JP2020109149A - Arylamine polymer including silicone, and electroluminescence device material and electroluminescence device using polymer - Google Patents

Abstract

To provide a technique that can improve luminous efficacy of an electroluminescent element.SOLUTION: An arylamine polymer including silicon, and having a structural unit (A) represented by Formula (1).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a silicon-containing arylamine polymer, and an electroluminescent device material and an electroluminescent device using the polymer.

Research and development of electroluminescent elements (EL elements) are being actively pursued. In particular, EL devices are considered to be promising for use as solid-state light emitting inexpensive large area full-color display devices and writing light source arrays. An EL device is a light emitting device having a thin film of an organic material of several nanometers to several hundred nanometers between an anode and a cathode. In addition, the EL device usually further includes a hole transport layer, a light emitting layer, an electron transport layer, and the like.

Among them, the light emitting layer includes a fluorescent light emitting material and a phosphorescent light emitting material. The phosphorescent material is a material expected to have a luminous efficiency about four times as high as that of the fluorescent material. Further, in order to cover a wide color gamut, the RGB light source is required to have an emission spectrum with a narrow half width. In particular, deep blue is required for blue, but at present, no element has been found that can satisfy the viewpoints of long life and color purity.

As a method for solving these problems, there is a light emitting device using "quantum dots" which are inorganic light emitting substances as a light emitting material (Patent Document 1). Quantum dots are semiconductor materials having a crystal structure with a size of several nanometers, and are composed of hundreds to thousands of atoms. Since the quantum dots are very small in size, they have a large surface area per unit volume. For this reason, most of the atoms are present on the surface of the nanocrystal, and exhibit a quantum confinement effect and the like. Due to such a quantum confinement effect, the quantum dot can adjust the emission wavelength only by adjusting its size, and has characteristics such as excellent color purity and high PL (photoluminescence) emission efficiency. Is attracting interest. A quantum dot light emitting device (QLED) includes a quantum transport layer (hole transport layer; HTL) and an electron transport layer (electron transport layer; three layers) at both ends of the quantum dot light emitting layer. Element is known as a basic element.

JP, 2010-199067, A

A conventional organic light emitting diode (OLED) includes a hole transport layer (HTL) and a light emitting layer. The HOMO (Highest Occupied Molecular Orbital) level of the material used for the hole transport layer (HTL) is 5.0 to 5.3 eV. In addition, since the HOMO level of the material used for the light emitting layer exists between 5.0 and 5.5 eV, the difference from the HOMO level of the material used for the hole transport layer (HTL) is small and the efficiency is high. It becomes possible to provide positive hole transport, and a highly efficient device can be provided.

On the other hand, the quantum band used in the QLED has a valence band level of about 6.8 eV. Therefore, the difference in band offset from the HOMO level of the hole transport layer material used in the existing organic electroluminescent device (OLED) is large, and the turn-on voltage, driving voltage, efficiency and carrier injection efficiency of the QLED are large. Cause problems such as a decrease in In order to solve these problems, a method of adjusting the HOMO level of the hole transport layer (HTL) or using a proper hole transport layer material to reduce the band offset from the QD (Quantum Dot) layer is available. Is being considered. However, almost no hole transport material having a HOMO level of 5.4 eV or higher (particularly higher than 5.55 eV) is known.

The present invention has been made in view of the above circumstances, and there is a need for a material that can be used for a hole transport layer of a quantum dot electroluminescent device. Considering the recent development competition of light emitting devices, light emitting devices having higher light emitting efficiency are required.

Therefore, 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 luminous efficiency of an electroluminescence element (especially even a quantum dot electroluminescence element).

The present inventors have conducted earnest research to solve the above problems. As a result, they have found that the above problems can be solved by using a polymer having a specific structure, and have completed the present invention.

That is, the above object can be achieved by a silicon-containing arylamine polymer having a structural unit (A) represented by the following formula (1).

However, Ar ₁ is each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms or a substituted or unsubstituted heterocyclic aromatic group having 12 to 25 carbon atoms. Represents a group;
Ar ₂ is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 25 carbon atoms or a substituted or unsubstituted divalent heterocyclic aromatic group having 12 to 25 carbon atoms. Represents;
R ₁ is each independently a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms. Represents.

It is a schematic diagram which shows the organic electroluminescent element which concerns on this embodiment.

In the first aspect, the present invention provides a silicon-containing arylamine polymer having a structural unit (A) represented by the following formula (1):

However, Ar ₁ is each independently a substituted or unsubstituted (optionally substituted) aromatic hydrocarbon group having 6 to 25 carbon atoms or a substituted or unsubstituted (optionally substituted). Good) represents a heterocyclic aromatic group having 12 to 25 carbon atoms;
Ar ₂ is a substituted or unsubstituted (optionally substituted) divalent aromatic hydrocarbon group having 6 to 25 carbon atoms, or a substituted or unsubstituted (optionally substituted) carbon number Represents a divalent heterocyclic aromatic group of 12 or more and 25 or less;
R _1's each independently represent a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms, or a substituted or unsubstituted (optionally substituted) carbon atom having 6 to 25. The following aromatic hydrocarbon groups are represented. In the present specification, the structural unit (A) represented by the formula (1) is also simply referred to as “structural unit (A)” or “structural unit (A) according to the present invention”. The silicon-containing arylamine polymer having the structural unit (A) represented by the formula (1) is also simply referred to as "silicon-containing arylamine polymer" or "silicon-containing arylamine polymer according to the present invention".

In a second aspect, the present invention provides an electroluminescent device material comprising the silicon-containing arylamine polymer of the present invention.

In a third aspect, the present invention is a composition for producing an electroluminescent device, comprising at least two polymers, wherein at least one of the polymers is a silicon-containing arylamine polymer of the present invention. A composition for use is provided.

In a fourth aspect, the present invention is an electroluminescent device including a first electrode, a second electrode, and one or more organic films arranged between the first electrode and the second electrode. There is provided an electroluminescent device, wherein at least one layer of the organic film contains the silicon-containing arylamine polymer of the present invention. In the present specification, the electroluminescent element is also simply referred to as “LED”. The quantum dot electroluminescent device is also simply referred to as “QLED”. The organic electroluminescent element is also simply referred to as “OLED”.

Various low molecular weight materials and high molecular weight materials are used as materials for forming a light emitting layer and a carrier transporting layer of an electroluminescence element. Of these, low molecular weight materials are excellent in terms of device efficiency and life. However, when a low molecular weight material is used, there is a problem that the manufacturing cost is high. On the other hand, as a polymer material, TFB or the like is known as a hole transport material (for example, paragraph “0037” of Patent Document 1). However, it cannot be said that such a polymer material has a sufficient luminous efficiency or a sufficiently low driving voltage (see Comparative Example 1 below). Therefore, there has been a demand for the development of a polymer material capable of improving the luminous efficiency and reducing the driving voltage. The inventors of the present invention have earnestly studied means for increasing the triplet energy level of polymer materials (and thus improving current efficiency and light emission efficiency), which is a problem of the existing technology. As a result, by applying the polymer having the structural unit (A) of the above formula (1) to the electroluminescent device, the luminous efficiency can be improved and a low driving voltage can be achieved as compared with the case of using a known material. Found. The mechanism of exerting the above-mentioned effects by the constitution of the present invention is presumed as follows. In the structural unit (A) of the above formula (1), the silicon atom cuts the conjugation of the main chain. Thereby, the triplet energy level of the polymer compound can be increased and high current efficiency can be achieved. Therefore, by using the polymer compound having the structural unit (A), it is possible to fabricate an electroluminescence device exhibiting high luminous efficiency.

Further, in the structural unit (A) of the above formula (1), the main chain is cut by a silicon atom. Therefore, the silicon-containing arylamine polymer of the present invention exhibits a low molecular weight compound-like property having an energy level close to that of quantum dots even when polymerized. Therefore, by using the silicon-containing arylamine polymer of the present invention, it is possible to reduce the driving voltage.

Therefore, the silicon-containing arylamine polymer of the present invention has a high triplet energy level and can achieve high current efficiency. Therefore, the electroluminescent device produced by using the silicon-containing arylamine polymer of the present invention can exhibit high luminous efficiency. Further, the silicon-containing arylamine polymer of the present invention can suppress an increase in driving voltage. Therefore, the electroluminescent device produced by using the silicon-containing arylamine polymer of the present invention can exhibit high luminous efficiency at a low driving voltage. In addition, since the silicon-containing arylamine polymer of the present invention is excellent in film forming property and solvent solubility, it is possible to form a film by a wet (coating) method. Therefore, by using the silicon-containing arylamine polymer of the present invention, it is possible to increase the area and productivity of the electroluminescence device. The above effects can be effectively exhibited when the silicon-containing arylamine polymer of the present invention is applied to an EL device, particularly a hole transport layer or a hole injection layer of a QLED.

The above mechanism is speculative, and the present invention is not limited to the above mechanism.

Embodiments of the present invention will be described below. The present invention is not limited to the following embodiments. Further, 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. Further, in the case where the embodiments of the present invention have been described with reference to the drawings, the same reference numerals are given to the same elements in the description of the drawings, and overlapping description will be omitted.

In the present specification, unless otherwise specified, operations and measurements of physical properties are carried out under conditions of room temperature (20° C. or higher and 25° C. or lower)/relative humidity 40% RH or higher and 50% RH or lower.

[Silicon-containing arylamine polymer]
The silicon-containing arylamine polymer of the present invention has a structural unit (A) represented by the following formula (1). The silicon-containing arylamine polymer having such a structural unit (A) has a high triplet energy level and can improve current efficiency. In addition, lower drive voltage can be achieved. The silicon-containing arylamine polymer of the present invention may contain one type of structural unit (A) or may contain two or more types of structural unit (A).

In the above formula (1), Ar _1's each independently represent a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms or a substituted or unsubstituted 12 to 25 carbon atoms. Represents a heterocyclic aromatic group. Here, examples of the aromatic hydrocarbon group having 6 to 25 carbon atoms include, but are not limited to, benzene (phenyl group), pentalene, indene, naphthalene, anthracene, azulene, heptalene, acenaphthene, phenalene, fluorene, 1 derived from aromatic hydrocarbon such as phenanthrin, biphenyl, terphenyl, quaterphenyl, quinkiphenyl, sexiphenyl, pyrene, 9,9-diphenylfluorene, 9,9'-spirobi[fluorene], 9,9-dialkylfluorene Valuable groups can be mentioned. The heterocyclic aromatic group having 12 or more and 25 or less carbon atoms is not limited to the following, and examples thereof include acridine, phenazine, benzoquinoline, benzoisoquinoline, phenanthridine, phenanthroline, anthraquinone, fluorenone, dibenzofuran, dibenzothiophene. , Carbazole, imidazophenanthridine, benzimidazophenanthridine, azadibenzofuran, 9-phenylcarbazole, azacarbazole, azadibenzothiophene, diazadibenzofuran, diazacarbazole, diazadibenzothiophene, xanthone, thioxanthone, pyridine, quinoline, A monovalent group derived from a heterocyclic aromatic compound such as anthraquinoline may be mentioned. Of these, at least one Ar ₁ is selected from benzene, fluorene, biphenyl, p-terphenyl, 9,9-diphenylfluorene, 9,9′-spirobi[fluorene], dibenzofuran, dibenzothiophene and 9-phenylcarbazole. It is preferably a monovalent group derived from the compound. More preferably, both Ar ₁ are selected from benzene, fluorene, biphenyl, p-terphenyl, 9,9-diphenylfluorene, 9,9′-spirobi[fluorene], dibenzofuran, dibenzothiophene and 9-phenylcarbazole. It is preferably a monovalent group derived from the compound. Particularly preferably, both Ar ₁ are biphenyl. With such Ar ₁ , higher triplet energy level, lower driving voltage, and higher efficiency can be achieved. In the above preferred embodiment, Ar ₁ may be unsubstituted or any hydrogen atom may be substituted with a substituent.

Here, the number of substituents introduced when any hydrogen atom of Ar ₁ is replaced 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 Is 1. When Ar ₁ has 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 Ar ₁ is linked. Due to the presence of the substituent at such a position, higher triplet energy level, lower driving voltage and higher efficiency can be achieved.

Further, the substituent which may be present when any hydrogen atom of Ar ₁ is substituted is not particularly limited, and an alkyl group, a cycloalkyl group, a hydroxyalkyl group, an alkoxyalkyl group, an alkoxy group, a cycloalkoxy group, Alkenyl group, 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 Examples thereof include a group (-SH) and a cyano group (-CN). In the above, the same substituent is not substituted. That is, the substituted alkyl group is not substituted with the alkyl group.

Here, the alkyl group may be linear or branched, but a linear or branched alkyl group having 1 to 18 carbon atoms is preferable. 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-isopropylpropyl 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, n-decyl group, isodecyl group, n-undecyl group, 1- Examples thereof include a methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group and n-octadecyl group.

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

Examples of the hydroxyalkyl group include those in which the above 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 (eg, hydroxymethyl group, hydroxyethyl group). It

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

As the alkoxy group, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, Dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, 2-ethylhexyloxy group, 3-ethylpentyloxy group and the like can be 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 a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-pentenyl group, a 2-pentenyl group and a 3-pentenyl group. 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, an acetylenyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-pentetyl group, a 2-pentetyl group, a 3-pentethyl 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 and the like can be mentioned.

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 azulenyl group, an acenaphthylenyl group, a terphenyl group, and a phenanthryl group.

Examples of the aryloxy group include a phenoxy group and a naphthyloxy group.

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.

Examples of the cycloalkylthio group include a cyclopentylthio group and a cyclohexylthio group.

Examples of the arylthio group include a phenylthio group and a naphthylthio group.

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.

That is, in a preferred embodiment of the present invention, Ar ₁ is each independently a group selected from the following group. In the following structure, R _{111 to} R ₁₃₄ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted 6 to 25 carbon atoms. Represents an aromatic hydrocarbon group. Here, as the linear or branched alkyl group having 1 to 12 carbon atoms, for example, 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-isopropylpropyl 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 Group, n-decyl group, isodecyl group, n-undecyl group, 1-methyldecyl group, n-dodecyl group and the like. The aromatic hydrocarbon group having 6 to 25 carbon atoms is not particularly limited, but the same examples as defined for Ar ₁ can be applied. From the viewpoint of higher triplet energy level and lower driving voltage, R _{111 to} R ₁₃₄ are preferably hydrogen atoms or linear or branched alkyl groups having 2 to 10 carbon atoms. More preferably, R _{111 to} R ₁₃₄ are a hydrogen atom (unsubstituted) or a linear alkyl group having 3 to 6 carbon atoms.

