TW202348685A - Composition, organic electroluminescent element and method for producing same, display device, and lighting device - Google Patents

Abstract

The present invention relates to a composition that comprises: a polymer compound having a repeat unit given by formula (1), having possibly substituted fluorene in the main chain and/or in side chain position, and having a crosslinking group; and an electron-accepting compound given by formula (81) and having a crosslinking group. (In formula (1) and formula (81), Ar1, G, *, Ar2, m, n, R81 to R84, Ph1 to Ph4, and X+ each have the definitions provided in the Description.).

Description

Composition, organic electric field light-emitting element and manufacturing method thereof, display device and lighting device

The invention relates to a composition, an organic electric field light-emitting element and a manufacturing method thereof, a display device and a lighting device.

In recent years, as thin-film electroluminescent elements, organic electroluminescent elements using organic thin films have been developed instead of using inorganic materials. Organic electric field light-emitting elements (Organic Light Emitting Diode (OLED)) usually have a charge injection layer, a charge transport layer, an organic light-emitting layer, an electron transport layer, etc. between the anode and the cathode, and are suitable for each layer. Materials are being developed, and regarding the luminous colors, red, green, and blue are also being developed separately. In addition, in recent years, quantum dot light-emitting elements using "quantum dots" which are inorganic light-emitting substances in the light-emitting layer of organic electroluminescent elements are also being developed.

Examples of methods for forming the organic layer of the organic electroluminescent element include a vacuum evaporation method and a wet film forming method (coating method). Since the vacuum evaporation method is easy to achieve lamination, it has the following advantages: it is easy to improve charge injection from the anode and/or cathode, and it is easy to seal excitons in the light-emitting layer. On the other hand, the wet film-forming method has the following advantages: it does not require a vacuum process, it is easy to achieve large area, and by using a coating liquid that mixes a variety of materials with various functions, it can easily form a coating containing various materials with various functions. Functional layers of multiple materials and more. Therefore, in recent years, research and development of organic electroluminescent elements based on film formation by a coating method have been actively conducted.

Patent Document 1 discloses an organic electroluminescent element having a composition including an arylamine polymer compound containing a crosslinking group and an electron-accepting compound. Patent Document 2, Patent Document 3, and Patent Document 4 disclose an organic electroluminescent element having a composition including a fluorine-containing arylamine polymer compound and an electron-accepting compound. [Prior art documents] [Patent Document]

Patent Document 1: International Publication No. 2017/164268 Patent Document 2: International Publication No. 2020/065920 Patent Document 3: Japanese Patent Application Publication No. 2020-115554 Patent Document 4: International Publication No. 2020/217520

[Problems to be solved by the invention] Generally speaking, if an organic electron donor and an organic electron acceptor of arylamines are mixed at an appropriate ratio, the N atoms of the arylamine are partially formed with the organic electron acceptor. By forming this ionic complex, the hole injection barrier from the anode is lowered, so materials that form stable ionic complexes are attracting attention. Patent Document 1 discloses that hole injection barriers have been successfully reduced using this technology. However, in the arylamine polymer compound disclosed in Patent Document 1, the highest occupied molecular orbital (Highest Occupied Molecular Orbital, HOMO) of the molecule is shallow, and in the hole transport layer using a hole transport material with a deep HOMO The charge injection barrier is generated and the driving voltage of the organic electroluminescent element is not sufficiently reduced. In the materials or techniques disclosed in Patent Documents 2 to 4, an ion complex is formed from an organic electron donor and an organic electron acceptor of an arylamine polymer compound containing fluorine. However, forming a film containing a charge injection layer containing this ion complex does not sufficiently reduce the driving voltage of the organic electroluminescent element. In addition, using an organic electron acceptor that does not contain a cross-linking group as a photopolymerization initiator does not sufficiently prevent the organic electron acceptor from diffusing into the light-emitting layer, thereby failing to improve the luminous efficiency and drive lifetime.

The present invention was made in view of the above-mentioned existing actual situation, and its object is to provide a composition for obtaining an organic electric field light-emitting element with low driving voltage, high luminous efficiency, and long driving life. [Means to solve the problem]

The inventors of the present invention conducted diligent research and found that by using a hole injection layer and/or hole transport using a cross-linking reaction product containing an arylamine polymer compound with a specific structure and an electron-accepting compound with a specific structure, This invention was completed by being able to solve the above problems in an organic electroluminescent element (OLED) or a quantum dot light-emitting element containing quantum dots in the light-emitting layer of the organic electroluminescent element.

That is, the gist of the present invention is as described in the following aspects 1 to 19.

Aspect 1 of the present invention is a composition including: a polymer compound having a repeating unit represented by the following formula (1), fluorene having a substituent in at least one of the main chain and the side chain, and having a cross-linking group; and an electron-accepting compound represented by the following formula (81) and having a cross-linking group.

[Chemical 1]

(In formula (1), Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms that may have a substituent, a divalent aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, or a divalent aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent. The aromatic hydrocarbon group of the substituent or the aromatic heterocyclic group which may have a substituent is a divalent group in which a plurality of aromatic heterocyclic groups are connected directly or via a connecting group, and G represents any of the formulas (1-1) to (1-3). The divalent group represented by one, "*" represents the bonding position with the adjacent structure, and the substituent A is each independently a fluorine atom, CF ₃ or SF ₅ ; Ar ² represents a hydrogen atom, and the substituent A may have The substituent may be an aromatic hydrocarbon group having 6 to 60 carbon atoms, an aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, or an aromatic hydrocarbon group that may have a substituent and an aromatic group that may have a substituent. A monovalent group in which multiple groups in the heterocyclic group are connected directly or via a connecting group; m is an integer from 1 to 4, n is an integer from 1 to 6)

[Chemicalization 2]

(In formula (81), five R ⁸¹ , five R ⁸² , five R ⁸³ , and five R ⁸⁴ are each independently independent, and R ⁸¹ to R ⁸⁴ are each independently a hydrogen atom, a deuterium atom, or a halogen atom, and may have An aromatic hydrocarbon group having 6 to 50 carbon atoms as a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, an alkyl group having 1 to 12 carbon atoms substituted with fluorine, or a crosslinking group; Ph ¹ , Ph ² , Ph ³ , Ph ⁴ refer to the symbols of their respective benzene rings; X ⁺ represents countercation)

Aspect 2 of the present invention is the composition according to aspect 1, including the electron-accepting compound represented by the formula (81) having at least two crosslinking groups.

Aspect 3 of the present invention is the composition according to aspect 1 or 2, wherein the compound represented by the formula (1) and the compound represented by the formula (81) each independently have a compound selected from the group consisting of: A cross-linking group in the following cross-linking group T. ＜Crosslinking group T＞

[Chemical 3]

(In the formula, Q represents a direct bond or connecting group; "*" represents the bonding position; R ¹¹⁰ in formula (X4), formula (X5), formula (X6) and formula (X10) represents a hydrogen atom or can Alkyl group with a substituent; In the formula (X1) to the formula (X4), the benzene ring and the naphthalene ring may have a substituent; in addition, the substituents may be bonded to each other to form a ring; in the formula (X1) and the formula (X2) , the cyclobutene ring may have substituents)

Aspect 4 of the present invention is the composition according to any one of aspects 1 to 3, wherein the G is represented by any one of the following formulas.

[Chemical 4]

(In the above formula, "*" indicates the bonding position with the adjacent structure)

Aspect 5 of the present invention is the composition according to any one of aspects 1 to 3, wherein the [-G-Ar ² ] is represented by any one of the following formulas.

[Chemistry 5]

(In the above formula, "*" indicates the bonding position with the adjacent structure)

Aspect 6 of the present invention is the composition according to any one of aspects 1 to 5, wherein Ar ¹ has one selected from the following formula (2-1) to formula (2-3) A partial structure, or a bonding structure in which two or more of the following formulas (2-1) to (2-3) are bonded to each other, and the bonding structure may also include a bonding structure selected from the following It is a structure in which at least one structure among the formulas (2-1) to (2-3) is bonded with two or more.

[Chemical 6]

(In each of the formulas (2-1) to (2-3), R ¹ and R ² are each independently a hydrogen atom, a deuterium atom, a halogen atom, or an aromatic carbon number of 6 to 18 that may have a substituent. Hydrocarbon group, aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, alkyl group having 1 to 12 carbon atoms, "*" indicates the bonding position with the adjacent structure)

Aspect 7 of the present invention is the composition according to any one of aspects 1 to 6, wherein the polymer compound further has a repeating unit represented by the following formula (3).

[Chemical 7]

(In the formula (3), Ar ³ is a 2-fluorenyl group which may have a substituent; Ar ⁴ represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or A plurality of at least two groups selected from the group consisting of the divalent aromatic hydrocarbon group which may have a substituent and the divalent aromatic heterocyclic group which may have a substituent are connected directly or via a linking group. into a divalent base)

Aspect 8 of the present invention is the composition according to any one of aspects 1 to 7, further containing a solvent.

Aspect 9 of the present invention is a method for manufacturing an organic electric field light-emitting element, which is a method of manufacturing an organic electric field light-emitting element having an anode and a cathode on a substrate and an organic layer between the anode and the cathode. The method for manufacturing an electroluminescent element includes the step of forming the organic layer using a wet film-forming method using the composition described in Aspect 8.

Aspect 10 of the present invention is the method for manufacturing an organic electroluminescent element according to aspect 9, wherein the organic layer is an organic layer present between the anode and the light-emitting layer.

Aspect 11 of the present invention is an organic electric field light-emitting element having an anode and a cathode on a substrate and an organic layer between the anode and the cathode. In the organic electric field light-emitting element, The organic layer contains a cross-linking reaction product of a polymer compound and an electron-accepting compound. The polymer compound has a repeating unit represented by the following formula (1) and has at least one of a main chain and a side chain. Fluorene having a substituent and having a cross-linking group, the electron-accepting compound is represented by the following formula (81) and has a cross-linking group.

[Chemical 8]

(In formula (1), Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms that may have a substituent, a divalent aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, or a divalent aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent. The aromatic hydrocarbon group of the substituent or the aromatic heterocyclic group which may have a substituent is a divalent group in which a plurality of aromatic heterocyclic groups are connected directly or via a connecting group, and G represents any of the formulas (1-1) to (1-3). The divalent group represented by one, "*" represents the bonding site with the adjacent structure, and the substituent A is each independently a fluorine atom, CF ₃ or SF ₅ ; Ar ² represents a hydrogen atom, and the substituent A may have The substituent may be an aromatic hydrocarbon group having 6 to 60 carbon atoms, an aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, or an aromatic hydrocarbon group that may have a substituent and an aromatic group that may have a substituent. A monovalent group in which multiple groups in the heterocyclic group are connected directly or via a connecting group; m is an integer from 1 to 4, n is an integer from 1 to 6)

[Chemical 9]

(In formula (81), five R ⁸¹ , five R ⁸² , five R ⁸³ , and five R ⁸⁴ are each independently independent, and R ⁸¹ to R ⁸⁴ are each independently a hydrogen atom, a deuterium atom, or a halogen atom, and may have An aromatic hydrocarbon group having 6 to 50 carbon atoms as a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, an alkyl group having 1 to 12 carbon atoms substituted with fluorine, or a crosslinking group; Ph ¹ , Ph ² , Ph ³ , Ph ⁴ refer to the symbols of their respective benzene rings; X ⁺ represents countercation)

A 12th aspect of the present invention is the organic electroluminescent element according to the 11th aspect, wherein the G is represented by any one of the following formulas.

[Chemical 10]

(In the above formula, "*" indicates the bonding position with the adjacent structure)

Aspect 13 of the present invention is the organic electroluminescent element according to aspect 11, wherein the [-G-Ar ² ] is represented by any one of the following formulas.

[Chemical 11]

(In the above formula, "*" indicates the bonding position with the adjacent structure)

Aspect 14 of the present invention is the organic electroluminescent device according to any one of aspects 11 to 13, wherein Ar ¹ has a formula selected from the following formula (2-1) to formula (2-3) A partial structure of one, or a bonding structure in which two or more selected from the following formulas (2-1) to (2-3) are bonded to each other, and the bonding structure may also include the selected A structure in which two or more structures from at least one of the following formulas (2-1) to formula (2-3) are bonded.

[Chemical 12]

(In each of the formulas (2-1) to (2-3), R ¹ and R ² are each independently a hydrogen atom, a deuterium atom, a halogen atom, or an aromatic carbon number of 6 to 18 that may have a substituent. Hydrocarbon group, aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, alkyl group having 1 to 12 carbon atoms, "*" indicates the bonding position with the adjacent structure)

Aspect 15 of the present invention is the organic electroluminescent device according to any one of aspects 11 to 14, wherein the polymer compound further has a repeating unit represented by the following formula (3).

[Chemical 13]

(In formula (3), Ar ³ is a 2-fluorenyl group that may have a substituent; Ar ⁴ represents a divalent aromatic hydrocarbon group that may have a substituent, a divalent aromatic heterocyclic group that may have a substituent, or a selected A plurality of at least two groups in the group consisting of the divalent aromatic hydrocarbon group which may have a substituent and the divalent aromatic heterocyclic group which may have a substituent are connected directly or via a linking group divalent base)

Aspect 16 of the present invention is an organic electric field light-emitting element manufactured using the method for manufacturing an organic electric field light-emitting element described in aspect 9 or 10.

Aspect 17 of the present invention is the organic electroluminescent device according to any one of aspects 11 to 16, wherein the light-emitting layer contains quantum dots.

Aspect 18 of the present invention is a display device including the organic electroluminescent element according to any one of aspects 11 to 17.

Aspect 19 of the present invention is a lighting device including the organic electroluminescent element according to any one of aspects 11 to 17. [Effects of the invention]

The composition of the present invention can provide an organic electric field light-emitting element with low driving voltage, high luminous efficiency and long driving life.

Hereinafter, embodiments of a composition, an organic electroluminescent element and a manufacturing method thereof, a display device, and a lighting device as one embodiment of the present invention will be described in detail. The following description is a first embodiment as an example (representative example) of embodiments of the present invention, but the present invention is not limited to these contents as long as it does not deviate from the gist of the present invention.

In the present invention, "may have a substituent" means that it may have one or more substituents.

[Definition] In the following, when the structures of the fluorine-containing arylamine polymer compound, the electron-accepting compound having a crosslinking group, and the charge-transporting polymer compound used in the present invention are described in detail, the common partial structures will be used unless otherwise specified. Set to the following structure.

＜Aromatic hydrocarbon group＞ The aromatic hydrocarbon group refers to a monovalent, divalent, or trivalent or higher aromatic hydrocarbon ring structure depending on the bonding state in the structure of the compound to be described later.

In the structure of the aromatic hydrocarbon ring, the number of carbon atoms is generally not limited, but is preferably 6 or more and 60 or less carbon atoms. As the upper limit of the carbon number, it is more preferably 48 or less carbon atoms, and more preferably 30 or less carbon atoms. Specific examples include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, pyrene ring, triphenyl ring, ethane naphthalene ring, fluorine ring A group consisting of a 6-membered monocyclic ring or a 2- to 5-membered fused ring such as an anthracene ring or a fluorene ring, or a structure in which a plurality of groups selected from these are linked together. When a plurality of aromatic hydrocarbon rings are connected, a structure in which two to ten are connected is generally used, and a structure in which two to five are connected is preferred. When a plurality of aromatic hydrocarbon rings are connected, the same structure may be connected or different structures may be connected.

As the aromatic hydrocarbon ring structure, a benzene ring, a biphenyl ring, which is a structure in which two benzene rings are connected, a terphenyl ring, which is a structure in which three benzene rings are connected, and an extended tetraphenyl ring, which is a structure in which four benzene rings are connected. A structure formed by connecting benzene rings, naphthalene ring, and fluorene ring.

＜Aromatic heterocyclic group＞ The term "aromatic heterocyclic group" refers to a monovalent, divalent, or trivalent or higher aromatic heterocyclic structure depending on the bonding state in the structure of the compound to be described later.

In the structure of the aromatic heterocyclic ring, the number of carbon atoms is generally not limited, but is preferably 3 or more and 60 or less carbon atoms. As the upper limit of the carbon number, it is more preferably 48 or less carbon atoms, and more preferably 30 or less carbon atoms. Specific examples include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring , Pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, Benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzo The imidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and other 5- to 6-membered monocyclic rings or 2- to 4-membered condensed ring divalent groups or the These bases are formed by connecting multiple ones. When a plurality of aromatic heterocycles are connected, the same structure may be connected or different structures may be connected. When a plurality of aromatic heterocyclic rings are connected, a structure in which two to ten are connected is usually exemplified, and a structure in which two to five are connected is preferred.

As the aromatic heterocyclic ring, a thiophene ring, a benzothiophene ring, a pyrimidine ring, a triazine ring, a carbazole ring, a dibenzofuran ring, and a dibenzothiophene ring are preferred.

＜Substituent＞ Unless otherwise specified, the substituent is any group, and is preferably a group selected from the following substituent group Z, and a crosslinking group. In addition, when it is described that the optional substituent is selected from the substituent group Z, preferable substituents are also those described in the following substituent group Z.

＜Substituent group Z＞ Substituent group Z includes alkyl, alkenyl, alkynyl, alkoxy, aryloxy, heteroaryloxy, alkoxycarbonyl, dialkylamino, diarylamine, arylalkyl A group of amino group, hydroxyl group, halogen atom, haloalkyl group, alkylthio group, arylthio group, silyl group, silyloxy group, cyano group, aromatic hydrocarbon group and aromatic heterocyclic group. These substituents may include any structure among linear, branched and cyclic structures.

More specifically, the substituent group Z includes the following structures. The carbon number is 1 or more, preferably 4 or more and 24 or less, preferably 12 or less, further preferably 8 or less, more preferably 6 or less linear, branched or cyclic alkyl groups. Specific examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-hexyl, cyclohexyl, dodecyl, etc. . The carbon number is usually 2 or more and usually 24 or less, preferably 12 or less linear, branched or cyclic alkenyl groups; specific examples include vinyl groups and the like. The carbon number is usually 2 or more and usually 24 or less, preferably 12 or less linear or branched alkynyl groups; specific examples include ethynyl and the like. An alkoxy group having a carbon number of 1 or more and 24 or less, preferably 12 or less. Specific examples include methoxy group, ethoxy group, and the like. An aryloxy group or heteroaryloxy group having a carbon number of 4 or more, preferably 5 or more and 36 or less, preferably 24 or less. Specific examples include phenoxy group, naphthyloxy group, pyridyloxy group, and the like. An alkoxycarbonyl group having a carbon number of 2 or more and 24 or less, preferably 12 or less. Specific examples include methoxycarbonyl group, ethoxycarbonyl group, and the like. A dialkylamino group having a carbon number of 2 or more and 24 or less, preferably 12 or less. Specific examples include dimethylamino group, diethylamine group, and the like. A diarylamine group having a carbon number of 10 or more, preferably 12 or more and 36 or less, preferably 24 or less. Specific examples include a diphenylamino group, a xylylamine group, an N-carbazolyl group, and the like. An arylalkylamino group having a carbon number of 7 or more and 36 or less, preferably 24 or less. Specific examples include phenylmethylamino groups. The carbon number is 2 or more and 24 or less, preferably 12 or less. Specific examples include an acetyl group and a benzyl group. Halogen atoms such as fluorine atoms and chlorine atoms. A fluorine atom is preferred. A haloalkyl group having a carbon number of 1 or more and 12 or less, preferably 6 or less. Specific examples include trifluoromethyl and the like. The alkylthio group has a carbon number of 1 or more and usually 24 or less, preferably 12 or less. Specific examples include methylthio group, ethylthio group, and the like. An arylthio group having a carbon number of 4 or more, preferably 5 or more and 36 or less, preferably 24 or less. Specific examples include phenylthio group, naphthylthio group, pyridylthio group, and the like. The silane group has a carbon number of usually 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less. Specific examples include trimethylsilyl group, triphenylsilyl group, and the like. A silanoxy group having a carbon number of 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less. Specific examples include trimethylsilyloxy group, triphenylsilyloxy group, and the like. Cyano. An aromatic hydrocarbon group having a carbon number of 6 or more and 36 or less, preferably 24 or less. Specific examples include a phenyl group, a naphthyl group, a group in which a plurality of phenyl groups are linked, and the like. An aromatic heterocyclic group having a carbon number of 3 or more, preferably 4 or more and 36 or less, preferably 24 or less. Specific examples include thienyl, pyridyl, and the like.

The substituent may include any structure of linear, branched or cyclic structures. In the case where the substituents are adjacent, the adjacent substituents may be bonded to each other to form a ring. Preferred ring sizes are 4-membered ring, 5-membered ring, and 6-membered ring. Specific examples include cyclobutane ring, cyclopentane ring, and cyclohexane ring.

Among the substituent groups Z, preferred ones are alkyl groups, alkoxy groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups.

In addition, each substituent of the substituent group Z may further have a substituent. Examples of these substituents include the same substituent group Z as described above or a crosslinking group. Preferably it has no further substituent, or it is an alkyl group with 8 or less carbon atoms, an alkoxy group with 8 or less carbon atoms, or a phenyl group, more preferably an alkyl group with 6 or less carbon atoms or an alkyl group with 6 or less carbon atoms. Oxygen, or phenyl. From the viewpoint of charge transport properties, it is more preferable to have no further substituent.

When each substituent of the substituent group Z may have a cross-linking group, the cross-linking group is preferably a cross-linking group selected from the following cross-linking group T. Preferably, the substituent having a crosslinking group is an alkyl group or an aromatic hydrocarbon group.

＜Crosslinking group＞ Here, the cross-linking group refers to a group that reacts with other cross-linking groups located in the vicinity of the cross-linking group by irradiation of heat and/or active energy rays to generate a new chemical bond. In this case, the reacting group may be the same group as the cross-linking group or a different group.

The crosslinking group is not limited, and examples thereof include: a group containing an alkenyl group, a group containing a conjugated diene structure, a group containing an alkynyl group, a group containing an oxetane structure, and a group containing an oxetane structure. A group, a group containing an aziridine structure, an azide group, a group containing a maleic anhydride structure, a group containing an alkenyl group bonded to an aromatic ring, a cyclobutene ring condensed on an aromatic ring, etc. As a specific example of a preferable cross-linking group, a cross-linking group represented by any one of the following formula (X1) to formula (X18) among the following cross-linking group T is preferable.

＜Crosslinking group T＞

[Chemical 14]

(In the formula, Q represents a direct bond or connecting group; "*" represents the bonding position; R ¹¹⁰ in formula (X4), formula (X5), formula (X6) and formula (X10) represents a hydrogen atom or can Alkyl group with a substituent; In the formula (X1) to the formula (X4), the benzene ring and the naphthalene ring may have a substituent; in addition, the substituents may be bonded to each other to form a ring; in the formula (X1) and the formula (X2) , the cyclobutene ring may have substituents)

(Q) When Q is a connecting group, the connecting group is not particularly limited, but is preferably an alkylene group, a divalent oxygen atom, or a divalent aromatic hydrocarbon group which may have a substituent. The alkylene group is usually an alkylene group having 1 to 12 carbon atoms, preferably an alkylene group having 1 to 8 carbon atoms, and more preferably an alkylene group having 1 to 6 carbon atoms. The divalent aromatic hydrocarbon group usually has a carbon number of 6 or more, usually a carbon number of 36 or less, preferably 30 or less, and further preferably 24 or less. The structure of the aromatic hydrocarbon ring is preferably a benzene ring, which may have The substituents of can be selected from the substituent group Z mentioned above.

The alkyl group represented by R ¹¹⁰ has a linear, branched or cyclic structure, and has a carbon number of 1 or more, preferably 24 or less, more preferably 12 or less, and even more preferably 8 or less.

As the substituent that the benzene ring and the naphthalene ring of the formulas (X1) to (X4) and R ¹¹⁰ of the formulas (X4) to (X6) and formula (X10) can have, an alkyl group, an aromatic hydrocarbon group, Alkyloxy, aralkyl.

The alkyl group as a substituent has a linear, branched or cyclic structure, and the number of carbon atoms is preferably 24 or less, more preferably 12 or less, further preferably 8 or less, preferably 1 or more.

The carbon number of the aromatic hydrocarbon group as a substituent is preferably 24 or less, more preferably 18 or less, further preferably 12 or less, preferably 6 or more. The aromatic hydrocarbon group may further have the alkyl group as a substituent.

The number of carbon atoms of the alkyloxy group as a substituent is preferably 24 or less, more preferably 12 or less, further preferably 8 or less, preferably 1 or more.

The carbon number of the aralkyl group as a substituent is preferably 30 or less, more preferably 24 or less, further preferably 14 or less, more preferably 7 or more. The alkylene group contained in the aralkyl group is preferably a linear or branched structure. The aryl group contained in the aralkyl group may further have the alkyl group as a substituent.

As a substituent that the cyclobutene ring of formula (X1) or formula (X2) may have, an alkyl group is preferred.

R ¹¹⁰ in formula (X4) is preferably a hydrogen atom or an alkyl group without a substituent. As R ¹¹⁰ in formula (X5), formula (X6), and formula (X10), an alkyl group which may have a substituent is preferred, and an alkyl group which does not have a substituent is more preferred.

The alkyl group as a substituent has a linear, branched or cyclic structure, and the number of carbon atoms is preferably 24 or less, more preferably 12 or less, further preferably 8 or less, preferably 1 or more.

As the cross-linking group, cross-linking represented by any one of formulas (X1) to (X3) is preferable in that the cross-linking reaction proceeds only by heat, has low polarity, and has little influence on charge transport.

The cross-linking group represented by the formula (X1) is represented by the following formula. The cyclobutene ring is ring-opened by heat, and the groups after the ring-opening are bonded to each other to form a cross-linked structure. In addition, below, description about the coupling group Q in formula (X1) - formula (X4) etc. is abbreviate|omitted.

[Chemical 15]

The cross-linking group represented by the formula (X2) is represented by the following formula. The cyclobutene ring is ring-opened by heat, and the groups after the ring-opening are bonded to each other to form a cross-linked structure.

[Chemical 16]

The cross-linking group represented by the formula (X3) is represented by the following formula. The cyclobutene ring is ring-opened by heat, and the groups after the ring-opening are bonded to each other to form a cross-linked structure.

[Chemical 17]

The cross-linking group represented by any one of the formulas (X1) to (X3) is formed by thermally opening the cyclobutene ring, and reacting with the double bond after the ring opening if a double bond exists nearby. Cross-linked structure.

Examples in which the ring-opened group of the cross-linked group represented by formula (X1) and the cross-linked group represented by formula (X4) having a double bond site form a cross-linked structure are shown below.

[Chemical 18]

Examples of the group containing a double bond that can react with the crosslinking group represented by any one of formulas (X1) to (X3) include formula (X5) in addition to the crosslinking group represented by formula (X4). , a cross-linking group represented by any one of formula (X6), formula (X12), formula (X15), formula (X16), formula (X17), and formula (X18). When these double bond-containing groups are used as cross-linking groups in the electron-accepting compound, other components that form the hole-transporting compound and the like to form the hole-injection layer and/or the hole-transport layer contain the formula (X1 ) to formula (X3) are preferred because they increase the possibility of forming a cross-linked structure.

As the cross-linking group, a cross-linking group represented by any one of radically polymerizable formulas (X4), (X5), and (X6) is preferred because it has small polarity and is less likely to interfere with charge transport.

