JP6995563B2 - Polymer compounds, compositions, liquid compositions, thin films, and materials for electroluminescence devices, and electroluminescence devices. - Google Patents

Description

The present invention relates to polymeric compounds, compositions, liquid compositions, thin films, and materials and electroluminescence devices for electroluminescence devices.

In recent years, display devices and lighting devices using an organic electroluminescence device (organic electroluminescence device), which is a self-luminous light emitting element, have been actively developed.

As the material of the organic electroluminescence element, various low molecular weight materials and high molecular weight materials are used for the light emitting layer and the carrier transport layer. In particular, since small molecule materials are excellent in terms of device efficiency and life, many materials have been proposed for small molecule materials, and their practical application has begun for mobile applications. However, the biggest problem of the organic electroluminescence device in which a small molecule material is used is its manufacturing cost. As a solution to this, the development of coating materials such as polymer materials is desired. As a coating polymer-based material, an arylamine polymer for a hole transporting material has been proposed (see, for example, Patent Documents 1 and 2).

Further, in recent years, an organic electroluminescence element using a phosphorescent material showing high luminous efficiency such as a tris (2-phenylpyridine) iridium complex [Ir (ppy) ₃ ] has been actively developed. As a carrier transport material to be combined with such a light emitting material, a material having a high triplet energy level (2.5 eV or more) is desired.

However, in a polymer-based material such as an arylamine polymer, even if the triplet energy level is sufficiently high as a repeating unit, the triplet energy level decreases as the repeating unit increases. Therefore, when an organic electroluminescence device is manufactured using a polymer-based material, there is a problem that the luminous efficiency is lowered. In order to suppress the decrease in the triplet energy level due to such high molecular weight, a structure that suppresses the conjugation of the main chain structure due to the introduction of a substituent into the aryl group is disclosed (for example, Patent Documents 3 to 5). reference).

Japanese Unexamined Patent Publication No. 2016-08437 Special Table 2016-503087 Gazette International Publication No. 2013/191086 International Publication No. 2013/191088 Japanese Unexamined Patent Publication No. 2014-065885

However, the conventional polymer compound has a problem that the hole transporting ability is lowered when the conjugate of the main chain structure is cleaved in order to raise the triplet energy level. Further, in the conventional polymer compound, there is a problem that the driving voltage of the electroluminescence element increases when the triplet energy level is increased.

Therefore, the present invention has been made in view of the above circumstances, and provides a polymer compound having a high triplet energy level and a hole transporting ability and capable of suppressing an increase in a driving voltage in an electroluminescence element. The purpose is to do.

Another object of the present invention is to provide a polymer compound suitable for film formation by a wet film forming method (coating method).

Another object of the present invention is to provide a material for an electroluminescence device (particularly a hole transport material) containing such a polymer compound, and an electroluminescence device using the material.

As a result of diligent research to solve the above problems, the present inventors have found that a polymer compound having a specific structural unit can solve the above problems.

That is, the above objectives can be achieved by a polymer compound containing a structural unit represented by the following formula (1).

In formula (1), Ar ¹ is a divalent aromatic hydrocarbon group having 6 or more and 30 or less substituted or unsubstituted ring carbon atoms, or 3 or more and 30 or less substituted or unsubstituted ring-forming atoms. Represents a divalent heterocyclic group of;
Ar ² is a divalent aromatic hydrocarbon group having 6 or more and 12 or less substituted or unsubstituted ring carbon atoms, or a divalent heterocyclic ring having 3 or more and 12 or less substituted or unsubstituted ring-forming atoms. Represents a group;
Ar ³ and Ar ⁴ are independently substituted or unsubstituted aromatic hydrocarbon groups having 6 or more and 30 or less ring carbon atoms, or substituted or unsubstituted ring-forming atoms having 3 or more and 30 or less. Represents a heterocyclic group;
L ₁ represents a single-bonded or divalent linking group, wherein the divalent linking group is a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms, substituted or unsubstituted. Ring formation Multiplex consisting of 2 to 4 groups selected from a heterocyclic group having 3 to 30 atoms and an substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms. Linking group, substituted or unsubstituted ring-forming Multiple linking group consisting of 2 to 4 groups selected from heterocyclic groups having 3 or more and 30 or less atoms, or substituted or unsubstituted ring. A multi-linking group consisting of 2 to 4 groups selected from an aromatic hydrocarbon group having 6 or more and 30 or less carbon atoms and a heterocyclic group having 3 or more and 30 or less substituted or unsubstituted ring-forming atoms. And;
R ₁ and R ₂ represent substituents, each of which is a deuterium atom, an substituted or unsubstituted aryl group having 6 or more and 50 or less ring carbon atoms, and an substituted or unsubstituted carbon number of 1 or more. Represents an alkyl group of 20 or less, an substituted or unsubstituted alkoxy group having 1 or more and 20 or less carbon atoms, or a substituted or unsubstituted ring-forming atomic group of 3 or more and 30 or less, and _R1 and R. When a plurality of ₂ 's are present, they may be the same or different from each other, or they may be combined with each other to form a ring structure;
a and b are independently integers of 0 or more and 3 or less.

According to one aspect of the present invention, it is possible to provide a polymer compound having a triplet energy level and a hole transporting ability. Further, according to one aspect of the present invention, it is possible to provide a polymer compound that reduces a driving voltage and improves durability in an electroluminescence device. Further, the polymer compound according to one aspect of the present invention can be suitably used for a material for an electroluminescence element, an electroluminescence element and the like.

It is a schematic diagram which shows the organic electroluminescence element which concerns on this embodiment. It is sectional drawing which shows the structure of the blue quantum dot which concerns on Example 9. FIG. It is a graph which shows the UV absorption spectrum of the blue quantum dot which concerns on Example 9. FIG. It is a graph which shows the fluorescence spectrum of the blue quantum dot which concerns on Example 9. FIG.

According to one aspect of the present invention, a polymer compound containing a structural unit represented by the following formula (1) is provided.

In formula (1), Ar ¹ is a divalent aromatic hydrocarbon group having 6 or more and 30 or less substituted or unsubstituted ring carbon atoms, or 3 or more and 30 or less substituted or unsubstituted ring-forming atoms. Represents a divalent heterocyclic group of;
Ar ² is a divalent aromatic hydrocarbon group having 6 or more and 12 or less substituted or unsubstituted ring carbon atoms, or a divalent heterocyclic ring having 3 or more and 12 or less substituted or unsubstituted ring-forming atoms. Represents a group;
Ar ³ and Ar ⁴ are independently substituted or unsubstituted aromatic hydrocarbon groups having 6 or more and 30 or less ring carbon atoms, or substituted or unsubstituted ring-forming atoms having 3 or more and 30 or less. Represents a heterocyclic group;
L ₁ represents a single-bonded or divalent linking group, wherein the divalent linking group is a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms, substituted or unsubstituted. Ring formation Multiplex consisting of 2 to 4 groups selected from a heterocyclic group having 3 to 30 atoms and an substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms. Linking group, substituted or unsubstituted ring-forming Multiple linking group consisting of 2 to 4 groups selected from heterocyclic groups having 3 or more and 30 or less atoms, or substituted or unsubstituted ring. A multi-linking group consisting of 2 to 4 groups selected from an aromatic hydrocarbon group having 6 or more and 30 or less carbon atoms and a heterocyclic group having 3 or more and 30 or less substituted or unsubstituted ring-forming atoms. And;
R ₁ and R ₂ represent substituents, each of which is a deuterium atom, an substituted or unsubstituted aryl group having 6 or more and 50 or less ring carbon atoms, and an substituted or unsubstituted carbon number of 1 or more. Represents an alkyl group of 20 or less, an substituted or unsubstituted alkoxy group having 1 or more and 20 or less carbon atoms, or a substituted or unsubstituted ring-forming atomic group of 3 or more and 30 or less, and _R1 and R. When a plurality of ₂ 's are present, they may be the same or different from each other, or they may be combined with each other to form a ring structure;
a and b are independently integers of 0 or more and 3 or less.

In the present specification, the structural unit represented by the above formula (1) is simply referred to as "constituent unit (1)".

In the present specification, the number of ring carbon atoms of an aromatic hydrocarbon group is the number of carbon atoms constituting the ring itself in a compound having a structure in which carbon atoms are cyclically bonded (for example, a single ring, a fused ring, or a ring assembly). Represents. When an atom that does not form a ring (for example, a hydrogen atom that terminates a bond of carbon that constitutes a ring) or a ring is substituted with a substituent, the carbon contained in the substituent is not included in the number of carbon rings. For example, a phenyl group has 6 ring carbons, a biphenyl group has 12 ring carbons, and a fluorenyl group has 13 ring carbons.

In the present specification, the number of ring-forming atoms of a heterocyclic group represents the number of atoms constituting the ring itself in a compound having a structure in which atoms are cyclically bonded (for example, a single ring, a fused ring, or a ring assembly). When an atom that does not form a ring (for example, a hydrogen atom that terminates a bond of an atom that constitutes a ring) or a ring is substituted with a substituent, the atom contained in the substituent is not included in the number of ring-forming atoms. For example, the carbazolyl group has 13 ring-forming atoms.

In the present specification, when the "divalent" or the "(2 + n) valence" described later is not limited, the valence of an organic group (or atomic group) such as an aromatic hydrocarbon group is 1. do.

The polymer compound of the present embodiment is characterized by being a polymer compound containing the structural unit (1).

The organic electroluminescence device is currently manufactured by a vapor deposition method or a wet method. Of these, the thin-film deposition method can be laminated in multiple layers by vapor deposition, and it is easy to optimize the energy diagram by stacking. Therefore, it is possible to improve the luminous efficiency and the life, and to reduce the drive voltage. However, on the other hand, low productivity and low yield are major issues. On the other hand, in the manufacturing of the electric field element by the wet method, a printing process is possible, so that a large area and high productivity can be expected. However, on the other hand, the design of stackable materials has become a major issue. Conventionally, stackable coating type hole transport materials have been developed based on soluble-insolubilization control technology, and are roughly classified into three types: pro-hydrophobic control type materials, polymer cross-linking materials, and small molecule cross-linking materials. There is. Currently, the development of polymer crosslinked materials is the mainstream from the viewpoint of the total number of laminates and the purity of the materials. However, the electrical characteristics when the polymer cross-linked material is used as the hole transport material are highly dependent on the optical properties of the constituent units, and the important characteristics such as hole transfer ability and triplet energy level are , The molecular weight dependence is particularly large. Increasing the molecular weight of the material increases the hole mobility while decreasing the triplet energy level. Further, when the triplet energy level is increased as in the polymer compounds described in Patent Documents 3 to 5, the hole transporting ability is decreased and the driving voltage is increased. Therefore, the present inventors have diligently studied means for suppressing a decrease in hole transport ability and suppressing an increase in drive voltage while maintaining a high triplet energy level. As a result, it was found that the polymer compound has a high triplet energy level and a hole transporting ability by containing the structural unit represented by the above formula (1), and can suppress an increase in the driving voltage.

As the triplet energy level increases, the singlet energy level also increases, so that the HOMO level related to hole injection / transport becomes deeper and the drive voltage rises. On the other hand, the structural unit represented by the formula (1) has a triplet energy level by binding the triarylamine structure to any of the 1st to 4th positions of the carbazole ring via Ar ² . While maintaining it, it is possible to suppress the deepening of the HOMO (Highest Occupied Molecular Orbital) level.

Therefore, the polymer compound of the present embodiment has a high triplet energy level and a hole transporting ability, and can suppress an increase in the driving voltage.

The above mechanism is speculative, and the present invention is not bound by the above mechanism.

Hereinafter, embodiments of the present invention will be described. The present invention is not limited to the following embodiments. Unless otherwise specified, operations and physical properties are measured under the conditions of room temperature (20 ° C. or higher and 25 ° C. or lower) and relative humidity of 40% RH or higher and 50% RH or lower.

<Polymer compound>
(Constituent unit represented by equation (1))
The polymer compound of the present embodiment contains the structural unit (1).

Here, the structural unit (1) is represented by the following equation (1). The polymer compound of the present embodiment may contain one structural unit (1) or two or more structural units (1).

In the above formula (1), Ar ¹ is a divalent aromatic hydrocarbon group having 6 or more and 30 or less substituted or unsubstituted ring carbon atoms, or 3 or more and 30 substituted or unsubstituted ring-forming atoms. Represents the following divalent heterocyclic group.

In the present specification, the positions of the two bonds in the divalent aromatic hydrocarbon group and the divalent heterocyclic group are not particularly limited. For example, in the case of a phenylene group, the two bonds may be in the ortho-position, the meta-position, and the para-position.

