JP6724310B2 - Organic electronic materials and organic electronic devices - Google Patents

Description

Embodiments of the present invention relate to an organic electronic material, an ink composition, an organic layer, an organic electronic element, an organic electroluminescent element (also referred to as “organic EL element”), a display element, a lighting device, and a display device.

Organic EL devices have been attracting attention as large-area solid-state light source applications as alternatives to incandescent lamps, gas-filled lamps and the like. Further, it has been attracting attention as a most prominent self-luminous display replacing a liquid crystal display (LCD) in the field of flat panel display (FPD), and is being commercialized.

The organic EL element is roughly classified into two types, a low molecular weight organic EL element and a high molecular weight organic EL element, depending on the organic material used. A polymer compound is used as the organic material in the polymer organic EL device, and a polymer compound is used in the low molecular organic EL device. On the other hand, the manufacturing method of the organic EL element is mainly a dry process in which film formation is performed in a vacuum system and a wet process in which film formation is performed by plate printing such as letterpress printing and intaglio printing and plateless printing such as inkjet printing. It is roughly divided into two. Since the simple film formation is possible, the wet process is expected as an indispensable method for future large-screen organic EL displays (see, for example, Patent Document 1 and Non-Patent Document 1).

JP, 2006-279007, A

Kengo Hirose, Daisuke Kumaki, Nobuaki Koike, Akira Kuriyama, Seiichiro Ikehata, Shizushi Tokito, 53rd Joint Lecture on Applied Physics, 26p-ZK-4 (2006)

The organic EL element manufactured by using the wet process has features that it is easy to reduce the cost and increase the area. However, regarding the characteristics of the organic EL element, further improvement is desired in the organic EL element including the organic layer produced by the wet process.

In view of the above, it is an object of the embodiments of the present invention to provide an organic electronic material and an ink composition that are suitable for a wet process and that are suitable for improving the life characteristics of an organic electronic element. Another embodiment of the present invention aims to provide an organic layer suitable for improving the life characteristics of an organic electronic device. Further, another embodiment of the present invention aims to provide an organic electronic element, an organic EL element, a display element, a lighting device, and a display device which have excellent life characteristics.

As a result of intensive studies, the present inventors have found an organic electronic material suitable for a wet process and for improving the life characteristics of an organic EL element, and have completed the present invention.

That is, the embodiment of the present invention includes at least one structural unit containing at least one sp ² carbon, having at least two aromatic rings, and having no fused ring in which three or more benzene rings are adjacently fused. The present invention relates to an organic electronic material containing a charge transporting polymer having an end.

In one embodiment, the charge transporting polymer has 3 or more ends. Preferably, the charge transporting polymer has the structural unit at 25% or more of the ends based on the total number of ends.

In one embodiment, the structural unit contains 2 to 6 aromatic rings. Preferably, the structural unit is a naphthalene structure, acenaphthylene structure, fluorene structure, spirobifluorene structure, carbazole structure, acridine structure, xanthene structure, dibenzofuran structure, indole structure, isoindole structure, benzimidazole structure, quinoline structure, isoquinoline structure. , A quinoxaline structure, a terphenyl structure, and a tetraphenylethylene structure.

Further, in one embodiment, the structural unit is formed of a monomer that contains 7 or more sp ² carbons, has 2 or more aromatic rings, and does not include a condensed ring in which 3 or more benzene rings are adjacently condensed. It Preferably, the charge transporting polymer is a polymer of a monomer containing at least the monomer and a monomer containing a structural unit having a hole transporting property.

In one embodiment, the charge transporting polymer further has a polymerizable functional group.

Another embodiment of the present invention relates to an ink composition containing any one of the organic electronic materials described above and a solvent.

Further, another embodiment of the present invention relates to an organic layer formed by using any one of the organic electronic materials described above or the ink composition.

Further, another embodiment of the present invention relates to an organic electronic element and an organic electroluminescent element having at least one organic layer. In one embodiment, the organic electroluminescent device further comprises a flexible substrate. In one embodiment, the organic electroluminescent device further comprises a resin film substrate.

Further, another embodiment of the present invention relates to a display element and a lighting device including any one of the organic electroluminescent elements, and a display device including the lighting device and a liquid crystal element as a display unit.

The organic electronic material and the ink composition which are the embodiments of the present invention are suitable for a wet process and for improving the life characteristics of an organic electronic device. Further, the organic layer according to the embodiment of the present invention is suitable for improving the life characteristics of the organic electronic device. Furthermore, the organic electronic element, the organic EL element, the display element, the lighting device, and the display device, which are the embodiments of the present invention, have excellent life characteristics.

It is a cross-sectional schematic diagram which shows an example of the organic EL element which is embodiment of this invention.

An embodiment of the present invention will be described.
<Organic electronics materials>
The organic electronic material that is an embodiment of the present invention has a structural unit containing 7 or more sp ² carbons, 2 or more aromatic rings, and not a condensed ring in which 3 or more benzene rings are adjacently condensed. The structural unit is also referred to as "structural unit T1") at least at one end of the charge-transporting polymer. The organic electronic material may contain only one type of charge transporting polymer, or may contain two or more types thereof. The charge transporting polymer is preferable in that it is excellent in film forming property in a wet process as compared with a low molecular weight compound.

[Charge-transporting polymer]
Charge transporting polymers have the ability to transport charges. Holes are preferable as the charge to be transported. The polymer chain of a charge transporting polymer comprises structural units that have the ability to transport charges. The charge transporting polymer may be a homopolymer having one type of structural unit or a copolymer having two or more types of structural units. When the charge transporting polymer is a copolymer, the copolymer may be an alternating, random, block or graft copolymer, or a copolymer having an intermediate structure between them, such as a block copolymer. It may be a tinged random copolymer. In one embodiment, structural unit means a monomer unit. Examples of the structural unit having the ability to transport charges include the structural unit L described later.

The charge transporting polymer may be linear or may have a branched structure. The linear charge transporting polymer has two ends, and the charge transporting polymer having a branched structure has three or more ends. The term “terminal” refers to the end of a polymer chain. The charge transporting polymer has the structural unit T1 at at least one end.

The charge-transporting polymer preferably contains at least a divalent structural unit L having a charge-transporting property and a monovalent structural unit T constituting a terminal portion, and a trivalent or higher valent structural unit B constituting a branch portion. It may further include. The structural unit T includes at least the structural unit T1. The charge-transporting polymer may include only one type of each structural unit, or may include a plurality of types of structural units. In the charge transporting polymer, the respective structural units are bound to each other at the “monovalent” to “trivalent or higher” binding sites.

(Construction)
Examples of the partial structure contained in the charge transporting polymer include the following. The charge transporting polymer is not limited to the polymer having the following partial structure. In the partial structure, "L" represents the structural unit L, "T" represents the structural unit T, and "B" represents the structural unit B. “*” represents a binding site with another structural unit. In the following partial structures, a plurality of Ls may be the same structural unit or different structural units. The same applies to T and B.

Linear charge transport polymer

Charge transporting polymer with branched structure

(Structural unit L)
The structural unit L is a divalent structural unit having a charge transporting property. The structural unit L is not particularly limited as long as it contains an atomic group capable of transporting charges. For example, the structural unit L is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, biphenylene structure, terphenylene structure, naphthalene structure, anthracene structure, tetracene structure, phenanthrene structure, dihydrogen structure. Phenanthrene structure, pyridine structure, pyrazine structure, quinoline structure, isoquinoline structure, quinoxaline structure, acridine structure, diazaphenanthrene structure, furan structure, pyrrole structure, oxazole structure, oxadiazole structure, thiazole structure, thiadiazole structure, triazole structure, benzo It is selected from a thiophene structure, a benzoxazole structure, a benzooxadiazole structure, a benzothiazole structure, a benzothiadiazole structure, a benzotriazole structure, and a structure containing one or more of these. The aromatic amine structure is preferably a triarylamine structure, more preferably a triphenylamine structure.