In the above formula (1), Ar ₂ is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 25 carbon atoms or a substituted or unsubstituted divalent aromatic group having 12 to 25 carbon atoms. Represents a heterocyclic aromatic group. Here, the divalent aromatic hydrocarbon group having 6 to 25 carbon atoms is not particularly limited, but a divalent aromatic hydrocarbon group derived from aromatic hydrocarbon having 6 to 25 carbon atoms defined by Ar ₁ is used. It can be illustrated. Similarly, the divalent heterocyclic aromatic group having 12 or more and 25 or less carbon atoms is not particularly limited, but 2 derived from the heterocyclic aromatic compound having 12 or more and 25 or less carbon atoms defined by Ar _{1 is used} . A valent group can be illustrated. Of these, Ar ₂ is benzene, biphenyl, terphenyl, quaterphenyl, quinkiphenyl, sexiphenyl, fluorene, 9-phenylcarbazole, dibenzofuran, dibenzothiophene, 9,9-diphenylfluorene and 9,9′-spirobi[. It is preferably a divalent group derived from a compound selected from fluorene]. More preferably, Ar ₂ is a divalent group derived from a compound selected from phenyl, biphenyl, terphenyl, quaterphenyl, quinkiphenyl and fluorene. Particularly preferably, Ar ₂ is a divalent group derived from a compound selected from biphenyl, p-terphenyl, p-quaterphenyl and p-kinkiphenyl. Ar ₂ is particularly preferably a divalent group derived from p-kinkiphenyl. With such Ar ₂ , higher triplet energy level, lower driving voltage, and higher efficiency can be achieved. In the above preferred embodiment, Ar ₂ may be unsubstituted or any hydrogen atom may be substituted with a substituent.

Here, the number of substituents to be introduced when any hydrogen atom of Ar ₂ is replaced 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 Is 2. When Ar ₂ has a substituent, the bonding position of the substituent is not particularly limited. For example, in the case of a plurality of substituents, the substituents are preferably present on the same aromatic ring or heterocycle, more preferably on the same aromatic ring, particularly preferably on the same phenyl ring. Further, for example, when two substituents are present on the p-phenylene group, the two substituents are present at any of the 2,3 position, the 2,5 position and the 3,5 position. Although it may be present, it is preferably present at the 2,5- and 3,5-positions, particularly preferably at the 2,5-positions. Further, when a plurality of substituents are present on an aromatic ring or a heterocycle in which a plurality of substituents are linked, the substituent is preferably present on the aromatic ring or the heterocycle near the center. Due to the presence of the substituent at such a position, higher triplet energy level, lower driving voltage and higher efficiency can be achieved.

Further, the substituent that may be present when any hydrogen atom of Ar ₂ is substituted is not particularly limited, and the same examples as those of Ar ₁ above can be applied.

That is, in a preferable mode of the present invention, Ar ₂ is a divalent group selected from the following group. In the structure below, R _{211 to} R ₂₆₉ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted 6 to 25 carbon atoms. Represents an aromatic hydrocarbon group. Here, the linear or branched alkyl group having 1 to 12 carbon atoms or the substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms is not particularly limited, and may be any of the above R _{111 to} R. The same example as ₁₃₄ can be applied. From the viewpoint of higher triplet energy level and lower driving voltage, R _{211 to} R ₂₆₉ are preferably a hydrogen atom or a linear or branched alkyl group having 2 to 10 carbon atoms. More preferably, R _{211 to} R ₂₆₉ are a hydrogen atom (unsubstituted) or a linear alkyl group having 3 to 6 carbon atoms.

Further, in the above formula (1), each R ₁ independently represents a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms, or a substituted or unsubstituted 6 carbon atom. It represents an aromatic hydrocarbon group of 25 or more and 25 or less. Here, the linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms is not particularly limited, and examples thereof include linear or branched alkyl groups, alkenyl groups, alkynyl groups and cycloalkyl groups. In addition, when R ₁ is an alkenyl group or an alkynyl group, the carbon number of R ₁ is 2 or more and 12 or less. Similarly, when R ₁ is a cycloalkyl group, the carbon number of R ₁ is 3 or more and 12 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-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4-dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl 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, n-decyl group, isodecyl Group, n-undecyl group, 1-methyldecyl group, n-dodecyl group and the like.

Examples of the alkenyl group having 2 to 12 carbon atoms include vinyl group, allyl group, 1-propenyl group, 2-butenyl group, 1,3-butadienyl group, 2-pentenyl group and isopropenyl group.

Examples of the alkynyl group having 2 to 12 carbon atoms include an ethynyl group and a propargyl group.

Examples of the cycloalkyl group having 3 to 12 carbon atoms include cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like.

Of these, R ₁ is preferably each independently a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms. From the viewpoint of higher triplet energy level and lower driving voltage, R ₁ is more preferably a hydrogen atom (unsubstituted) or a linear alkyl group having 3 to 6 carbon atoms.

The degree of polymerization of the structural unit (A) is not particularly limited, but is preferably an integer of 5 or more and 1,000 or less. From the viewpoint of higher triplet energy level and lower driving voltage, the degree of polymerization of the structural unit (A) is more preferably 5 or more and 500 or less, still more preferably 10 or more and 300 or less, and particularly preferably 10 or more or less. It is 150 or less.

In the present embodiment, the structural unit (A) represented by the formula (1) is preferably the following formula (A-) from the viewpoint of further improving the triplet energy level and hole transporting ability and further lowering the driving voltage. 1) to (A-4) are selected from the structural units. Particularly preferably, the structural unit (A) represented by the formula (1) is a structural unit represented by the following formula (A-1). In the following, "Alkyl" means "unsubstituted or substituted with an alkyl group". Preferably, “Alkyl” means unsubstituted (that is, Alkyl=hydrogen atom) or substituted with a linear or branched alkyl group having 1 to 18 carbon atoms. More preferably, "Alkyl" means unsubstituted or substituted by a linear or branched alkyl group having 3 to 6 carbon atoms. Moreover, "Alkyl" may be the same alkyl group or different alkyl groups.

The composition of the structural unit (A) in the silicon-containing arylamine polymer of the present invention is not particularly limited. Considering the effect of further improving the hole transport ability of the layer (eg, hole injection layer, hole transport layer) formed using the obtained silicon-containing arylamine polymer, the structural unit (A) is a silicon-containing aryl group. It is preferably 10 mol% or more and 100 mol% or less, more preferably 50 mol% or more and 100 mol% or less, and particularly preferably 100 mol% with respect to all the constituent units constituting the amine polymer. That is, in a preferred embodiment of the present invention, the structural unit (A) is contained in a proportion of 10 mol% or more and 100 mol% or less based on all the structural units. In a more preferred form of the present invention, the structural unit (A) is contained in a proportion of 50 mol% or more and 100 mol% or less based on all the structural units. In a particularly preferred embodiment of the present invention, the silicon-containing arylamine polymer is composed only of the structural unit (A) (that is, the ratio of the structural unit (A) to all the structural units=100 mol %). When the silicon-containing arylamine polymer 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 silicon-containing arylamine polymer of the present invention may be composed of the structural unit (A) only. Alternatively, the silicon-containing arylamine polymer of the present invention may further contain a structural unit other than the structural unit (A). When the other structural unit is included, the other structural unit is not particularly limited as long as it does not hinder the effects of the silicon-containing arylamine polymer (particularly high triplet energy level, low driving voltage). Specific examples include structural units selected from the following group. In addition, below, the structural unit shown by the following groups is also called "structural unit (B)."

The composition of the constituent unit (B) in the silicon-containing arylamine polymer of the present embodiment is not particularly limited. Considering the film-forming easiness and the effect of further improving the film strength by the obtained polymer compound, the structural unit (B) is preferably 1 mol% or more based on all the structural units constituting the silicon-containing arylamine polymer. It is 10 mol% or less. When the silicon-containing arylamine polymer 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).

When the silicon-containing arylamine polymer is composed of two or more constituent units, the structure of the silicon-containing arylamine polymer is not particularly limited. The silicon-containing arylamine polymer may be a random copolymer, an alternating copolymer, a periodic copolymer, or a block copolymer.

The weight average molecular weight (Mw) of the silicon-containing arylamine polymer is not particularly limited as long as the effects of the present invention can be obtained. The weight average molecular weight (Mw) is, for example, preferably 10,000 or more and 500,000 or less, and more preferably 20,000 or more and 300,000 or less. With 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 a silicon-containing arylamine polymer is appropriately adjusted to obtain a uniform coating. It is possible to form a layer having a film thickness.

The number average molecular weight (Mn) of the silicon-containing arylamine polymer is not particularly limited as long as the effects of the present invention can be obtained. The number average molecular weight (Mn) is, for example, preferably 10,000 or more and 500,000 or less, and more preferably 10,000 or more and 200,000 or less. With such a number average molecular weight, the viscosity of a coating solution for forming a layer (for example, a hole injection layer, a hole transport layer) using a silicon-containing arylamine polymer is appropriately adjusted to obtain a uniform coating solution. It is possible to form a layer having a film thickness. The polydispersity (weight average molecular weight/number average molecular weight) of the silicon-containing arylamine polymer 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 the present specification, measurement of the number average molecular weight (Mn) and the weight average molecular weight (Mw) is not particularly limited, and a known method can be used or a known method can be appropriately modified and applied. In the present specification, as the number average molecular weight (Mn) and the weight average molecular weight (Mw), the values measured by the following method are adopted. The polydispersity index (Mw/Mn) of the polymer is calculated by dividing the weight average molecular weight (Mw) by 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 the weight average molecular weight (Mw) of the polymer material are measured by SEC (Size Exclusion Chromatography) using polystyrene as a standard substance under the following conditions.

(SEC measurement conditions)
Analyzer (SEC): Shimadzu, Prominence
Column: PL 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% by mass)
Eluent: Tetrahydrofuran (THF)
Detector (UV-VIS detector): Shimadzu Corporation, SPD-10AV
Standard sample: polystyrene.

The terminal of the main chain of the silicon-containing arylamine polymer of the present embodiment is not particularly limited and is appropriately defined depending on the type of raw material used, but is usually a hydrogen atom.

The silicon-containing arylamine polymer of this embodiment can be synthesized by using a known organic synthesis method. The specific method of synthesizing the silicon-containing arylamine polymer of the present embodiment can be easily understood by those skilled in the art with reference to the examples described later. Specifically, the silicon-containing arylamine polymer of the present embodiment is produced by a polymerization reaction using one or more monomers (1) represented by the following formula (1′) or by the following formula (1′) It can be produced by a copolymerization reaction using at least one monomer (1) shown and another monomer corresponding to the above-mentioned other structural unit. The above-mentioned monomer used for the polymerization of the silicon-containing arylamine polymer can be synthesized by appropriately combining known synthetic reactions, and its structure can also be determined by a known method (for example, NMR, LC-MS, etc.). Check.

In the above formula (1′), Ar ₁ and R ₁ and R ₂ have the same definitions as in the above formula (1). Further, Ar _{2 'and Ar 2 "are} joined together, .X ₁ and _{X 2} forming the Ar ₂ in the formula (1) are each independently a halogen atom (fluorine atom, chlorine atom , A bromine atom, an iodine atom, especially a bromine atom) or a group having the following structure, wherein R _{A to} R _D are each independently an alkyl group having 1 to 3 carbon atoms. R _{A to} R _D are methyl groups.

Alternatively, the silicon-containing arylamine polymer of the present embodiment includes one or more monomers (1) represented by the following formula (1″) and one or more monomers (1) represented by the following formula (2″) ( By a polymerization reaction using 2) or one or more monomers (1) represented by the following formula (1″) and one or more monomers (2) represented by the following formula (2″) and It can be produced by a copolymerization reaction using another monomer corresponding to the above-mentioned other structural unit.

In the above formulas (1″) and (2″), Ar ₁ and R ₁ and R ₂ have the same definitions as in the above formula (1). Further, Ar _2′ , Ar _2″ and Ar _2′″ are bonded together to form Ar ₂ in the above formula (1). X ₁ and X ₂ are each independently a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, especially bromine atom) or a group having the following structure. In the structure below, R _{A to} R _D are each independently an alkyl group having 1 to 3 carbon atoms. Preferably, R _{A to} R _D are methyl groups. In addition, X ₁ and X ₂ in the above formulas (1″) and (2″) may be the same or different.

The silicon-containing arylamine polymer of this embodiment has a structural unit (A). Therefore, it has a high triplet energy level and a low driving voltage. When the silicon-containing arylamine polymer according to this embodiment is used as a hole injection material or a hole transport material (particularly a hole transport material), current efficiency can be improved. Furthermore, when the silicon-containing arylamine polymer of the present embodiment is used for an electroluminescence device, high charge mobility is achieved. Therefore, particularly when the silicon-containing arylamine polymer of the present embodiment is used as a hole transport material, the deterioration effect on electrons can be reduced and the device life (driving life) can be improved. Therefore, the electroluminescence device using the silicon-containing arylamine polymer according to the present embodiment has excellent luminous efficiency and durability. Furthermore, when the silicon-containing arylamine polymer of the present embodiment has another structural unit having a crosslinkable group, the stability of the coating film can be improved. Therefore, it is possible to improve the light emission characteristics and stability when the electroluminescent element is formed in a laminated structure.

