode 180 disposed on the electron injection layer 170 .

Here, the arylamine-fluorene alternating copolymer of the present embodiment is contained in, for example, any one organic layer (organic layer) disposed between the first electrode 120 and the second electrode 180 . Specifically, the arylamine-fluorene alternating copolymer is preferably included in the hole injection layer 130 as the hole injection material or the hole transport layer 140 as the hole transport material or the light emitting layer 150 as the light emitting material (host). do. The arylamine-fluorene alternating copolymer is more preferably included in the hole injection layer 130 as a hole injection material or in the hole transport layer 140 as a hole transport material. It is particularly preferable that the arylamine-fluorene alternating copolymer is included in the hole transport layer 140 as a hole transport material. That is, in a preferred embodiment of the present invention, the organic film containing the arylamine-fluorene alternating copolymer is a hole transport layer, a hole injection layer, or a light emitting layer. In a more preferred aspect of the present invention, the organic film containing the arylamine-fluorene alternating copolymer is a hole transport layer or a hole injection layer. In a particularly preferred embodiment of the present invention, the organic film comprising an arylamine-fluorene alternating copolymer is a hole transport layer.

In addition, the organic film containing the arylamine-fluorene alternating copolymer/EL element material of this embodiment is formed by the application|coating method (solution application|coating method). Specifically, the organic film is a spin coat method, a casting method, a micro gravure coat method, a gravure coat method, a bar coat method, a roll coat method ( roll coat method, wire bar coat method, dip coat method, spray coat method, screen printing method, flexographic printing method, offset printing A film is formed using a solution coating method such as a method or an ink jet printing method.

In addition, the solvent used for the solution application method can be any solvent as long as it can dissolve the arylamine-fluorene alternating copolymer/EL device material, and it depends on the type of the arylamine-fluorene alternating copolymer to be used. You can choose accordingly. For example, toluene, xylene, ethylbenzene, diethylbenzene, mesitylene, propylbenzene, cyclohexylbenzene, dimethoxybenzene, anisole, ethoxytoluene, phenoxytoluene, isopropylbiphenyl, dimethylanisole, acetic acid phenyl, phenyl propionate, methyl benzoate, ethyl benzoate, cyclohexane, and the like can be exemplified. In addition, the amount of solvent used is not particularly limited, but considering the ease of application and the like, the concentration of the arylamine-fluorene alternating copolymer is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass. It is the quantity used as about 5 mass % or less more than 5 mass %.

In addition, the film-forming method of the layer other than the organic film containing the arylamine-fluorene alternating copolymer/EL element material is not specifically limited. Layers other than the organic film comprising the arylamine-fluorene alternating copolymer/EL device material of the present embodiment may be formed by, for example, vacuum evaporation or a solution coating method.

As the substrate 110 , a substrate used in a general EL device can be used. For example, the substrate 110 may be a glass substrate, a semiconductor substrate such as a silicon substrate, or a transparent plastic substrate.

A first electrode 120 is formed on the substrate 110 . The first electrode 120 is specifically, an anode, and is formed of a metal, an alloy, or a conductive compound having a large work function. For example, the first electrode 120, indium tin oxide is excellent in transparency and conductivity _{(In 2 O 3 -SnO 2:} ITO), indium zinc oxide (In ₂ O ₃ -ZnO), tin oxide (SnO ₂₎ , zinc oxide (ZnO) or the like may be formed as a transmissive electrode. Further, the first electrode 120 may be formed as a reflective electrode by laminating magnesium (Mg), aluminum (Al), or the like on the transparent conductive film. In addition, after the first electrode 120 is formed on the substrate 110 , if necessary, cleaning and UV-ozone treatment may be performed.

A hole injection layer 130 is formed on the first electrode 120 . The hole injection layer 130 is a layer that facilitates injection of holes from the first electrode 120, and specifically, has a thickness of about 10 nm or more and about 1000 nm or less, more specifically about 20 nm or more and about 50 nm or less ( dry film thickness; the same hereinafter) may be formed.

The hole injection layer 130 may be formed of a known hole injection material. As a well-known hole injection material for forming the hole injection layer 130, for example, triphenylamine-containg poly(ether ketone) (TPAPEK), 4-isopropyl-4'-methyldi Phenyliodonium tetrakis (pentafluorophenyl) borate (4-isopropyl-4'-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate: PPBI), N,N'-diphenyl-N,N'-bis-[4-( Phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine (N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl ]-biphenyl-4,4'-diamine: DNTPD), copper phthalocyanine, 4,4',4"-tris (3-methylphenylphenylamino)triphenylamine (4,4',4"-tris (3-methylphenylphenylamino)triphenylamine: m-MTDATA), N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine (N,N'-di(1-naphthyl)-N,N' -diphenylbenzidine: NPB), 4,4',4"-tris(diphenylamino)triphenylamine (4,4',4"-tris(diphenylamino)triphenylamine: TDATA), 4,4',4"-tris (N,N-2-naphthylphenylamino)triphenylamine (4,4',4"-tris(N,N-2-naphthylphenylamino)triphenylamine: 2-TNATA), polyaniline/dodecylbenzenesulfonic acid (polyaniline/ dodecylbenzenesulphonic acid), poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate): PEDOT/PSS), and polyaniline/10 - Camphor sulfonic acid (polyaniline/10-camphorsulfonic acid) and the like.

A hole transport layer 140 is formed on the hole injection layer 130 . The hole transport layer 140 is a layer having a function of transporting holes, and for example, may be formed to a thickness of about 10 nm or more and about 150 nm or less, more specifically, about 20 nm or more and about 50 nm or less. The hole transport layer 140 is preferably formed by a solution coating method using the arylamine-fluorene alternating copolymer of the present embodiment. According to this method, it is possible to extend the durability (light emission lifetime) of the EL element 100 . Also, it is possible to improve the current efficiency of the EL element 100 and reduce the driving voltage. In addition, since the hole transport layer can be formed by the solution application method, a large area can be efficiently formed.

However, when the other organic film of any one of the EL elements 100 includes the arylamine-fluorene alternating copolymer of the present embodiment, the hole transport layer 140 may be formed of a known hole transport material. Known hole transport materials include, for example, 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (1,1-bis[(di-4-tolylamino)phenyl]cyclohexane:TAPC); Carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1, 1-biphenyl]-4,4'-diamine (N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1-biphenyl]-4,4'-diamine: TPD), 4,4',4"-tris(N-carbazolyl)triphenylamine (4,4',4"-tris(N-carbazolyl)triphenylamine: TCTA), and N,N'-di(1-naph tyl)-N,N'-diphenylbenzidine (N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine: NPB).

A light emitting layer 150 is formed on the hole transport layer 140 . The light emitting layer 150 is a layer that emits light by fluorescence, phosphorescence, or the like, and is formed using a vacuum deposition method, a spin coating method, an inkjet printing method, or the like. The light emitting layer 150 may be formed, for example, with a thickness of about 10 nm or more and about 60 nm or less, and more specifically, about 20 nm or more and about 50 nm or less. As a light emitting material of the light emitting layer 150, a well-known light emitting material can be used. However, the light emitting material included in the light emitting layer 150 is preferably a light emitting material capable of light emission from triplet excitons (ie, phosphorescent light emission). In this case, the driving life of the EL element 100 can be further improved.

The light emitting layer 150 is not particularly limited and may have a known configuration. Preferably, the light emitting layer contains semiconductor nanoparticles or an organometallic complex. That is, in a preferred embodiment of the present invention, the organic film has a light emitting layer containing semiconductor nanoparticles or an organometallic complex. When the light emitting layer includes semiconductor nanoparticles, the EL device is a quantum dot electroluminescence device (QLED), a quantum dot light emitting device, or a quantum dot light emitting device. In addition, when the light emitting layer contains an organometallic complex, the EL element is an organic electroluminescent element (OLED).

In a form in which the light emitting layer includes semiconductor nanoparticles (QLED), the light emitting layer includes a plurality of semiconductor nanoparticles (quantum dots) arranged in a single layer or a plurality of layers. Here, the semiconductor nanoparticles (quantum dots) are particles of a predetermined size having a quantum confinement effect. Although the diameter in particular of a semiconductor nanoparticle (quantum dot) is not restrict|limited, It is about 1 nm or more and 10 nm or less.

The semiconductor nanoparticles (quantum dots) arranged in the light emitting layer may be synthesized by a wet chemical process, an organometallic chemical vapor deposition process, a molecular beam epitaxy process, or other similar processes. Among them, the wet chemical process is a method of growing particles by adding a precursor substance to an organic solvent.

In the wet chemical process, when the crystal grows, the organic solvent spontaneously coordinates to the surface of the quantum dot crystal and acts as a dispersant, thereby controlling the crystal growth. Accordingly, in the wet chemical process, compared to vapor deposition methods such as metal organic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE), easily and at low cost, It is possible to control the growth of semiconductor nanoparticles.

By controlling the size of semiconductor nanoparticles (quantum dots), the energy band gap can be adjusted, and light in various wavelength bands can be obtained from the light emitting layer (quantum dot light emitting layer). Accordingly, by using a plurality of quantum dots of different sizes, a display that emits (or emits light) light of a plurality of wavelengths is possible. The size of the quantum dot can be selected so that red, green, and blue light are emitted to form a color display. In addition, the size of the quantum dot is combined so that various color lights emit white light.

Examples of the semiconductor nanoparticles (quantum dots) include group II-VI semiconductor compounds; III-V semiconductor compounds; group IV-VI semiconductor compounds; Group IV element or compound; and a semiconductor material selected from the group consisting of a combination thereof and the like.

The group II-VI semiconductor compound is not particularly limited, and for example, a binary compound selected from the group consisting of CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, and mixtures thereof; 3 element compounds selected from the group consisting of CdSeS, CdSeTe, CdSTe, ZnSeS, ZnTeSe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe and mixtures thereof; and a quaternary compound selected from the group consisting of CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and mixtures thereof.

The group III-V semiconductor compound is not particularly limited, but is, for example, selected from the group consisting of GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and mixtures thereof. a binary compound being; a ternary compound selected from the group consisting of GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, and mixtures thereof; and quaternary compounds selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof.