In one embodiment, the structural unit L is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, pyrrole structure, and these, from the viewpoint of obtaining an excellent hole transport property. Selected from the structures containing one or more of the above, and selected from the substituted or unsubstituted aromatic amine structure, the carbazole structure, and the structure containing one or more of these. Is more preferable. In another embodiment, the structural unit L is a substituted or unsubstituted fluorene structure, a benzene structure, a phenanthrene structure, a pyridine structure, a quinoline structure, and one or two of these, from the viewpoint of obtaining an excellent electron transport property. It is preferably selected from structures containing more than one species.

The following are specific examples of the structural unit L. The structural unit L is not limited to the following.

Each R independently represents a hydrogen atom or a substituent. Preferably, R is ^{independently, -R 1, -OR 2, -SR} 3, -OCOR 4, -COOR 5, -SiR 6 R 7 R 8, a halogen atom, and, which will be described later polymerizable functional group Selected from the group consisting of: R ^{1 to} R ⁸ each independently represent a hydrogen atom; a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; or an aryl group or heteroaryl group having 2 to 30 carbon atoms. The alkyl group may be further substituted with an aryl group or a heteroaryl group having 2 to 20 carbon atoms, and the aryl group or the heteroaryl group may further have a linear, cyclic or branched group having 1 to 22 carbon atoms. It may be substituted with an alkyl group. R is preferably a hydrogen atom, an alkyl group, an aryl group, or an alkyl-substituted aryl group. Ar represents an arylene group or a heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group.

In the present specification, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. The heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocycle. The arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. The heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic heterocycle. Examples of the aromatic hydrocarbon include a monocycle, a condensed ring, and a polycycle in which two or more selected from a monocycle and a condensed ring are bonded via a single bond. Examples of the aromatic heterocycle include a monocycle, a condensed ring, and a polycycle in which two or more selected from a monocycle and a condensed ring are bonded via a single bond.

(Structural unit T)
The structural unit T is a monovalent structural unit that constitutes the terminal portion of the charge transporting polymer. The structural unit T may have the same structure as the structural unit L, or may have a different structure. The charge-transporting polymer includes, as the structural unit T, a condensed ring containing at least one terminal having 7 or more sp ² carbons, having at least 2 aromatic rings, and having at least 3 benzene rings adjacent to each other and being condensed. With no structural unit T1. The charge-transporting polymer may have only one type of structural unit T1, or may have two or more types. It is considered that the charge-transporting polymer has an electron-transporting property by including the structural unit T1 at the terminal. In particular, when the charge-transporting polymer has a structural unit having a hole-transporting property and a structural unit T1 at the end, the charge-transporting polymer is stable to electrons while maintaining the hole-transporting property. As a result, it is considered that high performance as an organic electronic material can be exhibited as a result.

“Containing 7 or more sp ² carbons” means that among the carbon atoms contained in the structural unit T1, 7 or more carbon atoms have an sp ² hybrid orbital. When the number of sp ² carbons contained in the structural unit T1 is less than 7, the effect of improving the life characteristics cannot be obtained. The number of sp ² carbons is preferably 10 or more, and more preferably 12 or more, from the viewpoint of sufficiently enhancing the life characteristics. Further, the number of sp ² carbons is preferably 40 or less, more preferably 35 or less, and further preferably 30 or less, from the viewpoint of preventing the formation of a rigid skeleton and enhancing the solubility. ..

The structural unit T1 includes two or more aromatic rings. The "aromatic ring" here means one ring exhibiting aromaticity. Examples of the “aromatic ring” include a benzene ring, a pyridine ring, a pyrrole ring, a furan ring, an imidazole ring, a pyrazole ring, an oxazole ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring and a phosphole ring. From the viewpoint of enhancing life characteristics, a benzene ring is preferable. When the structural unit T1 contains two or more benzene rings, the luminous efficiency and the emission lifetime tend to be improved as compared to the case where the structural unit T1 does not contain a benzene ring (for example, bipyridine) or the case where only one benzene ring is contained. ..

From the viewpoint of maintaining good hole transportability, the number of aromatic rings is preferably 8 or less, more preferably 7 or less, and further preferably 6 or less. If the number of aromatic rings is one, the effect of improving the life characteristics cannot be obtained.

The two or more aromatic rings may include condensed rings condensed with each other, or may include single rings. Embodiments of two or more aromatic rings include fused rings; two or more monocycles bound to each other; two or more fused rings bound to each other; monocycles and fused rings bound to each other. The bond may be a single bond or a bond through a linking group. Examples of the linking group include an alkylene group and an alkenylene group, with an alkenylene group being preferred. However, the condensed ring (for example, anthracene, phenanthrene, pyrene, perylene, etc.) in which three or more benzene rings are adjacently condensed is not included in the structural unit T1. When a condensed ring in which three or more benzene rings are adjacently condensed is included, good performance cannot be obtained because a low energy level is locally generated by the conjugated system.

In a preferred embodiment, the structural unit T1 contains a condensed ring as two or more aromatic rings. The condensed ring is preferably naphthalene, acenaphthylene, fluorene, spirobifluorene, carbazole, carboline, acridine, carbazine, indenocarbazole, indolocarbazole, xanthene, dibenzofuran, fluorenone, anthraquinone, thianthrene, dibenzothiophene, indole, isoindole. , Benzimidazole, quinoline, isoquinoline, and quinoxaline, more preferably naphthalene, acenaphthylene, fluorene, spirobifluorene, carbazole, acridine, xanthene, dibenzofuran, indole, isoindole, benzimidazole, quinoline, isoquinoline. , And quinoxaline. Although not particularly limited, the structural unit T1 is more preferably a group consisting of naphthalene, fluorene, spirobifluorene, carbazole, acridine, and dibenzofuran, from the viewpoint of easily obtaining excellent durability. At least one structure selected is included.

In another preferred embodiment, the structural unit T1 includes monocyclic rings connected to each other as two or more aromatic rings. The monocycles linked to each other are preferably selected from the group consisting of biphenyl, terphenyl (o-terphenyl, m-terphenyl, p-terphenyl), and tetraphenylethylene. Although not particularly limited, the structural unit T1 is more preferably terphenyl (o-terphenyl, m-terphenyl, p-terphenyl) from the viewpoint of easily obtaining excellent durability. , And at least one structure selected from the group consisting of tetraphenylethylene.

According to one embodiment, the structural unit T1 preferably has a condensed ring containing a nitrogen atom such as carbazole or acridine, from the viewpoint of obtaining excellent emission efficiency and emission lifetime. Further, according to another embodiment, the structural unit T1 preferably has mutually connected benzene rings such as terphenyl and tetraphenylethylene from the viewpoint of obtaining excellent luminous efficiency and luminous lifetime.

The fused ring or monocycle may be substituted or unsubstituted. As the substituent, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 15 and further preferably 1 to 10) and an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 15) , And more preferably 1 to 10). The alkyl group and the alkoxy group may be linear, branched or cyclic. When it has a substituent, an alkyl group is preferable from the viewpoint of excellent solubility, stability and the like. The number of the substituents is 1 or 2 or more, and the 2 or more substituents may be bonded to each other to form a ring.