As a cross-linking group, the cross-linking group represented by Formula (X7) is preferable from the viewpoint of improving electron acceptability. In addition, when the crosslinking group represented by formula (X7) is used, the following crosslinking reaction proceeds.

[Chemical 19]

Crosslinking represented by either formula (X8) or formula (X9) is preferable in terms of high reactivity. In addition, when using the crosslinking group represented by formula (X8) and the crosslinking group represented by formula (X9), the following crosslinking reaction is performed.

[Chemistry 20]

The crosslinking group is preferably a crosslinking group represented by any one of cationically polymerizable formula (X10), formula (X11), and formula (X12) in terms of high reactivity.

＜Charge transport material＞ The charge transport material used in the present invention is a material that can transport holes and/or electrons. In addition, the charge transport material used in the present invention is preferably a material that has hole transport properties, and is oxidized by an electron-accepting compound and cationically radicalized. In the present invention, as the charge transporting material, a polymer compound is preferred, a hole transporting polymer compound is preferred, and a polymer compound containing an arylamine structure as a repeating unit is preferred. In this case, the so-called electric charges are usually holes, the so-called transferred charges are transferred holes, the so-called charge transport film is a hole transport film, and the so-called charge injection layer is a hole injection layer.

[Composition of the present invention] The composition of the present invention is a composition containing a polymer compound (hereinafter, sometimes referred to as "the fluorine-containing arylamine polymer compound of the present invention") and having a repeating unit represented by the following formula (1) , having fluorene which may have a substituent in at least one of the main chain and the side chain, and having a crosslinking group; and an electron-accepting compound (hereinafter, sometimes referred to as the "electron-accepting compound of the present invention"), consisting of It is represented by the following formula (81) and has a crosslinking group.

[Chemistry 21]

(In formula (1), Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms that may have a substituent, a divalent aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, or a divalent aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent. The aromatic hydrocarbon group of the substituent or the aromatic heterocyclic group which may have a substituent is a divalent group in which a plurality of aromatic heterocyclic groups are connected directly or via a connecting group, and G represents any of the formulas (1-1) to (1-3). The divalent group represented by one, "*" represents the bonding position with the adjacent structure, and the substituent A is each independently a fluorine atom, CF ₃ or SF ₅ ; Ar ² represents a hydrogen atom, and the substituent A may have The substituent may be an aromatic hydrocarbon group having 6 to 60 carbon atoms, an aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, or an aromatic hydrocarbon group that may have a substituent and an aromatic group that may have a substituent. A monovalent group in which multiple groups in the heterocyclic group are connected directly or via a connecting group; m is an integer from 1 to 4, n is an integer from 1 to 6)

[Chemistry 22]

(In formula (81), five R ⁸¹ , five R ⁸² , five R ⁸³ , and five R ⁸⁴ are each independently independent, and R ⁸¹ to R ⁸⁴ are each independently a hydrogen atom, a deuterium atom, or a halogen atom, and may have An aromatic hydrocarbon group having 6 to 50 carbon atoms as a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, an alkyl group having 1 to 12 carbon atoms substituted with fluorine, or a crosslinking group; Ph ¹ , Ph ² , Ph ³ , Ph ⁴ refer to the symbols of their respective benzene rings; X ⁺ represents countercation)

The composition of the present invention may be a composition including: a polymer compound having a repeating unit represented by the following formula (1) and a cross-linking group; and an electron-accepting compound represented by the following formula (81) , and has at least two cross-linking groups.

[Chemistry 23]

(In formula (1), Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms that may have a substituent, a divalent aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, or a divalent aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent. The aromatic hydrocarbon group of the substituent or the aromatic heterocyclic group which may have a substituent is a divalent group in which a plurality of aromatic heterocyclic groups are connected directly or via a connecting group, and G represents any of the formulas (1-1) to (1-3). In the divalent group represented by A, the substituent A is each independently a fluorine atom, CF ₃ or SF ₅ ; Ar ² represents the substituent A, an aromatic hydrocarbon group having 6 to 60 carbon atoms that may have a substituent, and may have a substituent. The group is an aromatic heterocyclic group having 3 to 50 carbon atoms, or a plurality of groups selected from an aromatic hydrocarbon group which may have a substituent and an aromatic heterocyclic group which may have a substituent are connected directly or via a connecting group. A monovalent base; m is an integer from 1 to 4, n is an integer from 1 to 6)

[Chemistry 24]

(In formula (81), five R ⁸¹ , five R ⁸² , five R ⁸³ , and five R ⁸⁴ are each independently independent, and R ⁸¹ to R ⁸⁴ are each independently a hydrogen atom, a deuterium atom, or a halogen atom, and may have An aromatic hydrocarbon group having 6 to 50 carbon atoms as a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, an alkyl group having 1 to 12 carbon atoms substituted with fluorine, or a crosslinking group; Ph ¹ , Ph ² , Ph ³ , Ph ⁴ refer to the symbols of their respective benzene rings; X ⁺ represents countercation)

＜Polymer compounds with cross-linking groups＞ The polymer compound having a crosslinking group is preferably a polymer compound having a crosslinking group that contains an arylamine structure having a repeating unit represented by the formula (1) as a repeating unit. Molecular compounds. The polymer compound is contained in the composition of the present invention as a charge transport material.

The carbon number of the aromatic hydrocarbon group (Ar ¹ ) is preferably 6 to 60, more preferably 6 to 30, and even more preferably 6 to 18. Specific examples of the aromatic hydrocarbon group include: benzene ring, naphthalene ring, fluorene ring, anthracene ring, tetraphenyl ring, phenanthrene ring, pyrene ring, benzanthracene ring or perylene ring, etc. The number of carbon atoms is usually: A divalent group of an aromatic hydrocarbon ring structure of 6 or more and usually 30 or less, preferably 18 or less, and even more preferably 14 or less, or a plurality of structures selected from these structures are bonded in a chain or branched manner. The divalent base of the structure. When a plurality of aromatic hydrocarbon rings are connected, a structure in which two to eight are connected is generally exemplified, and a structure in which two to five are connected is preferred. When a plurality of aromatic hydrocarbon rings are connected, the same structure may be connected or different structures may be connected.

The carbon number of the aromatic heterocyclic group is preferably 3 to 50, more preferably 3 to 30, and even more preferably 3 to 18. Specific examples of the aromatic heterocyclic group include: triazine ring, pyrimidine ring, pyridine ring, benzofuran, benzothiophene, dibenzofuran, dibenzothiophene, carbazole ring, etc. The carbon number is usually: A divalent group of an aromatic heterocyclic structure of 3 or more and usually 30 or less, preferably 18 or less, and even more preferably 12 or less, or a plurality of structures selected from these structures are bonded in a chain or branch form The divalent base of the structure.

Ar ¹ is preferably one or more selected from the group consisting of divalent aromatic hydrocarbons having 6 to 60 carbon atoms which may have substituents, and divalent aromatic heterocyclic groups having 3 to 50 carbon atoms which may have substituents. A divalent group bonded directly or via a connecting group. In terms of improving hole transport properties, the group directly bonded to a nitrogen atom is preferably an aromatic hydrocarbon group which may have a substituent. As an aromatic The family hydrocarbon group is preferably a plurality of structures selected from one to four benzene rings, one or two naphthalene rings, one or two fluorene rings, one or two multiple phenanthrene rings, and one tetraphenyl ring. A divalent group formed by chain or branch bonding in any order, or a 1,4-phenylene group, a 1,3-phenylene group, a 2,7-fluorenyl group, or a divalent spirobifluorenyl group, Furthermore, a divalent group formed by a plurality of structures selected from one to four benzene rings and one or two fluorene rings in a chain or branch bonding manner in any order is more preferred, and one or two extension groups are particularly preferred. Phenyl, 2,7-fluorenyl, a divalent radical formed by one or two phenylene groups sequentially bonded in a chain, phenylene group, biphenyl group, p-triphenyl group, or 2, 7-Fluorenyl. The fluorene structure may have a substituent at positions 9 and 9', and the substituent it may have is preferably a group selected from the substituent group Z.

These aromatic hydrocarbon structures may have substituents. The optional substituents are as described above, and specifically, they can be selected from the substituent group Z. Preferred substituents are preferred substituents of the substituent group Z.

(Preferable range of Ar ¹ ) From the viewpoint of the solubility and durability of the polymer compound, Ar ¹ preferably has at least one selected from the following formulas (2-1) to formula (2-7) structure.

[Chemical 25]

In each of the formulas (2-1) to (2-7), * represents a bond with an adjacent structure or a hydrogen atom, and at least one of two * represents a bonding position with an adjacent structure. , at least one of any two * selected from four * represents a bonding position with an adjacent structure. In the following records, unless otherwise specified, the definition of * will also be the same. R ¹ and R ² are each independently a hydrogen atom, a deuterium atom, a halogen atom, an aromatic hydrocarbon group having 6 to 18 carbon atoms that may have a substituent, an aromatic heterocyclic group having 3 to 12 carbon atoms that may have a substituent, Alkyl group with 1 to 12 carbon atoms.

Ar ¹ preferably has a partial structure selected from one of the above formulas (2-1) to formula (2-3), or has a partial structure selected from the above formulas (2-1) to formula (2-3) A bonding structure formed by two or more mutually bonded structures. The bonding structure may also include at least one structure selected from the formula (2-1) to formula (2-3) bonded with two or more structures. formed structure.

That is, the bonded structure may include, for example, a structure in which two or more of the structures (2-1) described above are bonded.

(R ¹ , R ² ) R ¹ and R ² are each independently a hydrogen atom, a deuterium atom, a halogen atom, an aromatic hydrocarbon group having 6 to 18 carbon atoms that may have a substituent, or a carbon number that may have a substituent. Aromatic heterocyclic group with 3 to 12 carbon atoms, alkyl group with 1 to 12 carbon atoms, preferably alkyl group with 6 to 12 carbon atoms, alkenyl group, alkynyl group, alkoxy group, aryloxy group, and alkoxycarbonyl group , hydroxyl group, halogen atom, haloalkyl group, alkylthio group, arylthio group, silyl group, silyloxy group, cyano group, aralkyl group, or monovalent aromatic hydrocarbon group with 6 to 30 carbon atoms, R ¹ , R ² Can bond together to form a ring. As the aromatic hydrocarbon ring structure, a phenyl group or a group in which a plurality of phenyl groups are connected is more preferred.

These groups may have substituents. The possible substituents are as described above, and specifically, they can be selected from the substituent group Z or a crosslinking group. A preferred substituent of the substituent group Z, an aromatic hydrocarbon group having 6 to 50 carbon atoms that may have a crosslinking group, or a crosslinking group is preferred.

As the partial structure, a structure selected from formula (2-1) to formula (2-7) is more preferred, a structure selected from formula (2-1) to formula (2-5) is still more preferred, and a structure selected from formula (2-5) is particularly preferred. It is a structure selected from formula (2-1) to formula (2-4). In terms of excellent charge transport properties, it is preferable to have a partial structure represented by formula (2-2) and formula (2-3).

As the formula (2-1), a 1,3-phenylene group or a 1,4-phenylene group is preferred.

As the formula (2-2), the following formula (2-2-2) is preferred.

[Chemical 26]

The formula (2-2) is more preferably the following formula (2-2-3).

[Chemical 27]

In addition, from the viewpoint of the solubility and durability of the compound, Ar ¹ preferably has a partial structure represented by formula (2-1) and a partial structure represented by formula (2-2) as a partial structure.

The partial structure having a partial structure represented by formula (2-1) and a partial structure represented by formula (2-2) is further preferably: a plurality of partial structures selected from the group consisting of partial structures represented by formula (2-1) and The structure of the partial structure represented by the formula (2-2) is a partial structure represented by at least one selected from the following formula (2-8) to the following formula (2-11).

[Chemical 28]

The partial structure having a partial structure represented by the formula (2-1) and a partial structure represented by the formula (2-3) and the formula (2-4) is further preferably: a plurality of parts selected from the group consisting of the formula (2-1) ) and the partial structure represented by formula (2-3) and formula (2-4), that is, the structure is selected from the following formula (2-12) to the following formula (2-15 ) is a partial structure represented by at least one of .

[Chemical 29]

(G) G represents a divalent group represented by any one of the formulas (1-1) to (1-3), and the substituents A are each independently a fluorine atom, CF ₃ or SF ₅ . Regarding the substituent A, among the above, a fluorine atom or CF ₃ is preferred from the viewpoint of not reducing the charge transport capability. From this viewpoint, m and n in Formula (1-1) to Formula (1-3) are preferably integers of 1 to 2.

G is preferably a group represented by any one of the following formulas.

[Chemical 30]

(In the above formula, "*" indicates the bonding position with the adjacent structure)

(Ar ² ) Ar ² represents a hydrogen atom, a substituent A, an aromatic hydrocarbon group having 6 to 60 carbon atoms that may have a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, or will be selected from the group consisting of A monovalent group in which a plurality of groups in the aromatic hydrocarbon group which may have a substituent and the aromatic heterocyclic group which may have a substituent are connected directly or via a connecting group.

In the polymer compound used in the present invention, when a plurality of Ar ² are present, the plurality of Ar ² may be the same or different.

Specific examples of the monovalent aromatic hydrocarbon group include: benzene ring, azulene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, pyrene ring, trisulfenyl ring Monovalent groups of 6-membered rings or 2-5 condensed rings such as benzene ring, ethane naphthalene ring, fluoranthene ring, and fluorene ring.

Specific examples of the monovalent aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, and an indole ring. , carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furanofuran ring, thienofuran ring, benzoisoxane Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, Monovalent groups of 5-membered or 6-membered single rings or 2-4 condensed rings such as phenanthridine ring, phenidine ring, quinazoline ring and quinazolinone ring.

Examples of the connecting group include an oxygen atom or a carbonyl group. By forming a non-conjugated structure with an aromatic ring, the triplet level can be improved. Therefore, a structure in which phenylene rings are connected to each other through oxygen atoms or carbonyl groups can also be used. A structure in which they are directly connected without a connecting group is preferred. The same applies to the connecting group in Ar ¹ .

Among these, in terms of excellent charge transport properties and excellent durability, a monovalent aromatic hydrocarbon group is preferred, a monovalent group of a benzene ring or a fluorene ring is more preferred, and a phenyl group or a fluorenyl group is even more preferred. , particularly preferably fluorenyl, and the most preferred is 2-fluorenyl.

In addition, in terms of solubility in the coating solvent, Ar ² is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms, and particularly preferably a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms. Fluorenyl. Furthermore, Ar ² is preferably a 9-alkyl-2-fluorenyl group substituted with an alkyl group at the 9-position of the 2-fluorenyl group, and particularly preferably a 9,9-dialkyl-2-substituted with two alkyl groups. Fluorenyl. Ar ² is a fluorenyl group substituted by an alkyl group, so it has improved solubility in the solvent and is preferable.

As a monovalent group in which a plurality of groups selected from an aromatic hydrocarbon group that may have a substituent and an aromatic heterocyclic group that may have a substituent are connected directly or via a connecting group, an aromatic group selected from the above can be used. A monovalent group in which a plurality of groups among the hydrocarbon group and the aromatic heterocyclic group are connected directly or via a connecting group.

(-G-Ar ² ) [-G-Ar ² ] is preferably a group represented by any one of the following formulas.

[Chemical 31]

(In the above formula, "*" indicates the bonding position with the adjacent structure)

(Specific example) Specific examples of the repeating unit represented by the formula (1) used in the present invention are shown below, but are not limited to these.

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35]

<Fluorene which may have a substituent> The polymer compound having a crosslinking group has fluorene which may have a substituent on at least one of the main chain and the side chain. The substituent is preferably a linear or branched alkyl group having 1 to 12 carbon atoms. The substituent is preferably introduced into the 5-membered ring portion of fluorene. Examples of the polymer compound having fluorene in which the substituent is introduced into the 5-membered ring portion include the polymer compound P-1 described below.

<Arylamine structure which is a preferred repeating unit combined with the repeating unit represented by the formula (1) used in the present invention> The repeating unit of the arylamine structure of the polymer compound having a preferred arylamine structure in combination with the repeating unit represented by the formula (1) used in the present invention as a repeating unit is represented by the following formula (50) .

[Chemical 36]

(In formula (50), Ar ⁵¹ represents an aromatic hydrocarbon group, an aromatic heterocyclic group, or a group in which a plurality of groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group are connected, and Ar ⁵² represents a divalent aromatic group. A hydrocarbon group, a divalent aromatic heterocyclic group, or at least one group selected from the group consisting of the divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group, connected directly or via a connecting group. divalent group; Ar ⁵¹ and Ar ⁵² may form a ring through a single bond or a connecting group; Ar ⁵¹ and Ar ⁵² may have substituents)

The substituent that Ar ⁵¹ and Ar ⁵² may have is preferably a substituent selected from the substituent group Z or a crosslinking group.

When Ar ⁵¹ and Ar ⁵² have a cross-linking group, the cross-linking group is preferably a cross-linking group selected from the cross-linking group T.

The substituents that the aromatic hydrocarbon group and the aromatic heterocyclic group of Ar ⁵¹ may have are not particularly limited as long as they do not significantly reduce the characteristics of the polymer compound used in the present invention. The substituent is preferably a group selected from the substituent group Z described below, more preferably an alkyl group, an alkoxy group, an aromatic hydrocarbon group, an aromatic heterocyclic group, and even more preferably an alkyl group.

From the viewpoint of solubility in a solvent, Ar ⁵¹ is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms, and particularly preferably a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms. More preferably, a 9-alkyl-2-fluorenyl group substituted with an alkyl group at the 9-position of the 2-fluorenyl group is particularly preferred, a 9,9'-dialkyl-2-fluorenyl group substituted with two alkyl groups. .

When at least one of the 9-position and 9'-position is a fluorenyl group substituted with an alkyl group, the solubility in the solvent and the durability of the fluorene ring tend to be improved. Furthermore, since both the 9-position and the 9'-position are fluorenyl groups substituted with alkyl groups, the solubility in the solvent and the durability of the fluorene ring tend to be further improved.

In addition, in terms of solubility in a solvent, Ar ⁵¹ is preferably a spirobifluorenyl group.

Examples of the repeating unit represented by the formula (50) include the repeating unit represented by the following formula (3).

[Chemical 37]

(In formula (3), Ar ³ is a 2-fluorenyl group that may have a substituent; Ar ⁴ represents a divalent aromatic hydrocarbon group that may have a substituent, a divalent aromatic heterocyclic group that may have a substituent, or a selected A plurality of at least two groups in the group consisting of the divalent aromatic hydrocarbon group which may have a substituent and the divalent aromatic heterocyclic group which may have a substituent are connected directly or via a linking group divalent base)

In addition, the polymer containing the repeating unit represented by the formula (50) preferably contains a group in which Ar ⁵¹ in the repeating unit represented by the formula (50) is a group represented by the following formula (51): A repeating unit of a group represented by the following formula (52) or a group represented by the following formula (53).

<Base represented by formula (51)>

[Chemical 38]

(In the formula (51), * represents a bond with the nitrogen atom in the main chain of the formula (50), and Ar ⁵³ and Ar ⁵⁴ each independently represent a divalent aromatic hydrocarbon group which may have a substituent, and an aromatic group which may have a substituent. Heterocyclic group, or a divalent group in which a plurality of optionally substituted aromatic hydrocarbon groups or optionally substituted aromatic heterocyclic groups are connected directly or via a connecting group, Ar ⁵⁵ represents an optionally substituted aromatic group A hydrocarbon group, an aromatic heterocyclic group which may have a substituent, or a monovalent group in which a plurality of aromatic hydrocarbon groups or aromatic heterocyclic groups which may have a substituent are connected directly or via a connecting group; Ar ⁵⁶ represents a hydrogen atom or substituent)

Here, each aromatic hydrocarbon group and each aromatic heterocyclic group may have a substituent. The optional substituent is preferably a group selected from the substituent group Z or a cross-linking group. When there is a cross-linking group, the cross-linking group is preferably selected from the cross-linking group T. in the base.

(Ar ⁵³ ) Ar ⁵³ is preferably a group in which one to six divalent aromatic hydrocarbon groups are linked together, more preferably two to four divalent aromatic hydrocarbon groups are linked together, and more preferably one to four divalent aromatic hydrocarbon groups are linked together. A group formed by connecting two phenylene rings, particularly preferably a biphenylene group formed by connecting two phenylene rings.

These groups may have substituents. The optional substituent is preferably a group selected from the substituent group Z or a cross-linking group. When there is a cross-linking group, the cross-linking group is preferably selected from the cross-linking group T. in the base. Preferably, Ar ⁵³ has no substituent.

In addition, when a plurality of these divalent aromatic hydrocarbon groups or divalent aromatic heterocyclic groups are connected, it is preferable that the plurality of divalent aromatic hydrocarbon groups are bonded in a non-conjugated manner. base. Specifically, a group containing a 1,3-phenylene group or a substituent and forming a twisted structure due to the stereoscopic effect of the substituent is preferred, and a 1,3-phenylene group without a substituent is more preferred. , or a group obtained by linking multiple 1,3-phenylene groups without a substituent.

(Ar ⁵⁴ ) In terms of excellent charge transport properties and excellent durability, Ar ⁵⁴ is preferably a group in which one or more divalent aromatic hydrocarbon groups, which may be the same or different, are linked together. The hydrocarbon group may have a substituent. When a plurality of groups are connected, the number of connected groups is preferably 2 to 10, more preferably 6 or less, and particularly preferably 3 or less from the viewpoint of film stability. Preferred aromatic hydrocarbon ring structures include benzene ring, naphthalene ring, anthracene ring, and fluorene ring, and more preferred ones are benzene ring and fluorene ring. As a group in which a plurality of phenylene rings are connected, a group in which one to four phenylene rings are connected, or a group in which a phenylene ring and a fluorene ring are connected are preferred. From the perspective of extending the lowest unoccupied molecular orbital (LUMO), a biphenylene group formed by connecting two phenylene rings is particularly preferred.

These groups may have substituents. The optional substituent is preferably a group selected from the substituent group Z or a cross-linking group. When there is a cross-linking group, the cross-linking group is preferably selected from the cross-linking group T. in the base. More preferred substituents include phenyl, naphthyl and fluorenyl. Moreover, it is also preferable that it does not have a substituent.

(Ar ⁵⁵ ) Ar ⁵⁵ is an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent connected directly or via a linking group. A single price basis. Preferably, it is a monovalent aromatic hydrocarbon group or a group in which a plurality of monovalent aromatic hydrocarbon groups are linked together.

These groups may have substituents. The optional substituent is preferably a group selected from the substituent group Z or a cross-linking group. When there is a cross-linking group, the cross-linking group is preferably selected from the cross-linking group T. in the base.

When a plurality of these groups are connected, it is a divalent group in which two to ten of these groups are connected, and preferably a monovalent group in which two to five of these groups are connected. As the aromatic hydrocarbon group and the aromatic heterocyclic group, the same aromatic hydrocarbon groups and aromatic heterocyclic groups as described for Ar ⁵¹ can be used.

Ar ⁵⁵ preferably has a structure represented by any one of the following Scheme 2A, Scheme 2B, and Scheme 2C.

[Chemical 39]

[Chemical 40]

[Chemical 41]

In the above-mentioned aspects 2A to 2C, "-*" represents the bonding position with Ar ^54. When there are multiple "-*"s, any one of them represents the bonding position with Ar ⁵⁴ . These structures may have substituents. The substituents that these structures may have are preferably groups or cross-linking groups selected from the substituent group Z. When there is a cross-linking group, the cross-linking group is preferably selected from the group Z. A group in the cross-linking group T.

(R ³¹ and R ³² ) R ³¹ and R ³² in Scheme 2A and Scheme 2B are preferably each independently a linear, branched or cyclic alkyl group which may have a substituent. The number of carbon atoms in the alkyl group is not particularly limited. However, in order to maintain the solubility of the polymer, the number of carbon atoms is preferably 1 or more and 6 or less, more preferably 3 or less, and more preferably a methyl group or an ethyl group.

R ³¹ and R ³² may be the same or different, but in order to uniformly distribute charges around the nitrogen atom and facilitate synthesis, it is preferable that all R ³¹ and R ³² are the same group.

(Ar ^d18 ) Ar ^d18 in Scheme 2B is each independently an aromatic hydrocarbon group or an aromatic heterocyclic group. From the viewpoint of stability, Ar ^d18 is preferably an aromatic hydrocarbon group, and more preferably a phenyl group. These groups may further have substituents. The optional substituent is preferably a group selected from the substituent group Z or a cross-linking group. When there is a cross-linking group, the cross-linking group is preferably selected from the cross-linking group T. in the base.

From the viewpoint of distributing the LUMO of the molecule, Ar ⁵⁵ is preferably selected from the group consisting of a-1 to a-4, b-1 to b-9, c-1 to c-4, d-1 to d-18, and the structures in e-1 to e-4. Furthermore, from the viewpoint of promoting the LUMO expansion of the molecule by having an electron-withdrawing group, it is preferable to be selected from a-1 to a-4, b-1 to b-9, d-1 to d-12, The structures in d-17, d-18, and e-1 to e-4. Furthermore, from the viewpoint of the effect of having a high triplet level and confining the formed excitons in the light-emitting layer, it is preferable to select from a-1 to a-4, d-1 to d-12, and d-17 , d-18, and the structures in e-1 to e-4. In addition, from the viewpoint of simple synthesis and excellent stability, d-1, d-10, d-17, d-18, and e-1 are more preferred, and the benzene ring structure of d-1 is particularly preferred. The fluorene ring structure of d-6 or the carbazole structure of d-17.

When Ar ⁵⁵ is a fluorene structure represented by d-6, it is preferably a 2-fluorenyl group. Furthermore, the 9, 9' position may have a substituent. The substituent that may be present is preferably a group selected from the substituent group Z or a cross-linking group. In the case of a cross-linking group, it is a cross-linking group. , preferably a group selected from the cross-linking group T. As the substituent, an alkyl group is preferred.

(Ar ⁵⁶ ) Ar ⁵⁶ represents a hydrogen atom or a substituent. When Ar ⁵⁶ is a substituent, it is not particularly limited. It is preferably an aromatic hydrocarbon group, an aromatic heterocyclic group or a crosslinking group. In the case of an aromatic hydrocarbon group or an aromatic heterocyclic group, it may be more selective. A substituent from the substituent group Z or a crosslinking group selected from the crosslinking group T. When Ar ⁵⁶ is a cross-linking group, it is preferably a cross-linking group selected from the cross-linking group T.

When Ar ⁵⁶ is a substituent, from the viewpoint of improving durability, it is preferably bonded to the 3-position of the carbazole structure to which Ar ⁵⁶ is bonded in the formula (51). From the viewpoint of ease of synthesis and charge transportability, Ar ⁵⁶ is preferably a hydrogen atom. From the viewpoint of durability improvement and charge transportability, Ar ⁵⁶ is preferably an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and more preferably an aromatic hydrocarbon group which may have a substituent.

From the viewpoint of ease of synthesis and charge transportability, Ar ⁵⁶ is preferably a hydrogen atom.

(Specific example of the base represented by formula (51)) Specific examples of the group represented by Formula (51) are listed below, but the group represented by Formula (51) is not limited to these.