Here, the aromatic hydrocarbon means a hydrocarbon having a carbon ring containing one or more aromatic rings. That is, an aromatic hydrocarbon group is a hydrocarbon-derived group having a carbon ring containing one or more aromatic rings. Further, when the aromatic hydrocarbon group contains two or more rings, the two or more rings may be condensed with each other. Further, one or more hydrogen atoms present in these aromatic hydrocarbon groups may be substituted with a substituent. The divalent aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms is not limited to the following, but is not limited to the following, but is limited to a phenylene group, a pentalenylene group, an indenylene group, a naphthylene group, anthrasenylene group, an azulenylene group, a heptalenylene group and an acenaphtylenylene. Group, phenalenylene group, fluorenylene group, anthraquinolylene group, phenanthrylene group, biphenylene group, triphenylenylene group, pyrenylene group, chrysenylene group, pisenylene group, peryleneylene group, pentaphenylene group, pentasenylene group, tetraphenyleneylene group, hexa Examples thereof include a phenylene group, a hexasenylene group, a rubisenylene group, a trinaphthyleneylene group, a heptaphenylene group, a pyrandrenylene group and the like.

Further, the heterocycle has one or more heteroatoms (for example, nitrogen atom (N), oxygen atom (O), phosphorus atom (P), sulfur atom (S)), and the remaining ring-forming atom is carbon. It means a ring composed of an atom (C). That is, the heterocyclic group has one or more heteroatoms (for example, nitrogen atom (N), oxygen atom (O), phosphorus atom (P), sulfur atom (S)), and the remaining ring-forming atoms are present. It is a ring-derived group composed of a carbon atom (C). Further, when the heterocyclic group contains two or more rings, the two or more rings may be condensed with each other. Further, one or more hydrogen atoms existing in these heterocyclic groups may be substituted with a substituent. The divalent heterocyclic group having 3 or more and 30 or less ring-forming atoms is not limited to the following, but is not limited to the following, but is limited to a pyridylene group, a pyrimidinylene group, a pyrazinylene group, a pyridadinylene group, a triazinylene group, a quinolylene group, an isoquinolinylene group, a naphthylidilenene group and a phthaladinylene group. , Kinoxalinylene group, quinazolinylene group, phenanthridinylene group, acridinylene group, phenanthrolinylene group, pyrrolylene group, imidazolylene group, pyrazolylene group, triazolylene group, tetrazolylene group, indolylene group, benzoimidazolylene group, indazolylene group, imidazolylen group Dinilen group, benzotriazolylen group, carbazolylen group, furylene group, thienylene group, oxazolilen group, thiazolylene group, isoxazolilen group, isothiazolylen group, oxadiazolylene group, thiadiazolilen group, benzofuranylene group, benzothiophenylene group, benzoxazoli Lene group, benzothiazolylen group, benzoisooxazolilen group, benzoisothiazolilen group, benzoxadiazolilen group, benzothia zolilen group, dibenzofuranylene group, dibenzothiophenylene group, piperidinylene group, pyrrolidinylene group , Piperadinylene group, morpholilen group, phenadynylene group, phenothiadinylene group, phenoxadinylene group and the like.

Of these, from the viewpoint of reducing the driving voltage, Ar ¹ is preferably any one of a phenylene group, a biphenylene group, and a fluorenylene group, and more preferably a phenylene group or a biphenylene group.

When a divalent aromatic hydrocarbon group having 6 or more and 30 or less ring carbons or a divalent heterocyclic group having 3 or more and 30 or less ring-forming atoms as Ar ¹ has a substituent, the substituent to be introduced is There are no particular restrictions. Specific examples thereof include halogen atoms, alkyl groups, alkoxy groups, aromatic hydrocarbon groups, and heterocyclic groups, and combinations thereof. When the divalent aromatic hydrocarbon group or heterocyclic group has a substituent, the further substituted structure becomes the same as the group before further substitution (aromatic hydrocarbon group or heterocyclic group). Is excluded. For example, when Ar ¹ is a phenylene group, the phenylene group is not further substituted with a phenylene group (the same applies hereinafter).

Here, examples of the halogen atom that may be introduced into the divalent aromatic hydrocarbon group or heterocyclic group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

The alkyl group that may be introduced into the divalent aromatic hydrocarbon group or heterocyclic group is not particularly limited, but may be a linear or branched alkyl group having 1 or more and 24 or less carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, Neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4- Dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2 -Methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1- Methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n- Examples thereof include a heneicosyl group, an n-docosyl group, an n-tricosyl group, and an n-tetracosyl group.

The alkoxy group that may be introduced into the divalent aromatic hydrocarbon group or heterocyclic group is not particularly limited, but may be a linear or branched alkoxy group having 1 or more and 24 or less carbon atoms. Specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, an undecyloxy group, and a dodecyloxy group. Examples thereof include a group, a tridecyloxy group, a tetradecyloxy group, a pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, a 2-ethylhexyloxy group and a 3-ethylpentyloxy group. Of these, linear or branched alkoxy groups having 1 or more and 8 or less carbon atoms are preferable.

For the aromatic hydrocarbon group and the heterocyclic group which may be introduced into the divalent aromatic hydrocarbon group or the heterocyclic group, the aromatic hydrocarbon group and the ring formation having 6 or more and 30 or less ring carbon atoms, respectively. It is the same group except that a divalent heterocyclic group having 3 or more and 30 or less atoms is monovalent.

In the above formula (1), Ar ² is a divalent aromatic hydrocarbon group having 6 or more and 12 or less substituted or unsubstituted ring carbon atoms, or 3 or more and 12 substituted or unsubstituted ring-forming atoms. Represents the following divalent heterocyclic group.

In the structural unit (1), when Ar ² is an aromatic hydrocarbon group having 6 or more and 12 or less ring carbon atoms or a heterocyclic group having 3 or more and 12 or less ring-forming atoms, the conjugate size becomes small and the triplet energy. The level can be kept high.

The divalent aromatic hydrocarbon group having 6 or more and 12 or less ring carbon atoms is not limited to the following, but is not limited to the following, but is limited to a phenylene group, a biphenylene group, a pentalenylene group, an indenylene group, a naphthylene group, an azulenylene group, a heptalenylene group and an acenaphtylenylene. A group, a phenalenylene group and the like can be mentioned.

The divalent heterocyclic group having 3 or more and 12 or less ring-forming atoms is not limited to the following, but is not limited to the following, but is limited to a pyridylene group, a pyrimidinylene group, a pyrazinylene group, a pyridazinylene group, a triazinylene group, a quinolylene group, an isoquinolinylene group, a naphthylidilenene group and a phthaladinylene group. , Kinoxalinylene group, Kinazolinylene group, Pyrrolylene group, Imidazolylene group, Pyrazolylene group, Triazolylene group, Tetrazolylene group, Indolylene group, Benzoimidazolylene group, Indazolylene group, Imidazopyridinylene group, Benzotriazolylene group, Carbazolylene group. , Thienylene group, oxazolylene group, thiazolylene group, isoxazolylene group, isothiazolylen group, oxadiazolylene group, thiadiazolilen group, benzofuranylene group, benzothiophenylene group, benzoxazolylene group, benzothiazolylen group, benzoisooxazolilen group. , Benzoisothiazolylene group, benzooxadiazolylene group, benzothiadiazolilen group, piperidinylene group, pyrrolidinylene group, piperazinylene group, morpholilen group and the like.

Of these, from the viewpoint of improving luminous efficiency, Ar ² is preferably either a phenylene group or a biphenylene group, and more preferably a phenylene group.

When a divalent aromatic hydrocarbon group having 6 or more and 12 or less ring carbons or a divalent heterocyclic group having 3 or more and 12 or less ring-forming atoms as Ar ² has a substituent, the substituent to be introduced is Since the definition is the same as that of the substituent in Ar ¹ , the description thereof is omitted here.

In the above formula (1), Ar ³ and Ar ⁴ are independently substituted or unsubstituted aromatic hydrocarbon groups having 6 or more and 30 or less ring carbon atoms, or substituted or unsubstituted ring formation. Represents a heterocyclic group having 3 or more and 30 or less atoms. Ar ³ and Ar ⁴ may be the same or different from each other. The "aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms" and the "complex ring group having 3 or more and 30 or less ring forming atoms" are the aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms in Ar ¹ and the above. Since the definition is the same except that a heterocyclic group (divalent group) having 3 or more and 30 or less ring-forming atoms is monovalent, the description thereof is omitted here. When an aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms or a heterocyclic group having 3 or more and 30 or less ring-forming atoms has a substituent, the substituent to be introduced is the same as the substituent in Ar ¹ described above. Since it is the definition of, the description is omitted here.

From the viewpoint of reducing the driving voltage, Ar ³ and Ar ⁴ are preferably any of a biphenyl group, a fluorenyl group and a triphenylene group, and preferably a biphenyl group or a fluorenyl group. Further, from the viewpoint of the triplet energy level, it is preferably any one of a benzofuranyl group, a benzothienyl group, a dibenzofranyl group and a dibenzothienyl group, and more preferably a dibenzothienyl group or a dibenzofuranyl group.

When Ar ³ or Ar ⁴ is a fluorenyl group having a substituent, the fluorenyl group is preferably any of the following from the viewpoint of improving luminous efficiency.

In the above formula, Z and Z'represent possible substituents (substituents detailed above), which may be the same or different. The substituent that may exist is preferably a linear or branched alkyl group having 1 or more and 24 or less carbon atoms, and more preferably a linear alkyl group having 1 or more and 20 or less carbon atoms from the viewpoint of solvent solubility. , More preferably, it is a linear alkyl group of 1 or more and 8 or less.

Specific examples of Ar ³ and Ar ⁴ are shown below. In the following, "*" is a binding site with another constituent unit. Further, in the following, "Alkyl" means "unsubstituted or substituted with an alkyl group". In addition, "Alkyl" may be the same alkyl group or a different alkyl group.

In the above formula (1), L ₁ represents a single bond or a divalent linking group. Here, the divalent linking group is an substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms, and a substituted or unsubstituted complex ring having 3 or more and 30 or less ring-forming atoms. Group, substituted or unsubstituted Multiple linking group consisting of 2 to 4 groups selected from aromatic hydrocarbon groups having 6 or more and 30 or less carbon atoms, substituted or unsubstituted ring formation A multi-linking group consisting of 2 to 4 groups bonded from a heterocyclic group having 3 or more and 30 or less atoms, or an substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms. It is a multi-linking group consisting of 2 to 4 groups selected from a substituted or unsubstituted ring-forming group having 3 or more and 30 or less ring-forming atoms.

In L ₁ , the "aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms" and the "heterocyclic group having 3 or more and 30 or less ring forming atoms" are aromatics having 6 or more and 30 or less ring carbon atoms in Ar ¹ . Since the definition is the same as that of the hydrocarbon group and the heterocyclic group having 3 or more and 30 or less ring-forming atoms, the description thereof is omitted here.

In L1, _a substituted or unsubstituted multi-linking group consisting of 2 to 4 groups selected from substituted or unsubstituted aromatic hydrocarbon groups having 6 or more and 30 or less ring carbon atoms. A multi-linking group consisting of two to four groups bonded from a heterocyclic group having 3 or more and 30 or less ring-forming atoms, or an substituted or unsubstituted aromatic hydrocarbon having 6 or more and 30 or less ring carbon atoms. Multiple linking groups formed by bonding 2 to 4 groups selected from hydrogen groups and substituted or unsubstituted ring-forming groups having 3 or more and 30 or less atoms are aromatic hydrocarbon groups and complex groups. Examples thereof include a divalent group formed by bonding 2 to 4 groups selected from the ring groups. The multiple linking groups include heterocyclic groups-aromatic hydrocarbon groups, aromatic hydrocarbon groups-heterocyclic groups, aromatic hydrocarbon groups-heterocyclic groups-aromatic hydrocarbon groups, and heterocyclic groups-aromatic hydrocarbons. Examples thereof include groups-heterocyclic groups, aromatic hydrocarbon groups-heterocyclic groups-aromatic hydrocarbon groups-heterocyclic groups, heterocyclic groups-aromatic hydrocarbon groups-heterocyclic groups-aromatic hydrocarbon groups and the like. The multiple linking group is preferably a divalent group formed by bonding the aromatic hydrocarbon group and the heterocyclic group one by one, that is, a heterocyclic group-aromatic hydrocarbon group and an aromatic hydrocarbon group. -It is a heterocyclic group.

Of these, from the viewpoint of solvent solubility, L ₁ is preferably a single bond, an aromatic hydrocarbon group having 6 or more and 20 or less ring carbon atoms, or an substituted or unsubstituted ring-forming atom number of 3 or more and 20 or less. Is a heterocyclic group, more preferably a single bond, a phenylene group or a carbazolyl group, and even more preferably a single bond or a phenylene group.

In the above formula (1), R ₁ and R ₂ represent substituents, each of which is a deuterium atom, a substituted or unsubstituted aryl group having 6 or more and 50 or less ring carbon atoms, substituted or substituted. An unsubstituted alkyl group having 1 to 20 carbon atoms, an substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted or unsubstituted ring-forming atomic group having 3 to 30 atoms. Represents. At this time, R ₁ and R ₂ may be the same or different from each other. Further, when there are a plurality of R _1s (that is, a is 2 or 3), R _1s may be the same or different from each other, or may be bonded to each other to form a ring structure together with carbon atoms to which each is bonded. good. Similarly, if there are multiple R _2s (ie, b is 2 or 3), the R _2s may be the same or different from each other and bond to each other to form a ring structure with the carbon atoms to which each bond. You may.