Further, it is preferable that the structural unit T1 does not include an acyclic tertiary aromatic amine structure. The acyclic tertiary aromatic amine is a tertiary aromatic amine in which RR′R″N (at least one of R, R′ and R″ is an aryl group or a heteroaryl group) is R, R′ and An amine in which a bond is not formed between at least two groups selected from R". That is, an acyclic tertiary aromatic amine is an amine in which a ring containing N as a constituent atom is not formed. Although the acyclic tertiary aromatic amine structure is excellent in hole transporting property, the structural unit T1 may not contain the acyclic tertiary aromatic amine structure from the viewpoint of electron stability. Preferred examples of the “acyclic tertiary aromatic amine” include triarylamine and diaryl(alkyl)amine. In addition, examples other than the "acyclic tertiary aromatic amine" include, for example, cyclic tertiary aromatic amines such as 9-phenylcarbazole, 10-phenyl-9,10-dihydroacridine, and 1-phenylbenzimidazole, and carbazole. And cyclic or acyclic secondary aromatic amines such as diphenylamine.

Examples of the structural unit T1 include the following structural unit t1.
<Structural unit t1>

In the formula, Ar ¹ represents a cyclic structure containing 7 or more sp ² carbons, 2 or more aromatic rings, and not containing a condensed ring in which 3 or more benzene rings are adjacently condensed. Ar ¹ is unsubstituted or has a substituent. As the substituent, for example, a linear, cyclic or branched alkyl group (preferably having a carbon number of 1 to 20, more preferably 1 to 15, further preferably 1 to 10); a linear, cyclic or branched alkoxy group. (Preferably having 1 to 20 carbon atoms, more preferably 1 to 15, and further preferably 1 to 10).

Specific preferred examples of the structural unit T1 are listed below.

In one embodiment, the charge transporting polymer has a structural unit other than the structural unit T1 (the structural unit is also referred to as “structural unit T2”) at the terminal. The charge transporting polymer may have only one type of structural unit T2, or may have two or more types. The structural unit T2 is not particularly limited. For example, the structural unit which has an aromatic hydrocarbon structure or an aromatic heterocyclic structure is mentioned. Examples of the structural unit having an aromatic hydrocarbon structure or an aromatic heterocyclic structure include the structural unit t2 shown below. The structural unit t2 has a structure different from that of the structural unit t1.

<Structural unit t2>

In the formula, Ar ² represents an aryl group or a heteroaryl group having 2 to 30 carbon atoms. From the viewpoint of easy introduction of the polymerizable functional group at the terminal, Ar ² is, for example, an aryl group, preferably a phenyl group. Ar ² may have a substituent, and examples of the substituent include the same groups as R in the structural unit L.

(Structural unit B)
The structural unit B is a trivalent or higher valent structural unit that constitutes a branched portion when the charge transporting polymer has a branched structure. From the viewpoint of improving the durability of the organic electronic element, the structural unit B is preferably hexavalent or less, and more preferably trivalent or tetravalent. The structural unit B is preferably a unit having a charge transporting property. For example, the structural unit B is a substituted or unsubstituted aromatic amine structure, carbazole structure, condensed polycyclic aromatic hydrocarbon structure, or one or two of these, from the viewpoint of improving the durability of the organic electronic device. Selected from structures containing more than one species. The structural unit B may have the same structure as the structural unit L, or may have a different structure, and may have the same structure as the structural unit T, or may have a different structure. You may have.

The following are specific examples of the structural unit B. The structural unit B is not limited to the following.

W represents a trivalent linking group, and represents, for example, an arenetriyl group having 2 to 30 carbon atoms or a heteroarenetriyl group. Ar's each independently represent a divalent linking group, for example, each independently represent an arylene group or heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group. Y represents a divalent linking group, and for example, R in the structural unit L (excluding a group containing a polymerizable functional group) having at least one hydrogen atom, and further one hydrogen atom. And a divalent group excluding. Z represents a carbon atom, a silicon atom, or a phosphorus atom. In the structural unit, the benzene ring and Ar may have a substituent, and examples of the substituent include R in the structural unit L.

In the present specification, the arenetriyl group is an atomic group obtained by removing 3 hydrogen atoms from an aromatic hydrocarbon. The heteroarenetriyl group is an atomic group obtained by removing 3 hydrogen atoms from an aromatic heterocycle.

(Polymerizable functional group)
In one embodiment, the charge transporting polymer preferably has at least one polymerizable functional group from the viewpoint of being cured by a polymerization reaction and changing the solubility in a solvent. The “polymerizable functional group” refers to a functional group capable of forming a bond with each other by applying heat and/or light.

As the polymerizable functional group, a group having a carbon-carbon multiple bond (for example, vinyl group, allyl group, butenyl group, ethynyl group, acryloyl group, acryloyloxy group, acryloylamino group, methacryloyl group, methacryloyloxy group, methacryloylamino group). Group, vinyloxy group, vinylamino group, etc.), group having a small ring (for example, cycloalkyl group such as cyclopropyl group, cyclobutyl group, etc.; cyclic ether group such as epoxy group (oxiranyl group), oxetane group (oxetanyl group), etc. A diketene group; an episulfide group; a lactone group; a lactam group), a heterocyclic group (for example, a furan-yl group, a pyrrol-yl group, a thiophen-yl group, a silole-yl group) and the like. As the polymerizable functional group, particularly, a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group, and an oxetane group are preferable, and from the viewpoint of reactivity and characteristics of the organic electronic device, a vinyl group, an oxetane group, or an epoxy group is more preferable. preferable.

From the viewpoint of increasing the degree of freedom of the polymerizable functional group and making it easier to cause a polymerization reaction, it is preferable that the main skeleton of the charge transporting polymer and the polymerizable functional group are linked by an alkylene chain. Further, for example, when forming an organic layer on an electrode, from the viewpoint of improving the affinity with a hydrophilic electrode such as ITO, it is preferable that they are linked by a hydrophilic chain such as an ethylene glycol chain or a diethylene glycol chain. preferable. Further, from the viewpoint of facilitating the preparation of the monomer used for introducing the polymerizable functional group, the charge-transporting polymer is a terminal portion of an alkylene chain and/or a hydrophilic chain, that is, is polymerized with these chains. The organic functional group may have an ether bond or an ester bond at the connecting part and/or at the connecting part between these chains and the skeleton of the charge transporting polymer. The above-mentioned “group containing a polymerizable functional group” means a polymerizable functional group itself or a group in which the polymerizable functional group and an alkylene chain or the like are combined. As the group having a polymerizable functional group, for example, the groups exemplified in WO 2010/140553 can be preferably used.

The polymerizable functional group may be introduced into the terminal portion (that is, the structural unit T) of the charge-transporting polymer or a portion other than the terminal portion (that is, the structural unit L or B), and the terminal portion. It may be introduced into both the terminal and the portion other than the terminal. From the viewpoint of curability, it is preferably introduced into at least the terminal portion, and from the viewpoint of achieving both curability and charge transportability, it is preferably introduced into the terminal portion only. When the charge transporting polymer has a branched structure, the polymerizable functional group may be introduced into the main chain of the charge transporting polymer or may be introduced into the side chain, and both the main chain and the side chain. May be introduced in.

From the viewpoint of contributing to the change in solubility, the polymerizable functional group is preferably contained in the charge transporting polymer in a large amount. On the other hand, from the viewpoint of not impairing the charge transport property, the amount contained in the charge transport polymer is preferably small. The content of the polymerizable functional group can be appropriately set in consideration of these.

For example, the number of polymerizable functional groups per molecule of the charge transporting polymer is preferably 2 or more, and more preferably 3 or more from the viewpoint of obtaining a sufficient change in solubility. The number of polymerizable functional groups is preferably 1,000 or less, more preferably 500 or less, from the viewpoint of maintaining charge transportability.