[Chemical 42]

<Base represented by formula (52)>

[Chemical 43]

(In formula (52), Ar ⁶¹ and Ar ⁶² are each independently an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or an optionally substituted aromatic hydrocarbon group. Or a divalent group in which a plurality of aromatic heterocyclic groups which may have a substituent are connected directly or via a connecting group, Ar ⁶³ to Ar ⁶⁵ are each independently a hydrogen atom or a substituent; * represents the direction in the formula (50) The bonding position of the nitrogen atom in the main chain)

(Ar ⁶³ to Ar ⁶⁵ ) Ar ⁶³ to Ar ⁶⁵ are each independently the same as Ar ⁵⁶ . Ar ⁶³ to Ar ⁶⁴ are preferably hydrogen atoms.

(Ar ⁶² ) Ar ⁶² is an optionally substituted divalent aromatic hydrocarbon group, an optionally substituted divalent aromatic heterocyclic group, or an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group. A bivalent group in which a plurality of ring groups are connected directly or via a linking group. Preferred is a divalent aromatic hydrocarbon group which may have a substituent or a group in which a plurality of divalent aromatic hydrocarbon groups which may have a substituent are linked together. Here, the substituents that the aromatic hydrocarbon group may have and the substituents that the aromatic heterocyclic group may have are preferably the same groups or crosslinking groups as the substituent group Z mentioned above. As the cross-linking group, a group selected from the cross-linking group T is preferred.

The specific structure of Ar ⁶² is the same as Ar ⁵⁴ .

A specific preferred group for Ar ⁶² is a divalent group of a benzene ring, a naphthalene ring, an anthracene ring, a fluorene ring or a group in which a plurality of these are connected, and more preferably a divalent group of a benzene ring or a group in which these are connected. A plurality of groups, particularly preferably a 1,4-phenylene group in which a benzene ring is linked with a divalent linkage at the 1,4-position, and a 2,7-phenylene group in which a fluorene ring is linked with a divalent linkage at the 2,7-position. The fluorenylene group, or a group obtained by connecting a plurality of these groups, is preferably a group containing "1,4-phenylene-2,7-fluorenyl-1,4-phenylene".

Among these preferred structures of Ar ⁶² , it is preferable that the phenylene group has no substituent except at the linking position, and that no twisting of Ar ⁶² due to the stereoscopic effect of the substituent occurs. In addition, from the viewpoint of improving solubility and durability of the fluorene structure, the fluorenyl group preferably has a substituent at the 9, 9' position. As the substituent, a substituent or a crosslinking group selected from the substituent group Z is preferred, and an alkyl group is more preferred. These substituents may be further substituted with crosslinking groups. As the cross-linking group, a cross-linking group selected from the cross-linking group T is preferred. Preferred are substituents selected from substituent group Z.

(Ar ⁶¹ ) Ar ⁶¹ and Ar ⁵³ are the same group and have the same preferred structure.

(Specific example of the base represented by formula (52)) Specific examples of the group represented by Formula (52) are listed below, but the group represented by Formula (52) is not limited to these.

[Chemical 44]

<The base represented by formula (53)>

[Chemical 45]

(In formula (53), * represents a bond with the nitrogen atom in the main chain of formula (50), Ar ⁷¹ represents a divalent aromatic hydrocarbon group, and Ar ⁷² and Ar ⁷³ independently represent an aromatic hydrocarbon group and an aromatic heterocyclic group. , or a monovalent group in which two or more groups selected from aromatic hydrocarbon groups and aromatic heterocyclic groups are connected directly or via a connecting group. These groups may have substituents. Ring HA contains a nitrogen atom. Aromatic heterocycle, X ² and Y ² independently represent a carbon atom or a nitrogen atom. When at least one of X ² and Y ² is a carbon atom, the carbon atom may have a substituent)

The optional substituent is preferably a group selected from the substituent group Z or a crosslinking group. When having a cross-linking group, the cross-linking group is preferably a group selected from the cross-linking group group T.

<Ar ⁷¹ > Ar ⁷¹ is the same group as Ar ⁵³ .

Ar ⁷¹ is particularly preferably a group in which two to six optionally substituted benzene rings are connected, and most preferably is an extended tetraphenyl group in which four optionally substituted benzene rings are connected.

In addition, Ar ⁷¹ preferably contains at least one benzene ring connected at the 1, 3-position of the non-conjugated site, and more preferably contains two or more benzene rings.

When Ar ⁷¹ is a group formed by connecting a plurality of divalent aromatic hydrocarbon groups which may have a substituent, from the viewpoint of charge transport properties or durability, it is preferable that all of them are directly bonded and connected.

Therefore, as Ar ⁷¹ , a preferable structure between the nitrogen atom connecting the polymer main chain and the ring HA in the formula (53) is as listed in the following scheme 2-1 and scheme 2-2. "-*" represents the bonding site with the nitrogen atom of the polymer main chain or the ring HA of the formula (53). Either one of the two "-*"s may be bonded to the nitrogen atom of the main chain of the polymer or to the ring HA.

[Chemical 46]

As the substituent that Ar ⁷¹ may have, any one of the substituent groups Z described above or a combination thereof can be used. The preferred range of substituents that Ar ⁷¹ may have is the same as the substituents that Ar ⁵³ may have when it is an aromatic hydrocarbon group.

<X ² and Y ² > X ² and Y ² each independently represent a C (carbon) atom or an N (nitrogen) atom. When at least one of X ² and Y ² is a C atom, it may have a substituent.

From the viewpoint of making it easier for LUMO to exist locally around ring HA, both X ² and Y ² are preferably N atoms.

When at least one of X ² and Y ² is a C atom, as the substituent that may be possessed, any one of the above-mentioned substituent groups Z or a combination thereof can be used. From the viewpoint of charge transport properties, it is further preferred that X ² and Y ² have no substituent.

<Ar ⁷² and Ar ⁷³ > Ar ⁷² and Ar ⁷³ are each independently an aromatic hydrocarbon group, an aromatic heterocyclic group, or two or more groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group, directly or via a connecting group A single price base formed by connecting multiple ones. These groups may have substituents, and the substituents they may have are preferably groups selected from the substituent group Z or a cross-linking group. When having a cross-linking group, the cross-linking group is preferably a group selected from the cross-linking group group T.

From the viewpoint of distributing the LUMO of the molecule, it is preferable that Ar ⁷² and Ar ⁷³ each independently have a-1 to a-4 and b-1 to b-9 selected from the group consisting of a-1 to a-4 and b-1 to b-9 shown in Schemes 2A to 2C. , c-1～c-4, d-1～d-16 and e-1～e-4 structures.

Furthermore, from the viewpoint of promoting the LUMO expansion of the molecule by having an electron-withdrawing group, it is preferable to be selected from the group consisting of a-1 to a-4, b-1 to b-9, c-1 to c-5, The structures in d-1 to d-12 and e-1 to e-4.

Furthermore, from the viewpoint of the effect of having a high triplet level and confining the formed excitons in the light-emitting layer, it is preferable to be selected from the group consisting of a-1 to a-4, d-1 to d-12, and e- The structures in 1~e-4.

In order to prevent aggregation of molecules, structures selected from d-1 to d-12 and e-1 to e-4 are more preferred. From the viewpoint of simple synthesis and excellent stability, Ar ⁷² =Ar ⁷³ =d-1 or d-10 is preferred, and a benzene ring structure of d-1 is particularly preferred. In addition, these structures may have substituents.

(Specific example of the base represented by formula (53)) Specific examples of the group represented by Formula (53) are listed below, but the group represented by Formula (53) is not limited to these.

[Chemical 47]

(Preferred repeating unit represented by formula (50)) The repeating unit represented by the formula (50) is preferably selected from the group consisting of a repeating unit represented by the following formula (54), a repeating unit represented by the following formula (55), and a repeating unit represented by the following formula (56). The repeating unit of , the repeating unit represented by the following formula (57), and the repeating unit represented by the following formula (60).

<Repeating unit represented by formula (54)>

[Chemical 48]

(In formula (54), Ar ⁵¹ is the same as Ar ⁵¹ in formula (50), and X is -C(R ²⁰⁷ )(R ²⁰⁸ )-, -N(R ²⁰⁹ )- or -C(R ²¹¹ ) (R ²¹² )-C(R ²¹³ )(R ²¹⁴ )-, R ²⁰¹ , R ²⁰² , R ²²¹ and R ²²² are each independently an alkyl group which may have a substituent, R ²⁰⁷ to R ²⁰⁹ and R ²¹¹ to R ²¹⁴ are each independently a hydrogen atom, an alkyl group that may have a substituent, an aralkyl group that may have a substituent, or an aromatic hydrocarbon group that may have a substituent; a and b are each independently an integer from 0 to 4, and c is 0 is an integer from 0 to 3, d is an integer from 0 to 4, i and j are each independently an integer from 0 to 3)

(R ²⁰¹ , R ²⁰² , R ²²¹ , R ²²² ) R ²⁰¹ , R ²⁰² , R ²²¹ and R ²²² in the repeating unit represented by the formula (54) are each independently an alkyl group which may have a substituent.

The alkyl group is a linear, branched or cyclic alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but in order to maintain the solubility of the polymer, it is preferably 1 or more and more preferably 8 or less, more preferably 6 or less, and still more preferably 3 or less. The alkyl group is more preferably methyl or ethyl.

When there are multiple R ^201s , the multiple R ^201s may be the same or different. When there are multiple R ^202s , the multiple R ^202s may be the same or different. It is preferable that all R ²⁰¹ and R ²⁰² are the same group so that the charge can be uniformly distributed around the nitrogen atom and the synthesis can be facilitated.

When there are multiple R ^221s , the multiple R ^221s may be the same or different. When there are multiple R ^222s , the multiple R ^222s may be the same or different. From the viewpoint of easy synthesis, it is preferable that all R ²²¹ and R ²²² are the same group.

(R ²⁰⁷ to R ²⁰⁹ and R ²¹¹ to R ²¹⁴ ) R ²⁰⁷ to R ²⁰⁹ and R ²¹¹ to R ²¹⁴ are each independently a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or Aromatic hydrocarbon group having a substituent.

The alkyl group is not particularly limited, but since it tends to improve the solubility of the polymer, the number of carbon atoms is preferably 1 or more and 24 or less, more preferably 8 or less, and even more preferably 6 or less. In addition, the alkyl group may be a linear, branched or cyclic structure.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-hexyl, and n-octyl. , cyclohexyl, dodecyl, etc.

The aralkyl group is not particularly limited, but since it tends to improve the solubility of the polymer, the number of carbon atoms is preferably 5 or more, preferably 60 or less, and more preferably 40 or less.

Specific examples of the aralkyl group include: 1,1-dimethyl-1-phenylmethyl, 1,1-di(n-butyl)-1-phenylmethyl, 1,1- Di(n-hexyl)-1-phenylmethyl, 1,1-di(n-octyl)-1-phenylmethyl, phenylmethyl, phenylethyl, 3-phenyl-1-propyl , 4-phenyl-1-n-butyl, 1-methyl-1-phenylethyl, 5-phenyl-1-n-propyl, 6-phenyl-1-n-hexyl, 6-naphthyl- 1-n-hexyl, 7-phenyl-1-n-heptyl, 8-phenyl-1-n-octyl, 4-phenylcyclohexyl, etc.

The aromatic hydrocarbon group is not particularly limited, but since it tends to improve the solubility of the polymer, the number of carbon atoms is preferably 6 or more, preferably 60 or less, and more preferably 30 or less.

Specific examples of the aromatic hydrocarbon group include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, cyclohexane ring, triphenyl ring, ethyl ring, etc. A monovalent group of a 6-membered ring such as an alkylated naphthalene ring, a fluoranthene ring, a fluorene ring, or a 2- to 5-membered fused ring, or a group in which a plurality of these are connected, etc.

From the viewpoint of improving charge transport properties and durability, R ²⁰⁷ and R ²⁰⁸ are preferably a methyl group or an aromatic hydrocarbon group, R ²⁰⁷ and R ²⁰⁸ are more preferably a methyl group, and R ²⁰⁹ is more preferably a phenyl group.

The alkyl groups of R ²⁰¹ , R ²⁰² , R ²²¹ and R ²²² , the alkyl groups of R ²⁰⁷ to R ²⁰⁹ and R ²¹¹ to R ²¹⁴ , the aralkyl group and the aromatic hydrocarbon group may have a substituent. Examples of the substituent include groups or crosslinking groups exemplified as preferred groups of the alkyl group, aralkyl group and aromatic hydrocarbon group of R ²⁰⁷ to R ²⁰⁹ and R ²¹¹ to R ²¹⁴ . Examples of the cross-linking group include cross-linking groups selected from the above-described cross-linking group T.

From the viewpoint of lowering the voltage, the alkyl groups of R ²⁰¹ , R ²⁰² , R ²²¹ and R ²²² , the alkyl groups of R ²⁰⁷ to R ²⁰⁹ and R ²¹¹ to R ²¹⁴ , the aralkyl groups and the aromatic hydrocarbon groups are preferably not Has substituents.

When the cross-linking group is bonded to the main chain structure of the repeating unit represented by formula (54), the cross-linking group is preferably bonded to R ²⁰⁷ to R when it is an alkyl group, an aralkyl group or an aromatic hydrocarbon group. ²⁰⁹ , R ²¹¹ ~ R ²¹³ or R ²¹⁴ .

(a, b, c, d, i and j) In the repeating unit represented by the formula (54), a and b are each independently an integer of 0 to 4. It is preferable that a+b is 1 or more, it is more preferable that a and b are each 2 or less, and it is more preferable that both a and b are 1. Here, when b is 1 or more, d is also 1 or more. In addition, when c is 2 or more, the plurality of a may be the same or different, and when d is 2 or more, the plurality of b may be the same or different.

If a+b is 1 or more, the aromatic ring of the main chain is twisted due to steric hindrance, the polymer has excellent solubility in the solvent, and the coating film formed by the wet film forming method and heated is The insolubility in the solvent tends to be excellent. Therefore, if a+b is 1 or more, when another organic layer (such as a light-emitting layer) is formed on the coating film by a wet film-forming method, the polymer can be suppressed from flowing into the other organic layer containing the organic solvent. Dissolution of the forming composition.

In the repeating unit represented by the formula (54), c is an integer of 0 to 3, and d is an integer of 0 to 4. It is preferable that c and d are respectively 2 or less, more preferably c and d are equal, and particularly preferably both c and d are 1, or both c and d are 2.

When both c and d in the repeating unit represented by the formula (54) are 1 or both c and d are 2 and both a and b are 2 or 1, R ²⁰¹ and R ²⁰² is best bonded in mutually symmetrical positions.

Here, the fact that R ²⁰¹ and R ²⁰² are bonded at symmetrical positions means that R ²⁰¹ and R ²⁰² are The bonding positions are symmetrical. At this time, a 180-degree rotation with the main chain as the axis is regarded as the same structure.

When present, R ²²¹ and R ²²² are preferably present independently at the 1st position, 3rd position, 6th position or 8th position based on the carbon atom of the benzene ring to which X is bonded. Due to the presence of R ²²¹ and/or R ²²² at this position, the condensed ring bonded by R ²²¹ and/or R ²²² and the adjacent benzene ring on the main chain are twisted through steric hindrance, and the polymer has the property of being in the solvent. It is preferable because it has excellent solubility and the coating film formed by a wet film formation method and subjected to heat treatment tends to have excellent insolubility in a solvent.

When a and b are 0, in order to increase the energy level of the molecule, a twisted structure is preferred. Therefore, it is preferable that i+j is 1 or more, and further, it is preferable that i and j are each 2 or less, and it is more preferable that both i and j be 1.

(X) In terms of high stability during charge transfer, X in the formula (54) is preferably -C(R ²⁰⁷ )(R ²⁰⁸ )- or -N(R ²⁰⁹ )-, more preferably is -C(R ²⁰⁷ )(R ²⁰⁸ )-.

(Better repeating unit) The repeating unit represented by the formula (54) is particularly preferably a repeating unit represented by any one of the following formulas (54-1) to formula (54-8).

[Chemical 49]

[Chemical 50]

In the formula, R ²⁰¹ and R ²⁰² are the same, and R ²⁰¹ and R ²⁰² are bonded at mutually symmetrical positions.

<Preferred examples of the main chain of the repeating unit represented by formula (54)> The main chain structure excluding nitrogen atoms in the formula (54) is not particularly limited, but for example, the following structure is preferred.

[Chemistry 51]

[Chemistry 52]

[Chemistry 53]

[Chemistry 54]

[Chemical 55]

[Chemical 56]

[Chemistry 57]

[Chemical 58]

<Repeating unit represented by formula (55)>

[Chemistry 59]

(In the formula (55), Ar ⁵¹ is the same as Ar ⁵¹ in the formula (54), R ³⁰³ and R ³⁰⁶ are each independently an alkyl group that may have a substituent, and R ³⁰⁴ and R ³⁰⁵ are each independently an alkyl group that may have a substituent. An alkyl group with a substituent, an alkoxy group that may have a substituent, or an aralkyl group that may have a substituent, l is 0 or 1, m is 1 or 2, n is 0 or 1, p is 0 or 1, q is 0 or 1)

(R ³⁰³ , R ³⁰⁶ ) R ³⁰³ and R ³⁰⁶ in the repeating unit represented by the formula (55) are each independently an alkyl group which may have a substituent.

Examples of the alkyl group include the same ones as R ²⁰¹ and R ²⁰² in the formula (54). The optional substituents and preferable structures also include the same ones as R ²⁰¹ and R ²⁰² .

When there are multiple R ^303s , the multiple R ^303s may be the same or different. When there are multiple R ^306s , the multiple R ^306s may be the same or different.

(R ³⁰⁴ , R ³⁰⁵ ) R ³⁰⁴ and R ³⁰⁵ in the repeating unit represented by the formula (55) are each independently an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an alkoxy group which may have a substituent. of aralkyl. An alkyl group which may have a substituent is preferred. Preferably, R ³⁰⁴ and R ³⁰⁴ are the same.

The alkyl group is a linear, branched or cyclic alkyl group. The number of carbon atoms in the alkyl group is not particularly limited, but since it tends to improve the solubility of the polymer, it is preferably 1 or more and 24 or less, more preferably 8 or less, and still more preferably 6 or less.

Specific examples of the alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second-butyl, third-butyl, n-hexyl, and n-octyl. , cyclohexyl, dodecyl, etc.

The alkoxy group is not particularly limited. The alkyl group represented by R ¹⁰ of the alkoxy group (-OR ¹⁰ ) may have any structure of linear, branched, or cyclic. Since it has the ability to improve the solubility of the polymer tendency, so the number of carbon atoms is preferably 1 or more, preferably 24 or less, and more preferably 12 or less.

Specific examples of the alkoxy group include methoxy, ethoxy, n-propoxy, n-butoxy, hexyloxy, 1-methylpentyloxy, cyclohexyloxy, and the like.

The aralkyl group is not particularly limited, but since it tends to improve the solubility of the polymer, the number of carbon atoms is preferably 5 or more, preferably 60 or less, and more preferably 40 or less.

Specific examples of the aralkyl group include: 1,1-dimethyl-1-phenylmethyl, 1,1-di(n-butyl)-1-phenylmethyl, 1,1- Di(n-hexyl)-1-phenylmethyl, 1,1-di(n-octyl)-1-phenylmethyl, phenylmethyl, phenylethyl, 3-phenyl-1-propyl , 4-phenyl-1-n-butyl, 1-methyl-1-phenylethyl, 5-phenyl-1-n-propyl, 6-phenyl-1-n-hexyl, 6-naphthyl- 1-n-hexyl, 7-phenyl-1-n-heptyl, 8-phenyl-1-n-octyl, 4-phenylcyclohexyl, etc.

Examples of substituents that the alkyl group, alkoxy group and aralkyl group of R ³⁰⁴ and R ³⁰⁵ may have include: the alkyl group, aralkyl group and aromatic hydrocarbon group of R ²⁰⁷ to R ²⁰⁹ and R ²¹¹ to R ²¹⁴ Examples of groups listed as preferred groups include crosslinking groups selected from the crosslinking group T described above.

From the viewpoint of lowering the voltage, it is preferable that the alkyl group, alkoxy group and aralkyl group of R ³⁰⁴ and R ³⁰⁵ have no substituent.

When the cross-linking group is bonded to the main chain structure of the repeating unit represented by formula (55), the cross-linking group is preferably bonded to R ³⁰⁴ and R ³⁰⁵ .

(l, m and n) l represents 0 or 1, n represents 0 or 1.

l and n are each independent, and l+n is preferably 1 or more, more preferably 1 or 2, and even more preferably 2. When l+n is in the above range, the solubility of the polymer can be improved and the tendency of precipitation from the composition of the present invention containing the polymer can be suppressed.

m represents 1 or 2, and 1 is preferred in that the organic electroluminescent element produced using the composition of the present invention can be driven at a low voltage, and hole injection capability, transport capability, and durability tend to be improved.

(p and q) p represents 0 or 1, q represents 0 or 1. When l is 2 or more, the plurality of p's may be the same or different. When n is 2 or more, the plurality of q's may be the same or different. In the case of l=n=1, p and q are not 0 at the same time. When p and q are not 0 at the same time, the solubility of the polymer can be improved and the tendency of precipitation from the composition of the present invention containing the polymer can be suppressed. In addition, for the same reason as a and b, if p+q is 1 or more, the aromatic ring of the main chain is twisted due to steric hindrance, and the solubility of the polymer in the solvent is excellent, and by wet process The coating film formed by the film formation method and subjected to heat treatment tends to have excellent insolubility in the solvent. Therefore, if p+q is 1 or more, when another organic layer (for example, a light-emitting layer) is formed on the coating film by a wet film-forming method, the transfer of the polymer to the other organic layer containing the organic solvent can be suppressed. Dissolution of the forming composition.

<Specific examples of the main chain of the repeating unit represented by formula (55)> The main chain structure excluding nitrogen atoms in formula (55) is not particularly limited, and examples thereof include the following structures.

[Chemical 60]

[Chemical 61]

[Chemical 62]

[Chemical 63]

[Chemical 64]

[Chemical 65]

[Chemical 66]

[Chemical 67]

<Repeating unit represented by formula (56)>

[Chemical 68]

(In formula (56), Ar ⁵¹ is the same as Ar ⁵¹ in formula (54), and Ar ⁴¹ is a divalent aromatic hydrocarbon group that may have a substituent, a divalent aromatic heterocyclic group that may have a substituent, or A divalent group in which at least one group selected from the group consisting of the divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group is connected directly or via a connecting group, R ⁴⁴¹ and R ⁴⁴² are respectively is independently an alkyl group which may have a substituent, t is 1 or 2, u is 0 or 1, r and s are each independently an integer from 0 to 4)

(R ⁴⁴¹ , R ⁴⁴² ) R ⁴⁴¹ and R ⁴⁴² in the repeating unit represented by the formula (56) are each independently an alkyl group which may have a substituent.

The alkyl group is a linear, branched or cyclic alkyl group. The number of carbon atoms in the alkyl group is not particularly limited. However, in order to maintain the solubility of the polymer, the number of carbon atoms is preferably 1 or more and preferably 10 or less, more preferably 8 or less, and even more preferably 6 or less. The alkyl group is more preferably methyl or hexyl.

When a plurality of R ⁴⁴¹ and R ⁴⁴² are present in the repeating unit represented by the formula (56), the plurality of R ⁴⁴¹ and R ⁴⁴² may be the same or different.

(r, s, t and u) In the repeating unit represented by formula (56), r and s are each independently an integer from 0 to 4. When t is 2 or more, the multiple r's may be the same or different. When u is 2 or more, the multiple s may be the same or different. It is preferable that r+s is 1 or more, and it is more preferable that r and s are each 2 or less. If r+s is 1 or more, it is considered that the driving life of the organic electric field light-emitting element is further extended for the same reason as a and b in the above-mentioned formula (54).

In the repeating unit represented by the formula (56), t is 1 or 2, and u is 0 or 1. t is preferably 1, and u is preferably 1.

(Ar ⁴¹ ) Ar ⁴¹ is a divalent aromatic hydrocarbon group that may have a substituent, a divalent aromatic heterocyclic group that may have a substituent, or a group selected from the divalent aromatic hydrocarbon group and the divalent aromatic heterocyclic group. A bivalent group is a bivalent group in which at least one group in a group of groups is connected to a plurality of groups directly or via a linking group.

Examples of the aromatic hydrocarbon group and the aromatic hydrocarbon group in Ar ⁴¹ include the same groups as Ar ⁵² in the formula (50). In addition, the aromatic hydrocarbon group and the substituent that the aromatic hydrocarbon group may have are preferably groups selected from the substituent group Z, and the substituent that the aromatic hydrocarbon group may have is also preferably the same as the substituent group Z.

<Repeating unit represented by formula (57)>

[Chemical 69]

(In the formula (57), Ar ⁵¹ is the same as Ar ⁵¹ in the formula (54), and R ⁵¹⁷ to R ⁵¹⁹ each independently represent an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an alkoxy group which may have a substituent. An aralkyl group as a substituent, an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group that may have a substituent, f, g, and h each independently represent an integer from 0 to 4, and e represents an integer from 0 to 3, Among them, when g is 1 or more, e is 1 or more)

(R ⁵¹⁷ to R ⁵¹⁹ ) The aromatic hydrocarbon group and aromatic heterocyclic group in R ⁵¹⁷ to R ⁵¹⁹ are each independently the same group as those listed for Ar ^51. In addition, these groups may have substituents. A group selected from the same group as the substituent group Z or a cross-linking group is preferred. The cross-linking group is preferably a cross-linking group selected from the cross-linking group T.

The alkyl group and aralkyl group in R ⁵¹⁷ to R ⁵¹⁹ are preferably the same groups as those listed for R ²⁰⁷ , and the optional substituent is preferably the same group as R ²⁰⁷ .

The alkoxy group in R ⁵¹⁷ to R ⁵¹⁹ is preferably an alkoxy group listed in the substituent group Z, and the optional substituent is preferably a group selected from the cross-linking group Z.

(f, g, h) f, g, and h each independently represent an integer from 0 to 4. When e is 2 or more, a plurality of g's may be the same or different. f+g+h is preferably 1 or more. f+h is preferably 1 or more, f+h is 1 or more, and f, g and h are more preferably 2 or less, f+h is 1 or more, and f and h are more preferably 1 or less, The optimal values for f and h are both 1.

When f and h are both 1, R ⁵¹⁷ and R ⁵¹⁹ are preferably bonded at mutually symmetrical positions. In addition, R ⁵¹⁷ and R ⁵¹⁹ are preferably the same,

More preferably, g is 2. When g is 2, it is best that the two R ^518s are bonded to each other at the opposite position. When g is 2, it is best that the two R ^518s are the same.

Here, the term "R ⁵¹⁷ and R ^519" are bonded at symmetrical positions to each other means the following bonding positions. Among them, in terms of expression, a 180-degree rotation with the main chain as the axis is regarded as the same structure.

[Chemical 70]

In addition, the repeating unit represented by the formula (57) is preferably a repeating unit represented by the following formula (58).

[Chemical 71]

In the case of the repeating unit represented by the formula (58), g=0 or 2 is preferred. When g=2, the bonding positions are 2nd and 5th position. When g=0, that is, when there is no steric hindrance caused by R ⁵¹⁸ , and when g=2 and the bonding positions are 2 and 5, that is, the steric hindrance becomes the diagonal angle of the two benzene rings bonded by R ⁵¹⁸ . When in position, R ⁵¹⁷ and R ⁵¹⁹ can be bonded at mutually symmetrical positions.

Furthermore, the repeating unit represented by the formula (58) is more preferably a repeating unit represented by the following formula (59) in which e=3.