[Electroluminescence device material]
The silicon-containing arylamine polymer according to the present embodiment is suitably used as an electroluminescence element material. The silicon-containing arylamine polymer according to the present embodiment provides an electroluminescent element material having a high triplet energy level (current efficiency) and a low driving voltage. Further, the silicon-containing arylamine polymer according to the present embodiment provides an electroluminescent element material having high charge mobility and excellent durability. Furthermore, the backbone of the silicon-containing arylamine polymer (constituent unit of formula (1)) has suitable flexibility. Therefore, the silicon-containing arylamine polymer according to this embodiment exhibits high solubility in a solvent and high heat resistance. Therefore, a film can be easily formed (thinned) by a wet (coating) method. Therefore, in a second aspect, there is provided an electroluminescent device material comprising the silicon-containing arylamine polymer of the present invention. Alternatively, the use of a silicon-containing arylamine polymer as an electroluminescent device material is provided.

Further, the silicon-containing arylamine polymer according to the present embodiment has a HOMO level of more than 5.55 eV, particularly 5.57 eV or more. Therefore, the silicon-containing arylamine polymer according to the present embodiment has a quantum dot electroluminescence. It can be suitably used for a device (in particular, a hole transport layer).

The electroluminescent element material according to the present embodiment may further contain other polymer in addition to the silicon-containing arylamine polymer of the present invention. That is, in the third aspect, a composition for producing an electroluminescent device, which comprises two or more polymers, wherein at least one of the polymers is the silicon-containing arylamine polymer of the present invention. Things are offered. Alternatively, the use of a composition comprising two or more polymers including a silicon-containing arylamine polymer as an electroluminescent device material is provided. In the following, the composition for producing an electroluminescent element according to the present invention will also be simply referred to as the “composition for LED” or the “composition according to the present invention”.

The object (or effect) of the present invention can also be achieved by such an electroluminescent element material or composition according to the present embodiment. The electroluminescent element material of this embodiment is an example of the electroluminescent element material according to the present invention. Similarly, the composition of the present embodiment is an example of the composition according to the present invention.

Polymers other than the silicon-containing arylamine polymer of the present invention that can be used in the third aspect are also simply referred to as “other polymers” below.

In the third aspect, the structure of the other polymer is not particularly limited as long as the effect of the present invention is not impaired. Preferably, the other polymer has a structural unit represented by the following formula (A). By using the polymer having the above structure (another polymer) in combination with the silicon-containing arylamine polymer, the HOMO level and the LUMO level are brought closer to each other, and the charge injection barrier is reduced (thus, the hole injection property is improved. To). Therefore, the electroluminescence device (particularly QLED) using the silicon-containing arylamine polymer according to the present invention in combination with another polymer having a constitutional unit represented by the following formula (A) can improve its emission life. The above mechanism is based on speculation, and its correctness does not affect the technical scope of the present invention.

That is, in a preferred embodiment of the present invention, at least one polymer has a structural unit represented by the following formula (A):

However, X is a group represented by the following formula (B), and Y is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a substituted or non-substituted group. A substituted divalent aromatic heterocyclic group having 3 to 60 ring-forming atoms,

However, Ar ₁₀₀ is a substituted or unsubstituted trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted trivalent aromatic group having 3 to 60 ring-forming atoms. A heterocyclic group,
Ar ₂₀₀ and Ar ₃₀₀ are each independently a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted 3 to 60 ring-forming atoms. The following monovalent aromatic heterocyclic group,
L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted ring-forming atom number. It is a divalent aromatic heterocyclic group of 3 or more and 60 or less,
Z _{1 to} Z ₈ are each independently a nitrogen atom or -CH=, in which case any of Z _{5 to} Z ₈ is -CH= and the hydrogen atom of -CH= is -L _2. -N(Ar ₂₀₀ )(Ar ₃₀₀ ),
R ₁₀₀ and R ₂₀₀ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or An unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted monovalent aromatic heterocyclic group having 3 to 60 ring-forming atoms,
R ₁₀₀ and R ₂₀₀ may combine with each other to form a ring,
a is an integer of 0 or more and 4 or less,
b is an integer of 0 or more and 3 or less,
When a is an integer of 1 or more and 4 or less, _one of Z _{1 to} Z ₄ is -CH=, the hydrogen atom of the -CH= is substituted with R ₁₀₀ , and b is 1 or more and 3 or less. When it is an integer, any of Z _{5 to} Z ₈ is —CH═, and the hydrogen atom of —CH═ is substituted with R ₂₀₀ .

Hereinafter, other polymers according to the above-described preferred embodiment will be described. The present invention is not limited to the following modes.

In this embodiment, the other polymer includes a segment of an alternating copolymer of the structural unit represented by the above formula (A). Here, the other polymer may contain one kind of X or two or more kinds of X as a constitutional unit. Similarly, the other polymer may contain one kind of Y or two or more kinds of Y as a constitutional unit.

In the above formula (A), X includes a nitrogen-containing aromatic heterocycle (for example, a carbazole skeleton) substituted with an amino group. Therefore, when another polymer is used in combination with the silicon-containing arylamine polymer of the present invention in the hole transport layer of the electroluminescence device, the hole transport property can be further improved.

In another polymer according to this embodiment, X is an aromatic group (Ar ₁₀₀ ) in the main chain, a nitrogen-containing aromatic heterocycle in the side chain and an amino group (N(Ar ₂₀₀ )(Ar ₃₀₀ )). Therefore, the other polymer according to the present embodiment has a deeper HOMO level, and as a result, when used in a quantum dot light emitting device, higher emission efficiency, lower driving voltage, and longer emission lifetime are obtained. Can be achieved.

In the above formula (B), Ar ₁₀₀ is a substituted or unsubstituted trivalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a substituted or unsubstituted 3 or more and 60 or less ring-forming atoms. Is a trivalent aromatic heterocyclic group.

Here, the aromatic hydrocarbon group is a group derived from an aromatic hydrocarbon compound containing one or more aromatic hydrocarbon rings. Here, when the aromatic hydrocarbon group includes two or more aromatic hydrocarbon rings, the two or more aromatic hydrocarbon rings may be condensed with each other. Moreover, the aromatic hydrocarbon group may be substituted with one or more substituents.

The aromatic hydrocarbon compound is not particularly limited, benzene, pentalene, indene, naphthalene, anthracene, azulene, heptalene, asenaphthalene, phenalene, fluorene, anthraquinone, phenanthrene, biphenyl, triphenylene, pyrene, chrysene, picene, perylene, Pentaphen, pentacene, tetraphene, hexaphene, hexacene, rubicene, trinaphthylene, heptaphene, pyrantrene and the like can be mentioned.

Further, the aromatic heterocyclic group has one or more hetero atoms (for example, a nitrogen atom (N), an oxygen atom (O), a phosphorus atom (P), a sulfur atom (S)), and forms the remaining ring. A group derived from an aromatic heterocyclic compound containing one or more aromatic heterocycles whose atoms are carbon atoms (C). In addition, when the aromatic heterocyclic group contains two or more aromatic heterocycles, the two or more aromatic heterocycles may be condensed with each other. Moreover, the aromatic heterocyclic group may be substituted with one or more substituents.

The aromatic heterocyclic compound is not particularly limited, but pyrazoline, imidazoline, oxazoline, thiazoline, triazoline, tetrazoline, oxadiazoline, pyridine, pyridazinine, pyrimidine, triazine, carbazoline, azacarbazoline, indoline, quinolinine, isoquinoline, benzimidazoline, Examples thereof include imidazopyridine, imidazopyrimidine, furan, benzofuran, dibenzofuran, azadibenzofuran, thiophene, benzothiophene, dibenzothiophene and azadibenzothiophene.

Examples of the trivalent aromatic hydrocarbon group for Ar ₁₀₀ include groups in which any three hydrogen atoms have been removed from the hydrogen atoms of the aromatic hydrocarbon compound. Examples of the trivalent aromatic heterocyclic group include groups obtained by removing any three hydrogen atoms from the above hydrogen atoms of the aromatic heterocyclic compound.

Of these, Ar ₁₀₀ is preferably a group shown below from the viewpoint of adjusting the HOMO level.

Note that the above structures, A is, -O -, - S -, - Se -, - NR 1 '- ( provided that, R _1' is a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or an unsubstituted aryl group or a substituted or unsubstituted heteroaryl group), or _{-CR 2 'R 3' -.} ( provided that, R 2 _'and R _3' are each independently a hydrogen atom, a deuterium atom , A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group), and * is a binding site.

The substituent in the case where the trivalent aromatic hydrocarbon group or the trivalent aromatic heterocyclic group is substituted is not particularly limited, but may be a halogen atom, an alkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic group. Group heterocyclic groups and the like can be mentioned, and two or more kinds may be used in combination.

Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

Examples of the alkyl group 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. 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-isopropylpropyl 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, 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, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, Examples thereof include an n-heneicosyl group, an n-docosyl group, an n-tricosyl group, and an n-tetracosyl group.

The alkyl group is preferably a linear or branched alkyl group having 1 to 24 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 8 carbon atoms.

As the alkoxy group, for example, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, Examples thereof include a dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, a pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, a 2-ethylhexyloxy group and a 3-ethylpentyloxy group.

The alkoxy group is preferably a linear or branched alkoxy group having 1 to 24 carbon atoms, and more preferably a linear or branched alkoxy group having 1 to 8 carbon atoms.

Examples of the aromatic heterocyclic group (or aromatic hydrocarbon group) that may be introduced into the trivalent aromatic hydrocarbon group (or trivalent aromatic heterocyclic group) include, for example, the aromatic heterocycle (or Examples include groups in which any one hydrogen atom has been removed from (aromatic hydrocarbon).

In formula (B), Ar ₂₀₀ and Ar ₃₀₀ each independently represent a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted ring. It is a monovalent aromatic heterocyclic group having 3 to 60 forming atoms.

Here, the monovalent aromatic hydrocarbon group and the monovalent aromatic heterocyclic group have the same formula (B) except that the trivalent aromatic hydrocarbon group and the trivalent aromatic heterocyclic group are monovalent. Since it is the same as Ar _{100 in (} ), the description is omitted here. Further, the substituent in the case where the monovalent aromatic hydrocarbon group or the monovalent aromatic heterocyclic group is substituted is the same as the substituent in Ar ₁₀₀ in the formula (B), and therefore, here, The description is omitted.

From the viewpoint of increasing the HOMO level, hole transporting property, and hole injecting property of the other polymer according to the present embodiment, the monovalent aromatic hydrocarbon group is a phenyl group, a biphenyl group, a fluorenyl group, a naphthyl group, Anthryl group, phenanthryl group, naphthacenyl group, pyrenyl group, terphenyl group, tolyl group, t-butylphenyl group, or (phenylpropyl)phenyl group is preferable, and phenyl group, biphenyl group, fluorenyl group, naphthyl group, It is more preferably an anthryl group, a terphenyl group or a tolyl group, and particularly preferably a biphenyl group or a fluorenyl group.

Further, from the viewpoint of enhancing the HOMO level, hole transporting property, and hole injecting property of the other polymer according to the present embodiment, the monovalent aromatic heterocyclic group is a pyridyl group, a bipyridyl group, a pyrrolyl group, or pyrazinyl. Group, pyridinyl group, pyrimidyl group, indolyl group, furyl group, benzofuranyl group, dibenzofuranyl group, quinolyl group, quinoxanyl group, carbazolyl group, phenanthridinyl group, acridinyl group, phenazinyl group, phenothiazinyl group, phenoxazinyl group, Oxazolyl group, oxadiazolyl group, flazanyl group, thienyl group, thiophenyl group, isothiophenyl group, or dibenzothiophenyl group is preferable, pyridyl group, pyrrolyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, Alternatively, it is more preferably a bipyridyl group.

Further, from the viewpoint of increasing the HOMO level, hole transporting property, hole injecting property, solubility, and coating property of the other polymer according to the present embodiment, a monovalent aromatic hydrocarbon group or a monovalent aromatic group is used. When the heterocyclic group is substituted, the substituent is an alkyl group having 1 to 8 carbon atoms, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio. Group, arylalkenyl group, arylalkynyl group, amino group, amino group substituted with a substituent, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, It is preferably a monovalent heterocyclic group, a carboxyl group, a carboxyl group substituted with a substituent, a cyano group, or a nitro group, and more preferably an alkyl group having 1 to 12 carbon atoms.

Specific examples of Ar ₂₀₀ and Ar ₃₀₀ are shown below.

In the above structure, R _3's are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted group. Or an unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted monovalent aromatic heterocyclic group having 3 to 60 ring forming atoms, and * is , Alkyl means substituted or unsubstituted with an alkyl group.

In the above formula (B), L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or It is an unsubstituted divalent aromatic heterocyclic group having 3 to 60 ring-forming atoms.

Here, the divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group are of the formula (B) except that the trivalent aromatic hydrocarbon group and the trivalent aromatic heterocyclic group are divalent. Since it is the same as Ar _{100 in (} ), the description is omitted here. Further, when the divalent aromatic hydrocarbon group or the divalent aromatic heterocyclic group is substituted, the substituent is the same as the substituent in Ar ₁₀₀ in the formula (B), and therefore, here, The description is omitted.

From the viewpoint of increasing the HOMO level, hole transporting property, and hole injecting property of the other polymer according to the present embodiment, the divalent aromatic hydrocarbon group is a phenylene group, a biphenylene group, a fluorenylene group, a naphthylene group, Anthrylene group, phenanthrylene group, naphthalenylene group, pyrenylene group, terphenylene group, tolylene group, t-butylphenylene group, or (phenylpropyl)phenylene group is preferable, phenylene group, biphenylene group, fluorenylene group, naphthylene group, An anthrylene group, a terphenylene group, or a tolylene group is more preferable, and a phenylene group is particularly preferable.

Further, from the viewpoint of enhancing the HOMO level, hole transporting property, and hole injecting property of the other polymer according to the present embodiment, the divalent aromatic heterocyclic group is a pyridinediyl group, a bipyridinediyl group, or pyrrolinediyl group. Group, pyrazinediyl group, pyridinyl group, pyrimidinediyl group, indolinediyl group, furandiyl group, benzofurandiyl group, dibenzofurandiyl group, quinolinediyl group, quinoxalinediyl group, carbazolediyl group, phenanthridinediyl group, acridinediyl group, phenazine Diyl group, phenothiazinediyl group, phenoxazinediyl group, oxazolediyl group, oxadiazolediyl group, furazandiyl group, thiophenediyl group, thiophenyl group, isothiophenediyl group, or dibenzothiophenediyl group, preferably pyridinediyl group More preferably, it is a group, a pyrrolinediyl group, a carbazolediyl group, a dibenzofurandiyl group, a dibenzothiophenediyl group, or a bipyridinediyl group.