The number of polymerizable functional groups per molecule of the charge transporting polymer is the amount of the polymerizable functional group used for synthesizing the charge transporting polymer (for example, the amount of the monomer having the polymerizable functional group), each structure. It can be determined as an average value by using the charged amount of the monomer corresponding to the unit, the weight average molecular weight of the charge transporting polymer, and the like. The number of polymerizable functional groups is the ratio of the integral value of the signal derived from the polymerizable functional group in the ¹ H NMR (nuclear magnetic resonance) spectrum of the charge transporting polymer to the integral value of all spectra, the charge transporting polymer. The average value can be calculated using the weight average molecular weight of When the charged amount is clear because it is simple, the value obtained by using the charged amount is preferably adopted.

(Ratio of structural units)
From the viewpoint of obtaining a sufficient charge transport property, the proportion of the structural unit L contained in the charge transporting polymer is preferably 10 mol% or more, more preferably 20 mol% or more, and 30 mol% or more based on the total structural units. Is more preferable. The proportion of the structural unit L is preferably 95 mol% or less, more preferably 90 mol% or less, still more preferably 85 mol% or less, in consideration of the structural unit T and the structural unit B introduced as necessary.

The proportion of the structural unit T contained in the charge-transporting polymer is based on all structural units from the viewpoint of improving the characteristics of the organic electronic device or from the viewpoint of suppressing the increase in viscosity and favorably synthesizing the charge-transporting polymer. 5 mol% or more is preferable, 10 mol% or more is more preferable, and 15 mol% or more is further preferable. In addition, the proportion of the structural unit T is preferably 60 mol% or less, more preferably 55 mol% or less, and further preferably 50 mol% or less, from the viewpoint of obtaining sufficient charge transportability.

The proportion of the structural unit T1 at all terminals of the charge-transporting polymer is 25 mol% or more, more preferably 30 mol% or more, and further preferably 35 mol%, based on the number of all terminals, from the viewpoint of improving the characteristics of the organic electronic device. That is all. The upper limit is not particularly limited and is 100 mol% or less.

When the charge transporting polymer has the structural unit T2, the ratio of the structural unit T2 at all terminals is preferably 75 mol% or less, more preferably 70% by mole or less based on the total number of terminals from the viewpoint of improving the characteristics of the organic electronic device. It is at most mol%, more preferably at most 65 mol%. The lower limit is not particularly limited, but in consideration of introduction of a polymerizable functional group described later, introduction of a substituent for improving film-forming property, wettability, and the like, for example, it can be 5 mol% or more.

When the charge-transporting polymer contains the structural unit B, the proportion of the structural unit B is preferably 1 mol% or more, more preferably 5 mol% or more, based on the total structural units, from the viewpoint of improving the durability of the organic electronic device. It is preferably 10 mol% or more, and further preferably. Further, the proportion of the structural unit B is preferably 50 mol% or less, and 40 mol% or less from the viewpoint of suppressing an increase in viscosity and satisfactorily synthesizing the charge transporting polymer, or from the viewpoint of obtaining sufficient charge transportability. Is more preferable, and 30 mol% or less is further preferable.

When the charge-transporting polymer has a polymerizable functional group, the proportion of the polymerizable functional group is preferably 0.1 mol% or more based on all structural units from the viewpoint of efficiently curing the charge-transporting polymer. 1 mol% or more is more preferable, and 3 mol% or more is further preferable. Further, the proportion of the polymerizable functional group is preferably 70 mol% or less, more preferably 60 mol% or less, and further preferably 50 mol% or less from the viewpoint of obtaining good charge transportability. The “ratio of the polymerizable functional group” here means the ratio of the structural units having the polymerizable functional group.

Considering the balance of charge transportability, durability, productivity, etc., the ratio (molar ratio) of the structural unit L and the structural unit T is preferably L:T=100:1 to 70, more preferably 100:3 to 50. Preferably, 100:5 to 30 is more preferable. When the charge-transporting polymer includes the structural unit B, the ratio (molar ratio) of the structural unit L, the structural unit T, and the structural unit B is L:T:B=100:10 to 200:10 to 100. 100:20 to 180:20 to 90 are more preferable, and 100:40 to 160:30 to 80 are still more preferable.

The ratio of the structural unit can be determined by using the charged amount of the monomer corresponding to each structural unit used for synthesizing the charge transporting polymer. Further, the ratio of the structural unit can be calculated as an average value by utilizing the integral value of the spectrum derived from each structural unit in the ¹ H NMR spectrum of the charge transporting polymer. When the charged amount is clear because it is simple, the value obtained by using the charged amount is preferably adopted.

The charge transporting polymer has a structural unit having an aromatic amine structure and/or a structural unit having a carbazole structure as a main structural unit (main skeleton) from the viewpoint of having a high hole injecting property, a hole transporting property and the like. It is preferably a compound. Further, the charge transporting polymer is preferably a compound having at least two polymerizable functional groups from the viewpoint of facilitating multilayer formation.

(Number average molecular weight)
The number average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film forming property, and the like. From the viewpoint of excellent charge transportability, the number average molecular weight is preferably 500 or more, more preferably 1,000 or more, and even more preferably 2,000 or more. Further, the number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, and more preferably 50,000 from the viewpoint of maintaining good solubility in a solvent and facilitating the preparation of the ink composition. The following is more preferable.

(Weight average molecular weight)
The weight average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of solubility in a solvent, film forming property, and the like. The weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, still more preferably 10,000 or more, from the viewpoint of excellent charge transportability. Further, the weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, and more preferably 400,000 from the viewpoint of maintaining good solubility in a solvent and facilitating the preparation of the ink composition. The following is more preferable.

The number average molecular weight and the weight average molecular weight can be measured by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene.

(Production method)
The charge transporting polymer can be produced by various synthetic methods and is not particularly limited. For example, known coupling reactions such as Suzuki coupling, Negishi coupling, Sonogashira coupling, Stille coupling, Buchwald-Hartwig coupling can be used. Suzuki coupling causes a cross-coupling reaction using a Pd catalyst between an aromatic boronic acid derivative and an aromatic halide. According to Suzuki coupling, a charge transporting polymer can be easily produced by bonding desired aromatic rings together.

In the coupling reaction, for example, a Pd(0) compound, a Pd(II) compound, a Ni compound or the like is used as a catalyst. It is also possible to use a catalyst species generated by mixing tris(dibenzylideneacetone)dipalladium(0), palladium(II) acetate, etc. as a precursor and mixing with a phosphine ligand. Regarding the method for synthesizing the charge transporting polymer, for example, the description in International Publication WO2010/140553 can be referred to.

Examples of the monomer that can be used in the Suzuki coupling reaction include the following.
<Monomer L>

<Monomer T1>

<Monomer T2>

<Monomer B>

In the formula, L represents the structural unit L, T ¹ represents the structural unit T1, T ² represents the structural unit T2, and B represents the structural unit B. R ^{1 to} R ⁴ each represent a functional group capable of forming a bond with each other, and preferably, each independently, any one selected from the group consisting of a boronic acid group, a boronic acid ester group, and a halogen group. Represents a species.

[Dopant]
The organic electronic material may further contain a dopant. The dopant is not particularly limited as long as it is a compound capable of exhibiting a doping effect by adding it to the organic electronic material and improving the charge transport property. The doping includes p-type doping and n-type doping. In p-type doping, a substance that acts as a dopant and an electron acceptor is used, and in n-type doping, a substance that acts as a dopant and an electron donor is used. It is preferable to perform p-type doping to improve the hole transport property and to perform n-type doping to improve the electron transport property. The dopant used in the organic electronic material may be a dopant that exhibits any of p-type doping and n-type doping effects. Further, one kind of dopant may be added alone, or a plurality of kinds of dopants may be mixed and added.