Here, the aryl group having 6 or more and 50 or less ring carbon atoms is not particularly limited, and is not particularly limited. Group, anthraquinolyl group, phenanthryl group, biphenyl group, triphenylenyl group, pyrenyl group, chrysenyl group, pisenyl group, perylenelyl group, pentaphenyl group, pentasenyl group, tetraphenylenyl group, hexaphenyl group, hexasenyl group, rubisenyl group, trinaphthylenyl group. Examples include a group, a heptaphenyl group, a pyrantrenyl group and the like.

The alkyl group having 1 or more and 20 or less carbon atoms is not particularly limited, and may be a linear or branched alkyl group having 1 or more and 20 or less carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, Neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4- Dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2 -Methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group, isodecyl group, n-undecyl group, 1- Methyldecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group and the like. Will be.

The alkoxy group having 1 or more and 20 or less carbon atoms is not particularly limited, and may be a linear or branched alkoxy group having 1 or more and 20 or less carbon atoms. Specifically, a methoxy group, an ethixi group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, an n-pentoxy group, an isopentoxy group, a tert-pentoxy group. , Neopentoxy group, 1,2-dimethylpropoxy group, n-hexyloxy group, isohexyloxy group, 1,3-dimethylbutoxy group, 1-isopropylpropoxy group, 1,2-dimethylbutoxy group, n-heptyloxy group , 1,4-dimethylpentyloxy group, 3-ethylpentyloxy group, 2-methyl-1-isopropylpropoxy group, 1-ethyl-3-methylbutoxy group, n-octyl group oxy, 2-ethylhexyloxy group, 3 -Methyl-1-isopropylbutoxy group, 2-methyl-1-isopropoxy group, 1-tert-butyl-2-methylpropoxy group, n-nonyloxy group, 3,5,5-trimethylhexyloxy group, n-decyloxy Group, isodecyloxy group, n-undecyloxy group, 1-methyldecyloxy group, n-dodecyloxy group, n-tridecyloxy group, n-tetradecyloxy group, n-pentadecyloxy group, n- Examples thereof include a hexadecyloxy group, an n-heptadecyloxy group, an n-octadecyloxy group, an n-nonadesyloxy group and an n-icosyloxy group.

A heterocyclic group having 3 or more and 30 or less ring-forming atoms has the same definition except that the heterocyclic group (divalent group) having 3 or more and 30 or less ring-forming atoms in Ar ¹ is monovalent. The description is omitted here.

Further, in R ₁ and R ₂ , when the aryl group, the alkyl group, the alkoxy group and the heterocyclic group have a substituent, the substituent to be introduced has the same definition as the substituent in Ar ¹ described above. Then, the explanation is omitted.

a represents the number of the substituent "R ₁ " bonded to the carbazole ring, and is an integer of 0 or more and 3 or less. a is preferably 0 or more and 2 or less, more preferably 0 or 1, and particularly preferably 0 (there is no substituent “R ₁ ”).

b represents the number of the substituent "R ₂ " bonded to the carbazole ring, and is an integer of 0 or more and 3 or less. b is preferably 0 or more and 2 or less, more preferably 0 or 1, and particularly preferably 0 (there is no substituent " _R2 ").

In the present embodiment, the structural unit represented by the formula (1) is preferably the following formula (1-1) to the following formula (1-1) from the viewpoint of further improvement of the triplet energy level and hole transport capacity and further reduction of the drive voltage. It is selected from the structural units represented by (1-4), and more preferably the following formulas (1-1-a) to (1-1-r) and (1-2-a) to (1-2-l). ), (1-3-a) to (1-3-l) and (1-4-a) to (1-4-l), and more preferably the following formula (1). It is selected from the structural units represented by -1-a) to (1-1-r). In the following, "Alkyl" means "unsubstituted or substituted with an alkyl group".

In the above formulas (1-1-a) to (1-1-r), "Alkyl" means "substituted with an alkyl group". The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Further, "Alkyl" may be the same alkyl group or different alkyl groups.

The composition of the structural unit (1) in the polymer compound of the present embodiment is not particularly limited. Considering the effect of further improving the hole transporting ability of the layer (for example, the hole injection layer, the hole transporting layer) formed by using the obtained polymer compound, the constituent unit (1) constitutes the polymer compound. It is preferably 40% or more and 95% or less, and more preferably 40% or more and 90% or less with respect to the total number of constituent units. When the polymer compound contains two or more kinds of structural units (1), the content of the structural units (1) means the total amount of the structural units (1).

(Constituent unit represented by equation (2))
The polymer compound of the present embodiment may further contain a structural unit represented by the following formula (2). In the present specification, the structural unit represented by the following formula (2) is simply referred to as "constituent unit (2)".

Since the structural unit (2) has a crosslinkable group, the polymer compound having the structural unit (2) can be easily formed into a film. The polymer compound of the present embodiment may contain one structural unit (2) or two or more structural units (2). Preferably, the polymer compound of the present embodiment contains two or more (more preferably two or three, particularly preferably two) structural units (2).

In the above formula (2), Ar ⁵ is a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms, or a substituted or unsubstituted ring-forming atom number 3. It represents a heterocyclic group having a (2 + n) valence of 30 or more. Here, the "(2 + n) -valent aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms" and the "(2 + n) -valent heterocyclic group having 3 or more and 30 or less ring-forming atoms" are represented by the above formula (1). The same definition is used except that the aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms and the heterocyclic group (divalent group) having 3 or more and 30 or less ring forming atoms in Ar ¹ are defined as (2 + n) valences. Therefore, the description thereof is omitted here. Of these, considering the ease of film formation and the effect of further improving the film strength of the obtained polymer compound, Ar ⁵ is preferably a fluorinatedyl group or a phenylene group, and is preferably a fluorinatedyl group. Is more preferable. That is, according to the preferred embodiment of the present invention, Ar ⁵ is a fluorinyl group or a phenylene group. Further, according to a more preferable form of the present invention, Ar ⁵ is a fluorinated yl group. Here, the fluorinated yl group as Ar ⁵ represents any of the following. In the following, Z and Z'represent the groups represented by the formula: -L ₂ -Q, which may be the same or different.

Of these, the fluorinated yl group preferably has the following structure.

In the definition of Ar ⁵ , "substituent that may exist in an aromatic hydrocarbon group or a heterocyclic group" has the same definition as the substituent in Ar ¹ in the above formula (1), and thus the description is given here. Omit.

In the above formula (2), L ₂ represents a single bond, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenylene group. Further, n is an integer of 1 or more. Here, when a plurality of L _2s exist (n is an integer of 2 or more), they may be the same or different.

Here, the "alkylene group having 1 or more and 20 or less carbon atoms" has the same definition except that the alkyl group having 1 or more and 20 or less carbon atoms in R ₁ and R ₂ in the above formula (1) is divalent. Therefore, the description thereof is omitted here. Of these, L ₂ is preferably a linear or branched alkylene group having 1 or more and 8 or less carbon atoms, more preferably a methylene group, an ethylene group, a trimethylene group, or a propylene group, and more preferably an ethylene group. Especially preferable. Further, in the definition of L ₂ , the "substituent group that may exist in the alkylene group or the phenylene group" has the same definition as the substituent in Ar ¹ in the above formula (1), and therefore the description thereof is omitted here. ..

Considering the ease of forming a film and the effect of further improving the film strength by the obtained polymer compound, L ₂ is preferably a single bond or a linear or branched alkylene group having 1 or more and 8 or less carbon atoms. It is more preferably a single bond or a linear or branched alkylene group having 1 or more and 6 or less carbon atoms.

In the above formula (2), Q represents a monovalent crosslinkable group. Here, when there are a plurality of Qs (n is an integer of 2 or more), they may be the same or different.

The crosslinkable group is not particularly limited as long as it is a group capable of inducing a crosslinking reaction by heat or active energy rays, but the following structure can be obtained in consideration of the ease of film formation and the effect of further improving the film strength by the obtained polymer compound. Preferred. That is, according to the preferred embodiment of the present invention, the crosslinkable group Q is selected from the following crosslinkable group group in the above formula (2).

In the above crosslinkable group, R ₁₀ to R ₁₆ each independently represent a hydrogen atom or an substituted or unsubstituted alkyl group having 1 or more and 10 or less carbon atoms, and p is an integer of 1 or more and 10 or less. Is.

The alkyl group having 1 or more and 10 or less carbon atoms is not particularly limited, but may be a linear or branched alkyl group having 1 or more and 10 or less carbon atoms. Specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, tert-pentyl group, Neopentyl group, 1,2-dimethylpropyl group, n-hexyl group, isohexyl group, 1,3-dimethylbutyl group, 1-isopropylpropyl group, 1,2-dimethylbutyl group, n-heptyl group, 1,4- Dimethylpentyl group, 3-ethylpentyl group, 2-methyl-1-isopropylpropyl group, 1-ethyl-3-methylbutyl group, n-octyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 2 -Methyl-1-isopropyl group, 1-tert-butyl-2-methylpropyl group, n-nonyl group, 3,5,5-trimethylhexyl group, n-decyl group and the like can be mentioned. Of these, R ₁₀ to R ₁₆ are preferably hydrogen atoms or linear or branched alkyl groups having 1 or more and 5 or less carbon atoms, respectively, and have hydrogen atoms or 1 or more and 3 or less carbon atoms. It is more preferably a linear or branched alkyl group, and particularly preferably a hydrogen atom. Further, since the "substituent that can exist in the alkyl group" has the same definition as the substituent in Ar ¹ in the above formula (1), the description thereof is omitted here.

Of these, considering the cross-linking reactivity (easiness of cross-linking, ease of film formation), stability of the cross-linked structure, electrochemical stability, etc., a group derived from the benzocyclobutene ring having the following structure (bicyclo [4.2]). .0] Octa-1,3,5-trienyl group) or vinyl group (-CH = CH ₂ ) is preferred. Further, from the viewpoint of crosslinking reactivity (easiness of crosslinking), cyclic ether groups such as epoxy groups and oxetane groups, and vinyl ether groups are preferable.

In the above equation (2), n is an integer of 1 or more and is uniquely defined by Ar ⁵ . That is, n is preferably an integer of 1 or more and 3 or less, more preferably 1 or 2, and particularly preferably 2.

That is, the structural unit (2) preferably has any of the following structures.

The composition of the structural unit (2) in the polymer compound of the present embodiment is not particularly limited. Considering the ease of film formation and the effect of further improving the film strength of the obtained polymer compound, the constituent unit (2) is preferably 1% or more and 15% with respect to the total number of constituent units constituting the polymer compound. Below, it is more preferably 1% or more and 10% or less. When the polymer compound contains two or more kinds of structural units (2), the content of the structural units (2) means the total amount of the structural units (2).

(Constituent unit represented by equation (3))
The polymer compound of the present embodiment may further contain a structural unit represented by the following formula (3). In the present specification, the structural unit represented by the following formula (3) is simply referred to as "constituent unit (3)".

The polymer compound having the structural unit (3) is excellent in solvent solubility. Therefore, by using the polymer compound having such a structural unit (3), the film formation can be easily performed by the coating method. The polymer compound of the present embodiment may contain one structural unit (3) or two or more structural units (3).

In the above formula (3), Ar ⁶ is a divalent aromatic hydrocarbon group having 6 or more and 30 or less substituted or unsubstituted ring carbon atoms, or 3 or more and 30 substituted or unsubstituted ring-forming atoms. Represents the following divalent heterocyclic group. Here, "a divalent aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms" and "a divalent heterocyclic group having 3 or more and 30 or less ring forming atoms" are referred to as Ar ¹ in the above formula (1). Since the definition is the same as that of the aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms and the heterocyclic group having 3 or more and 30 or less ring forming atoms in the above, the description thereof is omitted here.

Ar ⁶ is preferably a phenylene group or a fluorenylene group, more preferably a phenylene group, in consideration of further improvement in solvent solubility.

Further, in the definition of Ar ⁶ , "substituent that may exist in an aromatic hydrocarbon group or an aromatic heterocyclic group" has the same definition as the substituent in Ar ¹ in the above formula (1). The description is omitted here. Of these, considering the effect of further improving the solvent solubility of the obtained polymer compound, the substituent is preferably a linear or branched alkyl group having 1 or more and 20 or less carbon atoms, and has 3 carbon atoms. More preferably, it is a linear or branched alkyl group of 10 or less.

That is, the structural unit (3) preferably has any of the following structures. In the following, "Alkyl" means "substituted with an alkyl group". Further, "Alkyl" may be the same alkyl group or different alkyl groups.

The composition of the structural unit (3) in the polymer compound of the present embodiment is not particularly limited. Considering the effect of further improving the solvent solubility of the obtained polymer compound, the constituent unit (3) is preferably 1% or more and 50% or less, more preferably, with respect to the total number of constituent units constituting the polymer compound. Is 10% or more and 50% or less. When the polymer compound contains two or more kinds of structural units (3), the content of the structural units (3) means the total amount of the structural units (3).