The group IV-VI semiconductor compound is not particularly limited, and for example, a binary compound selected from the group consisting of SnS, SnSe, SnTe, PbS, PbSe, PbTe, and mixtures thereof; a ternary compound selected from the group consisting of SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, and mixtures thereof; and a quaternary compound selected from the group consisting of SnPbSSe, SnPbSeTe, SnPbSTe, and mixtures thereof.

Although the group IV element or compound is not specifically limited, For example, Si, Ge, and a single-element compound selected from the group which consists of a mixture; and a binary compound selected from the group consisting of SiC, SiGe, and mixtures thereof.

The semiconductor nanoparticles (quantum dots) may have a homogeneous single structure or a core-shell double structure. The core/shell may comprise different materials. Materials constituting each of the core and the shell may be made of different semiconductor compounds. However, the energy band gap of the shell material is larger than the energy band gap of the core material. Specifically, structures such as ZnTeSe/ZnSe/ZnS, CdSe/ZnS, InP/ZnS and the like are preferable.

For example, a case in which a quantum dot having a core (CdSe)/shell (ZnS) structure is fabricated will be described. _{First, as a surfactant, a precursor material of the core (CdSe) such as (CH 3} ) ₂ Cd (dimethylcadmium) and TOPSe (trioctylphosphine selenide) is injected into an organic solvent using TOPO (trioctylphosphine oxide) to generate crystals. At this time, after maintaining at a high temperature for a certain period of time so that the crystal grows to a certain size, a precursor material of the shell (ZnS) is injected to form a shell on the surface of the already created core. Thereby, it is possible to fabricate a quantum dot of CdSe/ZnS capped with TOPO.

In addition, in the form (OLED) in which the light emitting layer contains an organometallic complex, the light emitting layer 150 is a host material, for example, 6,9-diphenyl-9'-(5'-phenyl-[1, 1':3',1"-terphenyl]-3-yl)3,3'-bi[9H-carbazole], 3,9-diphenyl-5-(3-(4-phenyl-6-( 5'-phenyl-[1,1':3',1"-terphenyl]-3-yl)-1,3,5,-triazin-2-yl)phenyl)-9H-carbazole, 9, 9'-diphenyl-3,3'-bi[9H-carbazole], tris(8-quinolinato)aluminum (tris(8-quinolinato)aluminium: Alq ₃ ), 4,4'-bis(carbazole -9-yl)biphenyl (4,4'-bis(carbazol-9-yl)biphenyl: CBP), poly(n-vinyl carbazole) (poly(n-vinyl carbazole): PVK), 9,10- Di(naphthalen-2-yl)anthracene (9,10-di(naphthalene)anthracene: ADN), 4,4',4"-tris(N-carbazolyl)triphenylamine (4,4',4" -tris(N-carbazolyl)triphenylamine: TCTA), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene(1,3,5-tris(N-phenyl-benzimidazol-2-yl) )benzene: TPBI), 3-tert-butyl-9,10-di (naphtho-2-yl) anthracene (3-tert-butyl-9,10-di (naphth-2-yl) anthracene: TBADN), Distyrylarylene (DSA), 4,4'-bis(9-carbazole)-2,2'-dimethyl-biphenyl (4,4'-bis(9-carbazole)-2,2'- dimethyl-bipheny: dmCBP) and the like may be included.

In addition, the light emitting layer 150 is a dopant material, for example, perylene and its derivatives, rubrene and its derivatives, coumarin and its derivatives, 4-dicynomethylene-2- (p-dimethylaminostyryl)-6-methyl-4H-pyran (4-dicyanomethylene-2-(pdimethylaminostyryl)-6-methyl-4H-pyran: DCM) and its derivatives, bis[2-(4,6- Difluorophenyl) pyridinate] picolinide iridium (III) (bis [2- (4,6-difluorophenyl) pyridinate] picolinate iridium (III): FIrpic), bis (1-phenyl isoquinoline) (acetylaceto nate) iridium (III) (bis (1-phenylisoquinoline) (acetylacetonate) iridium (III): Ir (piq) ₂ (acac)), tris (2-phenylpyridine) iridium (III) (tris (2-phenylpyridine) iridium (III): Ir(ppy) ₃ ), tris(2-(3-p-xylyl)phenyl)pyridineiridium(III), etc., iridium (Ir) complex, osmium (Os) complex, platinum complex, etc. may be included. . Among these, it is preferable that the luminescent material is a luminescent organometallic complex compound.

The method of forming a light emitting layer is not specifically limited. It can form by apply|coating the coating liquid containing semiconductor nanoparticles or an organometallic complex (solution application method). At this time, as the solvent constituting the coating liquid, it is preferable to select a solvent that does not dissolve the material in the hole transport layer (hole transport material, particularly, arylamine-fluorene alternating copolymer).

On the emission layer 150 , an electron transport layer 160 is formed. The electron transport layer 160 is a layer having a function of transporting electrons, and is formed using a vacuum deposition method, a spin coating method, an inkjet method, or the like. The electron transport layer 160 may be formed, for example, to have a thickness of about 15 nm or more and about 50 nm or less.

The electron transport layer 160 may be formed of a known electron transport material. Known electron transport materials include, for example, (8-quinolinato)lithium (lithium quinolate) (Liq), tris(8-quinolinato)aluminium (tris(8-quinolinato)aluminium: Alq ₃ ), and compounds having a nitrogen-containing aromatic ring. Specific examples of the compound having a nitrogen-containing aromatic ring include, for example, 1,3,5-tri[(3-pyridyl)-phen-3-yl]benzene (1,3,5-tri[(3-pyridyl) A compound containing a pyridine ring, such as )-phen-3-yl]benzene), 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1, Contains triazine rings such as 3,5-triazine (2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine) compound, 2-(4-(N-phenylbenzoimidazolyl-1-yl-phenyl)-9,10-dinaphthylanthracene (2-(4-(N-phenylbenzoimidazolyl-1-yl-phenyl)- 9,10-dinaphthylanthracene), 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (1,3,5-tris(N-phenyl-benzimidazol-2-yl)benzene: TPBI) and a compound containing an imidazole ring, etc. The electron transport material may be used alone or as a mixture of two or more.

On the electron transport layer 160 , an electron injection layer 170 is formed. The electron injection layer 170 is a layer having a function of facilitating injection of electrons from the second electrode 180 . The electron injection layer 170 is formed using a vacuum deposition method or the like. The electron injection layer 170 may be formed to a thickness of about 0.1 nm or more and about 5 nm or less, more specifically, about 0.3 nm or more and about 2 nm or less. As the material for forming the electron injection layer 170 , any known material may be used. For example, the electron injection layer 170 may include a lithium compound such as (8-quinolinato)lithium (lithium quinolate) ((8-quinolinato)lithium: Liq) and lithium fluoride (LiF), sodium chloride (NaCl), cesium fluoride (CsF), lithium oxide (Li ₂ O), barium oxide (BaO), or the like may be formed.

A second electrode 180 is formed on the electron injection layer 170 . The second electrode 180 is formed using a vacuum deposition method or the like. The second electrode 180 is specifically a cathode, and is formed of a metal, an alloy, or a conductive compound having a small work function. For example, the second electrode 180 may include a metal such as lithium (Li), magnesium (Mg), aluminum (Al), or calcium (Ca), or aluminum-lithium (Al-Li), magnesium-indium (Mg). -In) or magnesium-silver (Mg-Ag), etc., may be formed as a reflective electrode. The second electrode 180 may be formed to a thickness of about 10 nm or more and about 200 nm or less, more specifically, about 50 nm or more and about 150 nm or less. Alternatively, the second electrode 180, 20nm thin film, an indium tin oxide or less of the metal material (In ₂ O ₃ -SnO ₂₎ and indium zinc oxide by a transparent conductive film made of (In ₂ O ₃ -ZnO) It may be formed as a transmissive electrode.

In the above, the EL element 100 according to the present embodiment has been described as an example of the electroluminescence element according to the present invention. In the organic EL device 100 according to the present embodiment, by providing an organic film (especially a hole transport layer or a hole injection layer) containing an arylamine-fluorene alternating copolymer, durability (luminescence lifetime) can be further improved. . In addition, the luminous efficiency (current efficiency) can be further improved and the driving voltage can be reduced.

Incidentally, the stacked structure of the EL element 100 according to the present embodiment is not limited to the above-described examples. The EL element 100 according to the present embodiment may be formed in another known laminate structure. For example, in the EL device 100 , one or more of the hole injection layer 130 , the hole transport layer 140 , the electron transport layer 160 , and the electron injection layer 170 may be omitted, and additionally another A layer may be provided. In addition, each layer of the EL element 100 may be formed in a single layer, respectively, and may be formed in multiple layers.

For example, the EL element 100 may further include a hole blocking layer between the hole transport layer 140 and the light emitting layer 150 to prevent excitons or holes from diffusing into the electron transport layer 160 . The hole blocking layer may be formed of, for example, an oxadiazole derivative, a triazole derivative, or a phenanthroline derivative.

In addition, the arylamine-fluorene alternating copolymer according to the present embodiment can be applied to electroluminescence devices other than the QLED or OLED. Although it does not specifically limit as another electroluminescent element to which the arylamine-fluorene alternating copolymer according to this embodiment can be applied, For example, there exist an organic-inorganic perovskite light emitting element etc.

The effect of this invention is demonstrated using the following Example and a comparative example. However, the technical scope of the present invention is not limited only to the following examples. In addition, in the following examples, unless otherwise indicated, operation was performed at room temperature (25 degreeC). In addition, unless otherwise indicated, "%" and "part" mean "mass %" and "part by mass", respectively.

Synthesis Example 1

(Synthesis of Compound A-1)

Compound A-1 was synthesized according to the following reaction.

In a 1L 4-neck flask, carbazole (35.0 g), 4-bromohexylbenzene (50.2 g), tris (dibenzylideneacetone) dipalladium (Pd ₂ (dba) ₃ ) (9.57 g), tri-tert -Butylphosphonium tetrafluoroborate (t-Bu ₃ P · BF ₄ ) (4.55 g), t-butoxysodium (t-BuONa) (40.2 g), toluene (500 mL) were added, and in a nitrogen atmosphere, 100 It was heated and stirred at ℃ for 8 hours. It stood to cool to room temperature (25 degreeC; hereinafter the same), and the insoluble matter was filtered with Celite (registered trademark, hereinafter the same). The solvent was distilled off from the filtrate under reduced pressure and purified by column chromatography to obtain 9-(4-hexylphenyl)-9-carbazole (51.4 g).