Further, from the viewpoint of increasing the HOMO level, hole transporting property, hole injecting property, solubility, and coatability of the other polymer according to the present embodiment, a divalent aromatic hydrocarbon group or a divalent aromatic group. When the heterocyclic group is substituted, the substituent is an alkyl group having 1 to 50 carbon atoms, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio. Group, arylalkenyl group, arylalkynyl group, amino group, amino group substituted with a substituent, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, A monovalent heterocyclic group, a carboxyl group, a carboxyl group substituted with a substituent, a cyano group, or a nitro group is preferable, and an alkyl group having 1 to 50 carbon atoms is more preferable.

Among these, L ₁ and L ₂ are a single bond, a phenylene group, a biphenylene group, a fluorenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a naphthalsenylene group, a pyrenylene group, a terphenylene group, a tolylene group, and a t-butylphenylene group Or a (phenylpropyl)phenylene group is preferable, a single bond, a phenylene group, a biphenylene group, a terphenylene group, or a fluorenylene group is more preferable, and a single bond or a phenylene group is particularly preferable.

In formula (B), Z _{1 to} Z ₈ constituting the nitrogen-containing aromatic heterocycle are each independently a nitrogen atom or —CH═. _Here, one of Z 5 to Z ₈ are -CH = a is and hydrogen atoms of the -CH = is replaced by _{-L 2 -N (Ar 200) (} Ar 300), _i.e., Z 5 to Z ₈ either _{-C [-L 2 -N (Ar 200} ) (Ar 300)] is =.

In formula (B), R ₁₀₀ and R ₂₀₀ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms. Group, substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or substituted or unsubstituted monovalent aromatic heterocyclic group having 3 to 60 ring forming atoms Is. Here, R ₁₀₀ and R ₂₀₀ may combine with each other to form a ring. Note that R ₁₀₀ and R ₂₀₀ may be the same or different. Moreover, when a is 2 or more and 4 or less, several R< ₁₀₀ > may be the same or may differ. Similarly, when b is 2 or 3, plural R _{200 s} may be the same or different.

Here, the alkyl group having 1 to 20 carbon atoms is not particularly limited, but a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group. 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-isopropylpropyl 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, 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, n-heptadecyl group, n- Examples include octadecyl group and n-eicosyl group.

The alkyl group having 1 to 20 carbon atoms is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and is preferably a linear or branched alkyl group having 1 to 8 carbon atoms. Is more preferable.

The alkoxy group having 1 to 20 carbon atoms is not particularly limited, but includes methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, n-pentoxy group, isopentoxy group, tert-pentoxy group, neopentoxy group, 1,2-dimethylpropoxy group, n-hexyloxy group, isohexyloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy group, 1 , 2-dimethylbutoxy group, n-heptyloxy group, 1,4-dimethylpentyloxy group, 3-ethylpentyloxy group, 2-methyl-1-isopropylpropoxy group, 1-ethyl-3-methylbutoxy group, n -Octyloxy group, 2-ethylhexyloxy group, 3-methyl-1-isopropylbutoxy group, 2-methyl-1-isopropoxy group, 1-tert-butyl-2-methylpropoxy group, n-nonyloxy group, 3, 5,5-trimethylhexyloxy group, n-decyloxy group, isodecyloxy group, n-undecyloxy group, 1-methyldecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyl Examples thereof include an oxy group, an n-pentadecyloxy group, an n-hexadecyloxy group, an n-heptadecyloxy group, an n-octadecyloxy group and an n-eicosyloxy group.

The alkoxy group having 1 to 20 carbon atoms is preferably a linear or branched alkoxy group having 1 to 20 carbon atoms, and is a linear or branched alkoxy group having 1 to 8 carbon atoms. Is more preferable.

Here, the monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms and the monovalent aromatic heterocyclic group having 3 to 60 ring atoms are a trivalent aromatic hydrocarbon group and a trivalent aromatic ring group. Except that the aromatic heterocyclic group is monovalent, it is the same as Ar ₁₀₀ in formula (B), and therefore the description thereof is omitted here. Further, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a monovalent group having 3 to 60 ring atoms. When the aromatic heterocyclic group of is substituted, the substituent is the same as the substituent of Ar ₁₀₀ in the formula (B), and therefore the description thereof is omitted here.

Of these, R ₁₀₀ and R ₂₀₀ are preferably a phenyl group or a fluorenyl group.

a is the number of R ₁₀₀ in the formula (B) bonded to the nitrogen-containing aromatic heterocycle located in the side chain, and is an integer of 0 or more and 4 or less, preferably an integer of 0 or more and 2 or less. , More preferably 0 or 1, and particularly preferably 0.

b is a number in which R ₂₀₀ in formula (B) is bonded to the nitrogen-containing aromatic heterocycle located in the side chain, and is an integer of 0 or more and 3 or less, preferably an integer of 0 or more and 2 or less. , More preferably 0 or 1, and particularly preferably 0.

Here, when a is an integer of 1 or more and 4 or less, any of Z _{1 to} Z ₄ is —CH═, and the hydrogen atom of the —CH═ is replaced with R ₁₀₀ . Therefore, the substituents (Z _{1 to} Z ₄ ) substituted with R ₁₀₀ are —CH═. Similarly, when b is an integer of 1 or more and 3 or less, any of Z _{5 to} Z ₈ is -CH=, and the hydrogen atom of the -CH= is replaced by R ₂₀₀ . Therefore, the substituent (Z _{5 to} Z ₈ ) substituted with R ₂₀₀ is —CH═.

The nitrogen-containing aromatic heterocycle preferably has the structure shown below. In addition, in the following structures, * is a binding site.

In the present embodiment, X is a structural unit represented by the following formulas (2-1) to (2-6) from the viewpoint of further improving the HOMO level and the hole transporting ability and further lowering the driving voltage. Is more preferably selected from formula (2-1) below. Here, the plurality of X contained in the segment of the alternating copolymer of the structural unit represented by the above formula (A) may be the same or different.

In the above formulas (2-4) to (2-6), Ar ₄₀₀ represents a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted monovalent aromatic hydrocarbon group. It is a monovalent aromatic heterocyclic group having 3 to 60 ring atoms.

Specific examples of X are shown below. In the structure below, * means a binding site, and Alkyl means that it is substituted with an alkyl group or is unsubstituted.

In the present embodiment, the other polymer has a structural unit represented by —Y— in addition to the structural unit represented by the above formula (A). Here, the other polymer according to the present embodiment may include one type of Y or two or more types of Y as a structural unit.

The other polymer according to the present embodiment contains Y as a constitutional unit and thus has excellent solubility. Therefore, when the other polymer according to this embodiment is used, a thin film can be easily formed by the coating method.

In the formula (A), Y is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a substituted or unsubstituted 2 or more ring-forming atoms having 3 or more and 60 or less atoms. It is a valent aromatic heterocyclic group.

Here, the divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group are of the formula (B) except that the trivalent aromatic hydrocarbon group and the trivalent aromatic heterocyclic group are divalent. Since it is the same as Ar _{100 in (} ), the description is omitted here.

Among these, Y is a phenylene group, a fluorenediyl group, a biphenylene group, a fluorenylene group, a naphthylene group, an anthrylene group, a phenanthrylene group, a naphthalcenylene group, a pyrenylene group, and a terphenylene, from the viewpoint of improving the solubility of other polymers. A group, a tolylene group, a t-butylphenylene group, or a (phenylpropyl)phenylene group is preferable, a phenylene group or a fluorenediyl group is more preferable, and a phenylene group is particularly preferable.

Further, when the divalent aromatic hydrocarbon group or the divalent aromatic heterocyclic group is substituted, the substituent is the same as the substituent in Ar ₁₀₀ in the formula (B), and therefore, here, The description is omitted.

Of these, from the viewpoint of improving the solubility of the other polymer according to the present embodiment, the substituent is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and 3 or more carbon atoms. A linear or branched alkyl group having 10 or less is more preferable, and a linear alkyl group having 6 to 8 carbon atoms is particularly preferable.

From the viewpoint of adjusting the HOMO level, Y is preferably selected from the structural units represented by the following formulas (2-7) to (2-14). Of these, the other polymer preferably has a structural unit represented by the following formula (2-7). Here, the plurality of Y contained in the segment of the alternating copolymer of the structural unit represented by the above formula (A) may be the same or different.

In the above formulas (2-7) to (2-14), Ar _{51 to} Ar ₅₅ each independently represent a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, A substituted or unsubstituted monovalent aromatic heterocyclic group having 3 to 60 ring-forming atoms, an alkyl group having 1 to 20 carbon atoms, or a hydrogen atom,
A ₁₁ to A ₁₃ are each independently, -O -, - S -, - Se -, - CR 3 R 4 -, - SiR 3 R 4 - ( provided that, _{R 3} and _{R 4} are each independently A hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,
A _{21 to} A ₂₈ are each independently -CR ₅ =, -N=, -SiR ₅ = (wherein R ₅ is a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl group, a substituted or non-substituted group). It is a substituted aryl group or a substituted or unsubstituted heteroaryl group.

Specific examples of Y are shown below. In addition, in the following structure, A is O, S, or Se, and when a plurality of Xs are present, the plurality of Xs may be the same or different. Further, * is a binding site, and Alkyl means that it is substituted with an alkyl group.

The other polymer according to this embodiment is preferably represented by the following formula (C). This prolongs the light emission life of the quantum dot light emitting device.

In the above formula (C), E is each independently a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted ring-forming atom number. A monovalent aromatic heterocyclic group of 3 or more and 60 or less,
m is an integer of 2 or more, and a plurality of Xs and Ys may be the same or different, independently of each other.

Here, the monovalent aromatic hydrocarbon group and the monovalent aromatic heterocyclic group have the formula (B) except that the trivalent aromatic hydrocarbon group and the trivalent aromatic heterocyclic group are divalent. Since it is the same as Ar _{100 in (} ), the description is omitted here. Further, the substituent in the case where the monovalent aromatic hydrocarbon group or the monovalent aromatic heterocyclic group is substituted is the same as the substituent in Ar ₁₀₀ in the formula (B), and therefore, here, The description is omitted.

Specific examples of E (terminal group) in the above formula (3) are shown below. In addition, in the following structures, * is a binding site.

The other polymer according to this embodiment can be used as a material for an electroluminescence (EL) device, but is particularly effective as a hole transport material for an EL device including quantum dots.

The number average molecular weight (Mn) of the other polymer according to this embodiment is preferably 10,000 or more and 1,000,000 or less, and more preferably 30,000 or more and 500,000 or less. This makes it possible to form a thin film having a uniform thickness by appropriately adjusting the viscosity of the coating liquid for forming a thin film containing another polymer (for example, a hole injection layer and a hole transport layer). Is.

Further, the weight average molecular weight (Mw) of the other polymer according to the present embodiment is preferably 10,000 or more, more preferably 50,000 or more and 500,000 or less. This makes it possible to form a thin film having a uniform thickness by appropriately adjusting the viscosity of the coating liquid for forming a thin film containing another polymer (for example, a hole injection layer and a hole transport layer). Is.

The other polymer according to this embodiment can be synthesized by appropriately combining known organic synthesis reactions. A person skilled in the art who refers to the examples described later can easily understand the specific method for synthesizing the other polymer according to the present embodiment. Specifically, the other polymer according to the present embodiment includes one or more kinds of monomers (1) represented by the following formula (D) and one or more kinds of monomers (1) represented by the following formula (E). 2) can be synthesized by copolymerizing 2) in a molar ratio of 1:1. The monomers (1) and (2) can be synthesized by appropriately combining known organic synthesis reactions. Further, the monomers (1) and (2) can be identified by using a known analysis method (for example, NMR, LC-MS).

In the above formulas (D) and (E), Ar ₁₀₀ , Ar ₂₀₀ , Ar ₃₀₀ , L ₁ , L ₂ , R ₁₀₀ , R ₂₀₀ , a and b are the same as the above formula (B). W _{1 to} W ₄ are each independently a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, particularly bromine atom) or a group having the following structure. In the structure below, R _{A to} R _D are each independently an alkyl group having 1 to 3 carbon atoms. Preferably, R _{A to} R _D are methyl groups.

In the LED composition according to the present embodiment, the mixing ratio of the silicon-containing arylamine polymer and the other polymer is not particularly limited as long as the effect of the present invention is not impaired. The mixing ratio of the silicon-containing arylamine polymer and the other polymer (silicon-containing arylamine polymer:other polymer (mass ratio)) is preferably more than 1:9 and less than 6:4, and more preferably 2:. It is 8 or more and 4:6 or less. With such a mixing ratio, the charge mobility can be adjusted more easily, and the performance of the LED element (for example, luminous efficiency and luminous lifetime) can be further improved.

[Electroluminescence element]
As described above, the silicon-containing arylamine polymer or the silicon-containing arylamine polymer and the other polymer (composition for LED) according to the present embodiment are suitably used for the electroluminescence device. That is, an electroluminescence device comprising a pair of electrodes and one or more organic films arranged between the electrodes and containing the silicon-containing arylamine polymer or the electroluminescence device material of the present embodiment or the composition for LED are provided. provide. Such an electroluminescent element can exhibit excellent luminous efficiency at a low driving voltage. Therefore, in a fourth aspect, the present invention provides an electroluminescent device including a first electrode, a second electrode, and one or more organic films arranged between the first electrode and the second electrode. An electroluminescent device, wherein at least one layer of the organic film comprises the silicon-containing arylamine polymer of the present invention or the composition for producing an electroluminescent device of the present invention. The object (or effect) of the present invention can also be achieved by such an electroluminescent element according to the present embodiment. As a preferable mode of the above aspect, the electroluminescent element further includes a light emitting layer which is disposed between the electrodes and includes a light emitting material capable of emitting light from triplet excitons. The electroluminescent element of the present embodiment is an example of the electroluminescent element according to the present invention.