[Chemical 72]

In the case of the repeating unit represented by the formula (59), g=0 or 2 is preferred. When g=2, the bonding positions are 2nd and 5th position. When g=0, that is, when there is no steric hindrance caused by R ⁵¹⁸ , and when g=2 and the bonding positions are 2 and 5, that is, the steric hindrance becomes the diagonal angle of the two benzene rings bonded by R ⁵¹⁸ . When in position, R ⁵¹⁷ and R ⁵¹⁹ can be bonded at mutually symmetrical positions.

<Specific examples of the main chain of the repeating unit represented by formula (57)> The main chain structure of the repeating unit represented by formula (57) is not particularly limited, and examples thereof include the following structures.

[Chemical 73]

<Repeating unit represented by formula (60)>

[Chemical 74]

(In the formula (60), Ar ⁵¹ is the same as Ar ⁵¹ in the above formula (50), and n ⁶⁰ represents an integer from 1 to 5)

(n ⁶⁰ ) n ⁶⁰ represents an integer of 1 to 5, preferably an integer of 1 to 4, and more preferably an integer of 1 to 3.

(terminal group) In this specification, the terminal group refers to the structure of the terminal portion of the polymer compound formed by the end-capping agent used when polymerization of the polymer compound is completed. In the composition of the present invention, the terminal group of the polymer compound containing the repeating unit represented by formula (1) is preferably a hydrocarbon group. The hydrocarbon group is preferably a hydrocarbon group with a carbon number of 1 or more and 60 or less, more preferably a hydrocarbon group with a carbon number of 1 or more and 40 or less, and even more preferably a hydrocarbon group with a carbon number of 1 or more and 30 or less. .

Examples of the hydrocarbon group include: Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, third butyl, n-hexyl, cyclohexyl, dodecyl, etc., usually have a carbon number of 1 or more, Preferably it is a linear, branched or cyclic alkyl group of more than 4 and usually less than 24, preferably less than 12; A linear, branched or cyclic alkenyl group with a carbon number of usually 2 to 24, preferably 12 or less, such as vinyl; A straight-chain or branched alkynyl group with a carbon number of usually 2 or more and 24 or less, preferably 12 or less, such as ethynyl group; Aromatic hydrocarbon groups with a carbon number of usually 6 to 36, preferably 24 or less, such as phenyl and naphthyl; The crosslinking group as the hydrocarbon group in the crosslinking group T is preferably a crosslinking group represented by the formula (X1) to the formula (X4).

These hydrocarbon groups may further have substituents, and the substituents that may further have are preferably alkyl groups or aromatic hydrocarbon groups. When there are multiple optional substituents, they may be bonded to each other to form a ring. When these hydrocarbon groups are groups other than cross-linking groups, the substituent may further have a cross-linking group selected from the cross-linking group group T.

From the viewpoint of charge transport properties and durability, the terminal group is preferably an alkyl group, an aromatic hydrocarbon group, or a crosslinking group that is a hydrocarbon group in the crosslinking group T, and more preferably an aromatic hydrocarbon group. When the group is not a cross-linking group, it is also preferred to have a cross-linking group selected from the cross-linking group group T.

[Molecular weight of polymer compound] Hereinafter, the molecular weight of the polymer compound contained in the composition of the present invention will be described.

The weight average molecular weight (Mw) of the fluorine-containing arylamine polymer compound is usually 1,000,000 or less, preferably 500,000 or less, more preferably 100,000 or less, further preferably 70,000 or less, particularly preferably 50,000 or less. In addition, the weight average molecular weight is usually 5,000 or more, preferably 10,000 or more, more preferably 12,000 or more, and particularly preferably 15,000 or more.

When the weight average molecular weight of the fluorine-containing arylamine polymer compound is equal to or less than the upper limit, there is a tendency to obtain excellent solubility in a solvent and film-forming properties. In addition, when the weight average molecular weight of the polymer compound is equal to or higher than the lower limit, the decrease in the glass transition temperature, melting point, and vaporization temperature of the polymer compound may be suppressed, thereby improving heat resistance in some cases. In addition, the insolubility of the coating film with respect to the organic solvent may be sufficient after the cross-linking reaction.

In addition, the number average molecular weight (Mn) of the fluorine-containing arylamine polymer compound is usually 750,000 or less, preferably 250,000 or less, more preferably 100,000 or less, and particularly preferably 50,000 or less. In addition, the number average molecular weight is usually 2,000 or more, preferably 4,000 or more, more preferably 6,000 or more, and still more preferably 8,000 or more.

Furthermore, the degree of dispersion (Mw/Mn) in the fluorine-containing arylamine polymer compound is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. In addition, the smaller the dispersion value, the better, so the lower limit value is ideally 1. When the dispersion degree of the polymer compound is equal to or less than the upper limit, purification is easy and the polymer compound has good solubility in the solvent and good charge transport capability.

Generally, the weight average molecular weight and number average molecular weight of a polymer compound are determined by SEC (size exclusion chromatography) measurement. In the SEC measurement, the higher the molecular weight component, the shorter the dissolution time, and the lower the molecular weight component, the longer the dissolution time. By using a calibration curve calculated based on the dissolution time of polystyrene (standard sample) with a known molecular weight , convert the dissolution time of the sample into molecular weight, and calculate the weight average molecular weight and number average molecular weight.

(Content of repeating units represented by formula (1)) In the polymer compound, the content of the repeating unit represented by formula (1) is not particularly limited. The polymer compound usually contains 10 mol% or more of the repeating unit represented by formula (1) in 100 mol% of the total repeating units. The repeating unit preferably contains 30 mol% or more, more preferably 40 mol% or more, and still more preferably 50 mol% or more.

In the polymer compound, the repeating units may only include repeating units represented by formula (1), but for the purpose of balancing various properties when making organic electroluminescent devices, they may have repeating units different from those represented by formula (1). other repeating units of the unit. In this case, the content of the repeating unit represented by formula (1) in the polymer is usually 99 mol% or less, preferably 95 mol% or less.

[Specific example] Specific examples of the polymer compound are shown below, but the polymer compound is not limited to these. Again, the numbers in the chemical formula represent the molar ratio of the repeating units.

These polymer compounds may be any of random copolymers, alternating copolymers, block copolymers, graft copolymers, etc., and the order in which the monomers are arranged is not limited.

[Chemical 75]

[Chemical 76]

[Chemical 77]

[Chemical 78]

[Chemical 79]

＜Production method of polymer＞ The method for producing the polymer compound contained in the composition of the present invention is not particularly limited and is arbitrary. Examples include: a polymerization method using Suzuki reaction, a polymerization method using Grignard reaction, a polymerization method using Yamamoto reaction, a polymerization method using Ullmann reaction, a polymerization method using cloth Polymerization methods such as Buchwald-Hartwig reaction, etc. In addition, it can be produced by the same production method as the polymer production method described in International Publication No. 2019/177175, International Publication No. 2020/171190, and International Publication No. 2021/125011.

In the case of a polymerization method utilizing the Ullmann reaction and a polymerization method utilizing the Buchwald-Hartwig reaction, for example, by making a dihalogenated aryl group represented by the following formula (2a) (Z represents I , halogen atoms such as Br, Cl, F) are reacted with a primary aminoaryl group represented by the following formula (2b), and a polymer containing a repeating unit represented by the above formula (54) is synthesized.

[Chemical 80]

(In the reaction formula, Ar ⁵¹ , R ²⁰¹ , R ²⁰² , X, a to d have the same meaning as the definitions in the formula (54))

In addition, in the case of a polymerization method utilizing the Ullmann reaction and a polymerization method utilizing the Buchwald-Hartwig reaction, for example, by using the dihalogenated aryl group represented by the formula (3a) (Z represents I , Br, Cl, F and other halogen atoms) react with the primary aminoaryl group represented by the formula (3b) to synthesize a polymer containing the repeating unit represented by the formula (55).

[Chemical 81]

(In the reaction formula, Ar ⁵¹ , R ³⁰³ to R ³⁰⁶ , n, m, l, p, q have the same meaning as the definitions in the formula (55))

Furthermore, in the polymerization method, usually, the reaction to form an N-aryl bond is performed in the presence of a base such as potassium carbonate, sodium tert-butoxide, or triethylamine. In addition, for example, it can also be carried out in the presence of a transition metal catalyst such as copper or palladium complex.

<Content of the fluorine-containing arylamine polymer compound of the present invention> From the viewpoint of reducing the injection barrier in the charge transport layer in the composition ratio of the solid content of the composition of the present invention, the content of the fluorine-containing arylamine polymer compound of the present invention is preferably 10 mass % or more, and more preferably Preferably, it is 25 mass % or more, and more preferably, it is 30 mass % or more. On the other hand, from the viewpoint of maintaining charge transport properties in the charge transport layer, the content of the fluorine-containing arylamine polymer compound of the present invention in the composition of the present invention is equal to the composition ratio of the solid content of the composition. The content is preferably 99 mass% or less, more preferably 90 mass% or less, and still more preferably 80 mass% or less.

[Electron-accepting compound] In order to improve the hole injection properties from the anode to the hole injection layer or the hole transport layer, or to improve the charge transport properties in the hole injection layer or the hole transport layer, the hole injection layer or the hole transport layer contains The charge transport material preferably contains cationic radical sites. In order to cationically radicalize the charge transport material, an electron-accepting compound is used when forming a hole injection layer or a hole transport layer. As the mother skeleton of the electron-accepting compound, an ionic compound containing a tetraarylborate ion, an anion with an ionic valence of 1, which will be described later, and a countercation is preferred because it has high stability.

(Cation radicalization of charge transport materials) Cation radicalization of the charge transport material is performed as follows. When the fluorine-containing arylamine polymer compound of the present invention is used as a charge transport material, if a tetraarylborate with diaryliodonium as a countercation is used as an electron-accepting compound, the hole injection When the layer or hole transport layer is formed, the countercation can change from the diaryliodonium cation to the arylamine cation as shown in the following formula.

[Chemical 82]

(For example, Ar, Ar ^1' to Ar ^4' are each independently an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or an aromatic hydrocarbon ring group which may have a substituent, and A monovalent group in which a plurality of structures of an aromatic heterocyclic group that may have a substituent are linked together)

Since the arylamine cation generated in the reaction has a semi-occupied orbital (Singly Occupied Molecular Orbital (SOMO)) that can accept electrons, the tetraarylborate as the arylamine ion countercation It is an electron-accepting compound.

In the present invention, a compound containing cations and anions of the charge transport material, that is, tetraarylborate ions, is called a charge transport ionic compound. Details will be described later.

As will be described later, the hole injection layer and/or the hole transport layer of the organic electroluminescent device of the present invention is preferably obtained by wet-filming the composition of the present invention. The composition of the present invention is preferably obtained by A composition obtained by dissolving or dispersing an electron-accepting compound having a tetraarylborate ion structure described below and a charge transport material described below in an organic solvent. Furthermore, the charge transport layer of the organic electroluminescent element of the present invention preferably contains a tetraarylborate ion structure in the present invention described later as an anion and a cation of the charge transport material of the present invention as a countercation. Charge-transporting ionic compounds.

(cross-linking reaction product) The composition of the present invention includes a polymer compound having a cross-linking group and an electron-accepting compound having a cross-linking group. Therefore, the organic layer formed by a wet film formation method using the composition of the present invention contains a crosslinking reaction product of a polymer compound having a crosslinking group and an electron-accepting compound having a crosslinking group. Furthermore, as will be described later, the electron-accepting compound of the present invention is preferably an ionic compound containing a tetraarylborate ion and a countercation described below, and it is preferred that the tetraarylborate ion has a cross-linking group. Therefore, the organic layer may contain a crosslinking reaction product containing the following crosslinked structure. ·Cross-linked structure of polymer compounds and electron-accepting compounds ·The cross-linked structure of the cross-linked groups of the polymer compound · Cross-linked structures of electron-accepting compounds ·Cross-linked structure of electron-accepting compound and tetraarylborate ion ·Compounds in which tetraarylborate ions are cross-linked with each other ·Cross-linked structure of polymer compounds and tetraarylborate ions

In addition, the tetraarylborate ion refers to an anion structural moiety constituting the electron-accepting compound. In the cross-linked structure, the so-called tetraarylborate ions are tetraarylborate ions that are ionically bonded to cationic radicals of the polymer compound. Details will be described later.

Here, the "tetraarylborate ion in the present invention" includes a case in which it exists as an electron-accepting compound that is an ionic compound containing a tetraarylborate ion and a countercation described below, and a case in which it exists as an electron-accepting compound containing a tetraarylborate ion and a countercation described below. The presence of charge-transporting ionic compounds such as tetraarylborate ions and cations of the charge-transporting material.

If the two cross-linking groups that carry out the cross-linking reaction can carry out the cross-linking reaction, they may be the same cross-linking group or they may be different cross-linking groups.

[Electron-accepting compound] The electron-accepting compound that is an ionic compound containing a tetraarylborate ion and a countercation is an electron-accepting ionic compound containing a counteranion and a countercation as a non-coordinating anion represented by the following formula (81), and has Cross-linking group. The non-coordinating anion represented by the following formula (81) preferably has the formula (83) described below as a tetraarylborate ion as an anion. In addition, the electron-accepting compound used in this invention may be called an electron-accepting ionic compound.

[Chemical 83]

(In formula (81), five R ⁸¹ , five R ⁸² , five R ⁸³ , and five R ⁸⁴ are each independently independent, and R ⁸¹ to R ⁸⁴ are each independently a hydrogen atom, a deuterium atom, or a halogen atom, and may have An aromatic hydrocarbon group having 6 to 50 carbon atoms as a substituent, an aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, an alkyl group having 1 to 12 carbon atoms substituted with fluorine, or a crosslinking group; Ph ¹ , Ph ² , Ph ³ , Ph ⁴ refer to the symbols of their respective benzene rings; X ⁺ represents countercation)

The electron-accepting compound represented by the formula (81) has a cross-linking group, and the number of cross-linking groups is preferably 2 or more. The crosslinking group is preferably present in the anion part of the electron-accepting compound represented by the above formula (81), that is, in the compound represented by the later-described formula (82) which is a tetraarylborate ion.

[tetraarylborate ion] As the parent skeleton of the electron-accepting compound, a boron atom is substituted with four optionally substituted aromatic hydrocarbon rings or optionally substituted aromatic heterocyclic rings, and contains an anion with an ionic valence of 1, that is, a tetraaryl Ionic compounds based on borate ions and countercations are preferred because of their high stability.

The tetraarylborate ion is an anionic form of the formula (81) represented by the following formula (82).

[Chemical 84]

(In formula (82), R ⁸¹ to R ⁸⁴ are respectively the same as R ⁸¹ to R ⁸⁴ of formula (81); Ph ¹ to Ph ⁴ are respectively the same as Ph ¹ to Ph ⁴ of formula (81) and refer to four benzene ring symbol)

The aromatic hydrocarbon group used for R ⁸¹ to R ⁸⁴ preferably has a carbon number of 6 to 50. As the aromatic hydrocarbon ring structure, a single ring or 2 to 6 fused rings, and a structure in which two to eight of these are connected are preferred. Specific examples of the aromatic hydrocarbon group include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, pyrene ring, triphenyl ring, and ethane A single monovalent group of a naphthalene ring, a fluoranthene ring, a fluorene ring, a biphenyl structure, a terphenyl structure or a tetraphenyl structure, and a monovalent group in which two to eight of these are connected.

The aromatic heterocyclic group that can be used for R ⁸¹ to R ⁸⁴ preferably has a carbon number of 3 to 50. As an aromatic heterocyclic structure, a monocyclic ring or 2 to 6 condensed rings, and a structure in which two to eight of these are connected are preferred. Specific examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carboxyl ring. Azole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furanofuran ring, thienofuran ring, benzisoxazole ring , benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthroline ring A single monovalent group of a ring, a phenidine ring, a quinazoline ring, a quinazolinone ring or an azulene ring, and a monovalent group in which two to eight of these are connected. Furthermore, the aromatic heterocyclic group described here only needs to include at least one of these individual structures, and the linked structure may include an aromatic hydrocarbon ring structure. When it contains an aromatic hydrocarbon ring structure, it may be a structure in which a total of two to eight aromatic heterocyclic rings and aromatic hydrocarbon rings are connected. Here, as the aromatic hydrocarbon ring, a single structure of the aromatic hydrocarbon ring used for R ⁸¹ to R ⁸⁴ can be used.

Among them, from the viewpoint of excellent stability and heat resistance, a monovalent group of a benzene ring, a naphthalene ring, a fluorene ring, a pyridine ring or a carbazole ring, or a combination of two to five of these groups is more preferred. Monovalent radicals such as biphenyl. Particularly preferred are a monovalent group of a benzene ring or a group in which two to five benzene rings are connected, specifically a phenyl group, a biphenyl group, a terphenyl group, etc.

The number of aromatic hydrocarbon groups and aromatic heterocyclic groups contained in a monovalent group formed by linking a plurality of structures selected from an aromatic hydrocarbon group that may have a substituent and an aromatic heterocyclic group that may have a substituent is 2 Above, preferably 8 or less, more preferably 4 or less, more preferably 3 or less. Among them, when the aromatic hydrocarbon group is a biphenyl group, a terphenyl group, and a tetraphenyl group, they are regarded as a structure in which two phenyl groups are connected, a structure in which three phenyl groups are connected, and a structure in which two phenyl groups are connected respectively. A structure composed of four phenyl groups connected together.

The substituent that R ⁸¹ to R ⁸⁴ may have is preferably a group selected from the substituent group Z or the crosslinking group T.

From the viewpoint of increasing the stability of anions and improving the effect of stabilizing cations, R ⁸¹ to R ⁸⁴ are preferably each independently a fluorine atom or a fluorine-substituted alkyl group. In addition, the number of fluorine atoms or fluorine-substituted alkyl groups is preferably two or more, more preferably three or more, and most preferably four.

The fluorine-substituted alkyl group that can be used for R ⁸¹ to R ⁸⁴ is preferably a linear or branched alkyl group having 1 to 12 carbon atoms and is substituted with a fluorine atom, more preferably a perfluoroalkyl group, and further Preferably it is a linear or branched perfluoroalkyl group having 1 to 5 carbon atoms, particularly preferably a linear or branched perfluoroalkyl group having 1 to 3 carbon atoms, and most preferably a perfluoromethyl group. This is because the charge injection layer containing the crosslinking reaction product of the electron-accepting compound having a crosslinking group or the coating film laminated thereon becomes stable. The fluorine-substituted alkyl group is preferably bonded to the para position of the boron atom.

In terms of further increasing the stability of the anion and further improving the effect of stabilizing the cation, the tetraarylborate ion is preferably *-Ph ¹ -(R ⁸¹ ) ₅ or * in the formula (82). At least one of -Ph ² -(R ⁸² ) ₅ , *-Ph ³ -(R ⁸³ ) ₅ , *-Ph ⁴ -(R ⁸⁴ ) ₅ (* represents a bond with boron B of the formula (82)) has The group represented by the following formula (84) with four fluorine atoms is more preferred in terms of improving the stability of the anion, and at least two groups represented by the same formula (84) are further preferred in terms of improving the stability of the anion. In terms of improvement, it is preferable to have at least three groups represented by the same formula (84) below.

[Chemical 85]

(In formula (84), * represents a bond with boron B in formula (82), F ₄ represents a substituted four fluorine atoms, and R ⁸⁵ represents an optionally substituted aromatic hydrocarbon group or a crosslinking group)

The aromatic hydrocarbon group used for R ⁸⁵ preferably has a carbon number of 3 to 40. As the aromatic hydrocarbon ring structure, a single ring or 2 to 6 condensed rings, or a structure in which two to five of these are connected is preferred. Specific examples include: benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, condensed tetraphenyl ring, pyrene ring, benzopyrene ring, pyrene ring, triphenyl ring, ethane naphthalene ring, fluorine ring An anthracene ring, a fluorene ring, a biphenyl structure, a terphenyl structure or a single monovalent group of a tetraphenyl structure, and a monovalent group in which two to six of these are connected. The crosslinking group that the aromatic hydrocarbon group may have is preferably a crosslinking group selected from the crosslinking group T.

The cross-linking group that can be used for R ⁸⁵ is preferably a cross-linking group selected from the cross-linking group T. As the aromatic hydrocarbon group and the substituent that the aromatic hydrocarbon group may have that is not a crosslinking group, a group selected from the substituent group Z is preferred. Among them, from the viewpoint of stability, a group selected from the group Z is preferred. It is an aromatic hydrocarbon group, and from the viewpoint of solubility, an alkyl group is preferred.

＜Ionic compounds containing tetraarylborate ions＞ Tetraarylborate ions can be used as electron-accepting ionic compounds containing tetraarylborate ions.

(Counter cation) As the counter cation, preferred are iodonium cations, sulfonium cations, carbocations, oxonium cations, ammonium cations, phosphonium cations, cycloheptyltrienyl cations or ferrocene cations with transition metals, and more preferred are iodonium cations and sulfonium cations. Cation, carbocation, ammonium cation, particularly preferred is the iodide cation.

As the iodonium cation, a structure represented by the following formula (83) is preferred, and the more preferred structures are also the same.

As the iodide cation, specifically, diphenyl iodide cation, bis(4-tert-butylphenyl) iodide cation, 4-tert-butoxyphenylphenyl iodide cation, and 4-methoxy Phenylphenyl cation, 4-isopropylphenyl-4-methylphenyl cation, etc.

As the sulfonium cation, specifically, triphenylsulfonium cation, 4-hydroxyphenyldiphenylsulfonium cation, 4-cyclohexylphenyldiphenylsulfonium cation, and 4-methanesulfonylphenyldiphenyl are preferred. sulfonyl cation, (4-tert-butoxyphenyl)diphenylsulfonium cation, bis(4-tert-butoxyphenyl)phenylsulfonium cation, 4-cyclohexylsulfonylphenyldiphenyl sulfide cation, etc.

As the carbocation, specifically, trisubstituted carbocations such as triphenyl carbocation, tris(methylphenyl)carbocation, and tris(dimethylphenyl)carbocation are preferred.

As the ammonium cation, specifically, trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tripropylammonium cation, tributylammonium cation, and tri(n-butyl)ammonium cation are preferred; N,N-diethylaniline cation, N,N-2,4,6-pentamethylaniline cation and other N,N-dialkylaniline cations; di(isopropyl)ammonium cation, dicyclohexylammonium cation etc. dialkyl ammonium cations, etc.

As the phosphonium cation, specifically, tetraarylphosphonium cations such as tetraphenylphosphonium cation, tetrakis(methylphenyl)phosphonium cation, and tetrakis(dimethylphenyl)phosphonium cation are preferred; tetrabutylphosphonium cation, Tetrapropylphosphonium cations and other tetraalkylphosphonium cations.

Among these, from the viewpoint of the film stability of the compound, iodon cations, carbocations, and sulfonium cations are preferred, and iodon cations are more preferred.

(X ⁺ : iodon cation) The counter cation X ⁺ in the formula (81) is preferably a iodon cation having a structure of the following formula (83).

[Chemical 86]

In formula (83), Ar ⁸¹ and Ar ⁸² are each independently an aromatic hydrocarbon group having 6 to 12 carbon atoms that may have a substituent.

The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms, and most preferably a phenyl group. The optional substituent is a group selected from the substituent group Z. Among them, an alkyl group is the most preferred.

Preferred aromatic hydrocarbon groups include phenyl, biphenyl, terphenyl, tetraphenyl, naphthyl, phenanthrenyl, triphenyl, naphthylphenyl, etc., depending on the stability of the compound. In other words, phenyl is the best.

(molecular weight) The molecular weight of the electron-accepting compound of the present invention is usually 900 or more, preferably 1,000 or more, more preferably 1,200 or more, and is usually 10,000 or less, preferably 5,000 or less, and more preferably 3,000 or less. If the molecular weight is too small, the delocalization of positive charges and negative charges may be insufficient, so the electron-accepting ability may decrease. If the molecular weight is too large, there may be a risk of hindering charge transport.

(Specific example) Specific examples of the electron-accepting compound of the present invention represented by formula (81) are listed below, but the electron-accepting compound of the present invention is not limited to these.

[Chemical 87]

[Chemical 88]

[Chemical 89]

<Composition ratio and content of the fluorine-containing arylamine polymer compound and the electron-accepting compound in the composition> In the composition of the present invention, the content of the polymer compound of the present invention is preferably 99 mass % or less based on the total amount of the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention. More preferably, it is 97 mass % or less, and still more preferably, it is 95 mass % or less. In addition, the content is preferably 50 mass% or more, more preferably 70 mass% or more, and still more preferably 80 mass% or more. By being within these ranges, the film formed using the composition of the present invention is sufficiently cross-linked without being dissolved, and wet coating can be directly performed on the film formed using the composition of the present invention to form a film, and the film will be formed using the composition of the present invention. When a film formed from the composition of the present invention is used as a charge injection film, the injection barrier in the charge transport layer is reduced, the charge transport properties are excellent, and the stability during charge transport properties is improved. It is considered that the film is formed using the composition of the present invention. The durability of the membrane element is improved.

[composition] The composition of the present invention may further contain a solvent, and may also contain polymerization initiators, additives, etc.

＜Solvent＞ The composition of the present invention preferably contains the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention. Preferably, it further contains a solvent. Particularly when the composition of the present invention is used to form a charge transport film by a wet film forming method, it is preferable to use a solvent to combine the fluorine-containing arylamine polymer compound of the present invention and the electronic material of the present invention. The state in which the receptive compound is dissolved.

The type of solvent contained in the composition of the present invention is not particularly limited as long as it can dissolve both the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention. Here, the solvent in which the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention are dissolved is preferably 0.005% by mass of the fluorine-containing arylamine polymer compound of the present invention. The above solvent is more preferably 0.5% by mass or more, further preferably 1% by mass or more. In addition, the electron-accepting compound is preferably dissolved in an amount of not less than 0.001% by mass, more preferably not less than 0.1% by mass, and even more preferably not less than 0.2% by mass.

Preferred solvents include, for example, aromatic hydrocarbon solvents, ether solvents, and ester solvents.

Specifically, examples of the aromatic hydrocarbon-based solvent include toluene, xylene, mesitylene, tetralin, and cyclohexylbenzene.

Examples of ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol monomethyl ether acetate (PGMEA); 1,2- Dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenylethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethyl Anisole, 2,4-dimethylanisole and other aromatic ethers.

Examples of the ester solvent include aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, Aromatic esters such as propyl benzoate and n-butyl benzoate.

Any one of these may be used alone, or two or more types may be used in any combination and ratio.

Examples of solvents that can be used in addition to the ether-based solvents and ester-based solvents include amide-based solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, dimethylformamide, etc. Chia Qi et al. Any one of these may be used alone, or two or more types may be used in any combination and ratio. In addition, one or more of these solvents may be used in combination with one or more of the ether solvent and ester solvent. In particular, aromatic hydrocarbon-based solvents such as benzene, toluene, and xylene have low ability to dissolve electron-accepting compounds and free carriers (cationic radicals), so they are preferably mixed with ether-based solvents and ester-based solvents.

When a solvent is used, the concentration of the solvent relative to the composition of the present invention is preferably 10 mass% or more, more preferably 30 mass% or more, and still more preferably 50 mass% or more. In addition, the concentration of the solvent relative to the composition is preferably 99.999 mass% or less, more preferably 99.99 mass% or less, and still more preferably 99.9 mass% or less. In addition, when two or more solvents are mixed and used, the total of these solvents shall satisfy|fill the said range.