In a 1L 4-neck flask, 9-(4-hexylphenyl)-9-carbazole (51.4 g) obtained above, potassium iodide (KI) (13.02 g), potassium urea (KIO ₃ ) (16.7 g), Ethanol (EtOH) (525 mL) was added, and 98% sulfuric acid (17.1 mL) was added dropwise in a nitrogen atmosphere and room temperature, followed by stirring at 75°C for 3 hours. It stood to cool to room temperature, toluene (500 mL) was added, and it wash|cleaned with water (100 mL*2), 10% sodium thiorate aqueous solution (100 mL*2), water (100 mL*2), and dried over magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by column chromatography to obtain 9-(4-hexylphenyl)-3-iod-9-carbazole (60.6 g).

In a 100 mL 3-neck flask, 9-(4-hexylphenyl)-3-iodo-9-carbazole (5.61 g) obtained above, bis(4-bromophenyl)amine (4.45 g), copper iodide (CuI) ) (0.105 g), t-butoxysodium (t-BuONa) (2.12 g), trans-1,2-cyclohexanediamine (0.251 g), 1,4-dioxane (28 mL) were added, and under a nitrogen atmosphere It refluxed at 90 degreeC for 11 hours. Using celite as a filter aid, insoluble matter was filtered off, and the residue was purified by column chromatography, and N,N-bis(4-bromophenyl)-9-(4-hexylphenyl)-9-carbazole -3-amine (Compound A-1) (1.05 g) was obtained.

Synthesis Example 2

(Synthesis of compound A-3)

Compound A-3 was synthesized according to the following reaction.

In a reaction vessel under argon, 3-bromocarbazole (3.5 g, 14.1 mmol), 4-iodo-1-pentyl benzene (4.6 g, 16.9 mmol), copper(I) iodide (CuI) (0.134 g, 0.7 mmol) ), trans-1,2-cyclohexanediamine (trans-CyHexDiAm) (0.32 g, 2.82 mmol), sodium tert-butoxide (t-BuONa) (2.71 g, 28.2 mmol), dioxane (50 ml) was added, After 5 h at 90° C., the mixture was stirred. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and impurities were filtered off using celite. After distilling off the solvent, it was purified by column chromatography to obtain 3-bromo-9-pentylphenyl-9-carbazole (4.5 g).

In a reaction vessel under argon, 3-bromo-9-pentylphenyl-9-carbazole (4.5 g, 11.5 mmol) obtained above, 4-(4,4,5,5-tetramethyl-1,3,2) -dioxaborolan-2-yl)aniline (2.6g, 12.0mmol), tetrakis(triphenylphosphine)palladium(0) (Pd(PPh ₃ ) ₄ ) (0.39 g, 0.345 mmol), sodium carbonate ( 2.4 g, 23.0 mmol), toluene (100 ml), and water (50 ml) were added, and the mixture was stirred at 85° C. for 10 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and impurities were filtered off using celite. After distilling off the solvent, it purified by column chromatography to obtain 4-(9-4-(pentylphenyl)-9-carbazol-3-yl)aniline (4.0 g).

In a four-neck flask substituted with argon, 4-(9-4-(pentylphenyl)-9-carbazol-3-yl)aniline (4.0g, 9.9mmol) obtained above, 4-bromo-iodobenzene ( 2.8 g, 10.0 mmol), tris (dibenzylideneacetone) dipalladium (Pd ₂ (dba) ₃ ) (0.091 g), 1,1'-bis (diphenylphosphino) ferrocene (dppf) (0.11 g), Sodium tert-butoxide (t-BuONa) (0.95 g, 9.9 mmol) and toluene (100 mL) were added, and the mixture was heated at 100°C for 20 hours. It stood to cool to room temperature, and filtered from the impurity using celite. After the solvent was distilled off under reduced pressure, the mixture was purified by column chromatography to obtain compound A-3 (1.7 g).

Synthesis Example 3

(Synthesis of Compound A-4)

Compound A-4 was synthesized according to the following reaction.

In a 1L 4-neck flask, 9-(4-hexylphenyl)-3-iodine-9-carbazole (20.0g), 4-(diphenylamino)phenylboronic acid (15.3g), sodium carbonate (9.51g) , tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) (2.49 g), toluene (221 mL), ethanol (110 mL), water (110 mL) were added, and at 120 ° C (bath temperature) Stirred for 3 hours. After cooling to room temperature, the aqueous layer was separated, and the organic layer was washed with water (100 L×2) and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, and the residue was purified by column chromatography to obtain 4-(9-(4-hexylphenyl)-9-carbazol-3-yl)-N,N-diphenyl)aniline (17.7 g) got

Into a 500 mL 4-neck flask, 4-(9-(4-hexylphenyl)-9-carbazol-3-yl)-N,N-diphenyl)aniline (17.7 g) obtained above, N,N-dimethyl Formamide (DMF) (310 mL) was added, cooled on ice, and N-bromosuccinimide (NBS) (11.7 g) dissolved in DMF (30 mL) under a nitrogen atmosphere was added dropwise, followed by stirring for 6 hours. The insoluble material was filtered off, washed with methanol (800 mL) and water (800 mL), dried under vacuum, and 4-bromo-N- (4-bromophenyl) -N- (4- (9- (4-) Hexylphenyl)-9-carbazol-3-yl)phenyl)aniline (14.0 g) was obtained.

4-bromo-N-(4-bromophenyl)-N-(4-(9-(4-hexylphenyl)-9-carbazol-3-yl)phenyl obtained above in a 500 mL 4-neck flask )aniline (14.0g), bispinacolatodiborate (14.8g), potassium acetate (KOAc) (11.4g), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II)dichloridedichloro A methane adduct (PdCl ₂ (dppf)CH ₂ Cl ₂ ) (0.477 g) and 1,4-dioxane (160 mL) were added, and the mixture was refluxed at 100° C. under a nitrogen atmosphere for 4 hours. The reaction solution was cooled to room temperature, the solid was separated by filtration using celite as a filter aid, and the filtrate was passed through silica gel. The solvent was distilled off under reduced pressure, dissolved in toluene (200 mL), activated carbon (14.2 g) was added, and the mixture was refluxed for 30 minutes. Activated carbon was separated by filtration, the solvent was distilled off under reduced pressure, and recrystallized using a mixed solvent of toluene and acetonitrile to obtain Compound A-4 (11.9 g).

Synthesis Example 4

(Synthesis of Compound A-5)

Compound A-5 was synthesized according to the following reaction.

In a 100 mL 4-neck flask, 2-bromocarbazole (20.0 g), 4-chloro-N- (4-chlorophenyl) -N- (4- (4,4,5,5-tetramethyl-1, 3,2-dioxaboran-2-yl)phenyl)aniline (10.0g), sodium carbonate (4.84g), tetrakis(triphenylphosphine)palladium(0) (Pd(PPh ₃ ) ₄ ) (1.31 g ), toluene (80 mL), ethanol (30 mL), and water (30 mL) were added, and the mixture was stirred at 100°C (bath temperature) for 3 hours. After cooling to room temperature, the aqueous layer was separated, and the organic layer was washed with water (100 L×2) and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, toluene (200 mL) was added to the residue, refluxed at 60° C. for 1 hour, the solid was filtered off and dried, and N-(4-(9-carbazol-2-yl)phenyl)- 4-Chloro-N- (4-chlorophenyl) aniline (6.08 g) was obtained.

In a four-neck flask substituted with argon, N-(4-(9-carbazol-2-yl)phenyl)-4-chloro-N-(4-chlorophenyl)aniline (6.00g) obtained above, 1- Bromo-4-hexylbenzene (3.00 g), tris (dibenzylideneacetone) dipalladium (Pd ₂ (dba) ₃ ) (0.580 g), tri-tert-butylphosphonium tetrafluoroborate (t-Bu ₃ P·BF ₃ ) (0.276 g), sodium tert-butoxide (t-BuONa) (2.43 g), and toluene (60 mL) were added, and the mixture was heated at 110° C. for 7 hours. It stood to cool to room temperature, and filtered from the impurity using celite. After the solvent was distilled off under reduced pressure, the mixture was purified by column chromatography, followed by 4-chloro-N-(4-chlorophenyl)-N-(4-(9-(4-hexylphenyl)-9-carbazol-2-yl ) phenyl) aniline (1.60 g) was obtained. In a 50 mL 3-neck flask, 4-chloro-N- (4-chlorophenyl) -N- (4- (9- (4-hexylphenyl) -9-carbazol-2-yl) phenyl) aniline (1.60 g ), bispinacoldivorate (1.90 g), potassium acetate (KOAc) (1.47 g), tris (dibenzylideneacetone) dipalladium (Pd ₂ (dba) ₃ ) (0.114), Xphos (0.177), 1, 4-dioxane (16 mL) was added, and the mixture was stirred for 3 hours at a bath temperature of 100°C under a nitrogen atmosphere. After cooling to room temperature, insoluble matter was removed using celite as a filter aid. The solvent was evaporated under reduced pressure, dissolved in a mixed solvent of toluene 20 mL and hexane (40 mL), activated carbon (2.0 g) was added, and the mixture was refluxed for 30 minutes. Celite was used as a filter aid to filter out insoluble substances, the solvent was distilled off under reduced pressure, and the residue was recrystallized from toluene/acetonitrile to obtain compound A-5 (1.85 g).

Synthesis Example 5

(Synthesis of compound B-3)

Compound B-3 was synthesized according to the following reaction.

In a 500 mL 3-neck flask, 9-(4-bromophenyl)-3,6-di-tert-butyl carbazole (15.0 g), bispinacoldivorate (15.7 g), potassium acetate (KOAc) (12.1 g), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II)dichloridedichloromethane adduct (PdCl ₂ (dppf) CH ₂ Cl ₂ ) (0.504 g), 1,4-dioxane (170 mL) was added and stirred for 6 hours at a bath temperature of 100°C under a nitrogen atmosphere. After cooling to room temperature, insoluble matter was removed using celite as a filter aid. The solvent was distilled off under reduced pressure, dissolved in 170 mL of toluene, activated carbon (17 g) was added, and the mixture was refluxed for 30 minutes. Celite is used as a filter aid to separate insoluble substances by filtration, the solvent is distilled off under reduced pressure, the residue is recrystallized from toluene/ethanol, and 3,6-di-tert-butyl-9-(4-(4,4,5) ,5-Tetramethyl-1,3,2-dioxaboran-2-yl)phenyl)-9-carbazole (16.0 g) was obtained.