The polymer compound of the present embodiment may be composed of only the structural unit (1). Further, the polymer compound of the present embodiment may be composed of the constituent unit (2) and / or the constituent unit (3) in addition to the constituent unit (1) (that is, the constituent unit (1) and the constituent unit (that is, the constituent unit (1)). The binary or ternary copolymer with 2) and / or the constituent unit (3) is composed of the constituent units (1), (2) and (3) (ie, the constituent unit (1). ), (2) and (3) are ternary copolymers). When the polymer compound of the present embodiment is a ternary copolymer, the composition of each structural unit in the polymer compound is 40, with respect to the total number of structural units constituting the polymer compound. % Or more and 95% or less, the constituent unit (2) is 5% or more and 15% or less, and the constituent unit (3) is 5% or more and 50% or less. Here, the total composition of the constituent units (1) to (3) is 100%.

The structure of the polymer compound is not particularly limited, and may be any of a random copolymer, an alternate copolymer, a periodic copolymer, and a block copolymer.

The weight average molecular weight (Mw) of the polymer compound according to the present embodiment is not particularly limited as long as the intended effect of the present invention can be obtained. The weight average molecular weight (Mw) is, for example, preferably 10,000 or more and 500,000 or less, and more preferably 20,000 or more and 350,000 or less. With such a weight average molecular weight, the viscosity of the coating liquid for forming a layer (for example, a hole injection layer, a hole transport layer) using a polymer compound is appropriately adjusted to have a uniform film thickness. It is possible to form a layer of.

Further, the number average molecular weight (Mn) of the polymer compound according to the present embodiment is not particularly limited as long as the intended effect of the present invention can be obtained. The number average molecular weight (Mn) is, for example, preferably 10,000 or more and 500,000 or less, and more preferably 20,000 or more and 200,000 or less. With such a number average molecular weight, the viscosity of the coating liquid for forming a layer (for example, a hole injection layer, a hole transport layer) using a polymer compound is appropriately adjusted to have a uniform film thickness. It is possible to form a layer of. The polydispersity (weight average molecular weight / number average molecular weight) of the polymer compound of the present embodiment is, for example, 1.5 or more and 5.0 or less, preferably 1.6 or more and 4.5 or less.

Here, the number average molecular weight (Mn) and the weight average molecular weight (Mw) are not particularly limited, and a known method can be used or a known method can be appropriately modified and applied. In the present specification, the number average molecular weight (Mn) and the weight average molecular weight (Mw) shall be the values measured by the following methods.

(Measurement of number average molecular weight (Mn) and weight average molecular weight (Mw))
The number average molecular weight (Mn) and the weight average molecular weight (Mw) of the polymer compound are measured by GPC (Gel Permeation Chromatography) using polystyrene as a standard substance under the following conditions.

・ Analytical instrument (GPC): Prominence manufactured by Shimadzu Corporation
-Column: PLgel MIXED-B manufactured by Polymer Laboratories
-Column temperature: 40 ° C
・ Flow rate: 1.0 mL / min
-Injection amount of sample solution: 20 μL (concentration: about 0.05% by mass)
-Eluent: Tetrahydrofuran (THF)
-Detector: UV-VIS detector (manufactured by Shimadzu Corporation, SPD-10AV)
-Standard sample: Polystyrene.

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

The polymer compound of the present embodiment can be synthesized by using a known organic synthesis method. A person skilled in the art with reference to the examples described later can easily understand the specific method for synthesizing the polymer compound of the present embodiment. Specifically, the polymer compound of the present embodiment is obtained by a polymerization reaction using one or more kinds of monomers (1) represented by the following formula (4), or one kind represented by the following formula (4). The above-mentioned monomer (1) and one or more kinds of monomers represented by the following formula (5) and / or one or more kinds of monomers represented by the following formula (6) are used. It can be produced by the copolymerization reaction. The above-mentioned monomer used for the polymerization of a polymer compound can be synthesized by appropriately combining known synthetic reactions, and its structure can also be confirmed by a known method (for example, NMR, LC-MS, etc.).

In the above formulas (4) to (6), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , Ar ⁵ , Ar ⁶ , R ₁ , R ₂ , L ₁ , L ₂ , Q, a, b and n are It has the same definition as in the above formulas ( ₁ ) to ( ₃ ); Y1 to Y6 are independently halogen atoms (fluorine atom, chlorine atom, bromine atom, iodine atom, particularly bromine atom) or It is a group having the following structure (in the structure, _RA to R _D are independently alkyl groups having 1 or more and 3 or less carbon atoms).

The polymer compound of this embodiment has a structural unit (1). Therefore, it has a high triplet energy level and a low drive voltage. Further, when the polymer compound according to the present embodiment is used as a hole injection material or a hole transport material (particularly, a hole transport material), the current density can be improved. Further, when the polymer compound of the present embodiment is used for an organic electroluminescence device, high charge mobility is achieved. Therefore, particularly when the polymer compound of the present embodiment is used as a hole transport material, the deterioration effect on electrons can be reduced and the device life (driving life) can be improved. Therefore, the organic electroluminescence element using the polymer compound according to the present embodiment is excellent in luminous efficiency and durability. Further, since the polymer compound of the present embodiment has a structural unit (2) having a crosslinkable group, the stability of the coating film can be improved. When the polymer compound of the present embodiment has the structural unit (3), the solvent solubility can be further improved. Therefore, it is possible to improve the light emission characteristics and stability when the organic electroluminescence device is formed in a laminated structure.

<Materials for organic electroluminescence devices>
The polymer compound according to this embodiment is suitably used as a material for an organic electroluminescence device. According to the polymer compound according to the present embodiment, there is provided a material for an organic electroluminescence element having a high triplet energy level (excellent current efficiency), high charge mobility, low drive voltage and excellent durability. .. Further, the polymer main chain of the polymer compound (the constituent unit of the formula (1)) has appropriate flexibility. Therefore, since the polymer compound exhibits high solubility in a solvent and high heat resistance, it can be easily formed into a film (thin film) by a wet (coating) method.

Therefore, in the present embodiment, the use of the polymer compound of the present embodiment as a material for an organic electroluminescence device is provided. That is, in the present embodiment, a material for an organic electroluminescence device containing the polymer compound of the present embodiment is provided. The object (or effect) of the present invention can also be achieved by such a material for an electroluminescence device according to the present embodiment. The material for an organic electroluminescence device of the present embodiment is an example of the material for an electroluminescence device according to the present invention.

Further provided is an organic electroluminescence element comprising a pair of electrodes and one or more organic layers arranged between the electrodes and containing the polymer compound of the present embodiment. The object (or effect) of the present invention can also be achieved by such an electroluminescence device according to the present embodiment. In a preferred embodiment of the above embodiment, the organic electroluminescence element is disposed between the electrodes and further includes a light emitting layer containing a light emitting material capable of emitting light from triplet excitons. The organic electroluminescence device of the present embodiment is an example of the electroluminescence device according to the present invention.

Further, the present embodiment is a method for manufacturing an organic electroluminescence element, comprising a pair of electrodes and one or more organic layers arranged between the electrodes and containing the polymer compound of the present embodiment. Provided is a method of forming at least one of the above organic layers by a coating method. Further, by such a method, the present embodiment provides an electroluminescence device in which at least one of the organic layers is formed by a coating method.

Since the material for an organic electroluminescence element according to the present embodiment has excellent solubility in an organic solvent, it is particularly preferably used for manufacturing an element (particularly a thin film) by a coating method (wet process). Therefore, the present embodiment provides a liquid composition containing the polymer compound of the present embodiment and a solvent or a dispersion medium. Such a liquid composition is an example of the liquid composition according to the present invention.

Further, from the viewpoint that the material for an organic electroluminescence device according to the embodiment as described above is suitably used for manufacturing a device (particularly a thin film) by a coating method (wet process), the present embodiment is higher than the present embodiment. A thin film containing a molecular compound is provided. Such a thin film is an example of the thin film according to the present invention.

Further, since the material for an organic electroluminescence device according to the present embodiment has excellent charge mobility, it can be used in the formation of any organic film such as a hole injection material, a hole transport material, and / or a light emitting material (host). Although it can be suitably used, it is suitably used as a hole injection material and / or a hole transport material from the viewpoint of hole mobility, and is particularly preferably used as a hole transport material.

That is, the present embodiment provides a composition containing a polymer compound and at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light emitting material. Here, the luminescent material contained in the composition is not particularly limited, but may contain a luminescent organometallic complex compound. Further, such a light emitting material may contain inorganic nanoparticles.

<Organic electroluminescence element>
Hereinafter, the organic electroluminescence device according to the present embodiment will be described in detail with reference to FIG. 1. FIG. 1 is a schematic diagram showing an organic electroluminescence device according to the present embodiment. In addition, in this specification, "organic electroluminescence element" may be abbreviated as "organic EL element".

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

Here, the polymer compound of the present embodiment is contained in, for example, any organic layer arranged between the first electrode 120 and the second electrode 180. Specifically, the polymer compound is preferably contained in the hole injection layer 130 as the hole injection layer, the hole transport layer 140 as the hole transport material, or the light emitting layer 150 as the light emitting layer material (host). It is more preferably contained in the hole injection layer 130 as the hole injection layer or in the hole transport layer 140 as the hole transport material, and particularly preferably to be contained in the hole transport layer 140 as the hole transport material.

Further, the organic layer containing the polymer compound of the present embodiment is formed by a coating method (solution coating method). Specifically, the organic layer containing the polymer compound is subjected to a spin coat method, a casting method, a microgravure coat method, a gravure coat method, and a bar coat method. Coat method, roll coat method, wire bar coat method, dip coat method, spray coat method, screen printing method, flexographic printing. The film is formed by a solution coating method such as a method, an offset printing method, or an ink jet printing method.

The solvent used in the solution coating method can be any solvent as long as it can dissolve the polymer compound, and can be appropriately selected depending on the type of the polymer compound used. For example, toluene, xylene, ethylbenzene, diethylbenzene, methicylene, propylbenzene, cyclohexylbenzene, dimethoxybenzene, anisole, ethoxytoluene, phenoxytoluene, isopropylbiphenyl, dimethylanisole, phenylacetate, phenylpropionate, methyl benzoate, ethyl benzoate, etc. Can be exemplified. The amount of the solvent used is not particularly limited, but the concentration of the polymer compound is preferably 0.1% by mass or more and 10% by mass or less, more preferably 0.5% by mass or more, in consideration of ease of application and the like. The amount is about 5% by mass or less.

The method for forming a layer other than the organic layer containing the polymer compound is not particularly limited. The layer other than the organic layer containing the polymer compound of the present embodiment may be formed by, for example, a vacuum vapor deposition method or a solution coating method.

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

The first electrode 120 is formed on the substrate 110. Specifically, the first electrode 120 is an anode, and is formed of a metal, an alloy, a conductive compound, or the like having a large work function. For example, the first electrode 120 has indium tin oxide (In ₂ O ₃ -SnO ₂ : ITO), indium zinc oxide (In ₂ O ₃ -ZnO), tin oxide (SnO ₂ ), and oxidation, which are excellent in transparency and conductivity. It may be formed as a transmissive electrode by zinc (ZnO) or the like. Further, the first electrode 120 may be formed as a reflective electrode by laminating magnesium (Mg), aluminum (Al), or the like on the transparent conductive film.

A hole injection layer 130 is formed on the first electrode 120. The hole injection layer 130 is a layer that facilitates the injection of holes from the first electrode 120, specifically, about 10 nm or more and about 1000 nm or less, and more specifically, about 10 nm or more and about 100 nm or less. It may be formed by thickness.

The hole injection layer 130 can be formed of a known hole injection material. Known hole-injecting materials that form the hole-injecting layer 130 include, for example, triphenylamine-containing polyether ketone (poly (ether ketone) -containg triphenyllamine: TCAPEK), 4-isopropyl-4'-methyldiphenyliodonium tetrakis. (Pentafluorophenyl) borate (4-isopropyl-4'-methyldiphenylliodonium tetracis (pentafluorophenyl) boreta: PPBI), N, N'-diphenyl-N, N'-bis- [4- (phenyl-m-tril-amino) -Phenyl] -biphenyl-4,4'-diamine (N, N'-diphenyl-N, N'-bis- [4- (phenyl-m-polyyl-amino) -phenyl] -biphenyl-4, 4'- diamine: DNTPD), copper phthalocyanine, 4,4', 4 "-tris (3-methylphenylphenylamino) triphenylamine (4,4', 4" -tris (3-methylphenylphenyllamino) triphenyllamine: m -MTDATA), N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (N, N'-di (1-naphthyl) -N, N'-diphenyllbenzidine: NPB), 4,4' , 4 "-tris (diphenylamino) triphenylamine (4,4', 4" -tris (diphenyllamino) triphenyllamine: TDATA), 4,4', 4 "-tris (N, N-2-naphthylphenylamino) Triphenylamine (4,4', 4 "-tris (N, N-2-naphylpenelylamino) triphenyllamine: 2-TNATA), polyaniline / dodecylbenzenesulfonic acid, poly (3,4-ethylenedi) Oxythiophene) / poly (4-styrene sulfonate) (PEDOT / PSS) (poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate)), and polyaniline / 10-camparsulfonic acid (polyaniline / 10-camphorsul). Fonic acid) and the like can be mentioned.