Furthermore, when the composition of the present invention is used in an organic electroluminescent element, since the organic electroluminescent element is formed by laminating layers containing a plurality of organic compounds, each layer is required to be a uniform layer. When the layer is formed by a wet film formation method, if moisture is present in the solution (composition) for thin film formation, the moisture will be mixed into the coating film and the uniformity of the film will be impaired, so a solution is preferred. contain as little moisture as possible. In addition, in general, organic electroluminescent elements often use materials such as cathodes that are significantly deteriorated by moisture, so the presence of moisture is also undesirable from the perspective of element degradation.

Specifically, the moisture content contained in the composition of the present invention is preferably suppressed to 1 mass % or less, and particularly preferably to 0.1 mass % or less, and further to 0.05 mass % or less.

Examples of methods for reducing the moisture content in the composition include nitrogen sealing, use of a desiccant, dehydration of the solvent in advance, use of a solvent with low water solubility, and the like. Among them, from the viewpoint of preventing the solution coating film from absorbing moisture in the atmosphere and whitening during the coating step, it is preferable to use a solvent with low water solubility.

When used for film formation by a wet film forming method, the composition of the present invention is preferably 10% by mass or more, particularly 30% by mass or more, relative to the entire composition. It is a solvent with low solubility containing water at a concentration of 50% by mass or more. Specifically, the solubility of water at 25°C is 1% by mass or less, preferably 0.1% by mass or less.

＜Composition for charge transport film＞ When the electron-accepting compound having a crosslinking group is the electron-accepting ionic compound, it is preferably used as a composition containing the electron-accepting ionic compound and the fluorine-containing aromatic compound of the formula (1). A composition of an amine polymer compound (hereinafter, appropriately referred to as "composition (A) for a charge transport film"), or a cationic radical containing a fluorine-containing arylamine polymer compound having a crosslinking group described below and a composition of a charge-transporting ionic compound that is a counteranion that is a part of the electron-accepting ionic compound (hereinafter, appropriately referred to as "charge-transporting film composition (B)"). Here, for the sake of convenience, the description is divided into the composition (A) for the charge transport film and the composition (B) for the charge transport film. However, the composition for the charge transport film also includes the following compositions. A cationic radical containing the electron-accepting ionic compound, a fluorine-containing arylamine polymer compound having a crosslinking group to be described later, and a fluorine-containing arylamine polymer compound having a crosslinking group to be described later, and the A part of the electron-accepting ionic compound is a charge-transporting ionic compound of a counteranion.

Furthermore, the composition (A) for charge transport films and the composition (B) for charge transport films are compositions that can be widely used in applications as charge transport materials (compositions for charge transport materials). Among them, it is usually formed into a film and used as a hole injection layer and/or a hole transport layer, that is, a "charge transport film" that transports holes as charges, so it is specifically called a "charge transport film composition" in this specification. ”.

<Composition (A) for charge transport film> The composition (A) for a charge transport film contains the fluorine-containing arylamine polymer compound having a cross-linking group, the electron-accepting compound having a cross-linking group, and a solvent. The fluorine-containing arylamine polymer compound may contain one type alone, or may contain two or more types.

＜Preparation method of composition (A) for charge transport film＞ The composition (A) for a charge transport film is prepared by mixing at least the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound having a crosslinking group. In this case, the charge transport film composition (A) preferably contains a solvent, and the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound having a crosslinking group are dissolved in the solvent. and mix.

The content of the electron-accepting compound having a crosslinking group of the present invention in the composition (A) for a charge transport film is calculated relative to the fluorine-containing arylamine polymer compound of the present invention, and is usually 0.1 mass% or more, preferably 1 mass% or more, and usually 100 mass% or less, preferably 40 mass% or less. If the content of the electron-accepting compound is at least the lower limit, free carriers (cationic radicals of the fluorine-containing arylamine polymer compound of the present invention) can be sufficiently generated, and it is preferable if the electron-accepting compound The content of the compound is preferably below the upper limit because sufficient charge transport capability can be ensured. When two or more electron-accepting compounds are used in combination, the total content of these compounds is included in the above range. The same applies to charge-transporting compounds.

<Composition for Charge Transport Film (B)> As described above, the composition (B) for a charge transport film is a charge transport ion containing a cationic radical of the fluorine-containing arylamine polymer compound of the present invention and a counter anion of the electron-accepting ionic compound. The composition of a compound.

The cationic radical of the fluorine-containing arylamine polymer compound of the present invention, which is a cation of the charge-transporting ionic compound, is an electrically neutral radical represented by the fluorine-containing arylamine polymer compound of the present invention. A chemical species obtained by removing an electron from a compound.

The cationic radical of the fluorine-containing arylamine polymer compound of the present invention is a fluorine-containing arylamine polymer compound having a structure represented by the following formula (110).

[Chemical 90]

[In the formula (110), Ar ^1a , Ar ^2a , and G ^1a are respectively the same as Ar ¹ , Ar ² , and G in the formula (1)]

Formula (110) is particularly preferably a fluorine-containing aryl group having a structure represented by the following formula (110-1) in terms of having a moderate redox potential and obtaining stable charge transport ions. Amine polymer compound.

[Chemical 91]

[In the formula (110-1), Ar ^1b is an aromatic hydrocarbon group, and the carbon number of the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 24, and even more preferably 6 to 18; as the aromatic hydrocarbon group , specifically, aromatic hydrocarbon rings with a carbon number of usually 6 or more and usually 30 or less, preferably 18 or less, and even more preferably 14 or less, such as benzene ring, naphthalene ring, fluorene ring, tetraphenyl ring, etc. A divalent group of a structure, or a divalent group of a structure in which a plurality of structures among these structures are linked together in a chain or branched manner; when multiple aromatic hydrocarbon rings are connected, usually two can be connected. A structure consisting of one to seven, preferably a structure consisting of two to five connected; when multiple aromatic hydrocarbon rings are connected, the same structure or different structures can be connected; Ar ^2a , G ^1a are respectively the same as Ar ² and G in the formula (1)]

Ar ^1b is preferably an aromatic hydrocarbon group having a substituent, and its specific examples, preferred groups, examples of possible substituents, and examples of preferred substituents are preferably selected from the substituent group Z. base. Particularly preferred is an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent.

From the viewpoint that the partial structure represented by formula (110-1) easily becomes a cationic radical and charges are transported, Ar ^1b is preferably a phenylene group, a biphenylene group, or a phenylfluorenyl group, and more preferably a phenylene group. , Diphenyl group, especially preferably phenyl group.

＜Charge transporting ionic compounds＞ The charge-transporting ionic compound is a compound in which a cationic radical of the fluorine-containing arylamine polymer compound of the present invention is ionically bonded to a counteranion that is a part of the electron-accepting ionic compound.

The charge-transporting ionic compound can be obtained by mixing a fluorine-containing arylamine polymer compound and an electron-accepting ionic compound, and is easily soluble in various solvents. Specifically, it can be obtained by the method described in the <Preparation method of the composition (B) for a charge transport film> mentioned later.

The weight average molecular weight (Mw) of the charge-transporting ionic compound is usually 1,000,000 or less, preferably 500,000 or less, more preferably 100,000 or less, still more preferably 70,000 or less, and particularly preferably 50,000 or less. In addition, the weight average molecular weight is usually 5,000 or more, preferably 10,000 or more, further preferably 12,000 or more, and particularly preferably 15,000 or more.

＜Preparation method of composition (B) for charge transport film＞ The charge-transporting ionic compound (B) is preferably prepared by dissolving the fluorine-containing arylamine polymer compound and the electron-accepting ionic compound of the present invention in a solvent and mixing them. In the solution, the fluorine-containing arylamine polymer compound of the present invention is oxidized by the electron-accepting ionic compound and cationically radicalized, thereby generating a counter anion of the electron-accepting ionic compound and the counter anion of the electron-accepting ionic compound of the present invention. The ionic compound of the cationic radical of the fluorine-containing arylamine polymer compound is a charge-transporting ionic compound.

This is due to the following reasons. That is, at this time, by mixing the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting ionic compound in a solution, the fluorine-containing arylamine polymer compound of the present invention is easily The probability that an electron-accepting ionic compound exists near the nitrogen atom of the arylamine, which is the oxidized site, becomes high. Furthermore, the arylamine nitrogen atom of the fluorine-containing polymer compound of the present invention is oxidized by the electron-accepting ionic compound and cationically radicalized, thereby easily generating a counter anion of the electron-accepting ionic compound and the present invention. The invented fluorine-containing polymer compound is a cationic radical ionic compound. At this time, from the viewpoint of promoting the reaction, it is preferable to heat the solution.

It is also preferable to prepare the mixture by heating a mixture of the electron-accepting ionic compound and the fluorine-containing polymer compound of the present invention. The mixture is preferably a film obtained by coating and drying a solution obtained by dissolving a mixture of an electron-accepting ionic compound and the fluorine-containing polymer compound of the present invention in a solvent.

This is due to the following reasons. That is, by heating the mixture, the electron-accepting ionic compound and the fluorine-containing polymer compound of the present invention diffuse into each other in the mixture, and the fluorine-containing polymer compound of the present invention is easily oxidized. The probability that an electron-accepting compound exists near the nitrogen atom of the arylamine site increases. Furthermore, an ionic compound is easily generated between the counter anion of the electron-accepting ionic compound and the cationic radical of the fluorine-containing polymer compound of the present invention. The heating temperature at this time is preferably a temperature at which the cross-linking groups of the composition do not undergo a cross-linking reaction. However, even if it is a temperature at which the cross-linking groups undergo a cross-linking reaction, the cross-linking reaction occurs simultaneously with diffusion, so it can be formed without any problem. Electron-accepting ionic compounds.

The composition (B) for a charge transport film may contain one type of the above-mentioned charge transport ionic compound alone, or may contain two or more types thereof. It is preferable to contain one or two types of charge-transporting ionic compounds, and it is more preferable to contain one type alone. The reason is that the charge transport ionic compound has little variation in ionization potential and has excellent hole transport properties.

The so-called composition containing one type of charge transporting ionic compound alone or two types of charge transporting ionic compounds is prepared using a total of only two or only three types of electron-accepting ionic compounds and the fluorine-containing polymer compound of the present invention. The composition is prepared by using at least one electron-accepting ionic compound and at least one fluorine-containing polymer compound of the present invention.

The charge transport film formed from the charge transport film composition (B) exhibits high hole injection/transport capability by moving positive charges from the charge transport ionic compound to a nearby neutral charge transport compound. Therefore, the mass ratio between the charge transporting ionic compound and the neutral fluorine-containing polymer compound of the present invention is preferably about 1:100 to 100:1, and more preferably about 1:20 to 20:1. .

<Relationship between charge transport film composition (A) and charge transport film composition (B)> The charge transport film formed by the charge transport film composition (A) has excellent heat resistance and high hole injection/transport capabilities. The reason why such excellent characteristics are obtained will be explained below.

The composition (A) for a charge transport film contains the electron-accepting compound and the hole-transporting compound. The cation in an electron-accepting ionic compound has a central atom with a superatom valence, and its positive charge is widely delocalized, so it has high electron acceptance. Thereby, electrons move from the charge transport compound to the cation of the electron-accepting ionic compound, thereby generating a charge transport ionic compound including a cation radical of the charge transport compound and a counter anion. The cationic radicals of the charge-transporting compound serve as charge carriers, thereby improving the electrical conductivity of the charge-transporting film. That is, it is considered that when the composition (A) for a charge transport film is prepared, a charge transport ionic compound containing at least a part of cationic radicals of the charge transport compound and counter anions of the electron accepting ionic compound is generated.

For example, when electrons move from a charge-transporting compound represented by the following formula (7) to an electron-accepting compound represented by the formula (6), a compound containing a charge-transporting compound represented by the formula (9) is generated. Charge-transporting ionic compounds of cationic radicals and counteranions.

[Chemical 92]

[Preparation of composition] The composition of the present invention can be obtained by mixing a functional material containing the fluorine-containing arylamine polymer compound of the present invention, the electron-accepting compound of the present invention, and preferably further containing the electron-accepting compound, and a solvent. And heat it for a certain period of time to dissolve or disperse it and prepare it. In order to uniformly dissolve or disperse the functional material in the solvent, the heating temperature is preferably 80°C or higher, more preferably 90°C or higher, and even more preferably 100°C or higher, for example, 100°C to 120°C. In addition, the heating time is preferably 30 minutes or more, more preferably 45 minutes or more, further preferably 60 minutes or more, for example, 60 minutes to 180 minutes.

The heated composition can be filtered using a membrane filter or depth filter to remove coarse particles before use. Considering that the coating composition is ejected from the nozzle of the inkjet head, the pore size of the filter is preferably 0.5 μm or less, more preferably 0.2 μm or less, and still more preferably 0.1 μm or less.

[Film-forming method using composition] When the composition of the present invention is used to form a film, the composition of the present invention is preferably a solution containing a solvent, and the composition of the present invention is preferably wet-film-formed.

The wet film formation method refers to a method in which a composition containing a solvent is applied to a substrate and the solvent is dried and removed to form a film. The coating method is not particularly limited, and examples thereof include spin coating, dip coating, die coating, rod coating, blade coating, roller coating, spray coating, capillary coating, and inkjet. , screen printing method, gravure printing method, flexographic printing method, etc.

As a method of drying and removing the solvent, heat drying is usually performed. Examples of the heating means used in the heating step include a clean oven, a hot plate, and infrared heating. As infrared heating, a halogen heater, a ceramic-coated halogen heater, a ceramic heater, etc. can be used.

Heating using infrared rays directly imparts thermal energy to the substrate or film, so drying can be achieved in a shorter time than heating using an oven or a hot plate. Therefore, the influence of gas (moisture or oxygen) in the heating environment or the influence of fine dust can be suppressed to a minimum, and productivity can be improved, which is preferable.

The heating temperature is usually 80°C or higher, preferably 100°C or higher, more preferably 150°C or higher. In addition, the heating temperature is usually 300°C or lower, preferably 280°C or lower, more preferably 260°C or lower.

The heating time is usually 10 seconds or more, preferably 60 seconds or more, more preferably 90 seconds or more, and usually 120 minutes or less, preferably 60 minutes or less, more preferably 30 minutes or less. In addition, it is also preferable to perform vacuum drying before heat drying.

The film thickness of the organic layer formed by using the composition of the present invention to form a film using a wet film forming method is usually 5 nm or more, preferably 10 nm or more, and even more preferably 20 nm or more. In addition, the film thickness is usually 1000 nm or less, preferably 500 nm or less, and more preferably 300 nm or less.

[Organic electric field light-emitting element] A film using the composition of the present invention and a film formed using the composition of the present invention can be preferably used as a charge transport layer. The charge transport layer is particularly preferably a charge transport film that can be used as an organic electroluminescent element.

An organic electroluminescent element is, for example, an organic electroluminescent element having an anode and a cathode on a substrate and an organic layer between the anode and the cathode. It is preferred to use the composition of the present invention and form the organic electroluminescent element by a wet film forming method. organic layer. The organic layer is preferably an organic layer located between the anode and the light-emitting layer. Elements using "quantum dots" as inorganic light-emitting substances in the light-emitting layer of the organic electroluminescent element are also called quantum dot light-emitting elements.

In addition, the organic layer preferably contains a crosslinking reaction product of a polymer compound having a crosslinking group represented by the formula (81) and an electron-accepting compound having a crosslinking group represented by the formula (81). The repeating unit represented has fluorene which may have a substituent on at least one of the main chain and side chain, and has a cross-linking group.

As an example of the structure of the organic electroluminescent element of the present invention, a schematic diagram (cross-section) of a structural example of the organic electroluminescent element 8 is shown in FIG. 1 . In Figure 1, 1 represents the substrate, 2 represents the anode, 3 represents the hole injection layer, 4 represents the hole transport layer, 5 represents the light-emitting layer, 6 represents the electron transport layer, and 7 represents the cathode.

[Substrate] The substrate 1 is the support body of the organic electroluminescent element, and usually a quartz or glass plate, a metal plate or metal foil, a plastic film or sheet, etc. are used. Among these, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polyester is preferred. In order to be less likely to cause deterioration of the organic electroluminescent element due to external air, the substrate is preferably made of a material with high gas barrier properties. Therefore, especially when a material with low gas barrier properties such as a synthetic resin substrate is generally used, it is preferable to provide a dense silicon oxide film or the like on at least one side of the substrate to improve the gas barrier properties.

[anode] The anode 2 has the function of injecting holes into the layer on the side of the light-emitting layer 5 .

The anode 2 usually includes: metals such as aluminum, gold, silver, nickel, palladium, and platinum; metal oxides such as indium and/or tin oxides; halide metals such as copper iodide; carbon black and poly(3-methylthiophene) , polypyrrole, polyaniline and other conductive polymers.

The anode 2 is usually formed by dry methods such as sputtering and vacuum evaporation. In addition, when the anode is formed using metal fine particles such as silver, copper iodide and other fine particles, carbon black, conductive metal oxide fine particles, conductive polymer fine powder, etc., it can also be dispersed in an appropriate binder. into a resin solution and coated onto the substrate to form. In addition, in the case of a conductive polymer, the anode can also be formed by directly forming a thin film on the substrate through electrolytic polymerization, or by coating the conductive polymer on the substrate (Appl. Phys. Lett.) , Vol. 60, p. 2711, 1992).

The anode 2 usually has a single-layer structure, but may also suitably adopt a laminated structure. When the anode 2 has a laminated structure, different conductive materials may also be laminated on the anode of the first layer.

The thickness of the anode 2 may be determined based on required transparency, material, etc. Particularly when high transparency is required, a thickness having a visible light transmittance of 60% or more is preferred, and a thickness having a visible light transmittance of 80% or more is more preferred. The thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less. On the other hand, when transparency is not required, the thickness of the anode 2 may be any thickness depending on required strength, etc. In this case, the anode 2 may have the same thickness as the substrate.

In the case where other layers are formed on the surface of the anode 2, it is preferable to perform ultraviolet/ozone, oxygen plasma, argon plasma, etc. treatment before film formation, thereby removing impurities on the anode 2 and adjusting them. The ionization potential improves the hole injectability.

[Hole injection layer] The layer responsible for transporting holes from the anode 2 side to the light-emitting layer 5 side is usually called a hole injection transport layer or a hole transport layer. Furthermore, when there are two or more layers responsible for the function of transporting holes from the anode 2 side to the light-emitting layer 5 side, the layer closer to the anode side may be called the hole injection layer 3 . In order to enhance the function of transporting holes from the anode 2 to the light-emitting layer 5 side, it is preferable to form the hole injection layer 3 . When the hole injection layer 3 is formed, the hole injection layer 3 is usually formed on the anode 2 .

The hole injection layer 3 formed using the composition of the present invention contains a crosslinking reaction product of the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention.

The method of forming the hole injection layer 3 is not particularly limited, and examples thereof include vacuum evaporation, wet film formation, and the like. When the layer is formed by a wet film-forming method, the composition of the present invention is prepared, applied to the anode 2 by a wet film-forming method such as spin coating or dip coating, and dried to form Hole injection layer 3.

Particularly preferred are the compositions using the fluorine-containing arylamine polymer compound of the present invention and the electron-accepting compound of the present invention, and the use of the fluorine-containing arylamine polymer compound of the present invention. A film formed from a composition of an arylamine polymer compound and the electron-accepting compound of the present invention. The film thickness of the hole injection layer 3 formed in this manner is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably 500 nm or less.

The hole injection layer may be formed by vacuum evaporation or wet film formation. In terms of excellent film-forming properties, it is preferably formed by a wet film-forming method. Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, and the like.

Examples of ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), and 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2 , 4-dimethylanisole and other aromatic ethers, etc.

Examples of the ester-based solvent include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.

Examples of aromatic hydrocarbon solvents include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, and 1,4-diisopropylbenzene. , cyclohexylbenzene, methylnaphthalene, etc.

Examples of the amide-based solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and the like.

In addition to these, dimethylstyrene and the like can also be used.

The hole injection layer 3 is usually formed by a wet film forming method by preparing a composition for forming the hole injection layer and then coating it to a layer corresponding to the lower layer of the hole injection layer 3 (usually for the anode 2) and proceed to drying.

The hole injection layer 3 is usually dried by heating or drying under reduced pressure after the film is formed.

[Hole transport layer] The hole transport layer 4 is a layer responsible for transporting holes from the anode 2 side to the light emitting layer 5 side. The hole transport layer 4 is not an essential layer in the organic electroluminescent device of the present invention, but it is preferable to form this layer in order to enhance the function of transporting holes from the anode 2 to the light-emitting layer 5 . When the hole transport layer 4 is formed, the hole transport layer 4 is usually formed between the anode 2 and the light-emitting layer 5 . In addition, when the hole injection layer 3 is present, it is formed between the hole injection layer 3 and the light-emitting layer 5 .

The film thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and on the other hand, is usually 300 nm or less, preferably 100 nm or less.

As a material for forming the hole transport layer 4, a material that has high hole transport properties and can efficiently transport injected holes is preferred. Furthermore, it is preferable that the injection barrier from the hole injection layer to the hole transport layer is low. Therefore, it is preferable that the ionization potential is appropriate, the transparency is high with respect to visible light, the hole mobility is large, the stability is excellent, and impurities that can become traps are unlikely to be generated during production or use. In addition, in most cases, the hole transport layer 4 is in contact with the light-emitting layer 5, so it is preferable that it does not extinguish the light emitted from the light-emitting layer 5 or form an exciplex with the light-emitting layer 5. ) and reduce efficiency.

The material of the hole transport layer 4 may be any material that has been previously used as a constituent material of the hole transport layer. For example, the hole transport compound used in the hole injection layer 3 may be used. exemplifier. In addition, arylamine derivatives, fluorene derivatives, spiro derivatives, carbazole derivatives, pyridine derivatives, pyrazine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, phenanthroline Derivatives, phthalocyanine derivatives, porphyrin derivatives, silole derivatives, oligothiophene derivatives, condensed polycyclic aromatic derivatives, metal complexes, etc.

Examples include polyvinylcarbazole derivatives, polyarylamine derivatives, polyvinyltriphenylamine derivatives, polyfluorene derivatives, polyarylene derivatives, and tetraphenylbenzidine-containing derivatives. Polyarylene ether tetranes derivatives, polyarylene vinylene derivatives, polysiloxane derivatives, polythiophene derivatives, poly(p-phenylene vinylene) derivatives, etc. These may be any of alternating copolymers, random polymers, block polymers or graft copolymers. In addition, it may be a polymer having branches in the main chain and three or more terminal portions, or a so-called dendrimer.

Among them, polyarylamine derivatives or polyarylene derivatives are preferred. As the polyarylamine derivative, a polymer containing a repeating unit represented by the following formula (I) is preferred. Particularly preferred is a polymer composed of repeating units represented by the following formula (I). In this case, Ar ^{a ′} or Ar ^{b ′} may be different in each repeating unit.

[Chemical 93]

(In formula (I), Ar ^a' and Ar ^b' each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent)

Examples of the polyarylene derivative include polymer compounds having an aryl group such as an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent in its repeating unit.

As the polyarylene derivative, a polymer compound having a repeating unit including the following formula (II-1) and/or the following formula (II-2) is preferred.

[Chemical 94]

(In formula (II-1), R ^a , R ^b , R ^c and R ^d each independently represent an alkyl group, an alkoxy group, a phenylalkyl group, a phenyl alkoxy group, a phenyl group, a phenoxy group, an alkyl group, or an alkyl group. phenyl, alkoxyphenyl, alkylcarbonyl, alkoxycarbonyl or carboxyl; x11 and x12 each independently represent an integer from 0 to 3; when x11 or x12 is 2 or more, the Multiple R ^a or R ^b may be the same or different, and adjacent R ^a or R ^b may form a ring with each other)

[Chemical 95]

(In the formula (II-2), R ^e and R ^f respectively and independently have the same meaning as R ^a , R ^b , R ^c or R ^d in the formula (II-1); x13 and x14 respectively and independently represent An integer from 0 to 3; when x13 or x14 is 2 or more, multiple R ^e and R ^f included in one molecule may be the same or different, and adjacent R ^e or R ^f may form a ring with each other; L represents the composition Atoms or groups of atoms of a 5-membered ring or a 6-membered ring)

Specific examples of L are an oxygen atom, a boron atom which may have a substituent, a nitrogen atom which may have a substituent, a silicon atom which may have a substituent, a phosphorus atom which may have a substituent, a sulfur atom which may have a substituent, and a sulfur atom which may have a substituent. The carbon atoms of the substituent or the groups formed by these bonds.

In addition, the polyarylene derivative preferably has the following formula (III-3) in addition to a repeating unit including the formula (II-1) and/or the formula (II-2). the repeating unit represented.

[Chemical 96]

(In formula (III-3), Ar ^c to Ar ⁱ each independently represent an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent; x15 and x16 each independently represent 0 or 1)

Specific examples of the formulas (III-1) to (III-3) and specific examples of the polyarylene derivatives include those described in Japanese Patent Application Laid-Open No. 2008-98619.

When the hole transport layer 4 is formed by a wet film formation method, in the same manner as the formation of the hole injection layer 3, after preparing the hole transport layer forming composition, heat and drying is performed after the wet film formation. .

The hole transport layer forming composition contains, in addition to the hole transport compound, a solvent. The solvent used is the same as the organic solvent used in the composition for forming the hole injection layer. In addition, film formation conditions, heating and drying conditions, etc. are also the same as in the case of forming the hole injection layer 3 .

In addition, when the hole transport layer is formed by vacuum evaporation, the film formation conditions and the like are also the same as the formation of the hole injection layer 3 .

In addition to the hole transporting compound described above, the hole transporting layer 4 may also contain various luminescent materials, electron transporting compounds, binder resins, coatability improving agents, and the like.

In addition, the hole transport layer 4 may be a layer formed by cross-linking a cross-linking compound. The cross-linking compound is a compound having a cross-linking group, and forms a network-like polymer compound by cross-linking.

Examples of the crosslinkable group include groups derived from cyclic ethers such as oxetane and epoxy; groups derived from vinyl groups, trifluorovinyl groups, styrene groups, acrylic groups, and methacrylic groups. Groups with unsaturated double bonds such as acyl group and cinnamyl group; groups derived from benzocyclobutene, etc.

The crosslinking compound may be any of a monomer, an oligomer, and a polymer. There may be only one type of cross-linking compound, or two or more types may be used in arbitrary combinations and ratios.

As the crosslinking compound, it is preferable to use a hole transporting compound having a crosslinking group. Examples of the hole transporting compounds include the compounds illustrated above. Examples of the crosslinking compounds include compounds in which a crosslinking group is bonded to a main chain or a side chain of these hole transporting compounds. Particularly preferably, the crosslinkable group is bonded to the main chain via a linking group such as an alkylene group. In addition, particularly as the hole-transporting compound, a polymer containing a repeating unit having a cross-linking group is preferred, and a polymer having a cross-linking group bonded directly or via a linking group to the formula (I) or A polymer compound having a repeating unit of formula (II-1) to formula (III-3).

When cross-linking the cross-linking compound to form the hole transport layer 4, a composition for forming the hole transport layer in which the cross-linking compound is dissolved or dispersed in a solvent is usually prepared, and is formed by wet film formation. Film formation and cross-linking.

The film thickness of the hole transport layer 4 formed in this way is usually 5 nm or more, preferably 10 nm or more, and usually 300 nm or less, preferably 150 nm or less.