3,6-di-tert-butyl-9-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaboran-2-yl obtained above) in a 500 mL 3-neck flask ) Phenyl)-9-carbazole (15.7 g), 4-bromotriphenylamine (9.00 g), sodium carbonate, tetrakis (triphenylphosphine) palladium (0) (Pd (PPh3) 4) (1.60 g) ), toluene (140 mL), ethanol (70 mL), and water (70 mL) were added, and the mixture was stirred under a nitrogen atmosphere at a bath temperature of 100° C. for 3 hours. It cooled to room temperature, the organic layer was liquid-separated, and the aqueous layer was extracted with toluene (50 mLx3). The organic layers were combined, washed with water (50 mL x 3), and dried over magnesium sulfate. The solvent was distilled off under reduced pressure, the residue was dissolved in tetrahydrofuran (THF) (150 mL), activated carbon (16 g) was added, and the mixture was refluxed for 30 minutes. Activated carbon was separated by filtration using celite as a filter aid, and the solvent was distilled off under reduced pressure. Ethanol (100 mL) was added to the obtained solid, refluxed for 30 minutes, the solid was separated by filtration and dried, and 4'-(3,6-di-tert-butyl-9-carbazol-9-yl)-N, N- Diphenyl- [1,1'-biphenyl] -4-amine (8.34 g) was obtained.

4'-(3,6-di-tert-butyl-9-carbazol-9-yl)-N,N-diphenyl-[1,1'-biphenyl] obtained above in a 300 mL 4-neck flask -4-amine (8.30 g) and dichloromethane (150 mL) were added, and N-bromosuccinimide (NBS) (0.762 g) dissolved in dichloromethane (15 mL) in advance at 0 ° C under a nitrogen atmosphere was added dropwise, Stirred for 3 hours. The precipitated solid was separated by filtration, washed with methanol, recrystallized from toluene/acetonitrile, and N,N-bis(4-bromophenyl)-4'-(3,6-di-tert-butyl-9- Carbazol-9-yl)-[1,1'-biphenyl]-4-amine (5.40 g) was obtained.

In a 200 mL three-necked flask, N,N-bis(4-bromophenyl)-4'-(3,6-di-tert-butyl-9-carbazol-9-yl)-[1, 1'-biphenyl]-4-amine (5.30 g), bispinacoldivorate (7.24 g), potassium acetate (KOAc) (4.20 g), [1,1'-bis (diphenyl phosphino) ferrocene] Palladium (II) dichloride dichloromethane adduct (PdCl ₂ (dppf) CH ₂ Cl ₂ ) (0.303 g) and 1,4-dioxane (60 mL) were added, and stirred for 3 hours at a bath temperature of 100° C. under a nitrogen atmosphere. did. After cooling to room temperature, insoluble matter was removed using celite as a filter aid. The solvent was distilled off under reduced pressure, dissolved in 170 mL of toluene, activated carbon (6 g) was added, and the mixture was refluxed for 30 minutes. Celite was used as a filter aid to filter out insoluble substances, the solvent was distilled off under reduced pressure, and the residue was recrystallized from toluene/acetonitrile to obtain compound B-3 (3.20 g).

Synthesis Example 6

(Synthesis of compound B-4)

Compound B-4 was synthesized according to the following reaction.

In a 2L 3-neck flask, aluminum chloride (43.9 g) and dichloromethane (500 mL) were put, cooled to 0 degrees under a nitrogen atmosphere, hexanoyl chloride (46.3 g) was added dropwise, followed by dichloromethane of carbazole (25.0 g) The solution (300 mL) was dripped. After completion of the dropwise addition, the mixture was stirred at room temperature for 12 hours. After completion of the reaction, the mixture was cooled to 0°C, and an aqueous sodium/potassium tartrate solution (90.0 g, 300 mL) was added dropwise, followed by stirring at room temperature for 1 hour. Ethyl acetate was added, and after washing with water, the organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 1,1-(9H-carbazole-3,6-diyl)bis(hexan-1-one) (43.0 g).

In a 2L 3-neck flask, put aluminum chloride (16.9 g) and tetrahydrofuran (THF) (180 _{mL), cooled to 0 degrees under a nitrogen atmosphere, lithium aluminum hydride (LiAlH 4} ) (10% tetrahydrofuran solution, 100 mL) was dropped Then, a tetrahydrofuran solution (240 mL) of 1,1-(9H-carbazole-3,6-diyl)bis(hexan-1-one) (23.0 g) obtained above was added dropwise, 0°C, nitrogen After stirring for 30 minutes in an atmosphere, the mixture was stirred at room temperature for 10 hours. After completion of the reaction, the mixture was cooled to 0°C, and an aqueous sodium/potassium tartrate solution (107.0 g, 360 mL) was added dropwise, followed by stirring at room temperature for 1 hour. Ethyl acetate was added, and after washing with water, the organic layer was dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain 3,6-dihexyl-9H-carbazole (16.2 g).

In a 500 mL three-necked flask, 3,6-dihexyl-9H-carbazole (9.0 g) obtained above, N-(4-chloro-(1,1-biphenyl)-N,N-diphenylamine ( 8.64 g), t-butoxy sodium (t-BuONa) (4.86 g), trisdibenzylideneacetonedipalladium (Pd ₂ (dba) ₃ ) (0.463 g), 2-dicyclohexylphosphino-2', 4', 6'-triisopropylbiphenyl (Xphos) (0.482 g) and toluene (127 mL) were added, and the mixture was stirred for 6 hours at a bath temperature of 110° C. under a nitrogen atmosphere. The solvent was distilled off under reduced pressure, dissolved in 150 mL of toluene, added activated carbon (1.0 g), and refluxed for 30 minutes.Use celite as a filter aid to filter out insolubles, and the solvent was distilled under reduced pressure. removed, and the residue was purified by column chromatography, and 4'-(3,6-dihexyl-9H-carbazol-9-yl)-N,N-diphenyl-[1,1'-biphenyl]- 4-amine (14.6 g) was obtained.

4'-(3,6-dihexyl-9H-carbazol-9-yl)-N,N-diphenyl-[1,1'-biphenyl]-4- obtained above in a 200 mL 4-neck flask Amine (11.0 g) and dimethylformamide (60 mL) were added, and N-bromosuccinimide (NBS) (5.98 g) dissolved in dimethylformamide (DMF) (25 mL) in advance at 0° C. under a nitrogen atmosphere was added dropwise. and stirred for 3 hours. Ethyl acetate was added, and after washing with water, the organic layer was dried over sodium sulfate and concentrated by distillation under reduced pressure. The concentrated solution was added dropwise to methanol, the precipitated solid was filtered off, and 4'-(3,6-diphenyl-9H-carbazol-9-yl)-N,N-diphenyl-[1,1'-b Phenyl]-4-amine (12.6 g) was obtained.

4'-(3,6-diphenyl-9H-carbazol-9-yl)-N,N-diphenyl-[1,1'-biphenyl]-4- obtained above in a 500 mL 3-neck flask Amine (12.6 g), bispinacoldivorate (11.8 g), potassium acetate (KOAc) (9.13 g), [1,1'-bis(diphenylphosphino)ferrocene]palladium(II)dichloride (PdCl _{2 )} (dppf)CH ₂ Cl ₂ ) (0.380 g) and 1,4-dioxane (160 mL) were added, and the mixture was stirred under a nitrogen atmosphere at a bath temperature of 100° C. for 5 hours. After cooling to room temperature, insoluble matter was removed using celite as a filter aid. The solvent was distilled off under reduced pressure, dissolved in 200 mL of toluene, and insoluble matter was removed by a silica gel (150 g) shot column. The solvent was evaporated under reduced pressure, and the residue was recrystallized from toluene/acetonitrile to obtain compound B-4 (11.0 g).

(Comparative Synthesis Example 1)

(Synthesis of Compound A-2)

Compound A-2 was synthesized according to the following reaction.

In a 200 mL 4-neck flask, 3- (4-bromophenyl) -9-phenyl carbazole (21.0 g), diphenyl amine (8.91 g), t-butoxy sodium (10.0 g), [1,1' -Bis(diphenyl phosphino)ferrocene]palladium(II)dichloridedichloromethane adduct (PdCl ₂ (dppf)CH ₂ Cl ₂ ) (2.14 g) and toluene (75 mL) were added, and under a nitrogen atmosphere, at 110 ° C. refluxed for 3 hours. Celite was used as a filter aid, and insoluble matter was filtered off, passed through silica gel, activated carbon (25 g) was added, and refluxed for 30 minutes. The activated carbon was separated by filtration using celite as a filter aid, and the solvent was distilled off under reduced pressure. The obtained solid was recrystallized using toluene and acetonitrile to obtain N,N-diphenyl-4-(9-phenyl-9-carbazol-3-yl)amine (19.9 g).

In a 500 mL four-necked flask, N,N-diphenyl-4-(9-phenyl-9-carbazol-3-yl)amine (17.7 g) and DMF (310 mL) obtained above were added to ice-cold, nitrogen N-bromosuccinimide (NBS) (11.7 g) dissolved in DMF (30 mL) was added dropwise under an atmosphere, followed by stirring for 6 hours. The insoluble matter was filtered off, washed with methanol (800 mL) and water (800 mL), dried under vacuum, and N, N-bis (4-bromophenyl) -4- (9-phenyl-9-carbazole-3) -yl)amine (14.0 g) was obtained.