The dopant used for p-type doping is an electron-accepting compound, and examples thereof include Lewis acids, protonic acids, transition metal compounds, ionic compounds, halogen compounds, and π-conjugated compounds. Specifically, Lewis acids include FeCl ₃ , PF ₅ , AsF ₅ , SbF ₅ , BF ₅ , BCl ₃ , and BBr ₃ ; protonic acids include HF, HCl, HBr, HNO ₅ , and H ₂ SO _4. , Inorganic acid such as HClO ₄ , benzenesulfonic acid, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, polyvinylsulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, trifluoroacetic acid, 1-butanesulfonic acid, vinylphenylsulfonic acid , Organic acids such as camphorsulfonic acid; transition metal compounds such as FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , AlCl ₃ , NbCl ₅ , TaCl ₅ , and MoF ₅ ; ionic compounds such as tetrakis (pentafluoro) Phenyl) borate ion, tris(trifluoromethanesulfonyl)methide ion, bis(trifluoromethanesulfonyl)imide ion, hexafluoroantimonate ion, AsF ₆ ⁻ (hexafluoroarsenate ion), BF ₄ ⁻ (tetrafluoroborate ion), PF ₆ ^- (hexafluorophosphate) salts having a perfluoroalkyl anions such, such as salts with conjugate base of the protonic acid as an anion. Examples of the halogen _{compound, Cl 2, Br 2, I} 2, ICl, ICl 3, IBr, IF, etc.; π-conjugated compounds include TCNE (tetracyanoethylene), TCNQ (tetracyanoquinodimethane), and the like. Further, it is also possible to use the electron-accepting compounds described in JP-A 2000-36390, JP-A 2005-75948, JP-A 2003-213002 and the like. Preferred are Lewis acids, ionic compounds, and π-conjugated compounds.

The dopant used for n-type doping is an electron-donating compound, for example, an alkali metal such as Li or Cs; an alkaline earth metal such as Mg or Ca; an alkali metal such as LiF or Cs ₂ CO ₃ and/or Examples thereof include salts of alkaline earth metals; metal complexes; electron-donating organic compounds.

When the charge transporting polymer has a polymerizable functional group, it is preferable to use a compound capable of acting as a polymerization initiator for the polymerizable functional group as a dopant in order to facilitate the change in solubility of the organic layer.

[Other optional ingredients]
The organic electronic material may further contain a charge transporting low molecular compound, a charge transporting polymer other than the above, and the like.

[Content]
The content of the charge transporting polymer is preferably 50% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more, based on the total mass of the organic electronic material, from the viewpoint of obtaining a good charge transporting property. preferable. It is also possible to set it to 100 mass %.

When the dopant is contained, its content is preferably 0.01% by mass or more and 0.1% by mass or more based on the total mass of the organic electronic material from the viewpoint of improving the charge transportability of the organic electronic material. More preferably, 0.5 mass% or more is still more preferable. Further, from the viewpoint of maintaining good film forming properties, it is preferably 50% by mass or less, more preferably 30% by mass or less, and further preferably 20% by mass or less, based on the total mass of the organic electronic material.

<Ink composition>
The ink composition that is an embodiment of the present invention contains the organic electronic material of the above embodiment and a solvent that can dissolve or disperse the material. By using the ink composition, the organic layer can be easily formed by a simple method such as a coating method.

[solvent]
Water, an organic solvent, or a mixed solvent thereof can be used as the solvent. Examples of the organic solvent include alcohols such as methanol, ethanol and isopropyl alcohol; alkanes such as pentane, hexane and octane; cyclic alkanes such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, tetralin and diphenylmethane; ethylene glycol. Aliphatic ethers such as dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, Aromatic ethers such as 4-methoxytoluene, 2,3-dimethylanisole, and 2,4-dimethylanisole; Aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, and n-butyl lactate; phenyl acetate, propionic acid Aromatic esters such as phenyl, methyl benzoate, ethyl benzoate, propyl benzoate and n-butyl benzoate; amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide; dimethyl sulfoxide, tetrahydrofuran, acetone , Chloroform, methylene chloride and the like. Preferred are aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, aromatic ethers and the like.

[Polymerization initiator]
When the charge transporting polymer has a polymerizable functional group, the ink composition preferably contains a polymerization initiator. As the polymerization initiator, known radical polymerization initiators, cationic polymerization initiators, anionic polymerization initiators and the like can be used. From the viewpoint of easily preparing the ink composition, it is preferable to use a substance having both a function as a dopant and a function as a polymerization initiator. Examples of such substances include the ionic compounds.

[Additive]
The ink composition may further contain an additive as an optional component. As the additive, for example, a polymerization inhibitor, a stabilizer, a thickener, a gelling agent, a flame retardant, an antioxidant, a reducing agent, an oxidizing agent, a reducing agent, a surface modifier, an emulsifier, an antifoaming agent, Examples thereof include dispersants and surfactants.

[Content]
The content of the solvent in the ink composition can be determined in consideration of application to various coating methods. For example, the content of the solvent is preferably such that the ratio of the charge transporting polymer to the solvent is 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.5% by mass or more. Is more preferable. The content of the solvent is preferably such that the ratio of the charge transporting polymer to the solvent is 20% by mass or less, more preferably 15% by mass or less, and further preferably 10% by mass or less. ..

<Organic layer>
The organic layer that is an embodiment of the present invention is a layer formed by using the organic electronic material or the ink composition of the above embodiment. By using the ink composition, the organic layer can be excellently formed by the coating method. Examples of the coating method include spin coating method; casting method; dipping method; letterpress printing method such as letterpress printing, intaglio printing, offset printing, lithographic printing, letterpress reverse offset printing, screen printing and gravure printing; ink jet method and the like. Known methods such as a plateless printing method can be mentioned. When the organic layer is formed by a coating method, the organic layer (coating layer) obtained after coating may be dried using a hot plate or an oven to remove the solvent.

When the charge transporting polymer has a polymerizable functional group, the solubility of the organic layer can be changed by advancing the polymerization reaction of the charge transporting polymer by light irradiation, heat treatment or the like. By stacking the organic layers having different solubilities, it becomes possible to easily achieve multi-layering of the organic electronic element. For the method of forming the organic layer, for example, the description of International Publication No. WO2010/140553 can be referred to.

The thickness of the organic layer after drying or curing is preferably 0.1 nm or more, more preferably 1 nm or more, and further preferably 3 nm or more, from the viewpoint of improving the efficiency of charge transport. The thickness of the organic layer is preferably 300 nm or less, more preferably 200 nm or less, still more preferably 100 nm or less, from the viewpoint of reducing electric resistance.

<Organic electronics element>
The organic electronic device that is an embodiment of the present invention has at least the organic layer of the above-described embodiment. Examples of organic electronics elements include organic EL elements, organic photoelectric conversion elements, and organic transistors. The organic electronic element preferably has a structure in which an organic layer is arranged between at least a pair of electrodes.

[Organic EL device]
The organic EL element which is an embodiment of the present invention has at least the organic layer of the above embodiment. The organic EL device usually comprises a light emitting layer, an anode, a cathode, and a substrate, and if necessary, other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer. I have it. Each layer may be formed by a vapor deposition method or a coating method. The organic EL device preferably has an organic layer as a light emitting layer or another functional layer, more preferably as a functional layer, and further preferably at least one of a hole injection layer and a hole transport layer.