A hole transport layer 140 is formed on the hole injection layer 130. The hole transport layer 140 is a layer having a function of transporting holes, and may be formed, for example, with a thickness of about 10 nm or more and about 150 nm or less. The hole transport layer 140 is preferably formed by a solution coating method using the polymer compound of the present embodiment. According to this method, a polymer compound capable of improving the current efficiency and drive life of the organic EL element 100 can be efficiently formed into a large area.

However, when any other organic layer of the organic EL element 100 contains the polymer compound of the present embodiment, the hole transport layer 140 may be formed of a known hole transport material. Known hole transport materials include, for example, 1,1-bis [(di-4-tolylamino) phenyl] cyclohexane (1,1-bis [(di-4-tolylamino) phenyl] cyclohexane: TAPC), N-. Carbazole derivatives such as phenylcarbazole and polyvinylcarbazole, N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl] -4. , 4'-diamine (N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1-biphenyl] -4,4'-diamine: TPD), 4,4', 4 " -Tris (N-carbazolyl) triphenylamine (4,4', 4 "-tris (N-carbazolyl) triphenyllamine: TCTA), and N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine (N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine: NPB) and the like can be mentioned.

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

The light emitting layer 150 may be used as a host material, for example, 6,9-diphenyl-9'-(5'-phenyl- [1,1': 3', 1 "-terphenyl] -3-yl) 3,3'. -Bi [9H-carbazole], 3,9-diphenyl-5-(3- (4-phenyl-6- (5'-phenyl- [1,1': 3', 1 "-terphenyl] -3-" Il) -1,3,5, -triazine-2-yl) phenyl) -9H-carbazole, 9,9'-diphenyl-3,3'-bi [9H-carbazole], tris (8-quinolinolato) aluminum ( tris (8-quinolinato) benzene: Alq3), 4,4'-bis (carbazole-9-yl) biphenyl (4,4'-bis (carbazol-9-yl) biphenyl: CBP), poly (n-vinylcarbazole) ) (Poly (n-vinyl carbazole): PVK), 9,10-di (naphthalen-2-yl) anthracene (9,10-di (naphthalene) anthracene: ADN), 4,4', 4 "-tris ( N-carbazolyl) triphenylamine (4,4', 4 "-tris (N-carbazolyl) triphenyllamine: TCTA), 1,3,5-tris (N-phenylbenzimidazol-2-yl) benzene (1,3) , 5-tris (N-phenyl-benzimidazol-2-yl) benzene: TPBI), 3-tert-butyl-9,10-di (naphth-2-yl) anthracene (3-tert-butyl-9,10-) di (naphth-2-yl) anthracene: TBADN), distyryllylene (DSA), 4,4'-bis (9-carbazole) -2,2'-dimethyl-biphenyl (4,4'-bis (4,4'-bis) 9-carbazole) 2,2'-dimethyl-biphenyl: dmCBP) and the like may be included.

Further, the light emitting layer 150 has, as a dopant material, for example, perylene and its derivative, rubrene and its derivative, coumarin and its derivative, 4-dicyanomethylene-2- (p-dimethylaminostyryl). ) -6-Methyl-4H-pyran (4-dyanomethylene-2- (plexhylaminostylyl) -6-methyl-4H-pyran: DCM) and its derivatives, bis [2- (4,6-difluorophenyl) pyridinate] picolinate. Iridium (III) (bis [2- (4,6-difluorophenyl) complex] picolinate iridium (III): FIrpic), bis (1-phenylisoquinoline) (acetylacetonate) iridium (III) (bis (1-phenylisokuinline)) (Acetylcatenate) derivative (III): Ir (piq) 2 (acac)), tris (2-phenylpyridine) iridium (III) (tris (2-phenylpyridine) iridium (III): Ir (ppy) 3), tris (2-phenylpyridine) iridium (III) It may contain an iridium (Ir) complex such as 2- (3-p-xyl) phenyl) pyridine iridium (III), an osmium (Os) complex, a platinum complex and the like. Of these, it is preferable that the luminescent material is a luminescent organometallic complex compound.

An electron transport layer 160 is formed on the light emitting layer 150. The electron transport layer 160 is a layer having a function of transporting electrons, and is formed by using a vacuum vapor deposition method, a spin coating method, an inkjet method, or the like. The electron transport layer 160 may be formed, for example, with a thickness of about 15 nm or more and about 50 nm or less.

The electron transport layer 160 may be formed of a known electron transport material. Examples of known electron transport materials include (8-quinolinolato) lithium (Liq), tris (8-quinolinato) aluminum (tris (8-quinolinato) aluminum: Alq3), and compounds having a nitrogen-containing aromatic ring. be able to. Specific examples of the compound having a nitrogen-containing aromatic ring include, for example, 1,3,5-tri [(3-pyridyl) -phen-3-yl] benzene (1,3,5-tri [(3-pyridyl)). -Pyridine ring-containing compounds such as -phenyl-3-yl] benzene), 2,4,6-tris (3'-(pyridin-3-yl) biphenyl-3-yl) -1,3. Compounds containing a triazine ring such as 5-triazine (2,4,6-tris (3'-(pyridin-3-yl) biphenyl-3-yl) -1,3,5-triazine), 2 -(4- (N-Phenylbenzoinidazolyl-1-yl-phenyl) -9,10-dinaphthylanthracene (2- (4- (N-phenylbenzoimidazolyl-1-yl-phenyl) -9,10-dinaphylanthracene) ), And the like, a compound containing an imidazole ring and the like can be mentioned.

An electron injection layer 170 is formed on the electron transport layer 160. The electron injection layer 170 is a layer having a function of facilitating the injection of electrons from the second electrode 180, and is formed by using a vacuum vapor deposition method or the like. The electron injection layer 170 may be formed with a thickness of about 0.3 nm or more and about 9 nm or less. As the electron injection layer 170, any material known as a material for forming the electron injection layer 170 can be used. For example, the electron injection layer 170 is composed of a lithium compound such as (8-quinolinato) lithium ((8-quinolinato) lithium: Liq) and lithium fluoride (LiF), sodium chloride (NaCl), and cesium fluoride (CsF). ), Lithium oxide (Li ₂ O), barium oxide (BaO), or the like.

A second electrode 180 is formed on the electron injection layer 170. The second electrode 180 is specifically a cathode, and is formed of a metal, an alloy, a conductive compound, or the like having a small work function. For example, the second electrode 180 may be a metal such as lithium (Li), magnesium (Mg), aluminum (Al), calcium (Ca), or aluminum-lithium (Al-Li), magnesium-indium (Mg-In), or the like. It may be formed as a reflective electrode with an alloy such as magnesium-silver (Mg-Ag). The second electrode 180 is a transmissive electrode made of a thin film of the metal material having a diameter of 20 nm or less, and a transparent conductive film such as indium tin oxide (In ₂ O ₃ -SnO ₂ ) and zinc oxide (In ₂ O ₃ -ZnO). May be formed as.

As described above, as an example of the electroluminescence device according to the present invention, the organic EL device 100 according to the present embodiment has been described. By having the organic layer containing the polymer compound, the organic EL element 100 according to the present embodiment can further improve the current density and the drive life.

The laminated structure of the organic EL element 100 according to the present embodiment is not limited to the above example. The organic EL element 100 according to the present embodiment may be formed by another known laminated structure. For example, in the organic EL element 100, one or more of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, and the electron injection layer 170 may be omitted, or another layer may be additionally used. You may be prepared. Further, each layer of the organic EL element 100 may be formed of a single layer or may be formed of a plurality of layers.

For example, the organic EL device 100 further includes a hole blocking layer between the hole transporting layer 140 and the light emitting layer 150 in order to prevent excitons or holes from diffusing into the electron transporting layer 160. May be good. The hole blocking layer can be formed by, for example, an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, or the like.

<Electroluminescence devices other than organic electroluminescence devices>
The polymer compound according to this embodiment can be applied to an electroluminescence element other than an organic electroluminescence element (organic EL element). The electroluminescence device other than the organic EL device to which the polymer compound according to the present embodiment can be applied is not particularly limited, but for example, a quantum dot light emitting device or a quantum point light emitting device (for example, Japanese Patent Application Laid-Open No. 2010-199067). (Refer to Japanese Patent Publication No.), organic-inorganic perovskite light emitting device, and the like.

Hereinafter, a quantum dot light emitting device will be described as an example of an electroluminescence device other than the organic EL device. The quantum dot light emitting device can be manufactured by forming a quantum dot light emitting layer instead of the light emitting layer 150 of the organic EL element 100.

A quantum dot light emitting layer is a single layer or a plurality of layers in which a large number of quantum dots are arranged. Here, the quantum dot refers to a particle of a predetermined size having a quantum constraint effect. The diameter of the quantum dot is about 1 nm to 10 nm. The quantum dots are an example of inorganic nanoparticles contained in a light emitting material in the composition containing the polymer compound according to the present invention.

The quantum dots arranged in the quantum dot light emitting layer can be synthesized by a wet chemical step, an organometallic chemical vapor deposition step, a molecular beam epitaxy step, or other similar steps. Among them, the wet chemical step is a method of putting a precursor substance in an organic solvent to grow particles.

In this wet chemical step, as the crystal grows, the organic solvent is naturally coordinated to the surface of the quantum dot crystal and acts as a dispersant, thereby regulating the growth of the crystal. Therefore, in the wet chemical step, the inorganic nano is easier and lower cost than the vapor deposition method such as organometallic chemical vapor deposition (MOCVD, Metalorganic Chemical Vapor Deposition) or molecular beam epitaxy (MBE, Molecular Beam Epitaxy). The growth of particles can be controlled.

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

Such quantum dots include II-VI group semiconductor compounds; III-V group semiconductor compounds; IV-VI group semiconductor compounds; Group IV elements or compounds; and semiconductor materials selected from the group consisting of combinations thereof and the like. Can be used.

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

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

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

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

Quantum dots can have a homogeneous single structure or a core-shell double structure. The core shell can contain different substances. The material constituting each core and shell can consist of different semiconductor compounds. However, the energy bandgap of the shell material is larger than the energy bandgap of the core material.

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

As described above, the polymer compound according to the present embodiment can be suitably used for electroluminescence devices other than organic electroluminescence devices (organic EL devices).

Hereinafter, the present invention will be described with reference to more detailed examples. In the following, "%" is a weight standard unless otherwise specified. The tests and evaluations were as follows.

[Synthesis Example 1] Synthesis of Compound 1 In a 300 mL flask under an argon atmosphere, 1,4-dihexyl-2,5-dibromobenzene (8.08 g, 20.0 mmol) and bis (pinacholate diboron) (12. 19 g, 48.0 mmol), PdCl ₂ (dppf) (0.98 g, 1.2 mmol), potassium acetate (11.78 g, 120.0 mmol), and dehydrated 1,4-dioxane (100 mL) were mixed and heated to reflux. It was stirred below for 6 hours.

After completion of the reaction, the mixture was cooled to room temperature, toluene and water were added to separate the liquids, and the mixture was washed with water. Anhydrous sodium sulfate and activated carbon were added, stirred, and then filtered through Celite (registered trademark). The filtrate was concentrated to give a crude product (11.94 g). It was recrystallized from hexane and washed with methanol. The obtained crystals were dried under reduced pressure to obtain 4.23 g of white needle-like crystals (Compound 1) (yield 42%). The structure of the obtained compound 1 was identified by a nuclear magnetic resonance apparatus ( ¹ H-NMR).

[Synthesis Example 2] Synthesis of Compound 2 Under an argon atmosphere, 2,7-dibromofluorene (22.7 g, 70.0 mmol), 5-bromo-1-pentene (21.9 g,) in a 500 mL four-mouthed flask. 147.0 mmol), potassium hydroxide (16.7 g, 297.6 mmol), potassium iodide (1.2 g, 7.2 mmol) and dimethyl sulfoxide (DMSO) (170 mL) were mixed and heated at 80 ° C. for 4 hours. Stirred.

After completion of the reaction, the mixture was cooled to room temperature, water (300 mL) and toluene (300 mL) were added to separate the liquids, and the obtained organic layer was washed 5 times with saturated brine (300 ml). The obtained organic layer was dried over anhydrous sodium sulfate and then purified by silica gel column chromatography and recrystallization to obtain 24.1 g of a white solid (compound 2) (yield 75%). The structure of the obtained compound 2 was identified by a nuclear magnetic resonance apparatus ( ¹ H-NMR).

[Synthesis Example 3] Synthesis of Compound 3 Compound 3 having the following structure was synthesized according to the following method.

Specifically, compound 3-1 (5.0 g, 9.1 mmol) and chloroform (24 ml) were added to the reaction vessel under an argon atmosphere, cooled to 0 ° C. in an ice bath, and then BF ₃ Et ₂ O (7). .0 ml) was added dropwise from the dropping funnel. After stirring for 1 hour, BF ₃ Et ₂ O (7.0 ml) was further added and the mixture was stirred for 1 hour, and the mixture was stirred at room temperature for 5 hours. After adding water (100 ml) and stirring, the mixture was transferred to a separating funnel and extracted 3 times with chloroform (50 ml). The obtained organic layer was dried over sodium sulfate, the solution was concentrated, and chloroform (30 ml) was added. Methanol (300 ml) was added while refluxing by heating for crystallization, and the obtained crystals were filtered. The crystals were added to chloroform (20 ml) and heated, methanol (200 ml) was added, and the mixture was stirred at room temperature for 2 hours. The resulting crystals were filtered and dried to give compound 3 (2.0 g, 41% yield). The structure of the obtained compound 3 was identified by a nuclear magnetic resonance apparatus ( ¹ H-NMR).