[Light-emitting layer] The light-emitting layer 5 is a layer responsible for the function of emitting light when the holes injected from the anode 2 and the electrons injected from the cathode 7 are recombined and excited when an electric field is applied between a pair of electrodes. The luminescent layer 5 is a layer formed between the anode 2 and the cathode 7. When there is a hole injection layer on the anode, the luminescent layer is formed between the hole injection layer and the cathode. When there is hole transport on the anode. In the case of a layer, it is formed between the hole transport layer and the cathode. As described above, the organic electroluminescent element in the present invention preferably contains a light-emitting layer forming material that is suitable as a light-emitting layer.

The film thickness of the light-emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but it is preferably thick in terms of making the film less likely to cause defects, and on the other hand, it is easy to form a low driving voltage. In terms of thickness, thinness is preferred. Therefore, it is preferably 3 nm or more, more preferably 5 nm or more, and on the other hand, it is generally preferably 200 nm or less, further preferably 100 nm or less.

The light-emitting layer 5 at least contains a material with light-emitting properties (light-emitting material), and preferably contains one or more host materials.

[Better material for forming light-emitting layer] The light-emitting layer in the present invention includes light-emitting materials and charge transport materials. The luminescent material may be a phosphorescent luminescent material or a fluorescent luminescent material. The charge transport film is preferably a red luminescent material, the green luminescent material is a phosphorescent luminescent material, and the blue luminescent material is a fluorescent luminescent material.

＜Phosphorescent material＞ Phosphorescent materials refer to materials that emit light from a self-excited triplet state. For example, metal complex compounds containing Ir, Pt, Eu, etc. are representative examples, and the structure of the material is preferably one containing a metal complex.

Among metal complexes, examples of phosphorescent organic metal complexes that emit light through a triplet state include those selected from the long period periodic table (hereinafter, unless otherwise agreed, the “periodic table” will be mentioned) In the case of , it refers to a Werner-type complex or an organic metal complex compound in which a metal from Group 7 to Group 11 of the long-period periodic table is used as the central metal. Examples of such phosphorescent materials include those described in International Publication No. 2014/024889, International Publication No. 2015-087961, International Publication No. 2016/194784, and Japanese Patent Application Laid-Open No. 2014-074000. A compound represented by the following formula (201) or a compound represented by the following formula (205) is preferred, and a compound represented by the following formula (201) is more preferred.

[Chemical 97]

In formula (201), ring A1 represents an aromatic hydrocarbon ring structure that may have a substituent or an aromatic heterocyclic structure that may have a substituent. Ring A2 represents an aromatic heterocyclic structure which may have a substituent. R ¹⁰¹ and R ¹⁰² each independently have a structure represented by formula (202), and "*" represents the bonding position with ring A1 or ring A2. R ¹⁰¹ and R ¹⁰² may be the same or different. When there are multiple R ¹⁰¹ and R ¹⁰² respectively, they may be the same or different.

Ar ²⁰¹ and Ar ²⁰³ each independently represent an aromatic hydrocarbon ring structure which may have a substituent, or an aromatic heterocyclic structure which may have a substituent. Ar ²⁰² represents an optionally substituted aromatic hydrocarbon ring structure, an optionally substituted aromatic heterocyclic structure, or an optionally substituted aliphatic hydrocarbon structure. The substituents bonded to ring A1, the substituents bonded to ring A2, or the substituents bonded to ring A1 and the substituents bonded to ring A2 may be bonded to each other to form a ring.

B ²⁰¹ -L ²⁰⁰ -B ²⁰² represent anionic bidentate ligands. B ²⁰¹ and B ²⁰² each independently represent a carbon atom, an oxygen atom or a nitrogen atom, and these atoms may also be atoms constituting a ring. L ²⁰⁰ represents a single bond or an atomic group constituting a bidentate ligand together with B ²⁰¹ and B ²⁰² . When there are multiple B ²⁰¹ -L ²⁰⁰ -B ²⁰² , they may be the same or different.

Furthermore, in the formulas (201) and (202), i1 and i2 each independently represent an integer of 0 or more and 12 or less, i3 represents an integer of 0 or more with the upper limit of the number that can be substituted for Ar ²⁰² , and i4 represents k1 and k2 each independently represent an integer of 0 or more, with the upper limit of the number that can be substituted for Ar ²⁰¹ being an integer of 0 or more, and z represents an integer of 1 to 3.

(substituent) Unless otherwise specified, the substituent in the material for forming the light-emitting layer is preferably a group selected from the following substituent group S.

<Substituent group S> ·Alkyl group, preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group having 1 to 12 carbon atoms, even more preferably an alkyl group having 1 to 8 carbon atoms, particularly preferably an alkyl group having 1 to 6 carbon atoms base. ·Alkoxy group, preferably an alkoxy group having 1 to 20 carbon atoms, more preferably an alkoxy group having 1 to 12 carbon atoms, even more preferably an alkoxy group having 1 to 6 carbon atoms. ·Aryloxy group, preferably an aryloxy group having 6 to 20 carbon atoms, more preferably an aryloxy group having 6 to 14 carbon atoms, even more preferably an aryloxy group having 6 to 12 carbon atoms, particularly preferably It is an aryloxy group having 6 carbon atoms. ·Heteroaryloxy group, preferably a heteroaryloxy group having 3 to 20 carbon atoms, more preferably a heteroaryloxy group having 3 to 12 carbon atoms. ·Alkylamino group, preferably an alkylamino group having 1 to 20 carbon atoms, more preferably an alkylamino group having 1 to 12 carbon atoms. ·Arylamine group, preferably an arylamine group having 6 to 36 carbon atoms, more preferably an arylamine group having 6 to 24 carbon atoms. ·Aralkyl group, preferably an aralkyl group having 7 to 40 carbon atoms, more preferably an aralkyl group having 7 to 18 carbon atoms, even more preferably an aralkyl group having 7 to 12 carbon atoms. ·Heteroaralkyl group, preferably a heteroaralkyl group having 7 to 40 carbon atoms, more preferably a heteroaralkyl group having 7 to 18 carbon atoms, ·Alkenyl group, preferably an alkenyl group having 2 to 20 carbon atoms, more preferably an alkenyl group having 2 to 12 carbon atoms, even more preferably an alkenyl group having 2 to 8 carbon atoms, particularly preferably an alkenyl group having 2 to 6 carbon atoms base. ·Alkynyl group, preferably an alkynyl group having 2 to 20 carbon atoms, more preferably an alkynyl group having 2 to 12 carbon atoms. ·Aryl group, preferably an aryl group having 6 to 30 carbon atoms, more preferably an aryl group having 6 to 24 carbon atoms, even more preferably an aryl group having 6 to 18 carbon atoms, particularly preferably an aryl group having 6 to 14 carbon atoms. base. ·Heteroaryl group, preferably a heteroaryl group having 3 to 30 carbon atoms, more preferably a heteroaryl group having 3 to 24 carbon atoms, even more preferably a heteroaryl group having 3 to 18 carbon atoms, particularly preferably 3 carbon atoms ~14 heteroaryl. ·Alkylsilyl group, preferably an alkylsilyl group having 1 to 20 carbon atoms in the alkyl group, more preferably an alkylsilyl group having 1 to 12 carbon atoms in the alkyl group. ·Arylsilyl group, preferably an arylsilyl group having 6 to 20 carbon atoms, more preferably an arylsilyl group having 6 to 14 carbon atoms. ·Alkylcarbonyl group, preferably an alkylcarbonyl group having 2 to 20 carbon atoms. ·Arylcarbonyl group, preferably an arylcarbonyl group having 7 to 20 carbon atoms.

One or more hydrogen atoms of the above group may be substituted with a fluorine atom, or one or more hydrogen atoms may be substituted with a deuterium atom. Unless otherwise specified, an aryl group is an aromatic hydrocarbon ring, and a heteroaryl group is an aromatic heterocyclic ring. ·Hydrogen atom, deuterium atom, fluorine atom, cyano group or -SF ₅ .

Among the substituent groups S, preferred ones are alkyl, alkoxy, aryloxy, arylamine, aralkyl, alkenyl, aryl, heteroaryl, alkylsilyl, and arylsilane groups, and groups in which one or more hydrogen atoms of these groups are substituted by fluorine atoms, fluorine atoms, cyano groups, or -SF ₅ , more preferably alkyl groups, arylamine groups, aralkyl groups, alkenyl groups, Aryl groups, heteroaryl groups, and groups in which one or more hydrogen atoms of these groups are substituted with fluorine atoms, fluorine atoms, cyano groups, or -SF ₅ , more preferably alkyl groups, alkoxy groups, and aryloxy groups group, arylamine group, aralkyl group, alkenyl group, aryl group, heteroaryl group, alkylsilyl group, arylsilyl group, particularly preferably alkyl group, arylamine group, aralkyl group, alkenyl group, aromatic group group, heteroaryl group, preferably alkyl group, arylamine group, aralkyl group, aryl group, heteroaryl group.

The substituent group S may further have a substituent selected from the substituent group S as a substituent. The preferable group, the more preferable group, the further preferable group, the particularly preferable group, and the optimal group of the substituent which it may have are the same as the preferable group in the substituent group S.

(Ring A1) Ring A1 represents an optionally substituted aromatic hydrocarbon ring structure or an optionally substituted aromatic heterocyclic structure.

As the aromatic hydrocarbon ring, an aromatic hydrocarbon ring having 6 to 30 carbon atoms is preferred. Specifically, preferred are a benzene ring, naphthalene ring, anthracene ring, triphenylyl ring, ethane naphthalene ring, fluoranthene ring, and fluorene ring.

As the aromatic heterocyclic ring, an aromatic heterocyclic ring having 3 to 30 carbon atoms containing any one of a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom is preferred. Further preferred ones are furan ring, benzofuran ring, thiophene ring and benzothiophene ring. The ring A1 is more preferably a benzene ring, a naphthalene ring, or a fluorene ring, particularly preferably a benzene ring or a fluorene ring, and most preferably a benzene ring.

(Ring A2) Ring A2 represents an aromatic heterocyclic structure which may have a substituent. As the aromatic heterocyclic ring, an aromatic heterocyclic ring having 3 to 30 carbon atoms containing any one of a nitrogen atom, an oxygen atom, or a sulfur atom as a hetero atom is preferred. Specific examples include: pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, oxazole ring, thiazole ring, benzothiazole ring, benzoxazole ring, benzimidazole ring, and quinoline ring , isoquinoline ring, quinoxaline ring, quinazoline ring, naphthyridine ring, phenanthridine ring, preferably pyridine ring, pyrazine ring, pyrimidine ring, imidazole ring, benzothiazole ring, benzoxazole ring , quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, more preferably pyridine ring, imidazole ring, benzothiazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazole The pholine ring is preferably a pyridine ring, an imidazole ring, a benzothiazole ring, a quinoline ring, a quinoxaline ring, or a quinazoline ring.

(combination of ring A1 and ring A2) As a preferred combination of ring A1 and ring A2, if it is expressed as (ring A1-ring A2), it is (benzene ring-pyridine ring), (benzene ring-quinoline ring), (benzene ring-quinoxaline ring) , (benzene ring-quinazoline ring), (benzene ring-benzothiazole ring), (benzene ring-imidazole ring), (benzene ring-pyrrole ring), (benzene ring-oxadiazole ring), and (benzene ring -thiophene ring).

(Substituents of Ring A1 and Ring A2) The substituents that ring A1 and ring A2 may have can be selected arbitrarily, but are preferably one or more substituents selected from the substituent group S.

(Ar ²⁰¹ , Ar ²⁰² , Ar ²⁰³ ) Ar ²⁰¹ and Ar ²⁰³ each independently represent an aromatic hydrocarbon ring structure which may have a substituent, or an aromatic heterocyclic structure which may have a substituent. Ar ²⁰² represents an optionally substituted aromatic hydrocarbon ring structure, an optionally substituted aromatic heterocyclic structure, or an optionally substituted aliphatic hydrocarbon structure.

When any one of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ is an aromatic hydrocarbon ring structure which may have a substituent, the aromatic hydrocarbon ring structure is preferably an aromatic hydrocarbon ring having 6 to 30 carbon atoms. . Specifically, a benzene ring, a naphthalene ring, an anthracene ring, a triphenyl ring, an ethane naphthalene ring, a fluoranthene ring, and a fluorene ring are preferred, and a benzene ring, a naphthalene ring, and a fluorene ring are more preferred, and benzene ring is the most preferred. ring.

When either Ar ²⁰¹ or Ar ²⁰² is a benzene ring which may have a substituent, it is preferable that at least one benzene ring is bonded to an adjacent structure at the ortho or meta position, and more preferably at least one benzene ring Bonds to adjacent structures at the meta position.

When any one of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ is a fluorene ring which may have a substituent, it is preferable that the 9-position and 9'-position of the fluorene ring have a substituent or be bonded to an adjacent structure.

When any one of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ is an aromatic heterocyclic structure that may have a substituent, the aromatic heterocyclic structure preferably contains a nitrogen atom, an oxygen atom, or a sulfur atom. As an aromatic heterocyclic ring having 3 to 30 carbon atoms as a heteroatom, specific examples include: pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, imidazole ring, oxazole ring, thiazole ring, Benzothiazole ring, benzoxazole ring, benzimidazole ring, quinoline ring, isoquinoline ring, quinoxaline ring, quinazoline ring, naphthyridine ring, phenanthridine ring, carbazole ring, dibenzo Furan ring and dibenzothiophene ring are preferably pyridine ring, pyrimidine ring, triazine ring, carbazole ring, dibenzofuran ring and dibenzothiophene ring.

When any one of Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ is a carbazole ring which may have a substituent, the N position of the carbazole ring preferably has a substituent or is bonded to an adjacent structure.

When Ar ²⁰² is an aliphatic hydrocarbon structure that may have a substituent, it is a linear, branched chain, or aliphatic hydrocarbon structure having a cyclic structure, and preferably has a carbon number of 1 or more and 24 or less, and more preferably The number of carbon atoms is from 1 to 12, and more preferably from 1 to 8.

(i1, i2, i3, i4, k1, k2) i1 and i2 each independently represent an integer of 0 to 12, preferably 1 to 12, more preferably 1 to 8, more preferably 1 to 6. By being in this range, it is expected that the solubility will be improved or the charge transport properties will be improved. i3 is preferably an integer representing 0 to 5, more preferably 0 to 2, more preferably 0 or 1. i4 is preferably an integer representing 0 to 2, and more preferably 0 or 1. It is preferable that k1 and k2 are each independently an integer representing 0 to 3, more preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.

(Preferred substituents for Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ ) The substituents that Ar ²⁰¹ , Ar ²⁰² , and Ar ²⁰³ may have can be selected arbitrarily, but are preferably one or more selected from the substituent group S. The substituent, the preferred group is the same as the substituent group S, but more preferably it is unsubstituted (hydrogen atom), alkyl group, aryl group, particularly preferably unsubstituted (hydrogen atom), alkyl group, most preferably Preferably, it is unsubstituted (hydrogen atom) or tertiary butyl group. The tertiary butyl group is preferably substituted by Ar 203 when Ar ²⁰³ is present, substituted by Ar ²⁰² when Ar ²⁰³ is not present, and is preferably substituted by Ar ²⁰² when Ar 203 is not present. When Ar ²⁰² and Ar ²⁰³ are present, it is replaced by Ar ²⁰¹ .

(Preferred aspect of the compound represented by formula (201)) The compound represented by the formula (201) is preferably a compound that satisfies at least one of the following (I) to (IV).

(I) Phenylene linkage formula Preferably, the structure represented by the formula (202) is a structure having a group connecting benzene rings, that is, a benzene ring structure, and i1 is 1 to 6, and at least one of the benzene rings is adjacent to the benzene ring in the ortho or meta position. structural bonding. Such a structure is expected to improve solubility and improve charge transport properties.

(II) (Phenylene)-aralkyl (alkyl) has the structure of an aromatic hydrocarbon group or aromatic heterocyclic group with an alkyl group or aralkyl group bonded to ring A1 or ring A2, that is, Ar ²⁰¹ is Aromatic hydrocarbon structure or aromatic heterocyclic structure, i1 is 1 to 6, Ar ²⁰² is an aliphatic hydrocarbon structure, i2 is 1 to 12, preferably 3 to 8, and Ar ²⁰³ is a benzene ring structure, i3 is 0 or The structure of 1 is preferably a structure in which Ar ²⁰¹ is the aromatic hydrocarbon structure, and more preferably a structure in which one to five benzene rings are connected, and more preferably one benzene ring. Such a structure is expected to improve solubility and improve charge transport properties.

(III) Dendron: A structure with dendrons bonded to ring A1 or ring A2. For example, Ar ²⁰¹ and Ar ²⁰² are benzene ring structures, Ar ²⁰³ is a biphenyl or terphenyl structure, and i1 and i2 are 1 ~6, i3 is 2, j is 2. Such a structure is expected to improve solubility and improve charge transport properties.

(IV) The structure represented by B ²⁰¹ -L ²⁰⁰ -B ²⁰² B ²⁰¹ -L ²⁰⁰ -B ²⁰² is preferably a structure represented by the following formula (203) or the following formula (204).

[Chemical 98]

In formula (203), R ²¹¹ , R ²¹² , and R ²¹³ each independently represent a substituent. In formula (204), Ring B3 represents an aromatic heterocyclic structure containing a nitrogen atom which may have a substituent. Ring B3 is preferably a pyridine ring.

(Better phosphorescent luminescent material) The phosphorescent light-emitting material represented by the formula (201) is not particularly limited, and the following can be cited as preferred phosphorescent light-emitting materials.

[Chemical 99]

[Chemical 100]

In addition, a phosphorescent material represented by the following formula (205) is also preferred.

[Chemistry 101]

[In formula (205), M ² represents a metal, T represents a carbon atom or a nitrogen atom; R ⁹² to R ⁹⁵ each independently represent a substituent; where, when T is a nitrogen atom, R ⁹⁴ and R ⁹⁵ do not exist ]

In the formula (205), specific examples of M ² include metals selected from Groups 7 to 11 of the periodic table. Among them, preferred examples include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold, and particularly preferred examples include bivalent metals such as platinum and palladium.

In addition, in the formula (205), R ⁹² and R ⁹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, an amine group, a hydroxyl group, an alkoxycarbonyl group, a carboxyl group, an alkyl group, or an alkyl group. Oxygen group, alkylamino group, aralkylamino group, haloalkyl group, hydroxyl group, aryloxy group, aromatic hydrocarbon group or aromatic heterocyclic group.

Furthermore, when T is a carbon atom, R ⁹⁴ and R ⁹⁵ each independently represent a substituent represented by the same example as R ⁹² and R ⁹³ . In addition, when T is a nitrogen atom, R ⁹⁴ or R ⁹⁵ directly bonded to T does not exist. In addition, R ⁹² to R ⁹⁵ may further have a substituent. The substituent may be the substituent described above. Furthermore, any two or more groups among R ⁹² to R ⁹⁵ may be connected to each other to form a ring.

(molecular weight) The molecular weight of the phosphorescent material is preferably 5,000 or less, more preferably 4,000 or less, and particularly preferably 3,000 or less. In addition, the molecular weight of the phosphorescent material is preferably 800 or more, more preferably 1,000 or more, and still more preferably 1,200 or more. It is considered that by being in the above molecular weight range, the phosphorescent light-emitting materials do not aggregate with each other and are uniformly mixed with the charge transport material, so that a light-emitting layer with high luminous efficiency can be obtained.

The Tg, melting point, decomposition temperature, etc. are high, the phosphorescent light-emitting material and the formed light-emitting layer have excellent heat resistance, and the film quality is not likely to deteriorate due to gas generation, recrystallization, molecular migration, etc. or the accompanying material. In view of an increase in the concentration of impurities resulting from thermal decomposition, the molecular weight of the phosphorescent light-emitting material is preferably large. On the other hand, the molecular weight of the phosphorescent light-emitting material is preferably small in order to facilitate purification of the organic compound.

＜Charge transport material＞ The charge transport material used in the light-emitting layer is a material having a skeleton with excellent charge transport properties, and is preferably selected from an electron transport material, a hole transport material, and a bipolar material capable of transporting both electrons and holes.

Specific examples of skeletons with excellent charge transport properties include aromatic structures, aromatic amine structures, triarylamine structures, dibenzofuran structures, naphthalene structures, phenanthrene structures, phthalocyanine structures, porphyrin structures, and thiophenes. Structure, benzylphenyl structure, fluorene structure, quinacridone structure, triphenyl structure, carbazole structure, pyrene structure, anthracene structure, phenanthroline structure, quinoline structure, pyridine structure, pyrimidine structure, triazine structure, Oxadiazole structure or imidazole structure, etc.

As the electron transport material, from the viewpoint of being a material with excellent electron transport properties and a relatively stable structure, a compound having a pyridine structure, a pyrimidine structure, or a triazine structure is more preferred, and a compound having a pyrimidine structure or a triazine structure is more preferred. compound.

The hole transport material is a compound having a structure with excellent hole transport properties. In the central skeleton with excellent charge transport properties, the structure with excellent hole transport properties is preferably a carbazole structure or a dibenzofuran structure. , triarylamine structure, naphthalene structure, phenanthrene structure or pyrene structure, preferably carbazole structure, dibenzofuran structure or triarylamine structure.

The charge transport material used in the light-emitting layer is preferably a compound having a condensed ring structure of three or more rings, more preferably two or more condensed ring structures of three or more rings, or a compound having at least one condensed ring structure of five or more rings. By using these compounds, it is easy to obtain the effects of increasing the rigidity of molecules and suppressing the degree of molecular motion in response to heat. Furthermore, from the viewpoint of charge transport properties and material durability, it is preferable that the condensed ring with three or more rings and the condensed ring with five or more rings have an aromatic hydrocarbon ring or an aromatic heterocyclic ring.

Specific examples of the condensed ring structure with three or more rings include an anthracene structure, a phenanthrene structure, a pyrene structure, a pyrene structure, a condensed tetraphenyl structure, a triphenyl structure, a fluorene structure, a benzofluorene structure, and an indenofluorene structure. , indolofluorene structure, carbazole structure, indenocarbazole structure, indolocarbazole structure, dibenzofuran structure, dibenzothiophene structure, etc. From the viewpoint of charge transportability and solubility, a phenanthrene structure, a fluorene structure, an indenofluorene structure, a carbazole structure, an indenocarbazole structure, an indolocarbazole structure, and a dibenzofuran structure are preferred. At least one of the group consisting of a dibenzothiophene structure and a dibenzothiophene structure is more preferably a carbazole structure or an indolocarbazole structure from the viewpoint of durability relative to charge.

In the present invention, from the viewpoint of the durability of the organic electroluminescent element with respect to charges, it is preferable that at least one of the charge transport materials in the light-emitting layer be a material having a pyrimidine skeleton or a triazine skeleton.

From the viewpoint of excellent flexibility, the charge transport material of the light-emitting layer is preferably a polymer material. A light-emitting layer formed using a material with excellent flexibility is suitable as the light-emitting layer of an organic electroluminescent element formed on a flexible substrate. When the charge transport material contained in the light-emitting layer is a polymer material, the molecular weight is preferably from 5,000 to 1,000,000, more preferably from 10,000 to 500,000, and even more preferably from 10,000 to 100,000.

In addition, from the viewpoint of ease of synthesis and purification, ease of design of electron transport performance and hole transport performance, and ease of viscosity adjustment when dissolved in a solvent, the charge transport material of the light-emitting layer is preferably a low molecular weight material. . When the charge transport material contained in the light-emitting layer is a low-molecular material, the molecular weight is preferably 5,000 or less, more preferably 4,000 or less, particularly preferably 3,000 or less, most preferably 2,000 or less, and more preferably 300 or more, More preferably, it is 350 or more, and further preferably, it is 400 or more.

＜Fluorescent materials＞ The fluorescent material is not particularly limited, but is preferably a compound represented by the following formula (211).

[Chemical 102]

In the formula (211), Ar ²⁴¹ represents an aromatic hydrocarbon condensed ring structure that may have a substituent, and Ar ²⁴² and Ar ²⁴³ each independently represent an alkyl group, an aromatic hydrocarbon group, an aromatic hetero group, or an alkyl group that may have a substituent. The base formed by these bonds. n41 is an integer from 1 to 4.

Ar ²⁴¹ preferably represents a condensed ring structure of an aromatic hydrocarbon having 10 to 30 carbon atoms. Specific ring structures include: naphthalene, ethane naphthalene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, pyrene, tetraphenyl,蓛, perylene, etc.

Ar ²⁴¹ is more preferably an aromatic hydrocarbon condensed ring structure having 12 to 20 carbon atoms. Specific ring structures include: ethanenaphthalene, fluorene, anthracene, phenanthrene, fluoranthene, pyrene, tetraphenyl, pyrene, and perylene .

Ar ²⁴¹ is more preferably an aromatic hydrocarbon condensed ring structure having 16 to 18 carbon atoms. Specific ring structures include fluoranthene, pyrene, and pyrene.

n41 is 1 to 4, preferably 1 to 3, more preferably 1 to 2, and most preferably 2.

The alkyl group of Ar ²⁴² and Ar ²⁴³ is preferably an alkyl group having 1 to 12 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms.

The aromatic hydrocarbon group of Ar ²⁴² and Ar ²⁴³ is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 24 carbon atoms, and most preferably a phenyl group or a naphthyl group.

The aromatic hetero group of Ar ²⁴² and Ar ²⁴³ is preferably an aromatic hetero group having 3 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 5 to 24 carbon atoms, and specifically, a carbazolyl group, Dibenzofuranyl group, dibenzothiophenyl group, more preferably dibenzofuranyl group.

The substituent that Ar ²⁴¹ , Ar ²⁴² , and Ar ²⁴³ may have is preferably a group selected from the substituent group S, more preferably a hydrocarbon group contained in the substituent group S, and even more preferably as the substituent group S Preferred groups are hydrocarbyl groups.

The charge transport material used together with the fluorescent light-emitting material is not particularly limited, but is preferably represented by the following formula (212).

[Chemical 103]

In the formula (212), R ²⁵¹ and R ²⁵² are each independently a structure represented by the formula (213). R ²⁵³ represents a substituent. When there are multiple R ^253s , they may be the same or different. n43 It is an integer from 0 to 8.

[Chemical 104]

In the formula (213), * represents a bond with the anthracene ring of the formula (212), and Ar ²⁵⁴ and Ar ²⁵⁵ each independently represent an aromatic hydrocarbon structure that may have a substituent, or a heterocyclic structure that may have a substituent. When there are multiple Ar ²⁵⁴ and Ar ²⁵⁵ , the aromatic ring structures may be the same or different. n44 is an integer of 1 to 5, and n45 is an integer of 0 to 5.

Ar ²⁵⁴ is preferably a monocyclic or condensed ring aromatic hydrocarbon structure having a carbon number of 6 to 30 which may have a substituent, and more preferably a monocyclic or condensed ring aromatic hydrocarbon structure having a carbon number of 6 to 12 which may have a substituent. structure.

Ar ²⁵⁵ is preferably an aromatic hydrocarbon structure of a monocyclic or condensed ring having 6 to 30 carbon atoms which may have a substituent, or an aromatic heterocyclic structure of a condensed ring having 6 to 30 carbon atoms which may have a substituent. Ar ²⁵⁵ is more preferably an aromatic hydrocarbon structure of a monocyclic or condensed ring having 6 to 12 carbon atoms which may have a substituent, or an aromatic heterocyclic structure of a condensed ring having 12 carbon atoms which may have a substituent.

n44 is preferably an integer of 1 to 3, more preferably 1 or 2. n45 is preferably an integer of 0 to 3, more preferably an integer of 0 to 2.