In a 200 mL four-necked flask, N,N-bis(4-bromophenyl)-4-(9-phenyl-9-carbazol-3-yl)amine (8.00 g) obtained above, potassium acetate (KOAc) (7.31 g), [1,1'-bis(diphenyl phosphino)ferrocene]palladium(II)dichloridedichloromethane adduct (PdCl ₂ (dppf)CH ₂ Cl ₂ ) (0.304 g), 1,4- Dioxane (100 mL was added, refluxed at 100° C. for 4 hours under a nitrogen atmosphere. The reaction solution was cooled to room temperature, the solid was separated by filtration using celite as a filter aid, and the filtrate was passed through silica gel. The solvent was reduced under reduced pressure. Removed by distillation, dissolved in toluene (100 mL) and hexane (150 mL), added activated carbon (8.0 g) and refluxed for 30 minutes.The activated carbon was filtered off, the solvent was distilled off under reduced pressure, and a mixed solvent of toluene and acetonitrile was added. and recrystallized to obtain compound A-2 (6.29 g).

(Comparative Synthesis Example 2)

(Synthesis of compound B-1)

Compound B-1 was synthesized according to the following reaction.

In a 500 mL 3-neck flask, carbazole (2.93 g), 4,4'-dibromo-4”-fluoro triphenylamine (7.58 g), 1-methyl-2-pyrrolidone (NMP) (175 mL) ), heated at a bath temperature of 120°C under a nitrogen atmosphere, sodium hydride (0.329 g) was added, and the mixture was stirred for 1 hour. The temperature rose to 185 degreeC, sodium hydride (0.329g) was added, and it stirred for 6 hours. It was cooled gradually to room temperature, and toluene (175 mL) and methanol (90 mL) were added. It washed with water (200 mL x 3), dried over magnesium sulfate, and the solvent was distilled off under reduced pressure. The residue was purified by column chromatography to obtain compound B-1 (1.26 g).

(Comparative Synthesis Example 3)

(Synthesis of compound B-2)

Compound B-2 was synthesized according to the following reaction.

In a 500 mL 3-neck flask, 9- [4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl] -9H-carbazole (5.34 g) ), 4,4'-dibromo-4”-iodine triphenylamine (7.50 g), sodium carbonate (2.69 g), tetrakis (triphenylphosphine) palladium (0) (Pd (PPh3) 4) ( 0.74 g), 1,4-dioxane (125 mL), and water (63 mL) were added, and the mixture was stirred under a nitrogen atmosphere at a bath temperature of 100° C. for 3 hours. It cooled to room temperature, toluene (125 mL) was added, it wash|cleaned with water (50 mL*3), and it dried over magnesium sulfate. The solvent was distilled off under reduced pressure, dissolved in toluene (50 mL) and hexane (100 mL), activated carbon (8 g) was added, and the mixture was refluxed for 30 minutes. After cooling to room temperature, using celite as a filter aid, activated carbon was removed, and the solvent was distilled off under reduced pressure. The residue was subjected to column chromatography and recrystallization (toluene/acetone) to obtain compound B-2 (6.38 g).

Example 1

Under argon atmosphere, compound A-1 (1.48 g) synthesized in Synthesis Example 1, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2) -)-9,9-di-n-octyl fluorene (1.45 g), palladium acetate (10.2 mg), tris (2-methoxyphenyl) phosphine (48.0 mg), toluene (60 mL), and 20 mass % An aqueous solution of tetraethylammonium hydroxide (11.7 g) was added to a four-necked flask, followed by stirring at 85°C for 6 hours. Then, phenylboronic acid (121 mg), tetrakis(triphenylphosphino)palladium (159 mg), and 20 mass % tetraethylammonium hydroxide aqueous solution (11.7g) were added, and it stirred for 3 hours. Then, N,N-diethyldithiocarbamate sodium trihydrate (5.92 g) dissolved in ion-exchange water (50 mL) was added, and the mixture was stirred at 85°C for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer was subjected to column chromatography filled with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was dripped at methanol, and the precipitated solid was made to melt|dissolve in toluene. Then, this solution was added dropwise to methanol to precipitate, and the precipitated solid was filtered and dried to obtain a polymer compound P-1 (1.19 g). The weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the obtained polymer compound P-1 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymer compound P-1 were 240,000 and 5.20, respectively.

The polymer compound P-1 thus obtained is presumed to be a polymer compound having the following structural units from the monomer content ratio.

Example 2

Under argon atmosphere, compound A-3 (1.01 g) synthesized in Synthesis Example 2, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2) -)-9,9-di-n-octylfluorene (0.971 g), palladium acetate (2.15 mg), tris (2-methoxyphenyl) phosphine (20.3 mg), toluene (40 mL), and 20 mass % An aqueous solution of tetraethylammonium hydroxide (7.61 g) was added to a four-necked flask, followed by stirring at 85°C for 7 hours. Then, N,N-diethyldithiocarbamate sodium trihydrate (6.86 g) dissolved in ion-exchange water (40 mL) was added, and the mixture was stirred at 85°C for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer was subjected to column chromatography filled with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was dripped at methanol, and the precipitated solid was melt|dissolved in toluene. Then, this solution was added dropwise to methanol to precipitate, and the precipitated solid was filtered and dried to obtain a polymer compound P-2 (0.92 g). The weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the obtained polymer compound P-2 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymer compound P-2 were 91,600 and 2.50, respectively.

The polymer compound P-2 thus obtained is presumed to be a polymer compound having the following structural units from the monomer content ratio.

Example 3

Under argon atmosphere, compound A-4 (1.64 g) synthesized in Synthesis Example 3, 2,7-dibromo-9,9-dihexylfluorene (0.983 g), palladium acetate (9.0 mg), tris ( 2-methoxyphenyl) phosphine (42.2 mg), toluene (53 mL), and a 20 mass % tetraethylammonium hydroxide aqueous solution (10.3 g) were added to a four-necked flask, and the mixture was stirred at 85°C for 6 hours. Then, phenylboronic acid (241 mg), tetrakis(triphenylphosphine)palladium (140 mg), and a 20% by mass aqueous solution of tetraethylammonium hydroxide (10.3 g) were added, followed by stirring for 3 hours. Then, N,N-diethyldithiocarbamate sodium trihydrate (13.5 g) dissolved in ion-exchange water (50 mL) was added, and the mixture was stirred at 85°C for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer was subjected to column chromatography filled with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was dripped at methanol, and the precipitated solid was melt|dissolved in toluene. Then, this solution was added dropwise to methanol to precipitate, and the precipitated solid was filtered and dried to obtain a polymer compound P-3 (1.35 g). The weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the obtained polymer compound P-3 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymer compound P-3 were 86,000 and 2.56, respectively.

The polymer compound P-3 obtained in this way is presumed to be a polymer compound having the following structural units from the monomer content ratio.

Example 4

Under argon atmosphere, compound A-4 (1.72 g) synthesized in Synthesis Example 3, 2,7-dibromo-9,9-dioctyl fluorene (1.15 g), palladium acetate (9.4 mg), tris ( 2-methoxyphenyl) phosphine (44.2 mg), toluene (57 mL), and a 20 mass % tetraethylammonium hydroxide aqueous solution (10.7 g) were added to a four-necked flask, and the mixture was stirred at 85°C for 6 hours. Then, phenylboronic acid (121 mg), tetrakis(triphenylphosphine)palladium (146 mg), and a 20 mass % tetraethylammonium hydroxide aqueous solution (10.7 g) were added, and the mixture was stirred for 3 hours. Then, N,N-diethyldithiocarbamate sodium trihydrate (14.1 g) dissolved in ion-exchange water (50 mL) was added, and the mixture was stirred at 85°C for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer was subjected to column chromatography filled with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was dripped at methanol, and the precipitated solid was melt|dissolved in toluene. Then, this solution was added dropwise to methanol to precipitate, and the precipitated solid was filtered and dried to obtain a polymer compound P-4 (1.14 g). The weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the obtained polymer compound P-4 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymer compound P-4 were 139,000 and 3.39, respectively.

The polymer compound P-4 thus obtained is presumed to be a polymer compound having the following structural units from the monomer content ratio.

Example 5

In an argon atmosphere, compound A-4 (1.46 g) synthesized in Synthesis Example 3, 2,7-dibromo-9,9- didecylfluorene (1.07 g), palladium acetate (8.0 mg), tris ( 2-methoxyphenyl) phosphine (37.5 mg), toluene (51 mL), and a 20 mass % tetraethylammonium hydroxide aqueous solution (9.15 g) were added to a four-necked flask, and the mixture was stirred at 85°C for 6 hours. Then, phenylboronic acid (214 mg), tetrakis(triphenylphosphine)palladium (124 mg), and a 20% by mass aqueous solution of tetraethylammonium hydroxide (9.15 g) were added, followed by stirring for 3 hours. Thereafter, N,N-diethyldithiocarbamate sodium trihydrate (12.0 g) dissolved in ion-exchange water (50 mL) was added, and the mixture was stirred at 85°C for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer was subjected to column chromatography filled with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was dripped at methanol, and the precipitated solid was melt|dissolved in toluene. Then, this solution was added dropwise to methanol to precipitate, and the precipitated solid was filtered and dried to obtain a polymer compound P-5 (1.29 g). The weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the obtained polymer compound P-5 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymer compound P-5 were 101,000 and 2.66, respectively.

The polymer compound P-5 thus obtained is presumed to be a polymer compound having the following structural units from the monomer content ratio.

Example 6

Under argon atmosphere, compound A-4 (1.39 g) synthesized in Synthesis Example 3, 2,7-dibromo-9,9-didodecyl fluorene (1.11 g), palladium acetate (7.6 mg), tris ( 2-methoxyphenyl) phosphine (35.6 mg), toluene (50 mL), and a 20 mass % tetraethylammonium hydroxide aqueous solution (8.67 g) were added to a four-necked flask, and the mixture was stirred at 85°C for 6 hours. Then, phenylboronic acid (121 mg), tetrakis(triphenylphosphine)palladium (118 mg), and a 20% by mass aqueous solution of tetraethylammonium hydroxide (8.67 g) were added, followed by stirring for 3 hours. Then, N,N-diethyldithiocarbamate sodium trihydrate (11.4 g) dissolved in ion-exchange water (50 mL) was added, and the mixture was stirred at 85°C for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer was subjected to column chromatography filled with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was dripped at methanol, and the precipitated solid was melt|dissolved in toluene. Then, this solution was added dropwise to methanol to precipitate, and the precipitated solid was filtered and dried to obtain a polymer compound P-6 (1.41 g). The weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the obtained polymer compound P-6 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymer compound P-6 were 108,000 and 2.70, respectively.

The polymer compound P-6 thus obtained is presumed to be a polymer compound having the following structural units from the monomer content ratio.