FIG. 1 is a schematic sectional view showing an embodiment of an organic EL element. The organic EL device of FIG. 1 is a device having a multi-layer structure, and includes a substrate 8, an anode 2, a hole injection layer 3 and a hole transport layer 6, which are the organic layers of the above-described embodiment, a light emitting layer 1, an electron transport layer 7, The electron injection layer 5 and the cathode 4 are provided in this order. Each layer will be described below.

[Light emitting layer]
As a material used for the light emitting layer, a light emitting material such as a low molecular weight compound, a polymer or a dendrimer can be used. A polymer is preferable because it has high solubility in a solvent and is suitable for a coating method. Examples of the light emitting material include a fluorescent material, a phosphorescent material, a heat activated delayed fluorescent material (TADF), and the like.

Low molecular weight compounds such as perylene, coumarin, rubrene, quinacdrine, stilbene, dye laser dyes, aluminum complexes, and their derivatives as fluorescent materials; polyfluorene, polyphenylene, polyphenylenevinylene, polyvinylcarbazole, fluorene-benzothiadiazole copolymer , Fluorene-triphenylamine copolymers, polymers such as derivatives thereof, and mixtures thereof.

As the phosphorescent material, a metal complex containing a metal such as Ir or Pt can be used. Examples of the Ir complex include FIr(pic) (iridium(III) bis[(4,6-difluorophenyl)-pyridinate-N,C ² ]picolinate) that emits blue light, and Ir(ppy) ₃ that emits green light. (Fact tris(2-phenylpyridine)iridium), which emits red light (btp) ₂ Ir(acac)(bis[2-(2′-benzo[4,5-α]thienyl)pyridinate-N,C ³ ]. Iridium (acetyl-acetonate)), Ir(piq) ₃ (tris(1-phenylisoquinoline)iridium), and the like. Examples of the Pt complex include PtOEP (2, 3, 7, 8, 12, 13, 17, 18-octaethyl-21H, 23H-forphine platinum) which emits red light.

When the light emitting layer contains a phosphorescent material, it is preferable to further contain a host material in addition to the phosphorescent material. A low molecular weight compound, a polymer, or a dendrimer can be used as the host material. Examples of the low molecular weight compound include CBP (4,4'-bis(9H-carbazol-9-yl)biphenyl), mCP (1,3-bis(9-carbazolyl)benzene), CDBP (4,4'- Examples of the polymer include bis(carbazol-9-yl)-2,2′-dimethylbiphenyl) and derivatives thereof, and examples of the polymer include the organic electronic materials of the above-described embodiment, polyvinylcarbazole, polyphenylene, polyfluorene, and derivatives thereof. To be

Examples of the heat-activated delayed fluorescence material include Adv. Mater., 21, 4802-4906 (2009); Appl. Phys. Lett., 98, 083302 (2011); Chem. Comm., 48, 9580 (2012). Appl. Phys. Lett., 101, 093306 (2012); J. Am. Chem. Soc., 134, 14706 (2012); Chem. Comm., 48, 11392 (2012); Nature, 492, 234 (2012 );Adv. Mater., 25, 3319 (2013); J. Phys. Chem. A, 117, 5607 (2013); Phys. Chem. Chem. Phys., 15, 15850 (2013); Chem. Comm., 49, 10385 (2013); Chem. Lett., 43, 319 (2014) and the like.

[Electron transport layer, electron injection layer]
Examples of the materials used for the electron transport layer and the electron injection layer include phenanthroline derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene, condensed ring tetracarboxylic acid anhydrides such as perylene, and carbodiimide. , Fluorenylidene methane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, aluminum complexes and the like. Further, the organic electronic material of the above-mentioned embodiment can be used.

[cathode]
As the cathode material, for example, a metal or metal alloy such as Li, Ca, Mg, Al, In, Cs, Ba, Mg/Ag, LiF, CsF is used.

[anode]
As the anode material, for example, a metal (for example, Au) or another material having conductivity is used. Other materials include, for example, oxides (eg, ITO: indium oxide/tin oxide), conductive polymers (eg, polythiophene-polystyrene sulfonic acid mixture (PEDOT:PSS)).

[substrate]
Glass, plastic or the like can be used as the substrate. The substrate is preferably transparent and has flexibility. Quartz glass, a light transmissive resin film and the like are preferably used.

As the resin film, for example, a film made of polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate, etc. Can be mentioned.

When a resin film is used, the resin film may be coated with an inorganic substance such as silicon oxide or silicon nitride in order to suppress the permeation of water vapor, oxygen and the like.

[Emitting color]
The emission color of the organic EL element is not particularly limited. The white organic EL element is preferable because it can be used for various lighting fixtures such as home lighting, vehicle lighting, clocks or liquid crystal backlights.

As a method of forming a white organic EL element, a method of using a plurality of light emitting materials to emit a plurality of emission colors at the same time and mixing colors can be used. The combination of a plurality of emission colors is not particularly limited, but a combination containing three emission maximum wavelengths of blue, green and red, a combination containing two emission maximum wavelengths of blue and yellow, yellow green and orange, etc. Are listed. The emission color can be controlled by adjusting the type and amount of the light emitting material.

<Display element, lighting device, display device>
A display element that is an embodiment of the present invention includes the organic EL element of the above embodiment. For example, a color display element can be obtained by using an organic EL element as an element corresponding to each pixel of red, green, and blue (RGB). Image formation methods include a simple matrix type in which individual organic EL elements arranged in a panel are directly driven by electrodes arranged in a matrix, and an active matrix type in which thin film transistors are arranged and driven in each element.

Further, the lighting device according to the embodiment of the present invention includes the organic EL element according to the embodiment of the present invention. Further, the display device according to the embodiment of the present invention includes a lighting device and a liquid crystal element as a display unit. For example, the display device can be a display device that uses the illumination device according to the embodiment of the present invention as a backlight and a known liquid crystal element as a display unit, that is, a liquid crystal display device.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

<Preparation of Pd catalyst>
Tris(dibenzylideneacetone)dipalladium (73.2 mg, 80 μmol) was weighed out in a sample tube in a glove box under a nitrogen atmosphere at room temperature, anisole (15 mL) was added, and the mixture was stirred for 30 minutes. Similarly, tris(t-butyl)phosphine (129.6 mg, 640 μmol) was weighed in a sample tube, anisole (5 mL) was added, and the mixture was stirred for 5 minutes. These solutions were mixed and stirred at room temperature for 30 minutes to obtain a catalyst. All solvents were used after degassing with a nitrogen bubble for 30 minutes or more.

<Synthesis of Charge Transporting Polymer 1>
In a three-necked round bottom flask, the following monomer L (5.0 mmol), the following monomer B-1 (2.0 mmol), the following monomer T1-1 (2.0 mmol), the following monomer T2-1 (2.0 mmol), and anisole (20 mL) was added, and then the prepared Pd catalyst solution (7.5 mL) was added. After stirring for 30 minutes, 10% tetraethylammonium hydroxide aqueous solution (20 mL) was added. All solvents were used after degassing with a nitrogen bubble for 30 minutes or more. The mixture was heated to reflux for 2 hours. All the operations up to this point were performed under a nitrogen stream.

After completion of the reaction, the organic layer was washed with water, and the organic layer was poured into methanol-water (9:1). The resulting precipitate was collected by suction filtration and washed with methanol-water (9:1). The obtained precipitate was dissolved in toluene and reprecipitated from methanol. The obtained precipitate was collected by suction filtration, dissolved in toluene, and a metal adsorbent (“Triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer” manufactured by Strem Chemicals, 200 mg per 100 mg of the precipitate) was added, Stir overnight. After completion of stirring, the metal adsorbent and the insoluble matter were removed by filtration, and the filtrate was concentrated with a rotary evaporator. The concentrate was dissolved in toluene and then reprecipitated from methanol-acetone (8:3). The generated precipitate was collected by suction filtration and washed with methanol-acetone (8:3). The obtained precipitate was vacuum dried to obtain a charge transporting polymer 1. The resulting charge transporting polymer 1 had a number average molecular weight of 6,900 and a weight average molecular weight of 45,700. The charge transporting polymer 1 includes a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-1), a structural unit T1 (derived from the monomer T1-1), and a structural unit T2 having an oxetane group ( (Derived from monomer T2-1), and the ratio (molar ratio) of each structural unit was 45.5%, 18.2%, 18.2%, and 18.2%.