Further, the present embodiment includes a pair of electrodes and one or more organic films disposed between the electrodes and containing the silicon-containing arylamine polymer of the present embodiment or the silicon-containing arylamine polymer and another polymer. Provided is a method for manufacturing an electroluminescence element, which comprises forming at least one layer of the organic film by a coating method. Further, according to this method, the present embodiment provides an electroluminescent element in which at least one layer of the organic film is formed by a coating method.

The electroluminescent element material (EL element material) according to this embodiment has excellent solubility in an organic solvent. Therefore, the EL material element material according to the present embodiment is particularly preferably used for manufacturing an element (particularly a thin film) by a coating method (wet process). Therefore, the present embodiment provides a liquid composition containing the silicon-containing arylamine polymer or the silicon-containing arylamine polymer of the present embodiment and another polymer, and a solvent or a dispersion medium. Such a liquid composition is an example of the liquid composition according to the present invention.

Moreover, as described above, the electroluminescent element material according to the embodiment is preferably used for manufacturing an element (particularly a thin film) by a coating method (wet process). In view of the above, the present embodiment provides a thin film containing the silicon-containing arylamine polymer or the silicon-containing arylamine polymer of the present embodiment and another polymer. Such a thin film is an example of the thin film according to the present invention.

Further, the EL device material or the LED composition according to the present embodiment has excellent charge mobility. Therefore, it can be suitably used in the formation of any organic film such as a hole injection material, a hole transport material, or a light emitting material (host). Among these, from the viewpoint of hole transportability, it is preferably used as a hole injection material or a hole transport material, and particularly preferably used as a hole transport material.

That is, the present embodiment contains a silicon-containing arylamine polymer or a silicon-containing arylamine polymer and another polymer, and at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material. A composition is provided. Here, the light emitting material contained in the composition is not particularly limited, but may contain an organic metal complex (light emitting organic metal complex compound) or semiconductor nanoparticles (semiconductor inorganic nanoparticles).

[Electroluminescence element]
Hereinafter, the electroluminescent element according to the present embodiment will be described in detail with reference to FIG. 1. FIG. 1 is a schematic diagram showing an electroluminescent element according to this embodiment. Note that in this specification, "electroluminescence element" may be abbreviated as "EL element".

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

Here, the silicon-containing arylamine polymer or the silicon-containing arylamine polymer of the present embodiment and the other polymer are, for example, any organic film (organic layer) disposed between the first electrode 120 and the second electrode 180. ) Included. Specifically, the silicon-containing arylamine polymer or the silicon-containing arylamine polymer and other polymers are used as the hole injection material, the hole injection layer 130, the hole transport material, the hole transport layer 140, or the light emitting material (host). It is preferably included in the light emitting layer 150. More preferably, the silicon-containing arylamine polymer or the silicon-containing arylamine polymer and other polymers are 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 preferred that silicon-containing arylamine polymers or silicon-containing arylamine polymers and other polymers are included in hole transport layer 140 as hole transport materials. That is, in a preferred embodiment of the present invention, the silicon-containing arylamine polymer or the organic film containing the silicon-containing arylamine polymer and another polymer is a hole transport layer, a hole injection layer or a light emitting layer. In a more preferred form of the invention, the organic film comprising a silicon-containing arylamine polymer or a silicon-containing arylamine polymer and other polymers is a hole transport layer or hole injection layer. In a particularly preferred form of the invention, the organic film comprising the silicon-containing arylamine polymer or the silicon-containing arylamine polymer and other polymers is the hole transport layer.

An organic film containing the silicon-containing arylamine polymer/EL device material/LED composition (combination of the silicon-containing arylamine polymer and another polymer) of the present embodiment is formed by a coating method (solution coating method). It 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, or a roll. Roll coat method, wire bar coat method, dip coat method, spray coat method, screen printing method, flexographic printing method, offset (offset) method. ) A film is formed by using a solution coating method such as a printing method or an ink jet (ink jet) printing method.

The solvent used in the solution coating method may be any solvent that can dissolve the silicon-containing arylamine polymer/EL device material/LED composition (combination of the silicon-containing arylamine polymer and another polymer). Any solvent can be used, and can be appropriately selected depending on the type of the silicon-containing arylamine polymer or other polymer used. For example, toluene, xylene, ethylbenzene, diethylbenzene, methicylene, propylbenzene, cyclohexylbenzene, dimethoxybenzene, anisole, ethoxytoluene, phenoxytoluene, isopropylbiphenyl, dimethylanisole, phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, Cyclohexane etc. can be illustrated. The amount of the solvent used is not particularly limited, but considering the ease of application and the like, the concentration of the silicon-containing arylamine polymer or the silicon-containing arylamine polymer and the other polymer is preferably 0.1% by mass or more and 10% by mass or more. % Or less, more preferably 0.5% by mass or more and 5% by mass or less. In the latter case, the concentration means the total concentration of the silicon-containing arylamine polymer and the other polymer.

The method for forming a layer other than the organic film containing the silicon-containing arylamine polymer/EL element material/LED composition (combination of the silicon-containing arylamine polymer and another polymer) is not particularly limited. Layers other than the organic film containing the silicon-containing arylamine polymer/EL device material/LED composition (combination of the silicon-containing arylamine polymer and another polymer) of the present embodiment are formed by, for example, a vacuum deposition method. Or may be formed by a solution coating method.

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

The 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, a conductive compound, or the like having a large work function. For example, the first electrode 120 includes indium tin oxide (In ₂ O ₃ —SnO ₂ :ITO), indium zinc oxide (In ₂ O ₃ —ZnO), tin oxide (SnO 2) and zinc oxide, which are excellent in transparency and conductivity. It may be formed as a transmissive electrode by (ZnO) or the like. 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. Further, after forming the first electrode 120 on the substrate 110, cleaning and UV-ozone treatment may be performed if necessary.

The 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 applies below).

The hole injection layer 130 can be formed of a known hole injection material. Known hole injection materials for forming the hole injection layer 130 include, for example, triphenylamine-containing polyether ketone (poly(ether ketone)-containg triphenylamine:TPAPEK) and 4-isopropyl-4′-methyldiphenyliodonium 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/dodecylbenzenesulphonic acid, poly(3,4-ethylenediene) Oxythiophene)/poly(4-styrenesulfonate) (poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate): PEDOT/PSS), and polyaniline/10-camphorsulfonic acid acid) and the like.

The 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 may be formed to have a thickness of, for example, 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 silicon-containing arylamine polymer of the present embodiment or the silicon-containing arylamine polymer and another polymer. According to this method, it is possible to improve the current efficiency of the EL element 100 and reduce the drive voltage. Further, since the hole transport layer can be formed by the solution coating method, it is possible to efficiently form a film in a large area.

However, when the other organic film of any of the EL devices 100 contains the silicon-containing arylamine polymer of the present embodiment or the silicon-containing arylamine polymer and another polymer, the hole transport layer 140 is a known hole transport material. May be formed in. Known hole transport materials include, for example, 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane (1,1-bis[(di-4-tolylamino)phenyl]cyclohexane: TAPC), N- Carbazole derivatives such as 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-naphthyl)-N,N'-diphenylbenzidine (N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine:NPB) etc. can be mentioned.

The 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 by a vacuum evaporation method, a spin coating method, an inkjet printing method, or the like. The light emitting layer 150 may be formed with a thickness of, for example, about 10 nm or more and about 60 nm or less, more specifically, about 20 nm or more and about 50 nm or less. As the light emitting material of the light emitting layer 150, a known light emitting material can be used. However, the light emitting material contained in the light emitting layer 150 is preferably a light emitting material capable of emitting light (that is, phosphorescence) from triplet excitons. In such a 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 structure. Preferably, the light emitting layer comprises 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 contains semiconductor nanoparticles, the EL element is a quantum dot electroluminescence element (QLED), a quantum dot light emitting element, or a quantum dot light emitting element. When the light emitting layer contains an organometallic complex, the EL device is an organic electroluminescence device (OLED).

In the form in which the light emitting layer includes semiconductor nanoparticles (QLED), the light emitting layer is 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 constraint effect. The diameter of the semiconductor nanoparticles (quantum dots) is not particularly limited, but is about 1 nm or more and 10 nm or less.

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

In the wet chemical process, when the crystal grows, the organic solvent is naturally coordinated with the surface of the quantum dot crystal, and acts as a dispersant to control the crystal growth. Therefore, in the wet chemical process, compared with vapor phase deposition methods such as metal organic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE), it is easier and cheaper to use semiconductor nano-layers. The growth of particles can be controlled.

By adjusting the size of the semiconductor nanoparticles (quantum dots), the energy band gap can be adjusted, and light in various wavelength bands can be obtained in the light emitting layer (quantum dot light emitting layer). Therefore, the use of multiple quantum dots of different sizes allows for displays that emit (or emit) light of multiple wavelengths. The size of the quantum dots can be selected to emit red, green, and blue light so that a color display can be constructed. Also, the sizes of the quantum dots are combined so that various colored lights emit white light.

As the semiconductor nanoparticles (quantum dots), a semiconductor substance selected from the group consisting of II-VI group semiconductor compounds; III-V group semiconductor compounds; IV-VI group semiconductor compounds; IV group elements or compounds; and combinations thereof. Etc. can be used.

The II-VI group semiconductor compound is not particularly limited, but is, for example, CdSe, CdTe, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, or a two-element compound selected from the group consisting of these; CdSeS, CdSeTe, CdSTe, ZnSeS, ZnTeSe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe and a mixture of these compounds, which are selected from the group consisting of three elements: HgZnS, HgZnSe and HgZnSe, HgZnSe and HgZnSe. , CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZnSeTe, HgZnSTe, and a group of four element compounds selected from the group consisting of a mixture thereof.

The III-V semiconductor compound is not particularly limited, but is selected from the group consisting of, for example, GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, and a mixture thereof. Binary compound; three-element 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 four elements selected from the group consisting of GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb, and mixtures thereof. It

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

The Group IV element or compound is not particularly limited, but is, for example, one element compound selected from the group consisting of Si, Ge, and a mixture thereof; and two elements selected from the group consisting of SiC, SiGe, and a mixture thereof. It is selected from the group consisting of elemental compounds.

Semiconductor nanoparticles (quantum dots) can have a homogeneous single structure or a core-shell double structure. The core shell can include different materials. The materials forming the respective cores and shells may be composed 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, a structure such as ZnTeSe/ZnSe/ZnS, InP/ZnSe/ZnS, CdSe/ZnS, InP/ZnS is preferable.

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

Moreover, in the form (OLED) in which the light emitting layer contains an organometallic complex, the light emitting layer 150 is used as 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)aluminium (Alq3), 4,4'-bis(carbazol-9-yl)biphenyl (4,4'-bis(carbazol -9-yl)biphenyl: CBP), 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(naphth- 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) may be included.

In addition, the light emitting layer 150 includes, as a dopant material, for example, perylene and its derivative, rubrene and its derivative, coumarin and its derivative, 4-dicyanomethylene-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]picolinate Iridium (III) (bis[2-(4,6-difluorophenyl)pyridinate]picolinate iridium(III):FIrpic), bis(1-phenylisoquinoline)(acetylacetonate)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( An iridium (Ir) complex such as 2-(3-p-xyyl)phenyl)pyridineiridium (III), an osmium (Os) complex, a platinum complex, or the like may be included. Of these, the light emitting material is preferably a light emitting organometallic complex compound.

The method for forming the light emitting layer is not particularly limited. It can be formed by applying a coating liquid containing semiconductor nanoparticles or an organometallic complex (solution coating method). At this time, a solvent that does not dissolve the materials in the hole transport layer (hole transport material, particularly silicon-containing arylamine polymer or silicon-containing arylamine polymer and other polymers) should be selected as the solvent constituting the coating liquid. Is preferred.

The electron transport layer 160 is formed on the light emitting layer 150. The electron-transporting layer 160 is a layer having a function of transporting electrons, and is formed by a vacuum evaporation method, a spin coating method, an inkjet method, or the like. The electron transport layer 160 may be formed to have a thickness of, for example, 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-quinolinolato) lithium (lithium quinolate) (Liq), tris(8-quinolinato)aluminium (Alq ₃ ), and nitrogen-containing aromatic ring. And the like. 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)-1,3 Compounds containing a triazine ring, such as 5-triazine (2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine), 2 -(4-(N-phenylbenzinazolyl-1-yl-phenyl)-9,10-dinaphthylanthracene (2-(4-(N-phenylbenzoimidazolyl-1-yl-phenyl)-9,10-dinaphthylanthracene ), 1,3,5-tris(N-phenyl-benzimidazol-2-yl)benzene (1,3,5-tris(N-phenyl-benzimidazol-2-yl)benzene:TPBI) ) A compound containing a ring, etc. The above-mentioned electron transport materials may be used alone or as a mixture of two or more kinds.

An electron injection layer 170 is formed on the electron transport layer 160. 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 with 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. Any material known as a material for forming the electron injection layer 170 can 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), It may be formed of cesium fluoride (CsF), lithium oxide (Li ₂ O), barium oxide (BaO), or the like.

The 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, a conductive compound, or the like having a low work function. For example, the second electrode 180 may be a metal such as lithium (Li), magnesium (Mg), aluminum (Al), calcium (Ca), or aluminum-lithium (Al-Li), magnesium-indium (Mg-In), The reflective electrode may be formed of an alloy such as magnesium-silver (Mg-Ag). 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 is a transmissive electrode made of a transparent conductive film such as a thin film of 20 nm or less of the above metal material, indium tin oxide (In ₂ O ₃ —SnO ₂ ) and indium zinc oxide (In ₂ O ₃ —ZnO). May be formed as.

The EL element 100 according to the present embodiment has been described above as an example of the electroluminescent element according to the present invention. The organic EL device 100 according to the present embodiment is provided with an organic film containing a silicon-containing arylamine polymer or a silicon-containing arylamine polymer and another polymer (in particular, a hole transport layer or a hole injection layer), thereby improving the luminous efficiency. It is possible to further improve (current efficiency) and reduce the driving voltage. Further, particularly in the latter case, the luminous efficiency can be maintained for a long period of time (the luminous lifetime can be improved).

The laminated structure of the EL element 100 according to this embodiment is not limited to the above example. The EL element 100 according to the present embodiment may be formed with another known laminated structure. For example, in the EL device 100, one or more layers 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 layer may be provided. May be. In addition, each layer of the EL element 100 may be formed as a single layer or a plurality of layers.