Example 7

Under argon atmosphere, compound B-4 (1.82 g) synthesized in Synthesis Example 6, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2) -)-9,9-di-n-octyl fluorene (1.10 g), palladium acetate (4.49 mg), tris (2-methoxyphenyl) phosphine (42.3 mg), toluene (58.5 mL), and 20 mass % tetraethylammonium hydroxide aqueous solution (7.36 g) was added to a four-necked flask, and the mixture was stirred at 85°C for 6 hours. Then, phenylboronic acid (97.5 mg), tetrakis(triphenylphosphine)palladium (56.1 mg), and a 20% by mass aqueous solution of tetraethylammonium hydroxide (7.36 g) were added, followed by stirring for 6 hours. Then, N,N-diethyldithiocarbamate sodium trihydrate (5.92 g) dissolved in ion-exchange water (50 mL) was added, and the mixture was stirred at 85°C for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water, 3% by mass hydrochloric acid, and water. The organic layer was subjected to column chromatography filled with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was dripped at methanol, and the precipitated solid was melt|dissolved in toluene. Then, this solution was added dropwise to methanol to precipitate, and the precipitated solid was filtered and dried to obtain a polymer compound P-7 (0.51 g). The weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the obtained polymer compound P-7 were measured by SEC. As a result, Mw and Mw/Mn of the polymer compound P-1 were 160,000 and 2.50, respectively.

The polymer compound P-7 thus obtained is presumed to be a polymer compound having the following structural units from the monomer content ratio.

Comparative Example 1

In an argon atmosphere, compound A-2 (1.43 g) synthesized in Comparative Synthesis Example 1, 2,7-dibromo-9,9-didecylfluorene (1.17 g), palladium acetate (8.7 mg), tris (2-methoxyphenyl) phosphine (40.9 mg), toluene (52 mL), and 20 mass % tetraethylammonium hydroxide aqueous solution (9.98 g) were added to a 4-necked flask, and it stirred at 85 degreeC for 6 hours. Then, phenylboronic acid (234 mg), tetrakis(triphenylphosphine)palladium (136 mg), and a 20% by mass aqueous solution of tetraethylammonium hydroxide (9.98 g) were added, followed by stirring for 3 hours. Thereafter, N,N-diethyldithiocarbamate sodium trihydrate (13.1 g) dissolved in ion-exchange water (50 mL) was added, and the mixture was stirred at 85°C for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer was subjected to column chromatography filled with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was dripped at methanol, and the precipitated solid was melt|dissolved in toluene. Then, this solution was added dropwise to methanol to precipitate, and the precipitated solid was filtered and dried to obtain a polymer compound P-8 (0.788 g). The weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the obtained polymer compound P-8 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymer compound P-8 were 209,000 and 1.90, respectively.

The polymer compound P-8 thus obtained is presumed to be a polymer compound having the following structural units from the monomer content ratio.

Comparative Example 2

Under argon atmosphere, compound A-2 (1.34 g) synthesized in Comparative Synthesis Example 1, 2,7-dibromo-9,9-didoceylfluorene (1.20 g), palladium acetate (8.2 mg), tris (2-methoxyphenyl) phosphine (38.6 mg), toluene (51 mL), and 20 mass % tetraethylammonium hydroxide aqueous solution (9.41 g) were added to the 4-necked flask, and it stirred at 85 degreeC for 6 hours. Then, phenylboronic acid (221 mg), tetrakis (triphenylphosphine) palladium (128 g), and 20 mass % tetraethylammonium hydroxide aqueous solution (941 g) were added, and it stirred for 3 hours. Thereafter, N,N-diethyldithiocarbamate sodium trihydrate (12.3 g) dissolved in ion-exchange water (50 mL) was added, and the mixture was stirred at 85°C for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer was subjected to column chromatography filled with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was dripped at methanol, and the precipitated solid was melt|dissolved in toluene. Then, this solution was added dropwise to methanol to precipitate, and the precipitated solid was filtered and dried to obtain a polymer compound P-9 (0.788 g). The weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the obtained polymer compound P-9 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymer compound P-9 were 79,000 and 2.56, respectively.

The polymer compound P-9 thus obtained is presumed to be a polymer compound having the following structural units from the monomer content ratio.

Example 8

In an argon atmosphere, compound A-4 (1.54 g) synthesized in Synthesis Example 3, 2,7-dibromo-9,9-(2-ethylhexyl) fluorene (1.03 g), palladium acetate (8.4 mg) ), tris(2-methoxyphenyl)phosphine (39.7 mg), toluene (52 mL), and a 20 mass % aqueous solution of tetraethylammonium hydroxide (9.69 g) were added to a four-necked flask, and stirred at 85°C for 6 hours. did. Then, phenylboronic acid (227 mg), tetrakis (triphenylphosphine) palladium (132 mg), and a 20 mass % aqueous solution of tetraethylammonium hydroxide (9.69 g) were added, and the mixture was stirred for 3 hours. Thereafter, N,N-diethyldithiocarbamate sodium trihydrate (12.7 g) dissolved in ion-exchanged water (50 mL) was added, followed by stirring at 85°C for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer was subjected to column chromatography filled with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was dripped at methanol, and the precipitated solid was melt|dissolved in toluene. Then, this solution was added dropwise to methanol to precipitate, and the precipitated solid was filtered and dried to obtain a polymer compound P-10 (1.07 g). The weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the obtained polymer compound P-10 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymer compound P-10 were 108,000 and 2.74, respectively.

The polymer compound P-10 thus obtained is presumed to be a polymer compound having the following structural units from the monomer content ratio.

Example 9

Under argon atmosphere, compound A-5 (1.54 g) synthesized in Synthesis Example 4, 2,7-dibromo-9,9-bis (2-ethylhexyl) fluorene (1.03 g), palladium acetate (4.2) mg), tris(2-methoxyphenyl)phosphine (39.7 mg), toluene (52 mL), and a 20 mass % aqueous solution of tetraethylammonium hydroxide (9.69 g) were added to a four-necked flask, and at 85°C for 6 hours. stirred. Then, phenylboronic acid (227 mg), tetrakis (triphenylphosphine) palladium (79.2 mg), and a 20 mass % tetraethylammonium hydroxide aqueous solution (9.36 g) were added, and the mixture was stirred for 3 hours. Then, N,N-diethyldithiocarbamate sodium trihydrate (6.35 g) dissolved in ion-exchange water (50 mL) was added, and the mixture was stirred at 85°C for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed with water, a 3% by mass aqueous acetic acid solution, and water. The organic layer was subjected to column chromatography filled with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was dripped at methanol, and the precipitated solid was melt|dissolved in toluene. Then, this solution was added dropwise to methanol to precipitate, and the precipitated solid was filtered and dried to obtain a polymer compound P-11 (1.03 g). The weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the obtained polymer compound P-11 were measured by SEC. As a result, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of the polymer compound P-6 were 45,900 and 2.19, respectively.

The polymer compound P-11 thus obtained is presumed to be a polymer compound having the following structural units from the monomer content ratio.

Example 10

As a 1st electrode (anode), the glass substrate with ITO by which indium tin oxide (ITO) was patterned with the film thickness of 150 nm was used. After washing this glass substrate with ITO one by one using a neutral detergent, deionized water, water, and isopropyl alcohol, UV-ozone treatment was performed. Then, on this ITO-attached glass substrate, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS) (manufactured by Sigma-Aldrich) was applied, and the dry film thickness was 30 nm. After coating by spin coating as much as possible, it was dried. As a result, a hole injection layer with a thickness (dry film thickness) of 30 nm was formed on the glass substrate with ITO. On this hole injection layer, a 1.0 mass % toluene solution of the polymer compound P-1 (hole transport material) of Example 1 was applied by spin coating to a dry film thickness of 30 nm, and then at 230° C. for 60 minutes. By heat treatment, a hole transport layer was formed. As a result, a hole transport layer having a thickness (dry film thickness) of 30 nm was formed on the hole injection layer.

In cyclohexane, the structure:

Blue quantum dots of ZnTeSe/ZnSe/ZnS (core/shell/shell: average diameter = about 10 nm) having On the other hand, the hole transport layer (especially the polymer compound P-1) does not dissolve in cyclohexane. This quantum dot dispersion was applied onto the hole transport layer by spin coating so that the dry film thickness was 30 nm, and then dried. As a result, a quantum dot light emitting layer having a thickness (dry film thickness) of 30 nm was formed on the hole transport layer. On the other hand, the light generated by irradiating the quantum dot dispersion with ultraviolet light had a central wavelength of 462 nm and a half width of 30 nm.

The quantum dot light emitting layer was completely dried. On this quantum dot light emitting layer, using a vacuum deposition apparatus, lithium quinolate (Liq) and 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) (Sigma- Aldrich) was co-deposited. As a result, an electron transport layer having a thickness of 36 nm was formed on the quantum dot light emitting layer.

Using a vacuum deposition apparatus, on this electron transport layer, (8-quinolinolato)lithium (lithium quinolate) (Liq) was deposited. As a result, an electron injection layer with a thickness of 0.5 nm was formed on the electron transport layer.

Using a vacuum deposition apparatus, aluminum (Al) was deposited on this electron injection layer. As a result, a second electrode (cathode) having a thickness of 100 nm was formed on the electron injection layer. Thus, a quantum dot electroluminescence device 1 was obtained.

Example 11

In Example 10, a quantum dot electroluminescence device 2 was fabricated in the same manner as in Example 10 except that the polymer compound P-2 of Example 2 was used instead of the polymer compound P-1.

Example 12

In Example 10, a quantum dot electroluminescence device 3 was fabricated in the same manner as in Example 10 except that the polymer compound P-3 of Example 3 was used instead of the polymer compound P-1.

Example 13

A quantum dot electroluminescence device 4 was fabricated in the same manner as in Example 10 except that the polymer compound P-4 of Example 4 was used instead of the polymer compound P-1 in Example 10.

Example 14

In Example 10, a quantum dot electroluminescence device 5 was produced in the same manner as in Example 10 except that the polymer compound P-5 of Example 5 was used instead of the polymer compound P-1.

Example 15

In Example 10, a quantum dot electroluminescence device 6 was fabricated in the same manner as in Example 10 except that the polymer compound P-6 of Example 6 was used instead of the polymer compound P-1.