The substituent that R ²⁵³ , Ar ²⁵⁴ and Ar ²⁵⁵ may have as a substituent is preferably a group selected from the substituent group S. The hydrocarbon group contained in the substituent group S is more preferable, and the hydrocarbon group in the group which is preferable as the substituent group S is even more preferable.

The molecular weight of the fluorescent light-emitting material and the charge transport material is preferably 5,000 or less, more preferably 4,000 or less, particularly preferably 3,000 or less, and most preferably 2,000 or less. In addition, it is preferably 300 or more, more preferably 350 or more, and still more preferably 400 or more. ＜Quantum dot＞ The light-emitting layer preferably contains quantum dots as a light-emitting substance. Quantum dots are luminescent semiconductor nanoparticles, usually with diameters ranging from 1 nm to 20 nm.

Quantum dots are preferably Group II-VI compounds, Group III-V compounds, Group IV-VI compounds, Group IV elements, Group IV compounds, or combinations containing these.

Examples of Group II-VI compounds include: CdSe, CdTe, CdS, ZnS, ZnSe, ZnTe, ZnO, HgS, HgSe, HgTe, MgSe, MgS, AgInS, CuInS, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HeSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HeZnSe, HeZnTe, MgZnSe, MgZnS, HgZnTeS, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHg STe, HgZnSeS, HgZnSeTe, HgZnSTe.

Examples of Group III-V compounds include: GaN, GaP, GaAs, GaSb, AlN, AlP, AlAs, AlSb, InN, InP, InAs, InSb, GaNP, GaNAs, GaNSb, GaPAs, GaPSb, AlNP, AlNAs, AlNSb, AlPAs, AlPSb, InGaP, InNP, InNAs, InNSb, InPAs, InPSb, GaAlNP, GaAlNAs, GaAlNSb, GaAlPAs, GaAlPSb, GaInNP, GaInNAs, GaInNSb, GaInPAs, GaInPSb, InAlNP, InAlNAs, InAlNSb, InAlPAs, InAlPSb.

Examples of Group IV-VI compounds include SnS, SnSe, SnTe, PbS, PbSe, PbTe, SnSeS, SnSeTe, SnSTe, PbSeS, PbSeTe, PbSTe, SnPbS, SnPbSe, SnPbTe, SnPbSSe, SnPbSeTe, and SnPbSTe.

Examples of Group IV elements include Si and Ge, and examples of Group IV compounds include SiC and SiGe.

Quantum dots can be a uniform single structure or a core/shell dual structure. In addition, it may also have a triple or quadruple or higher structure like core/shell/shell. The materials that make up the core and shell contain different compounds. In this case, the energy band gap of the shell compound is preferably larger than the energy band gap of the core compound. Specifically, structures such as ZnTeSe/ZnSe/ZnS, CdSe/ZnS, and InP/ZnS are preferred.

[Composition for forming a light-emitting layer containing quantum dots] The formation method of the light-emitting layer containing quantum dots can be either a vacuum evaporation method or a wet film formation method, and the wet film formation method is preferred. In the case of the wet film-forming method, the light-emitting layer forming composition containing an organic solvent is applied to the light-emitting layer and dried to form a film. The composition for forming a light-emitting layer containing quantum dots contains quantum dots and an organic solvent.

(organic solvent) The organic solvent contained in the composition for forming a light-emitting layer containing quantum dots is a volatile liquid component used to form a layer containing quantum dots by wet film formation.

The organic solvent is not particularly limited as long as it is an organic solvent in which the solute, that is, the quantum dots can be well dissolved.

Preferred organic solvents include, for example, alkanes such as n-decane, cyclohexane, ethylcyclohexane, decalin, and dicyclohexane; toluene, xylene, mesitylene, and phenylcyclohexane. , tetralin, methylnaphthalene and other aromatic hydrocarbons; chlorobenzene, dichlorobenzene, trichlorobenzene and other halogenated aromatic hydrocarbons; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene , anisole, phenylethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole , diphenyl ether and other aromatic ethers; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate and other aromatic esters; cyclohexanone, cyclohexanone, Alicyclic ketones such as octanone and fenchone; alicyclic alcohols such as cyclohexanol and cyclooctanol; aliphatic ketones such as methyl ethyl ketone and dibutyl ketone; butanol and hexanol Aliphatic alcohols such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA) and other aliphatic ethers, etc.

Among these, from the viewpoint of viscosity and boiling point, alkanes, aromatic hydrocarbons, and aromatic esters are preferred.

One type of these organic solvents may be used alone, or two or more types may be used in any combination and ratio.

The boiling point of the organic solvent used is usually 80°C or higher, preferably 100°C or higher, more preferably 120°C or higher, and usually 350°C or lower, preferably 330°C or lower, more preferably 300°C or lower. If the boiling point of the organic solvent is lower than this range, the solvent derived from the composition for forming the light-emitting layer evaporates during wet film formation, which may result in decreased film formation stability. If the boiling point of the organic solvent exceeds this range, during wet film formation, the film formation stability may decrease due to residual solvent after film formation.

(content) The content of quantum dots in the composition for forming a light-emitting layer containing quantum dots is usually 0.001 mass% or more, preferably 0.01 mass% or more, and is usually 30.0 mass% or less, preferably 20.0 mass% or less. By setting the content within the above range, holes or electrons can be efficiently injected into the light-emitting layer from an adjacent layer (for example, a hole transport layer or a hole blocking layer), thereby reducing the driving voltage. Furthermore, only one type of quantum dots may be included in the composition for forming the light-emitting layer, or two or more types may be included in combination.

The content of the organic solvent contained in the composition for forming a light-emitting layer containing quantum dots is usually 10 mass% or more, preferably 50 mass% or more, particularly preferably 80 mass% or more, and usually 99.95 mass% or less, preferably The optimum is 99.9 mass% or less, and the particularly optimum is 99.8 mass% or less. If the content of the organic solvent is more than the above lower limit, the film will have a moderate viscosity and the coating properties will be improved. If it is less than the above upper limit, a uniform film will be easily obtained and the film forming properties will be good.

(other ingredients) The composition for forming a light-emitting layer containing quantum dots may further contain other compounds in addition to the above-mentioned compounds, if necessary. Preferred examples of other compounds include phenols such as dibutylhydroxytoluene and dibutylphenol, which are known as antioxidants, and known charge transport compounds.

(film forming method) The method for forming the light-emitting layer containing quantum dots is preferably a wet film forming method. The wet film-forming method is a method of applying a composition to form a liquid film, drying and removing the organic solvent to form a film of the light-emitting layer. As the coating method, for example, spin coating, dip coating, die coating, rod coating, blade coating, roller coating, spray coating, capillary coating, inkjet, nozzle printing, screen coating, etc. A wet film forming method such as plate printing, gravure printing, flexographic printing, etc. is used, and the coated film is dried to form the film. Among these coating methods, spin coating, spray coating, inkjet, nozzle printing, etc. are preferred. When manufacturing a quantum dot display device including a quantum dot light-emitting element, an inkjet method or a nozzle printing method is preferred, and the inkjet method is particularly preferred.

The drying method is not particularly limited, and natural drying, reduced pressure drying, heated drying, or reduced pressure drying with heating can be suitably used. Heating drying can be implemented after natural drying or reduced pressure drying to further remove residual organic solvent.

In the reduced-pressure drying, the pressure is preferably reduced to less than the vapor pressure of the organic solvent contained in the composition for forming a light-emitting layer containing quantum dots.

When heating is performed, the heating method is not particularly limited, and heating using a hot plate, heating in an oven, infrared heating, etc. can be used. The heating temperature is usually 80°C or higher, preferably 100°C or higher, more preferably 110°C or higher, and preferably 200°C or lower, further preferably 150°C or lower.

The heating time is usually 1 minute or more, preferably 2 minutes or more, and usually 60 minutes or less, preferably 30 minutes or less, and more preferably 20 minutes or less.

[Hole blocking layer] A hole blocking layer may also be provided between the light-emitting layer 5 and the electron injection layer described below. The hole blocking layer is a layer laminated on the light-emitting layer 5 so as to be in contact with the interface on the cathode 7 side of the light-emitting layer 5 .

The hole blocking layer has the function of preventing holes moving from the anode 2 from reaching the cathode 7 and of efficiently transporting electrons injected from the cathode 7 toward the light-emitting layer 5 . Physical properties required for the material constituting the hole blocking layer include high electron mobility and low hole mobility, a large energy gap (difference between HOMO and LUMO), and a high excited triplet energy level (T ₁ ).

Examples of materials for the hole blocking layer that satisfy such conditions include: bis(2-methyl-8-hydroxyquinoline)(phenol)aluminum, bis(2-methyl-8-hydroxyquinoline)(tris Mixed coordination complexes such as bis(2-methyl-8-quinolinolato)(triphenyl silanolato)aluminum, bis(2-methyl-8-hydroxyquinoline)aluminum-μ-oxygen Meta-bis-(2-methyl-8-hydroxyquinoline) aluminum dinuclear metal complex and other metal complexes, distyryl biphenyl derivatives and other styryl compounds (Japanese Patent Laid-Open No. 11-242996 Publication No.), 3-(4-biphenyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole and other triazole derivatives (Japanese Patent Application Publication No. 7-41759), phenanthroline derivatives such as bathocuproin (Japanese Patent Application Laid-Open No. 10-79297), etc. Furthermore, the compound having at least one pyridine ring substituted at positions 2, 4, and 6 described in International Publication No. 2005/022962 is also suitable as a material for the hole blocking layer.

The formation method of the hole blocking layer is not limited. Therefore, it can be formed by wet film forming method, evaporation method or other methods.

The film thickness of the hole blocking layer is arbitrary as long as the effect of the present invention is not significantly impaired. It is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less.

[Electron transport layer] For the purpose of further improving the current efficiency of the element, the electron transport layer 6 is provided between the light-emitting layer 5 and the cathode 7 .

The electron transport layer 6 is formed of a compound that can efficiently transport electrons injected from the cathode 7 toward the light-emitting layer 5 between electrodes to which an electric field is applied. The electron-transporting compound used in the electron-transporting layer 6 needs to be a compound that has high electron injection efficiency from the cathode 7, has a high electron mobility, and can efficiently transport the injected electrons.

Specific examples of the electron transport compound used in the electron transport layer include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), 10 -Metal complexes of hydroxybenzo[h]quinoline, oxadiazole derivatives, distyrylbiphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes Compounds, benzoxazole metal complexes, benzothiazole metal complexes, triphenzimidazolylbenzene (US Patent No. 5645948), quinoxaline compounds (Japanese Patent Laid-Open No. 6-207169) , phenanthroline derivatives (Japanese Patent Application Laid-Open No. 5-331459), 2-tert-butyl-9,10-N,N'-dicyananthraquinonediimide, n-type hydrogenated amorphous silicon carbide , n-type zinc sulfide, n-type zinc selenide, etc.

The film thickness of the electron transport layer 6 is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.

The electron transport layer 6 is formed by laminating the hole blocking layer by a wet film forming method or a vacuum evaporation method in the same manner as described above. Vacuum evaporation is usually used. In the present invention, as mentioned above, the electron transport layer can be formed on the light-emitting layer containing a preferred light-emitting layer forming material using a wet film forming method.

[Electron injection layer] In order to efficiently inject electrons injected from the cathode 7 into the electron transport layer 6 or the light emitting layer 5, an electron injection layer may be provided.

In order to efficiently inject electrons, the material forming the electron injection layer is preferably a metal with a low work function. As examples, alkali metals such as sodium and cesium, alkaline earth metals such as barium and calcium, and the like can be used. The film thickness is generally preferably from 0.1 nm to 5 nm.

Furthermore, organic electron transport materials represented by nitrogen-containing heterocyclic compounds such as haphenanthroline or metal complexes such as aluminum complexes of 8-hydroxyquinoline are doped with alkali metals such as sodium, potassium, cesium, lithium, and rubidium. (Described in Japanese Patent Laid-Open No. 10-270171, Japanese Patent Laid-Open No. 2002-100478, Japanese Patent Laid-Open No. 2002-100482, etc.) It can also improve electron injection and transport properties while maintaining excellent film quality, so it is relatively good.

The film thickness of the electron injection layer is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.

The electron injection layer is formed by laminating the light-emitting layer 5 or the hole blocking layer or the electron transport layer 6 thereon using a wet film forming method or a vacuum evaporation method. The details of the wet film formation method are the same as those of the light-emitting layer.

Sometimes, the hole blocking layer, the electron transport layer, and the electron injection layer are formed into one layer by co-doping the electron transport material with the lithium complex.

[cathode] The cathode 7 plays a role of injecting electrons into the layer on the side of the light-emitting layer 5 (electron injection layer, light-emitting layer, etc.).

As the material of the cathode 7, the material used for the anode 2 can be used. In terms of efficiently injecting electrons, it is preferable to use a metal with a low work function. For example, tin, magnesium, indium, calcium can be used. , aluminum, silver and other metals or their alloys, etc. Specific examples include low work function alloy electrodes such as magnesium-silver alloys, magnesium-indium alloys, and aluminum-lithium alloys.

In terms of the stability of the organic electroluminescent element, it is preferable to laminate a metal layer with a high work function and stable to the atmosphere on the cathode to protect the cathode containing a metal with a low work function. Examples of laminated metals include metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum.

The film thickness of the cathode is usually the same as that of the anode.

[Other layers] As long as the effect of the present invention is not significantly impaired, the organic electroluminescent element of the present invention may also have other layers. That is, the other arbitrary layers mentioned above may be provided between the anode and the cathode.

[Other component structures] The organic electroluminescent element of the present invention can also have a structure opposite to the above description, that is, for example, a cathode, an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, a hole transport layer, and a hole are formed on a substrate. The injection layer and the anode are laminated in this order.

When the organic electric field light-emitting element of the present invention is applied to an organic electric field light-emitting device, it can be used as a single organic electric field light-emitting element, or it can be used in a structure in which a plurality of organic electric field light-emitting elements are arranged in an array, or it can be used. It can be used in a structure in which the anode and the cathode are arranged in an X-Y matrix.

[display device] The display device (organic electric field light-emitting element display device) of the present invention includes the organic electric field light-emitting element of the present invention. There is no particular limitation on the model or structure of the display device of the present invention. The organic electric field light-emitting element of the present invention can be used and assembled according to conventional methods.

For example, the organic EL display of the present invention can be formed using the method described in "Organic EL Display" (Ohmsha, published on August 20, 2004, written by Seishi Toto, Chihaya Adachi, and Hideyuki Murata) device.

[lighting device] The lighting device (organic electric field light-emitting element lighting device) of the present invention includes the organic electric field light-emitting element of the present invention. There is no particular limitation on the model or structure of the lighting device of the present invention. The organic electric field light-emitting element of the present invention can be used and assembled according to conventional methods.

＜Quantum dot display device＞ The quantum dot display device (quantum dot light-emitting element display device) of the present invention includes the quantum dot light-emitting element of the present invention. There is no particular limitation on the model or structure of the quantum dot display device of the present invention. The quantum dot light-emitting element of the present invention can be used and assembled according to conventional methods.

For example, the organic light-emitting layer is replaced by referring to the method described in "Organic EL Display" (Ohmsha, published on August 20, 2004, written by Seishi Toto, Chihaya Adachi, and Hideyuki Murata). The quantum dot display device of the present invention can be formed as a light-emitting layer containing quantum dots.

＜Quantum dot lighting device＞ The quantum dot lighting device (quantum dot light-emitting element lighting device) of the present invention includes the quantum dot light-emitting element of the present invention. There is no particular limitation on the model or structure of the quantum dot lighting device of the present invention. The quantum dot light-emitting element of the present invention can be used and assembled according to conventional methods. [Example]

Hereinafter, an Example is shown and this invention is demonstrated more concretely. However, the present invention is not limited to the following examples, and the present invention can be implemented with arbitrary modifications without departing from the gist of the present invention.

＜Synthesis of intermediates＞ [Synthesis of Compound 1]

[Chemical 105]

Put 270 mL of toluene, 135 mL of ethanol, and 2,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborane-2-yl) into a 1 L flask. )-9,9-dihexylfluorene (20.0 g, 34.1 mmol), 50.72 g (136.5 mmol) of 5-bromo-2-iodotoluene, 102 mL of potassium phosphate aqueous solution (2M, 2 mol/L concentration) , the obtained solution was degassed under vacuum and then replaced with nitrogen. Heat under nitrogen flow and stir for 30 minutes. After that, 0.48 g (0.68 mmol) of bis(triphenylphosphine)dichloropalladium(II) was added, and the reaction was carried out at 65°C for 6 hours. Water was added to the reaction solution, extracted with toluene, and treated with MgSO ₄ and activated clay. After heating the toluene solution to reflux, the insoluble matter was filtered and recrystallized to obtain compound 1 as a colorless solid (yield: 16.5 g, yield 72.1%).

[Synthesis of compound 3]

[Chemical 106]

Then, 3-bromo-3'-iodo-1,1-biphenyl (29.4 g, 81.9 mmol), commercially available compound 2 (20.0 g, 81.9 mmol), potassium phosphate (2M aqueous solution, 103 g, 205 mmol), toluene (200 mL) and ethanol (100 mL) were put into the flask, the system was fully replaced with nitrogen, and the system was heated to 60°C. Tetrakis(triphenylphosphine)palladium(0) (2.37 g, 2.05 mmol) was added and stirred at 85°C for 6 hours. Water was added to the reaction liquid, and extraction was performed with toluene. The organic layer was dried with anhydrous magnesium sulfate and crudely purified with activated clay. The crude product was purified by column chromatography (developing solution: hexane/dichloromethane = 950/50) to obtain compound 3 (23.1 g, yield 81%).

[Synthesis of compound 4]

[Chemical 107]

Compound 3 (23.1 g, 66.1 mmol), commercially available 3-aminophenylboronic acid (9.8 g, 63.0 mmol), potassium phosphate (2M aqueous solution, 79 g, 158 mmol), toluene (160 mL), ethanol ( 80 mL) into a flask, fully replace nitrogen in the system, and heat to 60°C. Tetrakis(triphenylphosphine)palladium(0) (1.85 g, 1.6 mmol) was added and stirred at 85°C for 4 hours. Water was added to the reaction liquid, and extraction was performed with toluene. The organic layer was dried with anhydrous magnesium sulfate and crudely purified with activated clay. The crude product was purified by column chromatography (developing solution: hexane/ethyl acetate = 8/2) to obtain compound 4 (22.2 g, yield 92.9%).

[Synthesis of compound 5] Compound 5 was synthesized by the method described in International Publication No. 2020/171190.

＜Synthesis of polymer compounds＞ [Synthesis of polymer compound P-1] Polymer compound P-1 is synthesized according to the following reaction formula.

[Chemical 108]

Load compound 1 (2.0 g, 2.97 mmol), compound 4 (1.1179 g, 3.09 mmol), 2,4-difluoroaniline (0.3686 g, 2.85 mmol), sodium tert-butoxide (2.2 g, 22.89 mmol) and toluene (40 g, 46 mL), fully replace the system with nitrogen, and heat it to 60°C (solution A1).

To a solution of tris(dibenzylideneacetone)dipalladium complex (0.055 g, 0.06 mmol) in 9.5 mL of toluene was added [4-(N,N-dimethylamino)phenyl]di-tert-butyl Amphos (0.126 g, 0.47 mmol), heated to 60°C (solution B1).

In a nitrogen flow, solution B1 was added to solution A1, and a heating and reflux reaction was performed for 1.0 hours. After confirming that compound 1 had disappeared, 4,4'-dibromobiphenyl (0.668 g, 2.14 mmol) was added. After heating and refluxing for 2 hours, bromobenzene (1.3 g, 8.2 mmol) was added, and the heating and refluxing reaction was performed for 2 hours. The reaction solution was allowed to cool, and then added dropwise to the ethanol/water (210 mL/30 mL) solution to obtain a capped crude polymer.

The end-capped crude polymer was dissolved in toluene and reprecipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ethanol containing ammonia. The filtered polymer was purified by column chromatography to obtain the target polymer compound P-1 (1.6 g). The molecular weight, etc. of the obtained polymer compound P-1 are as follows.

Weight average molecular weight (Mw) = 16360 Number average molecular weight (Mn) =11680 Dispersion (Mw/Mn)=1.40

[Synthesis of polymer compound P-2] Polymer compound P-2 is synthesized according to the following reaction formula.

[Chemical 109]

Load compound 1 (2.0 g, 2.97 mmol), compound 4 (1.1179 g, 3.09 mmol), 3,5-difluoroaniline (0.3686 g, 2.85 mmol), sodium tert-butoxide (2.2 g, 22.89 mmol) and toluene (40 g, 46 mL), fully replace nitrogen in the system, and heat to 60°C (solution A2).

To a solution of tris(dibenzylideneacetone)dipalladium complex (0.055 g, 0.06 mmol) in 9.5 mL of toluene was added [4-(N,N-dimethylamino)phenyl]di-tert-butyl Amphos (0.126 g, 0.47 mmol), heated to 60°C (solution B2).

In a nitrogen flow, solution B2 was added to solution A2, and a heating and reflux reaction was performed for 1.0 hours. After confirming that compound 1 had disappeared, 4,4'-dibromobiphenyl (0.668 g, 2.14 mmol) was added. After heating and refluxing for 2 hours, bromobenzene (1.3 g, 8.2 mmol) was added, and the heating and refluxing reaction was performed for 2 hours. The reaction solution was allowed to cool, and then added dropwise to the ethanol/water (210 mL/30 mL) solution to obtain a capped crude polymer.

The end-capped crude polymer was dissolved in toluene and reprecipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ethanol containing ammonia. The filtered polymer was purified by column chromatography to obtain the target polymer compound P-2 (1.5 g). The molecular weight, etc. of the obtained polymer compound P-2 are as follows.

Weight average molecular weight (Mw) = 13610 Number average molecular weight (Mn) =10230 Dispersion (Mw/Mn)=1.33

[Synthesis of polymer compound P-3] Polymer compound P-3 is synthesized according to the following reaction formula.

[Chemical 110]

Load 4,4'-dibromobiphenyl (2.56 g, 8.21 mmol), compound 4 (1.9465 g, 5.38 mmol), 3,5-difluoroaniline (0.96 g, 7.44 mmol), sodium tert-butoxide (4.75 g, 49.43 mmol) and toluene (40 g, 46 mL), fully replace nitrogen in the system, and heat to 60°C (solution A3).

To a solution of tris(dibenzylideneacetone)dipalladium complex (0.1174 g, 0.13 mmol) in 20 mL of toluene was added [4-(N,N-dimethylamino)phenyl]di-tert-butyl Amphos (0.272 g, 1.02 mmol), heated to 60°C (solution B3).

In a nitrogen flow, solution B3 was added to solution A3, and a heating and reflux reaction was performed for 2.0 hours. After confirming that 4,4'-dibromobiphenyl has disappeared, add compound 1 (1.811 g, 2.69 mmol). After heating and refluxing for 2 hours, bromobenzene (3.0 g, 19.11 mmol) was added, and the heating and refluxing reaction was performed for 2 hours. The reaction solution was allowed to cool, and then added dropwise to the ethanol/water (255 mL/60 mL) solution to obtain a capped crude polymer.

The end-capped crude polymer was dissolved in toluene and reprecipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ethanol containing ammonia. The filtered polymer was purified by column chromatography to obtain the target polymer compound P-3 (2.1 g). The molecular weight, etc. of the obtained polymer compound P-3 are as follows.

Weight average molecular weight (Mw) = 11250 Number average molecular weight (Mn) =8272 Dispersion (Mw/Mn)=1.36

[Synthesis of polymer compound P-4] Polymer compound P-4 is synthesized according to the following reaction formula.

[Chemical 111]

Load 4,4'-dibromobiphenyl (3.0 g, 9.62 mmol), compound 4 (1.5294 g, 4.23 mmol), 3,5-difluoroaniline (1.5642 g, 12.12 mmol), 2-amino-9 , 9'-dihexylfluorene (1.0083 g, 2.88 mmol), sodium tert-butoxide (7.12 g, 74.09 mmol) and toluene (45 g, 52 mL), fully replace nitrogen in the system, and heat to 60°C (Solution A4).

To a solution of tris(dibenzylideneacetone)dipalladium complex (0.1761 g, 0.192 mmol) in 30 mL of toluene was added [4-(N,N-dimethylamino)phenyl]di-tert-butyl Amphos (0.408 g, 1.54 mmol), heated to 60°C (solution B4).

In a nitrogen flow, solution B4 was added to solution A4, and a heating and reflux reaction was performed for 1.0 hours. After confirming that 4,4'-dibromobiphenyl has disappeared, add 4,4'-dibromobiphenyl (2.415 g, 7.74 mmol). After heating and refluxing for 2 hours, bromobenzene (2.94 g, 18.7 mmol) was added, and the heating and refluxing reaction was performed for 2 hours. The reaction solution was allowed to cool, and then added dropwise to the ethanol/water (315 mL/50 mL) solution to obtain a capped crude polymer.

The end-capped crude polymer was dissolved in toluene and reprecipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ethanol containing ammonia. The filtered polymer was purified by column chromatography to obtain the target polymer compound P-4 (2.1 g). The molecular weight, etc. of the obtained polymer compound P-4 are as follows.

Weight average molecular weight (Mw) = 13500 Number average molecular weight (Mn) =9854 Dispersion (Mw/Mn)=1.37

[Synthesis of polymer compound P-a] The polymer compound P-a is synthesized according to the following reaction formula.

[Chemical 112]

Load 4,4'-dibromo-p-triphenyl (3.0 g, 7.73 mmol), 2-amino-9,9-dihexylfluorene (2.205 g, 6.31 mmol), compound 5 (0.565 g, 1.42 mmol) , 3,5-difluoroaniline (0.998 g, 7.73 mmol), sodium tert-butoxide (5.73 g, 59.63 mmol) and toluene (83 ml), fully replace nitrogen in the system, and heat to 60°C (Solution A5).

To a solution of tris(dibenzylideneacetone)dipalladium complex (0.142 g, 0.155 mmol) in 9.5 ml of toluene was added [4-(N,N-dimethylamino)phenyl]di-tert-butyl Amphos (0.328 g, 1.24 mmol), heated to 60°C (solution B5).

In a nitrogen flow, solution B5 was added to solution A5, and a heating and reflux reaction was performed for 1.0 hours. After confirming that compound 5 had disappeared, 2,7-bis(4-bromophenyl)9,9-dihexylfluorene (3.54 g, 5.49 mmol) was added. After heating to reflux for 2 hours, bromobenzene (3.52 g, 22.42 mmol) was added, and the reaction was heated to reflux for 2 hours. The reaction solution was allowed to cool, and then added dropwise to the ethanol/water (275 ml/50 ml) solution to obtain a capped crude polymer.

The end-capped crude polymer was dissolved in toluene and reprecipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ethanol containing ammonia. The filtered polymer was purified by column chromatography to obtain the target polymer compound P-a (2.0 g). The molecular weight, etc. of the obtained polymer compound P-a are as follows. Weight average molecular weight (Mw) = 18320 Number average molecular weight (Mn) =14774 Dispersion (Mw/Mn)=1.24

[Synthesis of polymer compound P-5]

[Chemical 113]

Polymer compound P-5 was synthesized in the same manner as the polymer compound P-1.