The number average molecular weight and the weight average molecular weight were measured by GPC (polystyrene conversion) using tetrahydrofuran (THF) as an eluent. The measurement conditions are as follows.
Liquid sending pump: L-6050 Hitachi High-Technologies UV-Vis Detector: L-3000 Hitachi High-Technologies Column: Gelpack ^(R) GL-A160S/GL-A150S Hitachi Chemical Co., Ltd.
Eluent: THF (for HPLC, without stabilizer) Wako Pure Chemical Industries, Ltd.
Flow rate: 1 mL/min
Column temperature: Room temperature Molecular weight standard substance: Standard polystyrene

<Synthesis of Charge Transporting Polymer 2>
In a three-neck round bottom flask, the monomer L (5.0 mmol), the monomer B-1 (2.0 mmol), the following monomer T1-2 (2.0 mmol), the monomer T2-1 (2.0 mmol), and anisole. (20 mL) was added, and then the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 2 was synthesized in the same manner as the charge transporting polymer 1. The resulting charge transporting polymer 2 had a number average molecular weight of 17,600 and a weight average molecular weight of 47,400. The charge transporting polymer 2 includes a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-1), a structural unit T1 (derived from the monomer T1-2), and a structural unit T2 having an oxetane group ( (From monomer T2-1) and the proportion of each structural unit was 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transporting Polymer 3>
In a three-neck round bottom flask, the monomer L (5.0 mmol), the monomer B-1 (2.0 mmol), the following monomer T1-3 (3.0 mmol), the monomer T2-1 (1.0 mmol), and anisole. (20 mL) was added, and then the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 3 was synthesized in the same manner as the charge transporting polymer 1. The obtained charge transporting polymer 3 had a number average molecular weight of 5,100 and a weight average molecular weight of 40,200. The charge transporting polymer 3 includes a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-1), a structural unit T1 (derived from the monomer T1-3), and a structural unit T2 having an oxetane group ( (From monomer T2-1) and the proportion of each structural unit was 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transporting Polymer 4>
In a three-neck round bottom flask, the monomer L (5.0 mmol), the monomer B-1 (2.0 mmol), the following monomer T1-4 (2.0 mmol), the monomer T2-1 (2.0 mmol), and anisole. (20 mL) was added, and then the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 4 was synthesized in the same manner as the charge transporting polymer 1. The resulting charge transporting polymer 4 had a number average molecular weight of 14,400 and a weight average molecular weight of 53,100. The charge transporting polymer 4 includes a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-1), a structural unit T1 (derived from the monomer T1-4), and a structural unit T2 having an oxetane group ( (From monomer T2-1) and the proportion of each structural unit was 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transporting Polymer 5>
In a three-neck round bottom flask, the monomer L (5.0 mmol), the monomer B-1 (2.0 mmol), the monomer T2-1 (2.0 mmol), the following monomer T2-2 (2.0 mmol), and anisole. (20 mL) was added, and then the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 5 was synthesized in the same manner as the charge transporting polymer 1. The resulting charge transporting polymer 5 had a number average molecular weight of 14,500 and a weight average molecular weight of 64,000. The charge transporting polymer 5 includes a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-1), a structural unit T2 having an oxetane group (derived from the monomer T2-1), and a benzene structure. It has a structural unit T2 (derived from the monomer T2-2), and the proportion of each structural unit was 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transporting Polymer 6>
In a three-necked round bottom flask, the monomer L (5.0 mmol), the following monomer B-2 (2.0 mmol), the following monomer T1-5 (2.0 mmol), the above monomer T2-1 (2.0 mmol), and anisole. (20 mL) was added, and then the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 6 was synthesized in the same manner as the charge transporting polymer 1. The resulting charge transporting polymer 6 had a number average molecular weight of 20,700 and a weight average molecular weight of 75,600. The charge transporting polymer 6 includes a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-2), a structural unit T1 (derived from the monomer T1-5), and a structural unit T2 having an oxetane group ( (From monomer T2-1) and the proportion of each structural unit was 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transporting Polymer 7>
In a three-neck round bottom flask, the monomer L (5.0 mmol), the monomer B-2 (2.0 mmol), the following monomer T1-6 (2.0 mmol), the monomer T2-1 (2.0 mmol), and anisole. (20 mL) was added, and then the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 7 was synthesized in the same manner as the charge transporting polymer 1. The resulting charge transporting polymer 7 had a number average molecular weight of 1,500 and a weight average molecular weight of 23,200. The charge transporting polymer 7 includes a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-2), a structural unit T1 (derived from the monomer T1-6), and a structural unit T2 having an oxetane group ( (From monomer T2-1) and the proportion of each structural unit was 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transporting Polymer 8>
In a three-neck round bottom flask, the monomer L (5.0 mmol), the monomer B-2 (2.0 mmol), the following monomer T1-7 (2.0 mmol), the monomer T2-1 (2.0 mmol), and anisole. (20 mL) was added, and then the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 8 was synthesized in the same manner as the charge transporting polymer 1. The obtained charge transporting polymer 8 had a number average molecular weight of 11,300 and a weight average molecular weight of 43,900. The charge transporting polymer 8 includes a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-2), a structural unit T1 (derived from the monomer T1-7), and a structural unit T2 having an oxetane group ( (From monomer T2-1) and the proportion of each structural unit was 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transporting Polymer 9>
In a three-neck round bottom flask, the monomer L (5.0 mmol), the monomer B-2 (2.0 mmol), the following monomer T1-8 (2.0 mmol), the monomer T2-1 (2.0 mmol), and anisole. (20 mL) was added, and then the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 9 was synthesized in the same manner as the charge transporting polymer 1. The resulting charge transporting polymer 9 had a number average molecular weight of 15,900 and a weight average molecular weight of 64,400. The charge transporting polymer 9 includes a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-2), a structural unit T1 (derived from the monomer T1-8), and a structural unit T2 having an oxetane group ( (From monomer T2-1) and the proportion of each structural unit was 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transporting Polymer 10>
In a three-neck round bottom flask, the monomer L (5.0 mmol), the monomer B-2 (2.0 mmol), the monomer T2-1 (2.0 mmol), the following monomer T2-3 (2.0 mmol), and anisole. (20 mL) was added, and then the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 10 was synthesized in the same manner as the charge transporting polymer 1. The obtained charge transporting polymer 10 had a number average molecular weight of 14,300 and a weight average molecular weight of 102,600. The charge transporting polymer 10 includes a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-2), a structural unit T2 having an oxetane group (derived from the monomer T2-1), and a benzene structure. It has a structural unit T2 (derived from the monomer T2-3), and the proportion of each structural unit was 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transporting Polymer 11>
In a three-neck round bottom flask, the monomer L (5.0 mmol), the monomer B-2 (2.0 mmol), the monomer T2-1 (2.0 mmol), the following monomer T2-4 (2.0 mmol), and anisole. (20 mL) was added, and then the prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transporting polymer 11 was synthesized in the same manner as the charge transporting polymer 1. The resulting charge transporting polymer 11 had a number average molecular weight of 14,500 and a weight average molecular weight of 53,900. The charge transporting polymer 11 includes a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-2), a structural unit T2 having an oxetane group (derived from the monomer T2-1), and a thiophene structure. It has a structural unit T2 (derived from the monomer T2-4), and the proportion of each structural unit was 45.5%, 18.2%, 18.2%, and 18.2%.