Example 16

In Example 10, a quantum dot electroluminescence device 7 was manufactured in the same manner as in Example 10 except that the polymer compound P-7 of Example 7 was used instead of the polymer compound P-1.

Example 17

A quantum dot electroluminescence device 8 was fabricated in the same manner as in Example 10 except that the polymer compound P-11 of Example 9 was used instead of the polymer compound P-1 in Example 10.

Comparative Example 3

In Example 10, in place of the polymer compound P-1, poly [(9,9-dioctyl fluorenyl-2,7-diyl)-co-(4,4'- (N-(4-sec-butylphenyl)diphenyl amine)] (TFB) (manufactured by Luminescence Technology Corp.) was performed in the same manner as in Example 10, except that Comparative Quantum Dot Electroluminescence Device 1 was prepared. Meanwhile, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of TFB were measured by SEC.As a result, the weight average molecular weight and Mw/Mn of TFB were 359,000 and 3.4, respectively.

Comparative Example 4

A comparative quantum dot electroluminescence device 2 was fabricated in the same manner as in Example 10 except that the polymer compound P-8 of Comparative Example 1 was used instead of the polymer compound P-1 in Example 10. .

Comparative Example 5

A comparative quantum dot electroluminescence device 2 was produced in the same manner as in Example 10 except that the polymer compound P-9 of Comparative Example 2 was used instead of the polymer compound P-1 in Example 10. .

[Evaluation of Quantum Dot Electroluminescence Device 1]

For the quantum dot electroluminescence devices 1 to 8 manufactured in Examples 10 to 17 and Comparative quantum dot electroluminescence devices 1 to 3 manufactured in Comparative Examples 3 to 5, the luminous efficiency was obtained by the following method. The luminescence lifetime was evaluated. The results are shown in Table 1 below.

(Luminous Efficiency)

When a voltage is applied to each quantum dot electroluminescence element, a current starts to flow at a constant voltage, and the quantum dot electroluminescence element emits light. Using a DC constant voltage power supply (manufactured by KEYENCE, a source meter), the voltage is gradually increased for each element, the current value is measured at that time, and the luminance at the time of light emission is measured by a luminance measuring device (manufactured by Topcom, SR-3) to measure. Here, the measurement ends at the point in time when the luminance starts to decline. By calculating the current value (current density) per unit area from the area of each element ^{, and dividing the luminance (cd/m 2} ) by the current density (A/m ² ), the current efficiency (cd/A) is calculated. In Table 1, the highest current efficiency in the measured voltage range is referred to as “cd/A max”. On the other hand, the current efficiency represents the efficiency (conversion efficiency) of converting current into luminescent energy, and the higher the current efficiency, the higher the device performance.

In addition, from the spectral radiation luminance spectrum measured by the luminance measuring device, it is assumed that Lambertian radiation is performed, and the external quantum efficiency (EQE) (%) at cd/A max is calculated to evaluate the luminous efficiency. .

In addition, when a voltage is applied to each quantum dot electroluminescence device using a DC constant voltage power supply (manufactured by KEYENCE, a source meter), a current starts to flow at a constant voltage, The element emits light. While measuring the light emission of each element using a luminance measuring device (manufactured by Topcom, SR-3), the current is gradually increased, the current is made constant at the point where the ^{luminance reaches 1000 nits (cd/m 2 ), and left alone.} Here, let the voltage at 1000 nits be "V@1000 nits".

(luminous lifetime)

A predetermined voltage is applied to each quantum dot electroluminescence device using a DC constant voltage power supply (manufactured by Kiens Corporation, a source meter) to cause each quantum dot electroluminescence device to emit light. While measuring the light emission of the quantum dot electroluminescence device with a luminance measuring device (manufactured by Topcom, Inc., SR-3), the current is gradually increased, and the current is kept constant at the point where the ^{luminance reaches 650 nits (cd/m 2 ).} and let it go The time until the value of the luminance measured by the luminance measuring device gradually decreases and becomes 50% of the initial luminance is defined as "LT50 (hr)".

high molecular compound cd/A max V@1000nit EQE [%] LT50 [hr] Example 10 P-1 1.9 3.0 2.7 42.6 Example 11 P-2 2.1 3.4 3.0 30.9 Example 12 P-3 2.5 3.2 4.0 51.2 Example 13 P-4 5.2 2.8 3.6 64.7 Example 14 P-5 1.9 3.9 2.9 36.3 Example 15 P-6 1.8 3.3 2.3 32.3 Example 16 P-7 6.8 3.1 10.6 30.3 Example 17 P-11 14.0 3.0 11.9 35.8 Comparative Example 3 TFB 3.0 3.7 5.0 22.2 Comparative Example 4 P-8 1.6 3.7 2.7 28.9 Comparative Example 5 P-9 1.3 3.8 2.6 27.4

In the results of Table 1, the quantum dot electroluminescence devices 1 to 8 of Examples were compared to comparative quantum dot electroluminescence devices 2 to 3 that did not use the arylamine-fluorene alternating copolymer according to the present invention. , it can be seen that remarkably high durability (remarkably long luminescence lifetime) can be exhibited. In addition, the quantum dot electroluminescence devices 1 to 8 of the examples are lower than the comparative quantum dot electroluminescence devices 2 to 3 that do not use the arylamine-fluorene alternating copolymer according to the present invention. It is also known that higher luminous efficiency can be exhibited by the driving voltage. On the other hand, the comparative quantum dot electroluminescence device 1 has a higher luminous efficiency (EQE) than that of the quantum dot electroluminescence devices 1 to 8 of Examples, but is very deteriorated in terms of the light emission lifetime (LT50). For this reason, when considered as a whole, the comparative quantum dot electroluminescence device 1 is higher than the quantum dot electroluminescence devices 1 to 8 of the Examples in terms of light emitting performance (balance between light emission efficiency and light emission lifetime) in actual use. It is thought that it deteriorates at the point. On the other hand, in this example, the blue quantum dot electroluminescence device was evaluated, but it is considered that the same results as the above will be obtained also in the red quantum dot electroluminescence device and the like.

Example 18

As a 1st electrode (anode), the glass substrate with ITO by which indium tin oxide (ITO) was patterned with the film thickness of 150 nm was used. After washing this glass substrate with ITO one by one using a neutral detergent, deionized water, water, and isopropyl alcohol, UV-ozone treatment was performed. Then, on this ITO-attached glass substrate, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS) (manufactured by Sigma-Aldrich) was applied to a dry film thickness of 30 nm. After coating by spin coating as much as possible, it was dried. As a result, a hole injection layer with a thickness (dry film thickness) of 30 nm was formed on the glass substrate with ITO. On this hole injection layer, a toluene solution containing 1.0 mass % of the polymer compound P-3 (hole transport material) of Example 3 was applied by spin coating so that the dry film thickness was 30 nm, and then at 230°C for 60 Minute heat treatment was performed to form a hole transport layer. As a result, a hole transport layer having a thickness (dry film thickness) of 30 nm was formed on the hole injection layer.

In cyclohexane, the structure:

Red quantum dots of InP/ZnSe/ZnS (core/shell/shell: average diameter = about 10 nm) having On the other hand, the hole transport layer (particularly the polymer compound P-3) does not dissolve in cyclohexane. This quantum dot dispersion was applied onto the hole transport layer by spin coating so that the dry film thickness was 30 nm, and then dried. As a result, a quantum dot light emitting layer having a thickness (dry film thickness) of 30 nm was formed on the hole transport layer. On the other hand, the light generated by irradiating the quantum dot dispersion with ultraviolet light had a central wavelength of 627 nm and a half width of 35 nm.

The quantum dot light emitting layer was completely dried. On this quantum dot light emitting layer, using a vacuum deposition apparatus, lithium quinolate (Liq) and 1,3,5-tris(N-phenyl benzimidazol-2-yl)benzene (TPBI) (Sigma- Aldrich) was co-deposited. As a result, an electron transport layer having a thickness of 36 nm was formed on the quantum dot light emitting layer.

Using a vacuum deposition apparatus, on this electron transport layer, (8-quinolinolato)lithium (lithium quinolate) (Liq) was deposited. As a result, an electron injection layer with a thickness of 0.5 nm was formed on the electron transport layer.

Using a vacuum deposition apparatus, aluminum (Al) was deposited on this electron injection layer. As a result, a second electrode (cathode) having a thickness of 100 nm was formed on the electron injection layer. Thus, a quantum dot electroluminescence device 9 was obtained.

Example 19

In Example 18, a quantum dot electroluminescence device 10 was fabricated in the same manner as in Example 18 except that the polymer compound P-4 of Example 4 was used instead of the polymer compound P-3.

Example 20

In Example 18, a quantum dot electroluminescence device 11 was fabricated in the same manner as in Example 18 except that the polymer compound P-10 of Example 8 was used instead of the polymer compound P-3.

Example 21

In Example 18, a quantum dot electroluminescence device 12 was fabricated in the same manner as in Example 18 except that the polymer compound P-7 of Example 7 was used instead of the polymer compound P-3.

Example 22

In Example 18, a quantum dot electroluminescence device 13 was produced in the same manner as in Example 18 except that the polymer compound P-11 of Example 9 was used instead of the polymer compound P-3.

Comparative Example 6

In Example 18, in place of the polymer compound P-3, poly[(9,9-dioctyl fluorenyl-2,7-diyl)-co-(4,4'- (N-(4-sec-butylphenyl)diphenyl amine)] (TFB) (manufactured by Luminescence Technology Corp.) was performed in the same manner as in Example 16, except that a comparative quantum dot electroluminescence device 4 was prepared. Meanwhile, the weight average molecular weight (Mw) and dispersion degree (Mw/Mn) of TFB were measured by SEC.As a result, the weight average molecular weight and Mw/Mn of TFB were 359,000 and 3.4, respectively.

[Evaluation of Quantum Dot Electroluminescence Device 2]

For the quantum dot electroluminescence devices 9 to 13 fabricated in Examples 18 to 22 and Comparative quantum dot electroluminescence device 4 fabricated in Comparative Example 6, the luminous efficiency and luminescence lifetime were evaluated by the following method. did. The results are shown in Table 2 below.