[Synthesis Example 4] Synthesis of Compound 6 [Synthesis Example 4-1] Synthesis of Compound 4 Under an argon atmosphere, 2-amino-N-[(1,1'-biphenyl) -4-yl] -N- (4-yl) To bromophenyl) -9,9-dimethylfluorene (10.0 g, 19.36 mmol), bis (pinacholate diboron) (7.38 g, 29.04 mmol), and potassium acetate (5.70 g, 58.09 mmol). Dehydration 1,4-dioxane (195 mL) was added and stirred for 30 minutes. Then, bis [(diphenylphosphino) ferrocene] dichloropalladium (0.22 g, 0.27 mmol) was added, and the mixture was heated under reflux and stirred for 3 hours. After completion of the reaction, the mixture was cooled to room temperature, filtered through Celite (registered trademark), and the filtrate was concentrated. Methanol was charged into the concentrated residue and washed to obtain 9.08 g of a solid (compound 4) (yield 79%).

[Synthesis Example 4-2] Synthesis of Compound 5 Under an argon atmosphere, 3-bromo-6-iodocarbazole (5.20 g, 14.0 mmol), the above compound 4 (8.00 g, 14.2 mmol) and Pd [PPh ₃ ]. ] ₄ (0.161 g, 0.14 mmol) was added with 200 mL of 1,4-dioxane and 100 mL (14.0 mmol) of a 2M Na ₂ CO ₃ aqueous solution, and the mixture was heated under reflux and stirred for 6 hours. After completion of the reaction, the sample was transferred to a separating funnel and extracted with toluene. The organic layer was dried with 41 ₄ and then filtered and concentrated. The concentrated residue was purified by silica gel column chromatography to obtain 5.56 g of a white solid (Compound 5) (yield 58%).

[Synthesis Example 4-3] Synthesis of Compound 6 Under an argon atmosphere, m-iodobromobenzene (1.41 g, 5.0 mmol), the above compound 5 (3.00 g, 4.4 mmol), copper iodide (0.045 g). , 0.24 mmol) and sodium tert-butoxide (0.58 g, 6.1 mmol) were added with 20 mL of dehydrated 1,4-dioxane, and the mixture was stirred at room temperature for 30 minutes. Then, trans-1,2-cyclohexanediamine (0.124 g, 1.09 mmol) was added, and the mixture was heated under reflux and stirred for 8 hours.

After completion of the reaction, the mixture was cooled to room temperature, filtered through Celite (registered trademark), and the filtrate was concentrated. The concentrated residue was purified by silica gel column chromatography to obtain 2.59 g of a pale yellow solid (Compound 6) (yield 70%).

[Synthesis Example 5] Synthesis of Compound 7 In the synthesis of Compound 6, the reaction was carried out in the same manner except that p-iodobromobenzene (2.00 g, 7.07 mmol) was used instead of m-iodobromobenzene. 2.28 g of a pale yellow solid (Compound 7) was obtained (yield 62%).

[Synthesis Example 6] Synthesis of Compound 12 [Synthesis Example 6-1] Synthesis of Compound 8 Under an argon atmosphere, N-phenyl-4-biphenylamine (2.00 g, 8.1 mmol), 2-bromo-9,9- Dioctylfluorene (3.99 g, 8.5 mmol), Pd ₂ (dba) ₃ 0.036 g (0.04 mmol), P (tBu) _3. HBF ₄ 0.023 g (0.08 mmol) and sodium tert-butoxide 1. To 05 g (10.96 mmol), 20 mL of anhydrous xylene was added, and the mixture was heated and stirred for 8 hours.

After completion of the reaction, the mixture was cooled to room temperature, filtered through Celite (registered trademark), and the filtrate was concentrated. The obtained concentrated residue was purified by silica gel column chromatography to obtain 2.56 g of a white solid (Compound 8) (yield 50%).

[Synthesis Example 6-2] Synthesis of Compound 9 Compound 8 (2.00 g, 3.1 mmol) and dimethylformamide (DMF) (40 mL) were placed in a four-necked flask substituted with argon and cooled with ice water. N-Bromosuccinimide (0.62 g, 3.5 mmol) dissolved in DMF (20 mL) was added dropwise, and the mixture was stirred for 2 hours. Toluene (150 mL) was added, washed with water and dried over magnesium sulfate. The solvent was distilled off under reduced pressure and purified by column chromatography to obtain 1.65 g of a solid (Compound 9) (yield 75%).

[Synthesis Example 6-3] Synthesis of Compound 10 In the synthesis of Compound 4, 2-amino-N-[(1,1'-biphenyl) -4-yl] -N- (4-bromophenyl) -9,9 -The same reaction was carried out except that the above compound 9 (1.50 g, 2.1 mmol) was used instead of dimethylfluorene, and 0.73 g of a solid (compound 10) was obtained (yield 46%).

[Synthesis Example 6-4] Synthesis of Compound 11 In the synthesis of Compound 5, the same reaction was carried out except that the above compound 10 (0.70 g, 0.92 mmol) was used instead of compound 4, and the reaction was 0.46 g. Solid (Compound 11) was obtained (yield 58%).

[Synthesis Example 6-5] Synthesis of Compound 12 Under an argon atmosphere, 4-bromo-4'-iodobiphenyl (0.19 g, 0.55 mmol), the above compound 11 (0.46 g, 0.52 mmol), copper iodide To (0.0053 g, 0.028 mmol) and sodium tert-butoxide (0.069 g, 0.72 mmol) were added 20 mL of dehydrated 1,4-dioxane, and the mixture was stirred at room temperature for 30 minutes. Then, trans-1,2-cyclohexanediamine (0.014 g, 0.128 mmol) was added, and the mixture was heated under reflux and stirred for 8 hours.

After completion of the reaction, the mixture was cooled to room temperature, filtered through Celite (registered trademark), and the filtrate was concentrated. The concentrated residue was purified by silica gel column chromatography to obtain 0.44 g of a pale yellow solid (Compound 12) (yield 77%).

[Synthesis Example 7] Synthesis of Compound 17 [Synthesis Example 7-1] Synthesis of Compound 13 N- (4-biphenylyl) -2-biphenylamine (manufactured by Tokyo Kasei Co., Ltd.) (manufactured by Tokyo Kasei Co., Ltd.) in a reaction vessel under an argon atmosphere. 6.26 g, 19.49 mmol), 1-bromo-4-iodobenzene (6.06 g, 21.44 mmol), copper (I) iodide (0.19 g, 0.97 mmol), trans-1,2-cyclohexane. Diamine (0.49 g, 4.29 mmol), sodium tert-butoxide (3.75 g, 38.97 mmol) and dioxane (60 ml) were added, and the mixture was stirred at 90 ° C. for 6 hours. After completion of the reaction, the reaction mixture was allowed to cool to room temperature, and impurities were filtered off using Celite (registered trademark). After distilling off the solvent, the residue was purified by column chromatography to obtain 6.68 g of a solid (Compound 13) (yield 72%).

[Synthesis Example 7-2] Synthesis of Compound 14 In the synthesis of Compound 4, 2-amino-N-[(1,1'-biphenyl) -4-yl] -N- (4-bromophenyl) -9,9 -The same reaction was carried out except that the above compound 13 (1.90 g, 4.0 mmol) was used instead of dimethylfluorene, and 1.17 g of a solid (compound 14) was obtained (yield 56%).

[Synthesis Example 7-3] Synthesis of Compound 15 To a solution of 5.16 g (21 mmol) of 2-bromocarbazole in glacial acetic acid (600 mL), 4.5 g (20 mmol) of N-iodosuccinic acid imide (NIS) was added little by little. After stirring at room temperature for 12 hours, the reaction mixture was added dropwise to 1200 mL of water, and the precipitate was collected by filtration. The filter was washed with water and then dissolved in 200 mL of ethyl acetate. This solution was washed with aqueous sodium hydrogen carbonate solution, water and saturated brine, and י4 was added and dried. The solution was filtered and concentrated to give 5.85 g of solid (Compound 15) (yield 75%).

[Synthesis Example 7-4] Synthesis of Compound 16 Under an argon atmosphere, the above-mentioned compound 15 (5.20 g, 14.0 mmol), the above-mentioned compound 14 (9.11 g, 14.2 mmol) and Pd [PPh3] 4 (0.161 g). , 0.14 mmol) was added with 200 mL of 1,4-dioxane and 100 mL (14.0 mmol) of a 2M Na2CO3 aqueous solution, and the mixture was heated under reflux and stirred for 6 hours. After completion of the reaction, the sample was transferred to a separating funnel and extracted with toluene. The organic layer was dried over regsvr4, filtered and concentrated. The concentrated residue was purified by silica gel column chromatography to obtain 4.94 g of a white solid (Compound 16) (yield 55%).

[Synthesis Example 7-5] Synthesis of Compound 17 In the synthesis of Compound 7, the reaction was carried out in the same manner except that Compound 16 (2.50 g, 3.89 mmol) was used instead of Compound 5, and the reaction amount was 2.10 g. A pale yellow solid (Compound 17) was obtained (yield 68%).

[Synthesis Example 8] Synthesis of Compound 22 [Synthesis Example 8-1] Synthesis of Compound 18 Under an argon atmosphere, 2-aminobiphenyl (1.69 g, 10.0 mmol) and 4- (4-bromophenyl) dibenzofuran (Tokyo Kasei) 50 ml of dehydrated toluene was added to sodium tert-butoxide (1.92 g, 20.0 mmol) manufactured by Co., Ltd. (3.23 g, 10.0 mmol) and stirred. Palladium acetate (45 mg, 0.2 mmol), tri-t-. Butylphosphine (40 mg, 0.2 mmol) was added and reacted at 80 ° C. for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, the reaction mixture was filtered through Celite / silica gel, and the filtrate was concentrated under reduced pressure. Concentrated residue. Was purified by silica gel column chromatography to obtain 2.51 g of a solid (compound 18) (yield 61%).

[Synthesis Example 8-2] Synthesis of Compound 19 In the synthesis of compound 13, compound 18 (2.00 g, 4.86 mmol) was used instead of N- (4-biphenylyl) -2-biphenylamine (manufactured by Tokyo Kasei Co., Ltd.). The reaction was carried out in the same manner except that (1) was used, and 1.65 g of a pale yellow solid (Compound 19) was obtained (yield 60%).

[Synthesis Example 8-3] In the synthesis of the synthetic compound 14 of the compound 20, the same reaction was carried out except that the above compound 19 (2.26 g, 4.0 mmol) was used instead of the compound 13, and 1.37 g. Solid (Compound 20) was obtained (yield 56%).

[Synthesis Example 8-4] Synthesis of Compound 21 Under an argon atmosphere, the above compound 20 (1.22 g, 2.0 mmol), 2,7-dibromocarbazole (manufactured by Tokyo Kasei Co., Ltd.) (0.81 g, 2.5 mmol) To Pd [PPh3] 4 (0.023 g, 0.02 mmol), 30 mL of 1,4-dioxane and 14 mL (0.02 mmol) of a 2M Na2CO3 aqueous solution were added, and the mixture was heated under reflux and stirred for 6 hours. After completion of the reaction, the sample was transferred to a separating funnel and extracted with toluene. The organic layer was dried over regsvr4, filtered and concentrated. The concentrated residue was purified by silica gel column chromatography to obtain 0.41 g of a white solid (Compound 21) (yield 28%).

[Synthesis Example 8-5] Synthesis of Compound 22 In the synthesis of Compound 17, the reaction was carried out in the same manner except that Compound 21 (1.00 g, 1.36 mmol) was used instead of Compound 16, and the reaction amount was 0.71 g. A pale yellow solid (Compound 22) was obtained (yield 59%).

[Example 1] Synthesis of polymer compound A-1 Compound 1 synthesized in Synthesis Example 1, Compound 2 synthesized in Synthesis Example 2, Compound 3 synthesized in Synthesis Example 3, and Synthesis Example 4 were synthesized. Using compound 6, a polymer compound A-1 having the following structural unit (A) and structural unit (B) having the following composition was synthesized.

Specifically, in a four-necked flask under an argon atmosphere, compound 1 (1.49 g, 3.0 mmol), compound 2 (0.138 g, 0.30 mmol), compound 3 (0.159 g, 0.30 mmol), and the like. Compound 6 (2.01 g, 2.40 mmol), palladium acetate (2.15 mg), tris (2-methoxyphenyl) phosphine (20.25 mg), toluene (45 mL), and 20 mass% tetraethylammonium hydroxide aqueous solution (11). .42 g) was added, and the mixture was refluxed for 7 hours. Next, phenylboronic acid (23.30 mg, 0.57 mmol), palladium acetate (2.15 mg), tris (2-methoxyphenyl) phosphine (10.12 mg) and a 20 mass% tetraethylammonium hydroxide aqueous solution (11.42 g). ) Was added, and the mixture was heated and refluxed for 7 hours. Then, the aqueous layer was removed, N, N-diethyldithiocarbamate sodium trihydrate (5.40 g, 23.97 mmol) and ion-exchanged water (50 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed successively with water, a 3 mass% acetic acid aqueous solution, and water. The organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene and passed through column chromatography packed with silica gel / alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was filtered off and dried to obtain the polymer compound A-1.