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

Furthermore, the silicon-containing arylamine polymer or the silicon-containing arylamine polymer according to the present embodiment and other polymers can be applied to electroluminescent devices other than the above QLED or OLED. Other electroluminescent elements to which the silicon-containing arylamine polymer or the silicon-containing arylamine polymer according to the present embodiment and other polymers can be applied are not particularly limited, and examples thereof include organic-inorganic perovskite light-emitting elements. To be

The effects of the present invention will be described using the following examples and comparative examples. However, the technical scope of the present invention is not limited to the following examples. In the following examples, unless otherwise specified, the operation was performed at room temperature (25°C). Further, unless otherwise specified, “%” and “part” mean “mass %” and “part by mass”, respectively.

Synthesis example 1
(Synthesis of Compound A-1 and Compound A-2)
Compound A-1 and compound A-2 were synthesized according to the following reactions.

Bis(4-bromophenyl)diphenylsilane (10.5 g), 4′-propyl-[1,1′-biphenyl]-4-amine (10.5 g), tris( Dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ )(0.371 g), 1,1′-bis(diphenylphosphino)ferrocene (DPPF) (0.448 g), sodium tert-butoxide (t-BuONa). (5.83 g) and toluene (200 mL) were added, and the mixture was heated at 95° C. for 2 hours. The mixture was allowed to cool to room temperature (25° C.; hereinafter the same), and the insoluble material was filtered off with Celite (registered trademark, the same hereinafter). The solvent was distilled off under reduced pressure from the filtrate, and the residue was purified by column chromatography to obtain compound A-1 (11.5 g).

Compound A-1 (10.0 g), 4-bromo-4′-iodo-1,1′-biphenyl (14.2 g), tris(dibenzylideneacetone)dipalladium( _{pd 2 (dba) 3) (} 0.606g), 1,1'- bis (diphenylphosphino) ferrocene (DPPF) (1.47 g), sodium tert- butoxide (t-BuONa) (5.09 g), xylene (200 mL) was charged and heated at 120° C. for 2 hours. The mixture was allowed to cool to room temperature and the insoluble material was filtered off with Celite. The solvent was distilled off under reduced pressure from the filtrate, and the residue was purified by column chromatography to obtain compound A-2 (9.50 g).

Synthesis example 2
(Synthesis of Compound B-1)
Compound B-1 was synthesized according to the following reaction.

N,N′-((diphenylsilanediyl)bis(4,1-phenylene)))(bis(4′-propyl[1,1′-biphenyl]-4-amine was added to a four-necked flask replaced with argon. (10.0 g), 4-bromo-1-iodobenzene (11.2 g), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ )(0.606 g), 1,1′-bis(diphenylphos) Fino)ferrocene (DPPF) (1.47 g), sodium tert-butoxide (t-BuONa) (5.09 g) and xylene (130 mL) were added and heated at 120° C. for 2 hours. The solvent was distilled off from the filtrate under reduced pressure and the residue was purified by column chromatography to obtain compound B-1 (8.60 g).

Synthesis example 3
(Synthesis of Compound C-1)
Compound C-1 was synthesized according to the following reaction.

Bis(4-bromophenyl)diphenylsilane (10.5 g), 4′-hexyl-[1,1′-biphenyl]-4-amine (12.6 g), tris( Dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ )(0.371 g), 1,1′-bis(diphenylphosphino)ferrocene (DPPF) (0.448 g), sodium tert-butoxide (t-BuONa). (5.83 g) and toluene (200 mL) were added, and the mixture was heated at 95° C. for 2 hours. The mixture was allowed to cool to room temperature and the insoluble material was filtered off with Celite. The solvent was distilled off under reduced pressure from the filtrate and purified by column chromatography to obtain N,N′-((diphenylsilanediyl)bis(4,1-phenylene))(bis(4′-hexyl[1,1′- Biphenyl]-4-amine)) (12.5 g) was obtained.

In a four-necked flask replaced with argon, N,N'-((diphenylsilanediyl)bis(4,1-phenylene)))(bis(4'-hexyl[1,1'-biphenyl]-4-amine (10.0 g), 4-bromo-1-iodobenzene (14.2 g), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ )(0.606 g), 1,1′-bis(diphenyl) Phosphino)ferrocene (DPPF) (1.47 g), sodium tert-butoxide (t-BuONa) (5.09 g), and xylene (200 mL) were added, and the mixture was heated at 120° C. for 2 hours. The product was separated by filtration through Celite, the solvent was distilled off from the filtrate under reduced pressure, and the residue was purified by column chromatography to obtain a compound C-1 (10.80 g).

Synthesis example 4
(Synthesis of Compound D-1 and Compound D-2)
Compound D-1 and compound D-2 were synthesized according to the following reactions.

In a four-necked flask purged with argon, bis(4-bromophenyl)bis(4-hexylphenyl)silane (20.0 g), 4'-propyl-[1,1'-biphenyl]-4-amine (15 .9 g), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ )(0.552 g), 1,1′-bis(diphenylphosphino)ferrocene (DPPF) (0.669 g), sodium tert- Butoxide (t-BuONa) (5.83 g) and toluene (200 mL) were added, and the mixture was heated at 95°C for 2 hours. The mixture was allowed to cool to room temperature and the insoluble material was filtered off with Celite. The solvent was distilled off under reduced pressure from the filtrate and the residue was purified by column chromatography to obtain compound D-1 (22.8 g).

In a four-necked flask substituted with argon, compound D-1 (20.0 g), 4-bromo-4′-iodobenzene (15.2 g), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ ). (0.396 g), 1,1′-bis(diphenylphosphino)ferrocene (DPPF) (0.480 g), sodium tert-butoxide (t-BuONa) (4.16 g), xylene (200 mL) were added, and 120 Heated at °C for 2 hours. The mixture was allowed to cool to room temperature and the insoluble material was filtered off with Celite. The solvent was distilled off under reduced pressure from the filtrate, and the residue was purified by column chromatography to obtain compound D-2 (20.5 g).

Synthesis example 5
(Synthesis of Compound E-1 and Compound E-2)
Compound E-1 and compound E-2 were synthesized according to the following reactions.

Under an argon atmosphere, 1,4-dibromo-2,5-dihexylbenzene (20.0 g), 4-chlorophenylboronic acid (23.2 g), tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ) (2). 0.85 g), sodium carbonate (Na ₂ CO ₃ ) (52.4 g), toluene (500 mL), ethanol (250 mL), water (125 mL) were added to the four-necked flask, and the mixture was stirred at 100° C. for 15 hours. The reaction solution was cooled to room temperature and the organic layer was separated. Further, the aqueous layer was extracted with toluene (100 mL×3), combined with the organic layer, washed with water (100 mL×3), and filtered using Celite and silica gel. The solvent was distilled off under reduced pressure, toluene (100 mL) and activated clay (10 g) were added, the mixture was refluxed for 30 minutes, and filtration with Celite was repeated twice. The solvent was evaporated under reduced pressure, ethanol (50 mL) was added to the obtained solid, and the mixture was refluxed for 30 minutes. The solid was filtered off and dried in vacuum to obtain monomer E-1 (18.5 g).

Compound E-1 (15.0 g) obtained above, 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1 under an argon atmosphere. ,3,2-Dioxaborolane (22.5 g), tris(dibenzylideneacetone)dipalladium (Pd ₂ (dba) ₃ )(1.46 g), 2-dicyclohexylphosphino-2′,4′,6′-tri Isopropylbiphenyl (2.29 g), potassium acetate (AcOK) (18.9 g) and 1,4-dioxane (320 mL) were placed in a four-necked flask and heated at 100° C. for 3 hours. The reaction solution was cooled to room temperature, the solvent was evaporated under reduced pressure, and filtered using toluene (300 mL) and Celite. The operation of adding activated carbon (10 g) to the filtrate and refluxing for 30 minutes was repeated twice. The solvent was distilled off under reduced pressure, and the obtained solid was repeatedly recrystallized using a hexane/ethanol mixed solvent and dried under vacuum. This gives the compound E-2 [2,2′-(2,5-dihexyl-[1,1′:4′,1″-terphenyl]4,4″-diyl)bis(4,4,5,5 5-Tetramethyl-1,3,2-dioxaborolane)] (19.5 g) was obtained.

Synthesis example 6
(Synthesis of Compound F-1 and Compound F-2)
Compound F-1 and compound F-2 were synthesized according to the following reactions.

In a four-necked flask substituted with argon, bis(4-bromophenyl)-bis(4-hexylphenyl)silane (6.6 g), 4-aminobiphenyl (4.5 g), tris(dibenzylideneacetone)dipalladium. (Pd ₂ (dba) ₃ ) (0.183 g), 1,1′-bis(diphenylphosphino)ferrocene (DPPF) (0.222 g), sodium tert-butoxide (t-BuONa) (1.92 g), Toluene (120 mL) was added and heated at 95° C. for 7 hours. The mixture was allowed to cool to room temperature and the insoluble material was filtered off with Celite. The solvent was distilled off from the filtrate under reduced pressure and the residue was purified by column chromatography to obtain monomer F-1 (6.0 g).

Compound F-1 (5.5 g) obtained above, 1-bromo-4-iodo-benzene (5.5 g), tris(dibenzylideneacetone)dipalladium( Pd ₂ (dba) ₃ ) (0.300 g), 1,1′-bis(diphenylphosphino)ferrocene (DPPF) (0.73 g), sodium tert-butoxide (t-BuONa) (1.9 g), xylene. (60 mL) was added, and the mixture was heated at 105° C. for 7 hours. The mixture was allowed to cool to room temperature, and the insoluble material was filtered off with Celite. The solvent was distilled off under reduced pressure from the filtrate and the residue was purified by column chromatography to obtain compound F-2 (6.9 g).

Synthesis example 7
(Synthesis of Compound G-1)
Compound G-1 was synthesized according to the following reaction.

1,4-dihexyl-2,5-dibromobenzene (8.08 g, 20.0 mmol), bis(pinacolate diboron) (4,4,4′,4′,5) in a reaction vessel under an argon atmosphere. , 5,5',5'-Octamethyl-2,2'-bi-1,3,2-dioxaborolane) (12.19 g, 48.0 mmol), [1,1'-bis(diphenylphosphino)ferrocene] Palladium (II) dichloride (PdCl ₂ (dppf)) (0.98 g, 1.2 mmol), potassium acetate (KOAc) (11.78 g, 120.0 mmol), and dioxane (100 ml) were added and mixed, and then heated. The mixture was stirred under reflux for 6 hours. Next, toluene and water were added, and after liquid separation, it was washed with water. Next, sodium sulfate and activated carbon were added, and the mixture was stirred and then filtered through Celite (registered trademark). Then, the filtrate was concentrated to obtain a crude product (11.94 g). Next, the crude product was recrystallized with hexane and then washed with methanol. Compound G-1 (4.23 g) was obtained by drying the obtained crystal under reduced pressure. The structure of the obtained compound G-1 was identified by a nuclear magnetic resonance apparatus ( ¹ H-NMR).

Synthesis example 8
(Synthesis of Compound H-1 and Compound H-2)
Compound H-1 and compound H-2 were synthesized according to the following reactions.

Under an argon atmosphere, 2-amino-N-[(1,1′-biphenyl)-4-yl]-N-(4-bromophenyl)-9,9-dimethylfluorene (15.00 g, 29.04 mmol), 3-(4,4,5,5,-tetramethyl-1,3,2-dioxaborolan-2-yl)carbazole (7.66 g, 26.14 mmol), bis(triphenylphosphine)palladium. (II) dichloride _{(Pd (PPh 3) 2 Cl} 2) (0.41g, 0.58mmol), sodium carbonate _{(Na 2 CO 3) (7.70g} , 72.61mmol), dioxane (290 ml), water (145 ml ) Was added and then mixed. Next, the mixture was stirred at 85° C. for 4 hours, and after the reaction was completed, the reaction mixture was allowed to cool to room temperature. Next, the reaction mixture was filtered using Celite (registered trademark), and impurities were filtered off. Next, the solvent was distilled off from the filtrate, and the residue was purified by column chromatography to obtain compound H-1 (12.7 g). The structure of the obtained compound H-1 was identified by a nuclear magnetic resonance apparatus ( ¹ H-NMR).

Compound H-1 (7.00 g, 11.6 mmol), 1,3-dibromo-5-iodobenzene (4.62 g, 12.77 mmol), and copper(I) iodide ( CuI) (0.11 g, 0.58 mmol), trans-1,2-cyclohexanediamine (0.29 g, 2.55 mmol), sodium tert-butoxide (t-BuONa) (2.23 g, 23.23 mmol), dioxane. (35 ml) was added and then mixed. Then, the mixture was stirred at 90° C. for 6 hours, and after the reaction was completed, the reaction mixture was allowed to cool to room temperature. Then, the reaction mixture was filtered using Celite (registered trademark), and impurities were filtered off. Next, the solvent was distilled off from the filtrate, and the residue was purified by column chromatography to obtain compound H-2 (6 g). The structure of the obtained compound H-2 was identified by a nuclear magnetic resonance apparatus ( ¹ H-NMR).

Synthesis Example 9
Under an argon atmosphere, compound G-1 (2.61 g) synthesized in Synthesis Example 7 above, compound H-2 (4.39 g) synthesized in Synthesis Example 8 above, palladium acetate (11.8 mg), tris(2-). After adding methoxyphenyl)phosphine (111 mg), toluene (70 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (27.0 g), the mixture was heated under reflux for 6 hours. Next, phenylboronic acid (63.6 g), tetrakis(triphenylphosphine)palladium (121 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (27.0 g) were added, and the mixture was heated under reflux for 7 hours. Next, the aqueous layer was removed from the reaction mixture, sodium N,N-diethyldithiocarbamate trihydrate (17.7 g) and ion-exchanged water (70 mL) were added, and the mixture was stirred at 85° C. for 6 hr. Next, the reaction mixture was separated into an organic layer and an aqueous layer, and the organic layer was sequentially washed with water, a 3% by mass acetic acid aqueous solution, and water. Next, the organic layer was dropped into methanol to cause precipitation, which was filtered off and dried to obtain a crude product. Next, the crude product was dissolved in toluene and purified using a column chromatograph packed with silica gel/alumina, and then the solvent was distilled off under reduced pressure. Next, the obtained liquid was dropped into methanol to cause precipitation, which was filtered off and dried to obtain a polymer compound P-9 (3.24 g). The number average molecular weight (Mn) and dispersity (Mw/Mn) of the obtained polymer compound P-9 were measured by SEC. As a result, the number average molecular weight (Mn) and Mw/Mn of the polymer compound P-9 were 95,900 and 4.77, respectively.