(Luminous Efficiency)

When a voltage is applied to each quantum dot electroluminescence element, a current starts to flow at a constant voltage, and the quantum dot electroluminescence element emits light. Using a DC constant voltage power supply (manufactured by KEYENCE, a source meter), the voltage is gradually increased for each element, the current value is measured at that time, and the luminance at the time of light emission is measured by a luminance measuring device (manufactured by Topcom, SR-3) to measure. Here, the measurement ends at the point in time when the luminance starts to decline. By calculating the current value (current density) per unit area from the area of each element ^{, and dividing the luminance (cd/m 2} ) by the current density (A/m ² ), the current efficiency (cd/A) is calculated. In Table 2 below, the highest current efficiency in the measured voltage range is referred to as “cd/A max”. On the other hand, the current efficiency represents the efficiency (conversion efficiency) of converting current into luminescent energy, and the higher the current efficiency, the higher the device performance.

Further, it is assumed that Lambertian radiation is performed from the spectral radiation luminance spectrum measured by the luminance measuring device, and the external quantum efficiency (EQE) (%) at cd/A max is calculated to evaluate the luminous efficiency.

In addition, when a DC constant voltage power supply (manufactured by KEYENCE, a source meter) is used and a voltage is applied to each quantum dot electroluminescence element, a current starts to flow at a constant voltage, and the quantum dot electroluminescence element The element emits light. While measuring the light emission of each element using a luminance measuring device (manufactured by Topcom, SR-3), the current is gradually increased, the current is made constant at the point where the ^{luminance reaches 1000 nits (cd/m 2 ), and left alone.} Here, let the voltage at 1000 nits be "V@1000 nits".

(luminous lifetime)

A predetermined voltage is applied to each quantum dot electroluminescence device using a DC constant voltage power supply (manufactured by Kiens Corporation, a source meter) to cause each quantum dot electroluminescence device to emit light. While measuring the light emission of the quantum dot electroluminescence device with a luminance measuring device (manufactured by Topcom, Inc., SR-3), the current is gradually increased, and the current is kept constant at the point where the ^{luminance reaches 4500 nits (cd/m 2 ).} and let it go The time until the value of the luminance measured by the luminance measuring device gradually decreases and reaches 80% of the initial luminance is defined as "LT80 (hr)".

high molecular compound cd/A max V@1000nit EQE [%] LT80 [hr] Example 18 P-3 22.9 2.3 19.7 145 Example 19 P-4 15.0 1.5 13.2 104 Example 20 P-10 15.4 2.3 13.3 210 Example 21 P-7 20.9 3.0 19.1 40 Example 22 P-11 14.5 2.5 12.0 179 Comparative Example 6 TFB 18.0 2.7 16.0 20

From the results of Table 2, it can be seen that the quantum dot electroluminescence devices 9 to 13 of the examples can exhibit significantly higher durability (remarkably long light emission lifetime) than the comparative quantum dot electroluminescence devices 4 . In addition, it can also be seen that the quantum dot electroluminescence devices 9 to 13 of the examples can exhibit substantially equivalent luminous efficiency with a lower driving voltage as compared to the comparative quantum dot electroluminescence device 4 . On the other hand, in this example, although the red quantum dot electroluminescence device was evaluated, it is considered that the same results as above will be obtained also in the blue quantum dot electroluminescence device or the like.

[Evaluation of properties of each polymer compound]

For the polymer compounds P-1 to P-7 and P-10 of Examples 1 to 7 and 15, HOMO trap (eV), LUMO trap (eV) and glass transition temperature (Tg) (°C) by the following method ) was measured. The results are shown in Table 3 below.

(Measurement of HOMO trap)

Each high molecular compound is dissolved in xylene so that the concentration is 1% by mass to prepare a coating solution. On a UV-cleaned glass substrate with ITO, using the coating solution prepared above, by spin coating at a rotation speed of 2000 rpm, drying on a hot plate at 150° C. for 30 minutes, measurement Make a dragon sample. The HOMO trap of the sample is measured using an atmospheric photoelectron spectrometer (manufactured by Riken Instrument Co., Ltd., AC-3). At this time, from the measurement result, the rising tangent intersection is calculated, and it is set as the HOMO trap (eV). On the other hand, the HOMO trap is usually a negative number.

(Measurement of LUMO trap)

Each high molecular compound is dissolved in toluene so that the concentration may be 3.2% by mass to prepare a coating solution. On a UV-cleaned glass substrate with ITO, using the coating solution prepared above, spin-coating at a rotation speed of 1600 rpm, drying on a hot plate at 250° C. for 60 minutes, measurement A dragon sample (film thickness of the formed film: about 70 nm) is prepared. The obtained sample is cooled to 77K (-196°C), and a photoluminescence (PL) spectrum is measured. The LUMO trap (eV) is calculated from the peak value on the shortest wavelength side of the PL spectrum.

(Glass Transition Temperature (Tg))

Using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments, trade name: DSC6000) for each high molecular compound, the temperature was increased to 300°C at a temperature increase rate of 10°C/min, and a sample held for 10 minutes was held at a temperature decrease rate of 10°C/min. After cooling to 25°C in minutes and holding for 10 minutes, the temperature is increased to 300°C at a temperature increase rate of 10°C/min and measurement is performed. After completion of the measurement, it is cooled to room temperature (25°C) at 10°C/min.

polymer
compound unit Mw
(Mw/Mn) HOMO
(eV) LUMO
(eV) Tg
(℃) Example 1 P-1

240,000
(5.20) 5.33 2.50 146 Example 2 P-2

91,600 (2.50) 5.44 2.57 147 Example 3 P-3

86,000 (2.56) 5.47 2.63 162 Example 4 P-4

139,000 (3.39) 5.45 2.60 150 Example 5 P-5

101,000 (2.66) 5.44 2.61 129 Example 6 P-6

108,000 (2.70) 5.44 2.62 110 Example 7 P-7

160,000 (2.50) 5.73 2.85 151.9 Example 8 P-10

108,000
(2.74) 5.49 2.63 162 Example 9 P-11

45,000 (2.19) 5.57 2.57 156

As mentioned above, although embodiment and Example were given and demonstrated about this invention, this invention is not limited to a specific embodiment and an Example, Within the scope of the invention described in the claims, various modifications and changes are possible. .

100: electroluminescence element (EL element)
110: substrate 120: first electrode
130: hole injection layer 140: hole transport layer
150: light emitting layer 160: electron transport layer
170: electron injection layer 180: second electrode

Claims (12)

An arylamine-fluorene alternating copolymer having a structural unit (A) represented by the following formula (1):

In formula (1), R ₁ to R ₄ each independently represent a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms,
L ₁ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent aromatic heterocyclic group,
x is 0, 1 or 2, and when x is 2, L ₁ may be the same or different, respectively,
L ₂ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent aromatic heterocyclic group, wherein L ₂ may form a ring with _{Ar 1,}
Ar ₁ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted divalent aromatic heterocyclic group, and forms a ring with _{Ar 2} or L _{2 ,}
Ar ₂ represents an aromatic hydrocarbon group or aromatic heterocyclic group having 6 to 25 carbon atoms or an aromatic heterocyclic group substituted with a straight chain or branched hydrocarbon group having 1 to 12 carbon atoms or less, and Ar ₂ is Ar ₁ and can form rings. According to claim 1,
In the formula (1), Ar ₁ forms a ring with L ₂ , an arylamine-fluorene alternating copolymer. 3. The method of claim 2,
_{-L 2} -N(Ar ₁ )(Ar ₂ ) in Formula (1) is a group selected from the following group, arylamine-fluorene alternating copolymer:

In the above formula, R ₂₁₁ to _{R 214} each independently represent a hydrogen atom, a linear or branched alkyl group having 3 to 10 carbon atoms or a branched alkyl group having 3 to 10 carbon atoms. According to claim 1,
In Formula (1), Ar ₁ forms a ring with Ar ₂ rh, -N(Ar ₁ )(Ar ₂ ) is a group selected from the following group, an arylamine-fluorene alternating copolymer:

In the above formula, R ₃₁₁ to _{R 323} each independently represents a hydrogen atom or a hydrocarbon group having 1 to 16 carbon atoms, and _{at least any one of R 311} to _{R 323} is a straight chain having 1 to 12 carbon atoms or 1 to 12 carbon atoms. Represents a branched alkyl group. According to claim 1,
The arylamine-fluorene alternating copolymer is a group derived from a compound selected from the group consisting of benzene, biphenyl, dibenzofuran, and fluorene, and is a linear chain having 4 or more and 10 or less carbon atoms, or 4 or more and 10 or less carbon atoms. Substituted with a branched alkyl group of, arylamine-fluorene alternating copolymer. According to claim 1,
The structural unit (A) is contained in a ratio of 10 mol% or more and 100 mol% or less with respect to the total structural units, arylamine-fluorene alternating copolymer. According to claim 1,
In the formula (1), x is 1 or 2, and L ₁ is a group selected from the following group, arylamine-fluorene alternating copolymer:

In the above formula, R ₁₁₁ to _{R 125} each independently represent a hydrogen atom or a linear or branched hydrocarbon group having 1 to 16 carbon atoms or a branched hydrocarbon group having 1 to 16 carbon atoms. According to claim 1,
The structural unit (A) is selected from the following group, arylamine-fluorene alternating copolymer:

In the above formula, R ₄₁₁ to _{R 431} each independently represent a linear or branched alkyl group having 1 to 12 carbon atoms or a branched alkyl group having 1 to 12 carbon atoms, and R ₅₁₁ to _{R 543} are each independently a hydrogen atom or 1 to 16 carbon atoms. The following hydrocarbon groups are shown. An electroluminescence device material comprising the arylamine-fluorene alternating copolymer according to any one of claims 1 to 8. An electroluminescence device comprising a first electrode, a second electrode, and at least one organic film disposed between the first electrode and the second electrode, the electroluminescence device comprising:
At least one layer of the organic film is an electroluminescent device comprising the arylamine-fluorene alternating copolymer according to any one of claims 1 to 8. 11. The method of claim 10,
The organic layer comprising the arylamine-fluorene alternating copolymer is a hole transport layer or a hole injection layer, an electroluminescence device. 11. The method of claim 10,
The electroluminescent element in which the said organic film has a light emitting layer containing semiconductor nanoparticles or an organometallic complex.

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