The polymer compound A-1 thus obtained has the following composition (constituent unit derived from compound 1: constituent unit derived from compound 6: constituent unit derived from compound 3: derived from compound 2) based on the charging ratio of the monomer. (Mole ratio = 50:40: 5: 5 (molar ratio)), it is presumed that the structural unit of (A) and the structural unit selected from (B) are alternately polymerized as a polymer compound. Further, when the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer compound A-1 were estimated by size exclusion chromatography (SEC), Mw = 200,000 and Mw / Mn = 4. It was 0.

[Example 2] Synthesis of polymer compound A-2 Compound 1 synthesized in Synthesis Example 1, Compound 2 synthesized in Synthesis Example 2, Compound 3 synthesized in Synthesis Example 3 and Synthesis Example 6 were synthesized. Using compound 12, polymer compound A-2 having the following structural unit (A) and structural unit (B) having the following composition was synthesized.

Specifically, in a four-necked flask under an argon atmosphere, compound 1 (1.49 g, 3.0 mmol), compound 2 (0.138 g, 0.30 mmol), compound 3 (0.159 g, 0.30 mmol), and the like. Compound 12 (2.66 g, 2,40 mmol), palladium acetate (2.15 mg), tris (2-methoxyphenyl) phosphine (20.25 mg), toluene (45 mL), and 20 mass% tetraethylammonium hydroxide aqueous solution (11). .42 g) was added, and the mixture was refluxed for 7 hours. Next, phenylboronic acid (23.30 mg, 0.57 mmol), palladium acetate (2.15 mg), tris (2-methoxyphenyl) phosphine (10.12 mg) and a 20 mass% tetraethylammonium hydroxide aqueous solution (11.42 g). ) Was added, and the mixture was heated and refluxed for 7 hours. Then, the aqueous layer was removed, N, N-diethyldithiocarbamate sodium trihydrate (5.40 g, 23.97 mmol) and ion-exchanged water (50 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed successively with water, a 3 mass% acetic acid aqueous solution, and water. The organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene and passed through column chromatography packed with silica gel / alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was filtered off and dried to obtain a polymer compound A-2.

The polymer compound A-2 thus obtained has the following composition (constituent unit derived from compound 1: constituent unit derived from compound 12: constituent unit derived from compound 3: derived from compound 2) based on the charging ratio of the monomers. (Mole ratio = 50:40: 5: 5 (molar ratio)), it is presumed that the constituent unit of (A) and the constituent unit selected from (B) are alternately polymerized as a polymer compound. Further, when the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer compound A-2 were estimated by size exclusion chromatography (SEC), Mw = 110,000 and Mw / Mn = 3. It was 1.

[Example 3] Synthesis of polymer compound A-3 Using the compound 1 synthesized in the above synthesis example 1 and the compound 6 synthesized in the above synthesis example 4, the following structural units (A) and the following structural units (B) are described below. The polymer compound A-3 having a composition was synthesized.

Specifically, in a four-necked flask under an argon atmosphere, compound 1 (0.998 g, 2.0 mmol), compound 6 (1.68 g, 2.0 mmol), palladium acetate (2.15 mg), and tris (2-). Methoxyphenyl) phosphine (20.25 mg), toluene (30 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (7.61 g) were added, and the mixture was refluxed for 4 hours. Next, phenylboronic acid (23.30 mg, 0.57 mmol), palladium acetate (2.15 mg), tris (2-methoxyphenyl) phosphine (10.12 mg) and a 20 mass% tetraethylammonium hydroxide aqueous solution (11.42 g). ) Was added, and the mixture was heated and refluxed for 7 hours. Then, the aqueous layer was removed, N, N-diethyldithiocarbamate sodium trihydrate (5.40 g, 23.97 mmol) and ion-exchanged water (40 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed successively with water, a 3 mass% acetic acid aqueous solution, and water. The organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene and passed through column chromatography packed with silica gel / alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was filtered off and dried to obtain polymer compound A-3.

The polymer compound A-3 thus obtained has the following composition (constituent unit derived from compound 1: structural unit derived from compound 6 = 50:50 (molar ratio)) based on the charging ratio of the monomers. , (A) and (B) are presumed to be a polymer compound in which the constituent units are alternately polymerized. Further, when the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of the polymer compound A-3 were estimated by size exclusion chromatography (SEC), Mw = 34,000 and Mw / Mn = 1. It was 5.

[Example 4] Synthesis of polymer compound A-4 Using the compound 1 synthesized in the above synthesis example 1 and the compound 7 synthesized in the above synthesis example 5, the following structural units (A) and the following structural units (B) are described below. The polymer compound A-4 having a composition was synthesized.

Specifically, in a four-necked flask under an argon atmosphere, compound 1 (0.998 g, 2.0 mmol), compound 7 (1.68 g, 2.0 mmol), palladium acetate (2.15 mg), and tris (2-). Methoxyphenyl) phosphine (20.25 mg), toluene (30 mL), and a 20 mass% tetraethylammonium hydroxide aqueous solution (7.61 g) were added, and the mixture was refluxed for 4 hours. Next, phenylboronic acid (23.30 mg, 0.57 mmol), palladium acetate (2.15 mg), tris (2-methoxyphenyl) phosphine (10.12 mg) and a 20 mass% tetraethylammonium hydroxide aqueous solution (11.42 g). ) Was added, and the mixture was heated and refluxed for 7 hours. Then, the aqueous layer was removed, N, N-diethyldithiocarbamate sodium trihydrate (5.40 g, 23.97 mmol) and ion-exchanged water (40 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed successively with water, a 3 mass% acetic acid aqueous solution, and water. The organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene and passed through column chromatography packed with silica gel / alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was filtered off and dried to obtain a polymer compound A-4.

The polymer compound A-4 thus obtained has the following composition (constituent unit derived from compound 1: structural unit derived from compound 6 = 50:50 (molar ratio)) based on the charging ratio of the monomers. , (A) and (B) are presumed to be a polymer compound in which the constituent units are alternately polymerized. Further, when the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of this polymer compound A-4 were estimated by size exclusion chromatography (SEC), Mw = 42,000 and Mw / Mn = 2. It was 1.

[Example 5] Synthesis of polymer compound A-5 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene ( Using the compound 17 synthesized in Tokyo Kasei Co., Ltd. and Synthesis Example 7 above, a polymer compound A-5 having the following structural unit (A) and structural unit (B) having the following composition was synthesized.

Specifically, in a four-necked flask under an argon atmosphere, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene. (Manufactured by Tokyo Kasei Co., Ltd.) (1.285 g, 2.0 mmol), Compound 17 (1.59 g, 2.0 mmol), Palladium acetate (2.15 mg), Tris (2-methoxyphenyl) phosphine (20.25 mg) , Toluene (30 mL), and 20 mass% tetraethylammonium hydroxide aqueous solution (7.61 g) were added, and the mixture was refluxed for 4 hours. Next, phenylboronic acid (23.30 mg, 0.57 mmol), palladium acetate (2.15 mg), tris (2-methoxyphenyl) phosphine (10.12 mg) and a 20 mass% tetraethylammonium hydroxide aqueous solution (11.42 g). ) Was added, and the mixture was heated and refluxed for 7 hours. Then, the aqueous layer was removed, N, N-diethyldithiocarbamate sodium trihydrate (5.40 g, 23.97 mmol) and ion-exchanged water (40 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed successively with water, a 3 mass% acetic acid aqueous solution, and water. The organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene and passed through column chromatography packed with silica gel / alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was filtered off and dried to obtain a polymer compound A-5.

The polymer compound A-5 thus obtained has the following composition (2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) based on the mixing ratio of the monomers. -2-Il) -9,9-Dioctylfluorene-derived constituent unit: Compound 17-derived constituent unit = 50:50 (molar ratio)), the constituent unit of (A) and the constituent unit of (B) are It is presumed to be a polymer compound that is polymerized alternately. Further, when the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of this polymer compound A-4 were estimated by size exclusion chromatography (SEC), Mw = 61,000 and Mw / Mn = 2. It was 5.

[Example 6] Synthesis of polymer compound A-6 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene ( Using the compound 22 synthesized in Tokyo Kasei Co., Ltd. and Synthesis Example 8 above, a polymer compound A-6 having the following structural unit (A) and structural unit (B) having the following composition was synthesized.

Specifically, in a four-necked flask under an argon atmosphere, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene. (Manufactured by Tokyo Kasei Co., Ltd.) (1.285 g, 2.0 mmol), Compound 22 (1.77 g, 2.0 mmol), Palladium acetate (2.15 mg), Tris (2-methoxyphenyl) phosphine (20.25 mg) , Toluene (30 mL), and 20 mass% tetraethylammonium hydroxide aqueous solution (7.61 g) were added, and the mixture was refluxed for 4 hours. Next, phenylboronic acid (23.30 mg, 0.57 mmol), palladium acetate (2.15 mg), tris (2-methoxyphenyl) phosphine (10.12 mg) and a 20 mass% tetraethylammonium hydroxide aqueous solution (11.42 g). ) Was added, and the mixture was heated and refluxed for 7 hours. Then, the aqueous layer was removed, N, N-diethyldithiocarbamate sodium trihydrate (5.40 g, 23.97 mmol) and ion-exchanged water (40 mL) were added, and the mixture was stirred at 85 ° C. for 2 hours. After separating the organic layer from the aqueous layer, the organic layer was washed successively with water, a 3 mass% acetic acid aqueous solution, and water. The organic layer was added dropwise to methanol to precipitate a polymer compound, which was collected by filtration and dried to obtain a solid. This solid was dissolved in toluene and passed through column chromatography packed with silica gel / alumina, and the solvent was distilled off under reduced pressure. The obtained liquid was added dropwise to methanol, and the precipitated solid was filtered off and dried to obtain a polymer compound A-6.

The polymer compound A-6 thus obtained has the following composition (2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolane) based on the mixing ratio of the monomers. -2-Il) -9,9-Dioctylfluorene-derived constituent unit: Compound 22-derived constituent unit = 50:50 (molar ratio)), the constituent unit of (A) and the constituent unit of (B) are It is presumed to be a polymer compound that is polymerized alternately. Further, when the weight average molecular weight (Mw) and the polydispersity (Mw / Mn) of this polymer compound A-4 were estimated by size exclusion chromatography (SEC), Mw = 52,000 and Mw / Mn = 2. It was 6.

The polymer compounds A-1, A-2 obtained in Examples 1 and 2 and the poly [(9,9-dioctylfluorenyl-2,7-diyl) -co having the following structural units -(4,4'-(N- (4-sec-butylphenyl) diphenylamine)] (TFB) (manufactured by Luminescence Technology Corp.) (Comparative Example 1) for triplet energy level (eV) according to the following method. The measurement was performed. The results are shown in Table 1 below.

[Measurement of triplet energy level]
Each compound was dissolved in toluene so as to have a concentration of 3.2% by mass to prepare a coating liquid. This coating liquid was applied by spin coating at a rotation speed of 1600 rpm and dried on a hot plate at 250 ° C. for 60 minutes to obtain a film (sample) having a thickness (dry film thickness) of about 70 nm. The sample was cooled to 77K (-196 ° C.) and the photoluminescence (PL) spectrum was measured. The triplet energy level (eV) was calculated from the peak value on the shortest wave side of this PL spectrum. The results are shown in Table 1 below.

From the results in Table 1, it is shown that the polymer compounds A-1 and A-2 of Examples 1 and 2 have a significantly higher triplet energy level than the conventionally used TFB.

[Example 7] Fabrication of organic electroluminescence element Device-1 On a glass substrate with ITO in which strip-shaped indium tin oxide (ITO) is formed in advance as a first electrode (anodode) at a film thickness of 150 nm. In addition, poly (3,4-ethylenedioxythiophene) / poly (4-styrene sulfonate) (poly (3,4-ethylene dioxythiophene) / poly (4-stylerene sulfonate): PEDOT / PSS) (manufactured by Sigma-Aldrich). Was applied by a spin coating method so that the dry film thickness was 30 nm to form a hole injection layer.

Next, the polymer compound A-1 (hole transport material A-1) synthesized in Example 1 was dissolved in xylene (solvent) at a concentration of 1% by mass to prepare a coating liquid for forming a hole transport layer. On the hole injection layer formed above, this hole transport layer forming coating was applied by a spin coating method so that the thickness (dry film thickness) was 30 nm, and heated at 230 ° C. for 1 hour. A hole transport layer having a thickness (dry film thickness) of 30 nm was formed on the hole injection layer.