The polymer compound P-9 thus obtained is presumed to be a polymer compound having the following constitutional units from the charging ratio of the monomers.

Example 1
Compound A-2 synthesized in Synthesis Example 1 (2.13 g) and 2,2′-(2,5-dihexyl-1,4-phenylene)bis(4,4,5,5-tetramethyl) under an argon atmosphere. 1,3,2-dioxaborolane) (Compound G-1 synthesized in Synthesis Example 7) (0.837 g), palladium acetate (3.9 mg), tris(2-methoxyphenyl)phosphine (37.0 mg), toluene ( 60 mL) and a 20 mass% tetraethylammonium hydroxide aqueous solution (9.03 g) were added to a four-necked flask, and the mixture was stirred at 85°C for 6 hours. Next, phenylboronic acid (24.2 mg), tetrakis(triphenylphosphine)palladium(0) (40.5 mg) and 20 mass% tetraethylammonium hydroxide aqueous solution (9.03 g) were added, and the mixture was stirred for 3 hours. Then, sodium N,N-diethyldithiocarbamate trihydrate (5.92 g) dissolved in ion-exchanged 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 acetic acid aqueous solution, and water. The organic layer was passed through column chromatography packed with silica gel/alumina, and the solvent was evaporated under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was dissolved in toluene. Next, this solution was added dropwise to methanol for precipitation, and the precipitated solid was separated by filtration and dried to obtain a polymer compound P-1 (1.19 g). The number average molecular weight (Mn) and the dispersity (Mw/Mn) of the obtained polymer compound P-1 were measured by SEC. As a result, the (Mn) and Mw/Mn of the polymer compound P-1 were 106,000 and 1.94, respectively.

The polymer compound P-1 thus obtained is presumed to be a polymer compound having the following constitutional units from the charging ratio of the monomers.

Example 2
Compound B-1 (2.13 g) synthesized in Synthesis Example 2 and 2,2′-(2,5-dihexyl-1,4-phenylene)bis(4,4,5,5-tetra under an argon atmosphere. Methyl-1,3,2-dioxaborolane) (Compound G-1 synthesized in Synthesis Example 7) (0.999 g), palladium acetate (2.1 mg), tris(2-methoxyphenyl)phosphine (20.2 mg), Toluene (60 mL) and a 20 mass% tetraethylammonium hydroxide aqueous solution (7.61 g) were added to the four-necked flask, and the mixture was stirred at 85°C for 6 hours. Next, phenylboronic acid (23.3 mg), tetrakis(triphenylphosphine)palladium(0) (13.4 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (7.61 g) were added, and the mixture was stirred for 3 hours. Then, sodium N,N-diethyldithiocarbamate trihydrate (5.40 g) dissolved in ion-exchanged 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 acetic acid aqueous solution, and water. The organic layer was passed through column chromatography packed with silica gel/alumina, and the solvent was evaporated under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was dissolved in toluene. Next, this solution was added dropwise to methanol for precipitation, and the precipitated solid was separated by filtration and dried to obtain a polymer compound P-2 (1.19 g). The number average molecular weight (Mn) and dispersity (Mw/Mn) of the obtained polymer compound P-2 were measured by SEC. As a result, (Mn) and Mw/Mn of the polymer compound P-2 were 121,000 and 1.60, respectively.

The polymer compound P-2 thus obtained is presumed to be a polymer compound having the following constitutional units from the charging ratio of the monomers.

Example 3
Compound A-1 (1.88 g) synthesized in Synthesis Example 1 above, 4,4′-dibromobiphenyl (0.623 g), tris(dibenzylideneacetone)dipalladium (41.8 mg), and tri- under an argon atmosphere. t-Butoxyphosphine (13.2 mg) and toluene (20 mL) were added to the four-necked flask, and the mixture was stirred at 65°C for 6 hours. Next, 4-bromobiphenyl (46.3 mg) was added, and the mixture was stirred for 3 hours. Then, sodium N,N-diethyldithiocarbamate trihydrate (6.81 g) dissolved in ion-exchanged 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 acetic acid aqueous solution, and water. The organic layer was passed through column chromatography packed with silica gel/alumina, and the solvent was evaporated under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was dissolved in toluene. Next, this solution was added dropwise to methanol for precipitation, and the precipitated solid was separated by filtration and dried to obtain a polymer compound P-3 (1.66 g). The number average molecular weight (Mn) and dispersity (Mw/Mn) of the obtained polymer compound P-3 were measured by SEC. As a result, (Mn) and Mw/Mn of the polymer compound P-3 were 89,000 and 1.89, respectively.

The polymer compound P-3 thus obtained is presumed to be a polymer compound having the following constitutional units from the charging ratio of the monomers.

Example 4
Compound B-1 (2.37 g) synthesized in Synthesis Example 2 and 4,4′-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) under an argon atmosphere. ) Biphenyl (0.902 g), palladium acetate (5.0 mg), tris(2-methoxyphenyl)phosphine (47.1 mg), toluene (65 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (11.4 g) were added. It was added to a four-necked flask and stirred at 85° C. for 6 hours. Next, phenylboronic acid (24.2 mg), tetrakis(triphenylphosphine)palladium(0) (31.3 g), and a 20 mass% tetraethylammonium hydroxide aqueous solution (11.4 g) were added, and the mixture was stirred for 3 hours. Then, sodium N,N-diethyldithiocarbamate trihydrate (5.40 g) dissolved in ion-exchanged 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 acetic acid aqueous solution, and water. The organic layer was passed through column chromatography packed with silica gel/alumina, and the solvent was evaporated under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was dissolved in toluene. Next, this solution was added dropwise to methanol for precipitation, and the precipitated solid was filtered and dried to obtain a polymer compound P-4 (0.78 g). The number average molecular weight (Mn) and dispersity (Mw/Mn) of the obtained polymer compound P-4 were measured by SEC. As a result, the polymer compound P-4 had (Mn) and Mw/Mn of 11,000 and 2.45, respectively.

The polymer compound P-4 thus obtained is presumed to be a polymer compound having the following constitutional units from the charging ratio of the monomers.

Example 5
In the same manner as in Example 2 except that the compound C-1 synthesized in Synthesis Example 3 was used in place of the compound B-1 in Example 2, the polymer compound P-5 was obtained (0 0.78 g). The number average molecular weight (Mn) and dispersity (Mw/Mn) of the obtained polymer compound P-5 were measured by SEC. As a result, the polymer compound P-5 had (Mn) and Mw/Mn of 73,000 and 3.70, respectively.

The polymer compound P-5 thus obtained is presumed to be a polymer compound having the following constitutional units from the charging ratio of the monomers.

Example 6
Compound D-2 (2.06 g) synthesized in Synthesis Example 4 above, 2,2′-(2,5-dihexyl-1,4-phenylene)bis(4,4,5,5-tetramethyl) under an argon atmosphere. 1,3,2-dioxaborolane) (Compound G-1 synthesized in Synthesis Example 7) (0.662 g), palladium acetate (3.7 mg), tris(2-methoxyphenyl)phosphine (34.6 mg), toluene ( 45 mL) and a 20 mass% tetraethylammonium hydroxide aqueous solution (8.44 g) were added to a four-necked flask, and the mixture was stirred at 85° C. for 6 hours. Next, phenylboronic acid (24.2 mg), tetrakis(triphenylphosphine)palladium(0) (37.9 mg) and 20 mass% tetraethylammonium hydroxide aqueous solution (8.44 g) were added, and the mixture was stirred for 3 hours. Then, sodium N,N-diethyldithiocarbamate trihydrate (5.53 g) dissolved in ion-exchanged water (20 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 acetic acid aqueous solution, and water. The organic layer was passed through column chromatography packed with silica gel/alumina, and the solvent was evaporated under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was dissolved in toluene. Next, this solution was added dropwise to methanol for precipitation, and the precipitated solid was separated by filtration and dried to obtain a polymer compound P-6 (1.44 g). The number average molecular weight (Mn) and dispersity (Mw/Mn) of the obtained polymer compound P-6 were measured by SEC. As a result, the average molecular weight (Mn) and Mw/Mn of the polymer compound P-6 were 58,000 and 1.52, respectively.

The polymer compound P-6 thus obtained is presumed to be a polymer compound having the following constitutional units from the charging ratio of the monomers.

Example 7
Compound D-2 (1.67 g) synthesized in Synthesis Example 4 and compound E-2 [2,2′-(2,5-dihexyl-[1,1′] synthesized in Synthesis Example 5 under an argon atmosphere. : 4',1"-terphenyl]4,4"-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)] (0.887 g), palladium acetate (3. 1 mg), tris(2-methoxyphenyl)phosphine (28.8 mg), toluene (50 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (7.61 g) were added to a four-necked flask and stirred at 85° C. for 6 hours. did. Next, phenylboronic acid (24.2 mg), tetrakis(triphenylphosphine)palladium(0) (31.5 mg), and a 20 mass% tetraethylammonium hydroxide aqueous solution (7.03 g) were added, and the mixture was stirred for 3 hours. Then, sodium N,N-diethyldithiocarbamate trihydrate (4.67 g) dissolved in ion-exchanged water (20 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 acetic acid aqueous solution, and water. The organic layer was passed through column chromatography packed with silica gel/alumina, and the solvent was evaporated under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was dissolved in toluene. Next, this solution was added dropwise to methanol for precipitation, and the precipitated solid was filtered and dried to obtain a polymer compound P-7 (1.36 g). The number average molecular weight (Mn) and dispersity (Mw/Mn) of the obtained polymer compound P-7 were measured by SEC. As a result, the polymer compound P-7 had (Mn) and Mw/Mn of 47,000 and 2.80, respectively.

The polymer compound P-7 thus obtained is presumed to be a polymer compound having the following constitutional units from the charging ratio of the monomers.

Example 8
As the first electrode (anode), an ITO-attached glass substrate on which indium tin oxide (ITO) was patterned with a film thickness of 150 nm was used. The glass substrate with ITO was washed successively with a neutral detergent, deionized water, water and isopropyl alcohol, and then subjected to UV-ozone treatment. Next, on this ITO-attached glass substrate, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS) (manufactured by Sigma-Aldrich) was dried to a thickness of 30 nm. After being applied by the spin coating method, it was dried. As a result, a hole injection layer having a thickness (dry film thickness) of 30 nm was formed on the glass substrate with ITO.

A 1.0% by mass toluene solution of the polymer compound P-1 (hole transport material) of Example 1 was applied onto this hole injection layer by spin coating so that the dry film thickness was 30 nm. Then, it heat-processed at 230 degreeC for 60 minute(s), and formed the positive 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.

The following structure in cyclohexane:

ZnTeSe/ZnSe/ZnS (core/shell/shell; average diameter=about 10 nm) having blue quantum dots were dispersed in an amount of 1.0% by mass to prepare a quantum dot dispersion liquid. The hole transport layer (particularly the polymer compound P-1) is not dissolved 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. The light emitted by irradiating the quantum dot dispersion liquid with ultraviolet rays 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 emission layer, lithium quinolate (Liq) and 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) (TPBI) (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.

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

Aluminum (Al) was vapor-deposited on the electron injection layer using a vacuum vapor deposition device. As a result, a second electrode (cathode) having a thickness of 100 nm was formed on the electron injection layer. Thereby, the quantum dot electroluminescent device 1 was obtained.

Example 9
A quantum dot electroluminescent device 2 was prepared in the same manner as in Example 8 except that the polymer compound P-2 in Example 2 was used instead of the polymer compound P-1. ..

Example 10
In Example 8, the quantum dot electroluminescent device 3 was produced by performing the same operation as in Example 8 except that the polymer compound P-3 of Example 3 was used instead of the polymer compound P-1. ..

Example 11
A quantum dot electroluminescent device 4 was prepared in the same manner as in Example 8 except that the polymer compound P-4 of Example 4 was used instead of the polymer compound P-1. ..

Example 12
A quantum dot electroluminescent device 5 was prepared in the same manner as in Example 8 except that the polymer compound P-5 in Example 5 was used in place of the polymer compound P-1. ..

Example 13
A quantum dot electroluminescent device 6 was prepared in the same manner as in Example 8 except that the polymer compound P-6 in Example 6 was used instead of the polymer compound P-1 in Example 8. ..

Example 14
A quantum dot electroluminescent device 7 was prepared in the same manner as in Example 8 except that the polymer compound P-7 of Example 7 was used in place of the polymer compound P-1. ..

Comparative Example 1
In Example 8, instead of the polymer compound P-1, poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4'-(N- (4-sec-Butylphenyl)diphenylamine)] (TFB) (manufactured by Luminescence Technology Corp.) was performed in the same manner as in Example 8 to fabricate a comparative quantum dot electroluminescent device 1. The number average molecular weight (Mn) and dispersity (Mw/Mn) of TFB were measured by SEC, and as a result, (Mn) and Mw/Mn of TFB were 359,000 and 3.4, respectively.

[Evaluation of quantum dot electroluminescent device 1]
Luminous efficiency of the quantum dot electroluminescent devices 1 to 4 manufactured in Examples 8 to 11 and the comparative quantum dot electroluminescent device 1 manufactured in Comparative Example 1 was evaluated by the following method.

When a voltage is applied to each quantum dot electroluminescent element using a DC constant voltage power source (manufactured by KEYENCE, source meter), a current starts to flow at a constant voltage, and the quantum dot electroluminescent element emits light. To do. The voltage at a current density of 5 mA/cm ² is defined as the drive voltage (Vop) [V]. In addition, while measuring the light emission of each element using a brightness measuring device (SR-3, manufactured by Topcom), the current was gradually increased, and the current was kept constant when the brightness reached 100 nit (cd/m ² ), put. Here, the current value per unit area (current density) is calculated from the area of each element, and the luminance (cd/m ² ) is divided by the current density (A/m ² ) to obtain the current efficiency (cd/ Calculate A). The current efficiency indicates the efficiency of converting a current into luminescence energy (conversion efficiency), and the higher the current efficiency, the higher the performance of the device.