[Manufacturing of organic electroluminescent devices] [Example 1] For those in which an indium-tin oxide (ITO) transparent conductive film is deposited on a glass substrate to a thickness of 50 nm (manufactured by Geomatec, a sputtered film product), ordinary photolithography technology and The anode is formed by etching with hydrochloric acid and patterning into 2 mm wide stripes. The substrate patterned with ITO in this way was cleaned in this order by ultrasonic cleaning with a surfactant aqueous solution, water washing with ultrapure water, ultrasonic cleaning with ultrapure water, and water washing with ultrapure water, and then compressed It is air dried and finally subjected to UV ozone cleaning.

As a composition for forming a hole injection layer, 3.1% by mass of a hole-transporting polymer compound having a structure of the following formula (P-1) and 0.6% by mass of the following electron-accepting compound (HI-1) were dissolved. Composition in ethyl benzoate.

[Chemical 114]

[Chemical 115]

The composition was spin-coated onto the substrate in the atmosphere, and dried using a heating plate at 230° C. for 30 minutes in the atmosphere to form a uniform thin film with a thickness of 40 nm to prepare a hole injection layer.

Next, 100 parts by mass of the charge transporting polymer compound having the following structural formula (HT-1) was dissolved in 1,3,5-trimethylbenzene to prepare a 2.0 mass% solution.

[Chemical 116]

The solution was spin-coated in a nitrogen glove box onto the substrate coated with the hole injection layer, and dried using a heating plate in the nitrogen glove box at 230°C for 30 minutes to form a uniform film thickness of 40 nm. The film is made into a hole transport layer.

Next, the host compound having the following structural formula (BH-1) and the doping compound having the following structural formula (BD-1) were dissolved in cyclohexylbenzene in parts by mass of 100:10 to prepare 4.4 mass %The solution.

[Chemical 117]

The solution was spin-coated in a nitrogen glove box onto the substrate coated with the hole transport layer to form a uniform thin film of 40 nm as a light-emitting layer. It was dried at 120° C. for 20 minutes using a hot plate in a nitrogen glove box to form a luminescent layer.

The substrate with the luminescent layer formed on it was placed in a vacuum evaporation device, and the inside of the device was evacuated to 2×10 ^-4 Pa or less.

Next, the compound represented by the following structural formula (ET-1) and lithium 8-hydroxyquinolate were co-evaporated on the light-emitting layer by a vacuum evaporation method at a film thickness ratio of 2:3 to form a film with a thickness of 30 nm electron transport layer.

[Chemical 118]

Next, as a mask for cathode vapor deposition, a 2 mm wide stripe-shaped shadow mask (shadow mask) is closely connected to the substrate in such a manner that it is orthogonal to the ITO stripes of the anode, and molybdenum is deposited through the vacuum evaporation method. The boat heats the aluminum to form an aluminum layer with a film thickness of 80 nm, thereby forming a cathode. By operating in the described manner, an organic electric field light-emitting element having a light-emitting area portion of 2 mm×2 mm size was obtained.

In a space filled with nitrogen, a moisture and oxygen adsorbent is bonded to the inside of a glass substrate with a hollow structure, so that the surface of the glass substrate with the organic electroluminescent element faces the surface of the insulating glass with the moisture and oxygen adsorbent. Ultraviolet curing resin is applied so as to surround the outer periphery of the organic electroluminescent element portion, and the surfaces are bonded to each other. Furthermore, the ultraviolet curable resin portion is irradiated with ultraviolet rays to form a structure that isolates the organic electroluminescent element portion from the external space. In this way, the organic electroluminescent element can be isolated from moisture or oxygen in a manner that no structure directly contacts the surface of the organic electroluminescent element, so that the influence of moisture or oxygen can be eliminated to evaluate the performance of the organic electroluminescent element.

[Example 2] Only 3.1 mass% of the hole-transporting polymer compound having the structure of the formula (P-2) and 0.6 mass% of the electron-accepting compound (HI-1) were dissolved in ethyl benzoate and used. An organic electroluminescent element was produced in the same manner as in Example 1, except that the composition was used as a hole injection layer forming composition.

[Example 3] A composition in which 3.1% by mass of the hole-transporting polymer compound having the structure of the above formula (P-4) and 0.6% by mass of the electron-accepting compound (HI-1) were dissolved in ethyl benzoate was prepared and used. An organic electroluminescent element was produced in the same manner as in Example 1, except that the composition was used as a hole injection layer forming composition.

[Comparative example 1] A composition in which 3.1% by mass of a hole-transporting polymer compound having the structure of Formula P-5 and 0.6% by mass of an electron-accepting compound (HI-1) were dissolved in ethyl benzoate was prepared and used. An organic electric field light-emitting element was produced in the same manner as in Example 1 except for the composition for forming the hole injection layer.

[Evaluation of Fluorescent Elements] When the organic electroluminescent elements obtained in Examples 1 to 3 and Comparative Example 1 are allowed to emit light, blue light emission with a peak wavelength of 468 nm can be obtained. The driving voltage (V) and current efficiency (cd/A) when the organic electroluminescent element was caused to emit light at 1,000 cd/m ² were measured. In addition, the brightness reduction life (95% brightness reduction) was measured when the organic electric field light-emitting element was continuously energized at a current density of 15 mA/cm ² .

When the driving voltage (V) of the organic electroluminescent element of Comparative Example 1 is 0.00 V, the difference in the driving voltage of the organic electroluminescent element of other examples and Comparative Example 1 (hereinafter referred to as "relative voltage") is shown in the table. 1 in.

When the current luminous efficiency (cd/A) of the organic electroluminescent element of Comparative Example 1 is set to 1.00, the ratio of the current luminous efficiency of the organic electroluminescent elements of other Examples and Comparative Examples, that is, "each organic electroluminescent element other than Comparative Example 1" The current luminous efficiency of the electroluminescent element/the current luminous efficiency of the organic electroluminescent element of Comparative Example 1 (hereinafter referred to as "relative current luminous efficiency") is shown in Table 1.

In addition, while these organic electroluminescent elements were continuously energized at a current density of 15 mA/cm ² , the time (hr) until the brightness of the elements dropped to 95% of the initial brightness was measured. Set this value to LT95. When the LT95 of the organic electroluminescent element of Comparative Example 1 is set to 1.00, the ratio of the LT95 of the organic electroluminescent elements of other Examples and Comparative Examples is calculated, that is, "LT95 of each organic electroluminescent element other than Comparative Example 1/Comparison The organic electroluminescent device of Example 1 is LT95" (hereinafter referred to as "relative lifetime") and is listed in Table 1.

[Table 1] Table 1 Composition for forming hole injection layer Relative voltage (V) Relative current luminous efficiency (cd/A) (relative value) Relative life LT polymer compounds electron-accepting compounds Example 1 P-1 HI-1 -0.20 1.03 1.26 Example 2 P-2 HI-1 -0.17 1.03 1.30 Example 3 P-4 HI-1 -0.19 1.03 1.20 Comparative example 1 P-5 HI-1 0.00 1.00 1.00

From the results in Table 1, it was found that blue fluorescence is formed using the composition of the present invention, that is, the composition of the present invention containing the fluorine-containing arylamine polymer compound and the electron-accepting compound having a crosslinking group. Organic electric field light-emitting elements have a tendency for voltage reduction, but have good current luminous efficiency and lifespan.

[Example 4] An electric field light-emitting element was produced in the same manner as in Example 1, except that the structure of the light-emitting layer in Example 1 was changed to the following light-emitting layer 5 .

When forming the light-emitting layer 5, 25 parts by mass of the compound (GH-1) represented by the following structural formula, 25 parts by mass of the compound (GH-2) represented by the following structural formula, and 50 parts by mass of the following The compound (GH-3) represented by the structural formula and 30 parts by mass of the compound (GD-1) represented by the following structural formula were dissolved in cyclohexylbenzene to prepare a 7.02 mass % solution.

The solution was spin-coated on the substrate coated with the hole transport layer in a nitrogen glove box, and dried at 120° C. for 20 minutes using a heating plate in the nitrogen glove box to form a uniform film thickness of 70 nm. thin film as the light-emitting layer 5.

[Chemical 119]

[Example 5] An organic electroluminescent element was produced in the same manner as in Example 4, except that the compound represented by the formula (P-1) was changed to the compound represented by the formula (P-2).

[Example 6] An organic electroluminescent element was produced in the same manner as in Example 4, except that the compound represented by the formula (P-1) was changed into the compound represented by the formula (P-4).

[Comparative example 2] An organic electroluminescent element was produced in the same manner as in Example 4, except that the compound represented by the formula (P-1) was changed to the compound represented by the formula (P-5).

[Evaluation of Phosphorescent Elements] When the organic electric field light-emitting elements obtained in Examples 4 to 6 and Comparative Example 2 are allowed to emit light, green phosphorescent emission with a peak wavelength of 524 nm can be obtained. The driving voltage (V) and current efficiency (cd/A) when the organic electroluminescent element was caused to emit light at 1,000 cd/m ² were measured. In addition, the brightness reduction life (95% brightness reduction) was measured when the organic electric field light-emitting element was continuously energized at a current density of 15 mA/cm ² .

When the drive voltage (V) of the organic electroluminescent element of Comparative Example 2 is 0.00 V, the difference in drive voltage (hereinafter referred to as "relative voltage") of the organic electroluminescent element of other examples and Comparative Example 2 is shown in the table. 2 in.

When the current luminous efficiency (cd/A) of the organic electroluminescent element of Comparative Example 2 is set to 1.00, the ratio of the current luminous efficiency of the organic electroluminescent element of other Examples and Comparative Examples, that is, "each organic electroluminescent element other than Comparative Example 2" The current luminous efficiency of the electroluminescent element/the current luminous efficiency of the organic electroluminescent element of Comparative Example 2 (hereinafter referred to as "relative current luminous efficiency") is shown in Table 2.

In addition, while these organic electroluminescent elements were continuously energized at a current density of 15 mA/cm ² , the time (hr) until the brightness of the elements dropped to 95% of the initial brightness was measured. Set this value to LT95. When the LT95 of the organic electroluminescent element of Comparative Example 2 is set to 1.00, the ratio of the LT95 of the organic electroluminescent elements of other Examples and Comparative Examples is found, that is, "LT95 of each organic electroluminescent element other than Comparative Example 2/Comparison The organic electroluminescent element LT95 of Example 1" (hereinafter referred to as "relative lifetime") is shown in Table 2.

[Table 2] Table 2 Composition for forming hole injection layer Relative voltage (V) Relative current luminous efficiency (cd/A) (relative value) Relative life LT polymer compounds electron-accepting compounds Example 4 P-1 HI-1 -0.30 1.01 1.14 Example 5 P-2 HI-1 -0.25 1.03 1.09 Example 6 P-4 HI-1 -0.24 1.05 1.09 Comparative example 2 P-5 HI-1 0.00 1.00 1.00

From the results in Table 2, it was found that the green phosphorescent organic electric field formed using the composition of the present invention, that is, the composition of the present invention containing the fluorine-containing arylamine polymer compound and the electron-accepting compound having a crosslinking group The light-emitting element also has a tendency of voltage reduction, but the current luminous efficiency and lifespan are good.

[Example 7] As the electron-accepting compound contained in the composition for forming the hole injection layer, a compound represented by the following formula (HI-2) is used instead of the compound represented by the formula (HI-1) to prepare the hole injection layer. An organic electroluminescent element was produced in the same manner as in Example 4, except that the hole injection layer forming composition was used.

[Chemical 120]

[Comparative example 3] As the electron-accepting compound contained in the composition for forming the hole injection layer, a compound represented by the following formula (HI-3) is used instead of the compound represented by the formula (HI-2) to prepare the hole injection layer. An organic electroluminescent element was produced in the same manner as in Example 7, except that the hole injection layer forming composition was used.

[Chemical 121]

[Example 8] As the hole-transporting polymer compound contained in the composition for forming the hole injection layer, the compound represented by the formula (P-2) is used instead of the compound represented by the formula (P-1) to prepare a hole-transporting polymer compound. An organic electroluminescent element was produced in the same manner as in Example 7, except that the composition for forming a hole injection layer was used.

[Comparative example 4] As the electron-accepting compound contained in the composition for forming the hole injection layer, the compound represented by the formula (HI-3) is used instead of the compound represented by the formula (HI-2) to prepare the hole injection layer. An organic electroluminescent element was produced in the same manner as in Example 8, except that the hole injection layer forming composition was used.

[Example 9] As the hole-transporting polymer compound contained in the composition for forming the hole injection layer, the compound represented by the formula (P-4) is used instead of the compound represented by the formula (P-1) to prepare a hole-transporting polymer compound. An organic electroluminescent element was produced in the same manner as in Example 7, except that the composition for forming a hole injection layer was used.

[Comparative example 5] As the electron-accepting compound contained in the composition for forming the hole injection layer, the compound represented by the formula (HI-3) is used instead of the compound represented by the formula (HI-2) to prepare the hole injection layer. An organic electroluminescent element was produced in the same manner as in Example 9, except that the hole injection layer forming composition was used.

[Example 10] As the hole transporting polymer compound contained in the composition for forming the hole injection layer, a compound represented by the following formula (P-a) is used instead of the compound represented by the above formula (P-1) to prepare the hole injection An organic electroluminescent element was produced in the same manner as in Example 4, except that the hole injection layer forming composition was used.

[Chemical 122] (Pa)

[Evaluation of Elements] The organic electroluminescent elements obtained in Examples 7, 8, 9, 10, Comparative Examples 2, 3, 4, and 5 were tested at 1,000 cd/m ^2. Measure the current efficiency (cd/A) when emitting light. In addition, while the organic electroluminescent element was continuously energized at a current density of 15 mA/cm ² , the time (hr) until the brightness of the element dropped to 95% of the initial brightness was measured. Set this value to LT95. When the current luminous efficiency (cd/A) of the organic electroluminescent element of Comparative Example 4 is set to 1.00, the ratio of the current luminous efficiency of the organic electroluminescent element of the Example and the Comparative Example is "the ratio of the current luminous efficiency of the Example or the Comparative Example" respectively. The current luminous efficiency of the organic electroluminescent element/the current luminous efficiency of the organic electroluminescent element of Comparative Example 4 (hereinafter referred to as "relative current luminous efficiency") is described in Table 3. When the LT95 of the organic electroluminescent element of Comparative Example 4 is set to 1.00, the ratio of the LT95 of the organic electroluminescent element of the Example and the Comparative Example is calculated, that is, "LT95 of the organic electroluminescent element of the Example or the Comparative Example" respectively. The comparative example of the organic electroluminescent element LT95" (hereinafter referred to as "relative lifetime") is shown in Table 3.

[Table 3] Table 3 Composition for forming hole injection layer Relative current luminous efficiency relative lifespan polymer compounds electron-accepting compounds Example 7 P-1 HI-2 1.48 8.52 Example 8 P-2 HI-2 1.52 4.81 Example 9 P-4 HI-2 1.51 4.81 Example 10 Pa HI-1 1.57 3.30 Comparative example 2 P-5 HI-1 1.49 3.33 Comparative example 3 P-1 HI-3 1.11 1.04 Comparative example 4 P-2 HI-3 1.00 1.00 Comparative example 5 P-4 HI-3 1.17 1.04

From the results in Table 3, it was found that compared to the phosphorescent organic electroluminescent element using a fluorine-free polymer compound and a crosslinking group-free electron-accepting compound, the composition of the present invention, that is, the composition containing the present invention The phosphorescent organic electric field light-emitting element formed from the composition of the present invention of a fluorine-containing arylamine polymer compound and an electron-accepting compound having a cross-linking group exhibits good current luminescence efficiency and lifetime.

＜Measurement method of ionization potential＞ The ionization potential (IP) was measured by photoelectron yield spectroscopy (PYS). This measurement is preferably performed using PCR-101 manufactured by Optel, but there is no limitation as long as an equivalent measurement can be performed. Specifically, a sample coating liquid is prepared by dissolving the host material in an appropriate solvent. The solvent is not limited, and the solvent exemplified as the solvent used in the composition for forming the light-emitting layer can be used, and the solvent used when actually forming the light-emitting layer is preferably used.

The concentration of the sample coating liquid is not particularly limited as long as it is a concentration that forms a film thickness of 50 nm after film formation and drying. The prepared sample was formed into a film on a quartz substrate using a coating solution. The film formation is preferably performed in the same manner as the method described in the film formation step of the light-emitting layer.

By drying the film after forming it, a measurement sample with a film thickness of 50 nm was obtained. In addition, drying is preferably performed in the same manner as the method described in the drying step of the light-emitting layer. This measurement sample was placed on the substrate holder in the measurement chamber of the measurement device (PCR-101 manufactured by Optel Corporation), and the door of the measurement chamber was closed. Use a turbomolecular pump to exhaust the measuring chamber until it reaches 10 ^-1 Pa or less. A voltage of -50 V is applied to the sample, the excitation light from the deuterium lamp is monochromated and incident on the sample, and the photoelectrons emitted from the sample due to excitation are detected using a micro-amperometer. The ionization potential is determined from a plot of the energy of the monochromated excitation light and the detected amount of photoelectrons.

Regarding the energy gap (Eg), as described above in the <Measurement Method of Ionization Potential>, the absorption curve of the film was measured using a UV-visible absorbance meter using the prepared sample. A tangent line is drawn at the rising point on the short wavelength side of the film, and the wavelength (λ) nm of the obtained intersection point is substituted into the following equation to obtain the target value. The value thus obtained is Eg(eV). Eg=1240/λ For example, when the λ value calculated by drawing a tangent line is 450 nm, the value of Eg at this time can be said to be Eg=1240/450=2.76 (eV). Ea (electron affinity) is the value obtained by subtracting Eg from Ip. The absolute value of the HOMO energy level is equivalent to the energy used to remove external (vacuum) electrons from the electron orbital molecule. The absolute value of the LUMO energy level is equivalent to the electron affinity. Therefore, P-1, P- 2. The HOMO and LUMO of P-3, P-4, P-a and P-5 are shown in Table 4.

[Table 4] Table 4 (eV) HOMO LUMO E P-1 5.65 2.62 3.03 P-2 5.75 2.71 3.04 P-3 5.73 2.76 2.97 P-4 5.50 2.56 2.94 Pa 5.54 2.70 2.84 P-5 5.30 2.45 2.85

According to the results in Table 4, the HOMO of the fluorine-containing arylamine polymer compound of the present invention is deeper than that of the fluorine-free polymer P-5. For an electric field light-emitting element having a light-emitting layer containing quantum dots, Good current luminous efficiency and longevity can be expected.

Although the present invention has been described in detail using specific aspects, it is obvious to those skilled in the art that various changes can be made without departing from the intention and scope of the present invention.

As mentioned above, the present invention has been described in detail with reference to specific embodiments. However, it is obvious to those skilled in the art that various changes or modifications can be made without departing from the spirit and scope of the present invention. This application is based on a Japanese patent application (Japanese Patent Application No. 2022-027242) filed on February 24, 2022, and the contents are incorporated into this application by reference.

1:Substrate 2:Anode 3: Hole injection layer 4: Hole transport layer 5: Luminous layer 6:Electron transport layer 7:Cathode 8: Organic electric field light-emitting components

FIG. 1 is a schematic cross-sectional view showing a structural example of the organic electroluminescent element of the present invention.

1:Substrate

2:Anode

3: Hole injection layer

4: Hole transport layer

5: Luminous layer

6:Electron transport layer

7:Cathode

8: Organic electric field light-emitting components

Claims (19)

A composition comprising: a polymer compound having a repeating unit represented by the following formula (1), fluorene having a substituent in at least one of the main chain and side chain, and having a cross-linking group; and electrons The receptive compound is represented by the following formula (81) and has a cross-linking group; In formula (1), Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, a divalent aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, or may have a substituent. A divalent group in which a plurality of aromatic hydrocarbon groups or aromatic heterocyclic groups which may have substituents are connected directly or via a connecting group, G represents any one of formulas (1-1) to formula (1-3) The divalent group represented by "*" represents the bonding position with the adjacent structure, and the substituent A is each independently a fluorine atom, CF ₃ or SF ₅ ; Ar ² represents a hydrogen atom, and the substituent A may have a substitution The base is an aromatic hydrocarbon group having 6 to 60 carbon atoms, an aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, or an aromatic hydrocarbon group that may have a substituent and an aromatic heterocyclic group that may have a substituent. A monovalent group in which multiple groups in the ring group are connected directly or via a connecting group; m is an integer from 1 to 4, n is an integer from 1 to 6, In formula (81), five R ⁸¹ , five R ⁸² , five R ⁸³ , and five R ⁸⁴ are each independently independent, and R ⁸¹ to R ⁸⁴ are each independently a hydrogen atom, a deuterium atom, or a halogen atom, and may have substitutions. Ph ¹ , Ph ² , Ph ³ , and Ph ⁴ refer to the symbols of their respective benzene rings; X ⁺ represents a countercation. The composition according to claim 1, comprising an electron-accepting compound represented by the formula (81) having at least two cross-linking groups. The composition according to claim 1 or 2, wherein the compound represented by the formula (1) and the compound represented by the formula (81) each independently have a crosslinking group T selected from the following. Cross-linking group; <Cross-linking group T> In the formula, Q represents a direct bond or connecting group; "*" represents a bonding position; R ¹¹⁰ in formula (X4), formula (X5), formula (X6) and formula (X10) represents a hydrogen atom or may have The alkyl group of the substituent; In the formula (X1) to the formula (X4), the benzene ring and the naphthalene ring may have a substituent; in addition, the substituents may be bonded to each other to form a ring; in the formula (X1) and the formula (X2), The cyclobutene ring may have a substituent. The composition according to any one of claims 1 to 3, wherein the G is represented by any one of the following formulas; In the above formula, "*" represents a bonding position with an adjacent structure. The composition according to any one of claims 1 to 3, wherein the [-G-Ar ² ] is represented by any one of the following formulas; In the above formula, "*" represents a bonding position with an adjacent structure. The composition according to any one of claims 1 to 5, wherein Ar ¹ has a partial structure selected from one of the following formulas (2-1) to formula (2-3), or has a selected A bonding structure in which two or more of the following formulas (2-1) to (2-3) are bonded to each other. The bonding structure may also include a combination selected from the following formula (2-1). ~A structure in which at least one structure in formula (2-3) is bonded with two or more; In each of the formulas (2-1) to (2-3), R ¹ and R ² are each independently a hydrogen atom, a deuterium atom, a halogen atom, or an aromatic hydrocarbon group having 6 to 18 carbon atoms that may have a substituent. , an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, an alkyl group having 1 to 12 carbon atoms, and "*" represents a bonding position with an adjacent structure. The composition according to any one of claims 1 to 6, wherein the polymer compound further has a repeating unit represented by the following formula (3); In the formula (3), Ar ³ is a 2-fluorenyl group that may have a substituent; Ar ⁴ represents a divalent aromatic hydrocarbon group that may have a substituent, a divalent aromatic heterocyclic group that may have a substituent, or a divalent aromatic heterocyclic group that may have a substituent. At least two groups selected from the group consisting of the divalent aromatic hydrocarbon group which may have a substituent and the divalent aromatic heterocyclic group which may have a substituent are connected directly or through a connecting group. of the divalent base. The composition according to any one of claims 1 to 7, further containing a solvent. A method of manufacturing an organic electroluminescent element, which is a method of manufacturing an organic electroluminescent element having an anode and a cathode on a substrate and an organic layer between the anode and the cathode, The method for manufacturing an organic electroluminescent element includes the step of forming the organic layer using a wet film-forming method using the composition according to claim 8. The method of manufacturing an organic electroluminescent element according to claim 9, wherein the organic layer is an organic layer existing between the anode and the light-emitting layer. An organic electric field light-emitting element having an anode and a cathode on a substrate and an organic layer between the anode and the cathode. In the organic electric field light-emitting element, the organic layer contains a polymer compound and an electron-accepting compound. A cross-linking reaction product, the polymer compound has a repeating unit represented by the following formula (1), fluorene which may have a substituent in at least one of the main chain and the side chain, and has a cross-linking group, The electron-accepting compound is represented by the following formula (81) and has a cross-linking group; In formula (1), Ar ¹ represents a divalent aromatic hydrocarbon group having 6 to 60 carbon atoms which may have a substituent, a divalent aromatic heterocyclic group having 3 to 50 carbon atoms which may have a substituent, or may have a substituent. A divalent group in which a plurality of aromatic hydrocarbon groups or aromatic heterocyclic groups which may have substituents are connected directly or via a connecting group, G represents any one of formulas (1-1) to formula (1-3) The divalent group represented by "*" represents a bonding site with an adjacent structure, and the substituent A is each independently a fluorine atom, CF ₃ or SF ₅ ; Ar ² represents a hydrogen atom, and the substituent A may have a substitution The base is an aromatic hydrocarbon group having 6 to 60 carbon atoms, an aromatic heterocyclic group having 3 to 50 carbon atoms that may have a substituent, or an aromatic hydrocarbon group that may have a substituent and an aromatic heterocyclic group that may have a substituent. A monovalent group in which multiple groups in the ring group are connected directly or via a connecting group; m is an integer from 1 to 4, n is an integer from 1 to 6, In formula (81), five R ⁸¹ , five R ⁸² , five R ⁸³ , and five R ⁸⁴ are each independently independent, and R ⁸¹ to R ⁸⁴ are each independently a hydrogen atom, a deuterium atom, or a halogen atom, and may have substitutions. Ph ¹ , Ph ² , Ph ³ , and Ph ⁴ refer to the symbols of their respective benzene rings; X ⁺ represents a countercation. The organic electric field light-emitting element according to claim 11, wherein the G is represented by any one of the following formulas; In the above formula, "*" represents a bonding position with an adjacent structure. The organic electroluminescent element according to claim 11, wherein the [-G-Ar ² ] is represented by any one of the following formulas; In the above formula, "*" represents a bonding position with an adjacent structure. The organic electroluminescent element according to any one of claims 11 to 13, wherein the Ar ¹ has a partial structure selected from one of the following formulas (2-1) to formulas (2-3), or It has a bonding structure in which two or more selected from the following formula (2-1) to formula (2-3) are bonded to each other, and the bonding structure may also include a combination selected from the following formula (2- 1) ~ A structure in which at least one structure in formula (2-3) is bonded with two or more; In each of the formulas (2-1) to (2-3), R ¹ and R ² are each independently a hydrogen atom, a deuterium atom, a halogen atom, or an aromatic hydrocarbon group having 6 to 18 carbon atoms that may have a substituent. , an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, an alkyl group having 1 to 12 carbon atoms, and "*" represents a bonding position with an adjacent structure. The organic electroluminescent element according to any one of claims 11 to 14, wherein the polymer compound further has a repeating unit represented by the following formula (3); In formula (3), Ar ³ is a 2-fluorenyl group which may have a substituent; Ar ⁴ represents a divalent aromatic hydrocarbon group which may have a substituent, a divalent aromatic heterocyclic group which may have a substituent, or will be selected from Two groups in which at least two groups in the group consisting of the divalent aromatic hydrocarbon group which may have a substituent and the divalent aromatic heterocyclic group which may have a substituent are connected directly or via a connecting group. price base. An organic electric field light-emitting element is manufactured by using the method for manufacturing an organic electric field light-emitting element described in claim 9 or 10. The organic electric field light-emitting element according to any one of claims 11 to 16, wherein the light-emitting layer contains quantum dots. A display device having the organic electric field light-emitting element according to any one of claims 11 to 17. A lighting device having the organic electric field light-emitting element according to any one of claims 11 to 17.