Further, the compound h-1 (6,9-diphenyl-9'-(5'-phenyl- [1,1': 3) having the following structure as a host material on the hole transport layer formed above. ', 1 "-Terphenyl] -3-yl) 3,3'-bi [9H-carbazole]) and compound h-2 (3,9-diphenyl-5-(3- (4-phenyl-6- (4-phenyl-6- ( 5'-Phenyl- [1,1': 3', 1 "-Terphenyl] -3-yl) -1,3,5-triazine-2-yl) Phenyl) -9H-carbazole), compound A toluene solution containing tris (2- (3-p-xyl) phenyl) pyridine iridium (III) (tris (2- (3-p-xylyl) phenyl) pyridine iridium (III)) was prepared as a material. At this time, a toluene solution was prepared so that the concentration of compound h-1 was 0.49 g / ml and the concentration of compound h-2 was 0.05 g / ml. The content of the dopant material was adjusted so that the doping amount was 10% by mass with respect to the total mass of the light emitting layer. The toluene solution prepared above was applied onto the hole transport layer by a spin coating method so that the dry film thickness was 30 nm, and a light emitting layer was formed on the hole transport layer.

Next, (8-quinolinolat) lithium (Liq) and KLET-03 (manufactured by Chemipro Kasei Co., Ltd.) are co-deposited on the light emitting layer formed above with a vacuum vapor deposition apparatus to form an electron transport layer having a film thickness of 50 nm. Was formed on the light emitting layer. Further, lithium fluoride (LiF) was vapor-deposited on the electron transport layer formed above by a vacuum vapor deposition apparatus to form an electron injection layer having a film thickness of 1 nm on the electron transport layer. Further, aluminum (Al) was deposited on the electron injection layer formed above by a vacuum vapor deposition apparatus, and a second electrode (cathode) having a film thickness of 100 nm was formed on the electron injection layer. An organic electroluminescence device (organic EL device) Device-1 was manufactured by the above manufacturing method.

[Example 8] Preparation of organic electroluminescence element Device-2 In Example 7, the polymer compound A-2 synthesized in Example 2 instead of the polymer compound A-1 (hole transport material A-1). An organic electroluminescence element (organic EL element) Device-2 was produced by the same method as in Example 7 except that the hole transport layer was formed using (hole transport material A-2).

[Comparative Example 2] Fabrication of Organic Electroluminescence Device Device-3 In Example 7, instead of the polymer compound A-1 (hole transport material A-1), a poly having the following structural units [(9,9-) Hole transport using dioctylfluorenyl-2,7-diyl) -co- (4,4'-(N- (4-sec-butylphenyl) diphenylamine)] (TFB) (Luminescence Technology Corp.). An organic electroluminescence device (organic EL device) Device-3 was produced by the same method as in Example 7 except that a layer was formed.

The organic electroluminescence element (organic EL element) Voltage-1 and Device-2 manufactured in Examples 7 and 8 and the organic electroluminescence element (organic EL element) Device-3 manufactured in Comparative Example 2 are described below. According to the method, the drive voltage and durability (drive life) were evaluated by the following methods. The results are shown in Table 2 below.

[Evaluation of drive voltage and durability (drive life)]
First, when a voltage is applied to each organic EL element using a DC constant voltage power supply (source meter manufactured by KEYENCE), a current starts to flow at a constant voltage and the organic EL element emits light. The voltage at this time was defined as the drive voltage (unit: V). While measuring the light emission of the organic EL element with a luminance measuring device (manufactured by Topcom, SR-3), the current was gradually increased, and when the luminance reached 6000 cd / m ² , the current was kept constant and left to stand.

Here, the time (time) until the value of the brightness measured by the brightness measuring device gradually fluctuates (decreases) and reaches 95% of the initial brightness is defined as the "driving life (time)".

From Table 2 above, Examples 7 and 8 (organic EL devices Device-1 to Device-2 using the polymer compounds A-1 and A-2 of Examples 1 and 2 as hole transport materials) have been conventionally used. It can be seen that both the drive voltage and the durability (drive life) are superior to those of Comparative Example 2 (organic EL element Device-3) using the hole transport material (TFB) of. Therefore, it is considered that the polymer compound of the present embodiment can be suitably used for electroluminescence devices (particularly hole transporting materials) and the like.

Further, when the polymer compounds A-1 to A-6 of Examples 1 to 6 are used, a hole transporting material can be formed by a coating method, which is preferable from the viewpoint of mass production.

[Example 9] Fabrication of quantum dot light emitting element (Device-4) As a first electrode (anode), a glass substrate with ITO in which ITO is patterned is used as a neutral detergent, deionized water, water and isopropeel alcohol. After washing sequentially with the above, UV-ozone treatment was performed. PEDOT / PSS (manufactured by Sigma-Aldrich) was applied onto a glass substrate with ITO by a spin coating method so that the thickness (dry film thickness) was 30 nm, and then dried. As a result, a hole injection layer having a thickness (dry film thickness) of 30 nm was formed on the glass substrate with ITO.

Next, a 1.0% by mass toluene solution of the polymer compound A-1 (hole transport material A-1) synthesized in Example 1 was placed on the hole injection layer to a thickness (dry film thickness). Was applied by a spin coating method so that the thickness was 25 nm. Then, it was heat-treated at 150 ° C. for 30 minutes to form a hole transport layer on the hole injection layer. Next, on the hole transport layer, 1.0 mass% of blue quantum dots (see FIG. 2) of ZnTeSe / ZnSe / ZnS (core / shell / shell) were added to cyclohexane in which the hole transport layer was not dissolved. It was dispersed so as to be. This dispersion was applied by a spin coating method so that the thickness (dry film thickness) was 25 nm, and then dried. As a result, a quantum dot light emitting layer having a thickness (dry film thickness) of 25 nm was formed on the hole transport layer. The blue quantum dots had an emission wavelength center of 458 nm and a half width of 29 nm in the dispersion liquid (see FIGS. 3 and 4).

After the quantum dot light emitting layer was completely dried, lithium quinolate (Liq) and the electron transport material TPBI (manufactured by Sigma-Aldrich) were co-deposited on the quantum dot light emitting layer using a vacuum vapor deposition apparatus. As a result, an electron transport layer having a thickness of 36 nm was formed on the quantum dot light emitting layer. Liq was deposited on this electron transport layer using a vacuum vapor deposition apparatus to form an electron injection layer having a thickness of 0.5 nm. Aluminum was vapor-deposited on this electron-injected layer using a vacuum-film vapor deposition apparatus to form a second electrode (cathode) having a thickness of 100 nm, and a quantum dot light emitting device (Device-4) was obtained.

[Example 10] Preparation of quantum dot light emitting device (Device-5) In Example 9, the polymer compound A synthesized in Example 4 instead of the polymer compound A-1 (hole transport material A-1). A quantum dot light emitting device (Device-5) was obtained by the same method as in Example 9 except that the hole transport layer was formed using -4 (hole transport material A-4).

[Comparative Example 3] Fabrication of Quantum Dot Light Emitting Device (Device-7) In Example 9, TFB (manufactured by Luminescence Technology Corp.) was used instead of the polymer compound A-1 (hole transport material A-1). A quantum dot light emitting device was obtained by the same method as in Example 9 except that the hole transport layer was formed.

Drive voltage, luminous efficiency EQE, color of the quantum dot light emitting elements (Device-4, Device-5) obtained in Examples 9 and 10 and the quantum dot light emitting element (Device-6) obtained in Comparative Example 3 above. The degree and emission wavelength were evaluated by the following methods. The results are shown in Table 3 below.

[Evaluation method of drive voltage, luminous efficiency EQE, chromaticity diagram and emission wavelength]
First, when a voltage is applied to each quantum dot light emitting element using a DC constant voltage power supply (source meter manufactured by KEYENCE), a current starts to flow at a certain voltage and the quantum dot light emitting element emits light. do. The voltage at this time was defined as the drive voltage (unit: V). While measuring the light emission of the quantum dot light emitting element using a brightness measuring device (manufactured by Topcom, SR-3), the current was gradually increased, and when the brightness reached 100 cd / m ² , the current was kept constant and left to stand. ..

The chromaticity was measured using a luminance measuring device. The luminous efficiency EQE was calculated from the spectral radiance spectrum measured by the luminance measuring device on the assumption that Lambasian radiation was performed.

The electric emission spectra when applied to the quantum dot light emitting element (Device-4) of Example 9 and the quantum dot light emitting element (Device-5) of Example 10 at different voltages have a center of emission wavelength of 454 nm. The half price width was 29 nm. Therefore, it is considered that the polymer compound of the present embodiment can be suitably used for a quantum dot light emitting device.

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

100 Organic electroluminescence element (organic EL element)
110 Substrate 120 First electrode 130 Hole injection layer 140 Hole transport layer 150 Light emitting layer 160 Electron transport layer 170 Electron injection layer 180 Second electrode

Claims (13)

The following formula (1):

(In the formula (1), Ar ¹ is a divalent aromatic hydrocarbon group having 6 or more and 30 or less substituted or unsubstituted ring carbon atoms, or 3 or more and 30 substituted or unsubstituted ring-forming atoms. Represents the following divalent heterocyclic groups;
Ar ² is a divalent aromatic hydrocarbon group having 6 or more and 12 or less substituted or unsubstituted ring carbon atoms, or a divalent heterocyclic ring having 3 or more and 12 or less substituted or unsubstituted ring-forming atoms. Represents a group;
Ar ³ and Ar ⁴ are independently substituted or unsubstituted aromatic hydrocarbon groups having 6 or more and 30 or less ring carbon atoms, or substituted or unsubstituted ring-forming atoms having 3 or more and 30 or less. Represents a heterocyclic group;
L ₁ represents a single-bonded or divalent linking group, wherein the divalent linking group is a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms, substituted or unsubstituted. Ring formation Multiplex consisting of 2 to 4 groups selected from a heterocyclic group having 3 to 30 atoms and an substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 carbon atoms. Linking group, substituted or unsubstituted ring-forming Multiple linking group consisting of 2 to 4 groups selected from heterocyclic groups having 3 or more and 30 or less atoms, or substituted or unsubstituted ring. A multi-linking group consisting of 2 to 4 groups selected from an aromatic hydrocarbon group having 6 or more and 30 or less carbon atoms and a heterocyclic group having 3 or more and 30 or less substituted or unsubstituted ring-forming atoms. And;
R ₁ and R ₂ represent substituents, each of which is a deuterium atom, an substituted or unsubstituted aryl group having 6 or more and 50 or less ring carbon atoms, and an substituted or unsubstituted carbon number of 1 or more. Represents an alkyl group of 20 or less, an substituted or unsubstituted alkoxy group having 1 or more and 20 or less carbon atoms, or a substituted or unsubstituted ring-forming atomic group of 3 or more and 30 or less, and _R1 and R. When a plurality of ₂ 's are present, they may be the same or different from each other, or they may be combined with each other to form a ring structure;
a and b are independently integers of 0 or more and 3 or less)
A polymer compound containing a structural unit represented by .
Furthermore, the following formula (3):

(In the formula (3), Ar ⁶ is a divalent aromatic hydrocarbon group having 6 or more and 30 or less substituted or unsubstituted ring carbon atoms, or 3 or more and 30 substituted or unsubstituted ring-forming atoms. Represents the following divalent heterocyclic group)
Including the building blocks represented by
Polymer compound. The polymer compound according to claim 1, wherein the structural unit represented by the formula (1) is selected from the structural units represented by the following formulas (1-1) to (1-4).

The polymer compound according to claim 1 or 2, further comprising a structural unit represented by the following formula (2):

In formula (2), Ar ⁵ is a substituted or unsubstituted aromatic hydrocarbon group having 6 or more and 30 or less ring carbon atoms, or a substituted or unsubstituted ring-forming atom number of 3 or more. Represents a (2 + n) valent heterocyclic group of 30 or less;
L ₂ represents a single-bonded, substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, or a substituted or unsubstituted phenylene group, and when a plurality of L ₂ are present, they are the same or different. May;
Q represents a monovalent crosslinkable group, and if there are multiple Qs, they may be the same or different;
n is an integer of 1 or more. The polymer compound according to claim 3, wherein the crosslinkable group Q is selected from the following crosslinkable group group:

In the crosslinkable group, R ₁₀ to R ₁₆ each independently represent a hydrogen atom or an substituted or unsubstituted alkyl group having 1 or more and 10 or less carbon atoms, and p is an integer of 1 or more and 10 or less. Is. A composition comprising the polymer compound according to any one of claims 1 to 4 and at least one material selected from the group consisting of a hole transporting material, an electron transporting material and a light emitting material. The composition according to claim 5 , wherein the luminescent material contains a luminescent organometallic complex compound. The composition according to claim 5 , wherein the light emitting material contains inorganic nanoparticles. A liquid composition containing the polymer compound according to any one of claims 1 to 4 and a solvent or a dispersion medium. A thin film containing the polymer compound according to any one of claims 1 to 4 . A material for an electroluminescence device containing the polymer compound according to any one of claims 1 to 4 . An electroluminescence element comprising a pair of electrodes and one or more organic layers arranged between the pair of electrodes and containing the polymer compound according to any one of claims 1 to 4 . The electroluminescence element according to claim 11, further comprising a light emitting layer arranged between the pair of electrodes and containing a light emitting material capable of emitting light from triplet excitons. The electroluminescence device according to claim 11 or 12 , wherein at least one of the organic layers is formed by a coating method.

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