Further, the external quantum efficiency (EQE) (%) at a luminance of 100 nit is calculated from the spectral radiance spectrum measured by the luminance measuring device, and the luminous efficiency is evaluated, assuming that the Lambertian emission is performed.

The results are shown in Table 1 below.

From the results of Table 1 above, the quantum dot electroluminescent elements 1 to 7 of the example are higher at a lower driving voltage than the comparative quantum dot electroluminescent element 1 not using the silicon-containing arylamine polymer according to the present invention. It can be seen that the performance (current efficiency, external quantum efficiency) can be exhibited.

Example 15
Compound F-2 (1.182 g) synthesized in Synthesis Example 6 and 2,2′-(2,5-dihexyl-1,4-phenylene)bis(4,4,5,5-tetra under an argon atmosphere. Methyl-1,3,2-dioxaborolane) (Compound G-1 synthesized in Synthesis Example 7) (0.502 g), palladium acetate (2.19 mg), tris(2-methoxyphenyl)phosphine (20.33 mg), Toluene (30 mL) and 20 mass% tetraethylammonium hydroxide aqueous solution (7.61 g) were added to the four-necked flask, and the mixture was refluxed for 8 hours. Next, phenylboronic acid (23.3 mg), bis(triphenylphosphine)palladium(II) dichloride (13.4 mg) and 20 mass% tetraethylammonium hydroxide aqueous solution (7.61 g) were added, and the mixture was heated under reflux for 7 hours. .. Then, the aqueous layer was removed, sodium N,N-diethyldithiocarbamate trihydrate (5.40 g) and ion-exchanged water (40 mL) were 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 acetic acid aqueous solution, and water. The organic layer was dropped into methanol to precipitate the polymer compound, which was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene and passed through column chromatography packed with silica gel/alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was filtered and dried to obtain polymer compound P-8 (0.91 g). The number average molecular weight (Mn) and dispersity (Mw/Mn) of the obtained polymer compound P-8 were measured by SEC. As a result, the polymer compound P-8 had a number average molecular weight (Mn) and Mw/Mn of 26,000 and 2.4, respectively.

The polymer compound P-8 thus obtained is presumed to be a polymer compound having the following constitutional units from the charging ratio of the monomers.

Example 16
As the first electrode (anode), a glass substrate with ITO in which indium tin oxide (ITO) was patterned to a film thickness of 150 nm was used. The glass substrate with ITO was sequentially washed with a neutral detergent, deionized water, water and isopropyl alcohol, and then subjected to UV-ozone treatment. Next, on this glass substrate with ITO, poly(3,4-ethylenedioxythiophene)/poly(4-styrenesulfonate) (PEDOT/PSS) (manufactured by Sigma-Aldrich) was dried to a thickness of 30 nm. After being applied by the spin coating method, it was dried. As a result, a hole injection layer having a thickness (dry film thickness) of 30 nm was formed on the glass substrate with ITO.

On the hole injecting layer, 0.2% by mass of the polymer compound P-3 (hole transporting material) of Example 3 and 0.2 mass% of the polymer compound P-9 (hole transporting material) of Synthesis example 9 were prepared. A toluene solution containing 8% by mass was applied by spin coating so that the dry film thickness was 30 nm, and then heat-treated at 230° C. for 60 minutes 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.

The following structure in cyclohexane:

A quantum dot dispersion liquid was prepared by dispersing red quantum dots of InP/ZnSe/ZnS (core/shell/shell; average diameter=about 10 nm) having 1 to 1.0% by mass. The hole transport layer (particularly the polymer compounds P-3 and P-9) is not dissolved 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. The light emitted by irradiating the quantum dot dispersion liquid with ultraviolet rays 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 emission layer, lithium quinolate (Liq) and 1,3,5-tris(N-phenylbenzimidazol-2-yl)benzene (TPBI) (TPBI) (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.

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

Aluminum (Al) was vapor-deposited on the electron injection layer using a vacuum vapor deposition device. As a result, a second electrode (cathode) having a thickness of 100 nm was formed on the electron injection layer. Thereby, the quantum dot electroluminescent element 8 was obtained.

Example 17
A quantum dot electroluminescent device 9 was prepared in the same manner as in Example 16, except that the polymer compound P-5 in Example 5 was used in place of the polymer compound P-3. ..

Example 18
A quantum dot electroluminescent device 10 was prepared in the same manner as in Example 16, except that the polymer compound P-8 of Example 15 was used in place of the polymer compound P-3. ..

Comparative example 2
In Example 16, instead of the polymer compounds P-3 and P-9, poly[(9,9-dioctylfluorenyl-2,7-diyl)-co-(4,4′) having the following structural units was used. -(N-(4-sec-butylphenyl)diphenylamine)](TFB) (manufactured by Luminescence Technology Corp.) was used, and the same operation as in Example 16 was carried out to produce the comparative quantum dot electroluminescent device 2. The number average molecular weight (Mn) and dispersity (Mw/Mn) of TFB were measured by SEC, and as a result, (Mn) and Mw/Mn of TFB were 359,000 and 3.4, respectively. there were.

[Evaluation of quantum dot electroluminescent device 2]
The quantum dot electroluminescent elements 8 to 10 produced in Examples 16 to 18 and the comparative quantum dot electroluminescent element 2 produced in Comparative Example 2 were evaluated for luminous efficiency and luminous lifetime by the following methods.

(Emission efficiency)
When a voltage is applied to each quantum dot electroluminescent element using a DC constant voltage power source (manufactured by KEYENCE, source meter), a current starts to flow at a constant voltage, and the quantum dot electroluminescent element emits light. To do. The voltage at a current density of 5 mA/cm ² is defined as the drive voltage (Vop) [V]. In addition, while measuring the light emission of each element using a brightness measuring device (SR-3, manufactured by Topcom), the current was gradually increased, and the current was kept constant when the brightness reached 100 nit (cd/m ² ), put. Here, the current value per unit area (current density) is calculated from the area of each element, and the luminance (cd/m ² ) is divided by the current density (A/m ² ) to obtain the current efficiency (cd/ Calculate A). The current efficiency indicates the efficiency of converting a current into luminescence energy (conversion efficiency), and the higher the current efficiency, the higher the performance of the device.

Further, the external quantum efficiency (EQE) (%) at a luminance of 100 nit is calculated from the spectral radiance spectrum measured by the luminance measuring device, and the luminous efficiency is evaluated, assuming that the Lambertian emission is performed.

The results are shown in Table 2 below. In addition, in Table 2 below, the weight average molecular weight (Mn) and the dispersity (Mw/Mn) are the polymer compounds P-3 (Example 16), P-5 (Example 17) and P-8 (Example). 18) Mn and Mw/Mn of 18) are shown, respectively.

(Emission life)
A predetermined voltage was applied to each EL element using a DC constant voltage power source (source meter manufactured by KEYENCE CORPORATION) to cause each quantum dot electroluminescence element to emit light. While measuring the light emission of the quantum dot electroluminescence element with a brightness measuring device (SR-3, manufactured by Topcon Corporation), the current was gradually increased and the current was kept constant when the brightness reached 325 nit (cd/m ² ). And left it. The time until the value of the luminance measured by the luminance measuring device gradually decreased and reached 50% of the initial luminance was defined as “LT50(hr)”.

The results are shown in Table 2 below. In Table 2 below, the relative value of each element when the LT50 of the comparative quantum dot electroluminescent element 2 is 1.0 is shown in parentheses after LT50.

From the results of Table 2 above, the quantum dot electroluminescent elements 8 to 10 of the example are higher at a lower driving voltage than the comparative quantum dot electroluminescent element 2 not using the silicon-containing arylamine polymer according to the present invention. It can be seen that the performance (current efficiency, external quantum efficiency) can be exhibited. Further, in the quantum dot electroluminescent elements 8 to 10 of the example, the LT50 was remarkably improved as compared with the comparative quantum dot electroluminescent element 2. From these results, it is considered that by using the quantum dot electroluminescence device of the present invention in which two kinds of polymer compounds are combined, the emission brightness and the emission life can be dramatically improved. In this example, it is considered that the same results as above can be obtained also in the blue quantum dot electroluminescent element or the like evaluated for the red quantum dot electroluminescent element.

[Characteristic evaluation of each polymer compound]
Regarding the polymer compounds P-1 to P-9 of Examples 1 to 7 and 15 and Synthesis Example 9, the HOMO level (eV), LUMO level (eV) and glass transition temperature (Tg) ( C) was measured. The results are shown in Table 3 below.

(Measurement of HOMO level)
A coating solution is prepared by dissolving each polymer compound in xylene so that the concentration becomes 1% by mass. On the UV-washed glass substrate with ITO, using the above-prepared coating solution, a film was formed by spin coating at a rotation speed of 2000 rpm, and then dried on a hot plate at 150° C. for 30 minutes. , Prepare a sample for measurement. The HOMO level of the sample is measured using an atmospheric photoelectron spectrometer (AC-3, manufactured by Riken Keiki Co., Ltd.). At this time, the rising tangent intersection is calculated from the measurement result and set as the HOMO level (eV). The HOMO level is usually a negative value.

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

(Glass transition temperature (Tg))
Each polymer compound was heated to 300° C. at a heating rate of 10° C./minute and held for 10 minutes using a differential scanning calorimeter (DSC) (manufactured by Seiko Instruments Inc., trade name: DSC6000). After cooling to 25° C. at a temperature decreasing rate of 10° C./minute and holding for 10 minutes, the temperature is increased to 300° C. at a temperature increasing rate of 10° C./minute for measurement. After the measurement, the temperature is cooled to room temperature (25°C) at 10°C/minute.

Although the present invention has been described with reference to the exemplary embodiments and examples, the present invention is not limited to the specific exemplary embodiments and examples, and various modifications are possible within the scope of the invention described in the claims. Can be modified and changed.

100... Electroluminescence element (EL element),
110... substrate,
120... the 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 (10)

Silicon-containing arylamine polymer having a structural unit (A) represented by the following formula (1):

However, Ar ₁ is each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms or a substituted or unsubstituted heterocyclic aromatic group having 12 to 25 carbon atoms. Represents a group;
Ar ₂ is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 25 carbon atoms or a substituted or unsubstituted divalent heterocyclic aromatic group having 12 to 25 carbon atoms. Represents;
R ₁ is each independently a hydrogen atom, a linear, branched or cyclic hydrocarbon group having 1 to 12 carbon atoms, or a substituted or unsubstituted aromatic hydrocarbon group having 6 to 25 carbon atoms. Represents. The silicon-containing arylamine polymer according to claim 1, wherein the structural unit (A) is contained in a proportion of 10 mol% or more and 100 mol% or less with respect to all the structural units. The silicon-containing arylamine polymer according to claim 1 or 2, wherein each Ar ₁ is independently a group selected from the following group:

However, R _{111 to} R ₁₃₄ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aromatic carbon atom having 6 to 25 carbon atoms. Represents a hydrogen group. The silicon-containing arylamine polymer according to claim 1, wherein Ar ₂ is a divalent group selected from the following group.

However, R _{211 to} R ₂₆₉ are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a substituted or unsubstituted aromatic carbon atom having 6 to 25 carbon atoms. Represents a hydrogen group. An electroluminescent device material comprising the silicon-containing arylamine polymer according to claim 1. A composition for producing an electroluminescence device, comprising two or more polymers, wherein at least one of the polymers is the silicon-containing arylamine polymer according to any one of claims 1 to 4. Composition. The composition for producing an electroluminescence device according to claim 6, wherein at least one polymer has a structural unit represented by the following formula (A):

However, X is a group represented by the following formula (B), and Y is a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 or more and 60 or less carbon atoms, or a substituted or non-substituted group. A substituted divalent aromatic heterocyclic group having 3 to 60 ring-forming atoms,

However, Ar ₁₀₀ is a substituted or unsubstituted trivalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted trivalent aromatic group having 3 to 60 ring-forming atoms. A heterocyclic group,
Ar ₂₀₀ and Ar ₃₀₀ are each independently a substituted or unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted 3 to 60 ring-forming atoms. The following monovalent aromatic heterocyclic group,
L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted ring-forming atom number. It is a divalent aromatic heterocyclic group of 3 or more and 60 or less,
Z _{1 to} Z ₈ are each independently a nitrogen atom or -CH=, in which case any of Z _{5 to} Z ₈ is -CH= and the hydrogen atom of -CH= is -L _2. -N(Ar ₂₀₀ )(Ar ₃₀₀ ),
R ₁₀₀ and R ₂₀₀ are each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, a substituted or An unsubstituted monovalent aromatic hydrocarbon group having 6 to 60 carbon atoms, or a substituted or unsubstituted monovalent aromatic heterocyclic group having 3 to 60 ring-forming atoms,
R ₁₀₀ and R ₂₀₀ may combine with each other to form a ring,
a is an integer of 0 or more and 4 or less,
b is an integer of 0 or more and 3 or less,
When a is an integer of 1 or more and 4 or less, _one of Z _{1 to} Z ₄ is -CH=, the hydrogen atom of the -CH= is substituted with R ₁₀₀ , and b is 1 or more and 3 or less. When it is an integer, any of Z _{5 to} Z ₈ is —CH═, and the hydrogen atom of —CH═ is substituted with R ₂₀₀ . An electroluminescence device comprising a first electrode, a second electrode, and one or more organic films arranged between the first electrode and the second electrode,
At least 1 layer of the said organic film is an electroluminescent element containing the silicon-containing arylamine polymer in any one of Claims 1-4, or the composition for electroluminescent element manufacturing of Claim 5 or 6. The electroluminescent device according to claim 8, wherein the organic film containing the silicon-containing arylamine polymer is a hole transport layer or a hole injection layer. The electroluminescent device according to claim 8 or 9, wherein the organic film has a light emitting layer containing semiconductor nanoparticles or an organometallic complex.