<Preparation 1 of organic EL element>
[Example 1]
Under a nitrogen atmosphere, the charge transporting polymer 1 (10.0 mg), the following electron accepting compound 1 (0.5 mg), and toluene (2.3 mL) were mixed to prepare an ink composition. A glass substrate on which ITO was patterned to have a width of 1.6 mm was spin-coated with the ink composition at a rotation speed of 3,000 min ⁻¹ , and then heated on a hot plate at 220° C. for 10 minutes to be cured to form a hole injection layer. (25 nm) was formed.

The substrate obtained above was transferred into a vacuum evaporator, and α-NPD (40 nm), CBP:Ir(ppy) ₃ (94:6, 30 nm), BAlq (10 nm), TPBi (on the hole injection layer). 30 nm), LiF (0.8 nm), and Al (100 nm) were formed in this order by a vapor deposition method, and sealing treatment was performed to manufacture an organic EL element.

[Example 2]
An organic EL device was produced in the same manner as in Example 1 except that the charge transporting polymer 1 was changed to the charge transporting polymer 2 in the hole injection layer forming step.

[Example 3]
An organic EL device was produced in the same manner as in Example 1 except that the charge transporting polymer 1 was changed to the charge transporting polymer 3 in the hole injection layer forming step.

[Example 4]
An organic EL device was produced in the same manner as in Example 1 except that the charge transporting polymer 1 was changed to the charge transporting polymer 4 in the step of forming the hole injection layer.

[Reference Example 1]
An organic EL device was produced in the same manner as in Example 1 except that the charge transporting polymer 1 was changed to the charge transporting polymer 5 in the hole injection layer forming step.

Table 1 collectively shows the layer structure of the organic EL devices produced in Examples 1 to 4 and Reference Example 1.

When voltage was applied to the organic EL devices obtained in Examples 1 to 4 and Reference Example 1, green light emission was confirmed. For each element, the luminescence was measured lifetime (luminance half-life) in the luminous efficiency, and initial luminance 5,000 cd / ^{m 2} in the emission luminance 1,000 cd / ^{m 2.} The measurement results are shown in Table 2.

As shown in Table 2, by using the organic electronic material according to the embodiment of the present invention for the hole injection layer, a device having high emission efficiency and excellent driving stability and long life was obtained.

<Fabrication of Organic EL Element 2>
[Example 5]
Under a nitrogen atmosphere, the charge transporting polymer 3 (10.0 mg), the following electron accepting compound 2 (0.5 mg), and toluene (2.3 mL) were mixed to prepare an ink composition. A glass substrate on which ITO was patterned to have a width of 1.6 mm was spin-coated with the ink composition at a rotation speed of 3,000 min ⁻¹ , and then heated on a hot plate at 220° C. for 10 minutes to be cured to form a hole injection layer. (25 nm) was formed.

Next, the charge transporting polymer 6 (10.0 mg) and toluene (1.15 mL) were mixed to prepare an ink composition. The ink composition was spin-coated on the hole injection layer formed above at a rotation speed of 3,000 min ⁻¹ , and then heated on a hot plate at 200° C. for 10 minutes to be cured, and then the hole transport layer (40 nm ) Was formed. The hole transport layer could be formed without dissolving the hole injection layer.

The substrate obtained above was transferred into a vacuum vapor deposition machine, and CBP:Ir(ppy) ₃ (94:6, 30 nm), BAlq (10 nm), TPBi (30 nm), LiF (0. 8 nm) and Al (100 nm) were formed in this order by a vapor deposition method, and sealing treatment was performed to produce an organic EL element.

[Example 6]
An organic EL device was produced in the same manner as in Example 5, except that the charge transporting polymer 6 was changed to the charge transporting polymer 7 in the hole transporting layer forming step.

[Example 7]
An organic EL device was produced in the same manner as in Example 5 except that the charge transporting polymer 6 was changed to the charge transporting polymer 8 in the step of forming the hole transporting layer.

[Example 8]
An organic EL device was produced in the same manner as in Example 5 except that the charge transporting polymer 6 was changed to the charge transporting polymer 9 in the step of forming the hole transporting layer.

[Reference Example 2]
An organic EL device was produced in the same manner as in Example 5 except that the charge transporting polymer 6 was changed to the charge transporting polymer 10 in the step of forming the hole transporting layer.

[Reference Example 3]
An organic EL device was produced in the same manner as in Example 5 except that the charge transporting polymer 6 was changed to the charge transporting polymer 11 in the step of forming the hole transporting layer.

Table 3 collectively shows the layer structure of the organic EL devices produced in Examples 5 to 8 and Reference Examples 2 and 3.

When voltage was applied to the organic EL devices obtained in Examples 5 to 8 and Reference Examples 2 and 3, green light emission was confirmed. For each element, the luminescence was measured lifetime (luminance half-life) in the luminous efficiency, and initial luminance 5,000 cd / ^{m 2} in the emission luminance 1,000 cd / ^{m 2.} The measurement results are shown in Table 4.

As shown in Table 4, by using the organic electronic material of the present invention for the hole transport layer, a long-life device having high luminous efficiency and excellent driving stability was obtained.

<Production of white organic EL element (illumination device)>
[Example 9]
Under a nitrogen atmosphere, the charge transporting polymer 3 (10.0 mg), the electron accepting compound 2 (0.5 mg), and toluene (2.3 mL) were mixed to prepare an ink composition. A glass substrate on which ITO was patterned to have a width of 1.6 mm was spin-coated with the ink composition at a rotation speed of 3,000 min ⁻¹ , and then heated on a hot plate at 220° C. for 10 minutes to be cured to form a hole injection layer. (25 nm) was formed.

Next, the charge transporting polymer 9 (20 mg) and toluene (1.15 mL) were mixed to prepare an ink composition. The ink composition was spin-coated on the hole-injection layer at a rotation speed of 3,000 min ⁻¹ and then heated on a hot plate at 200° C. for 10 minutes to be cured to form a hole-transport layer (40 nm). .. The hole transport layer could be formed without dissolving the hole injection layer.

Then, in nitrogen, CDBP (15 mg), FIr(pic) (0.9 mg), Ir(ppy) ₃ (0.9 mg), (btp) ₂ Ir(acac) (1.2 mg), and dichlorobenzene ( 0.5 mL) was mixed to prepare an ink composition. The ink composition was spin-coated at a rotation speed of 3,000 min ⁻¹ , heated on a hot plate at 80° C. for 5 minutes and dried to form a light emitting layer (40 nm). The light emitting layer could be formed without dissolving the hole transport layer.

The glass substrate was transferred into a vacuum vapor deposition machine, and BAlq (10 nm), TPBi (30 nm), LiF (0.5 nm), and Al (100 nm) were sequentially deposited on the light emitting layer by a vapor deposition method. Then, a sealing treatment was performed to produce a white organic EL element. The white organic EL element could be used as a lighting device.

[Reference Example 4]
A white organic EL device was produced in the same manner as in Example 9 except that the charge transporting polymer 9 was changed to the charge transporting polymer 10. The light emitting layer could be formed without dissolving the hole transport layer. The white organic EL element could be used as a lighting device.

A voltage was applied to the white organic EL devices obtained in Example 9 and Reference Example 4, and the emission lifetime (luminance half-life) was measured with an initial luminance of 1,000 cd/m ² . Assuming that the light emission lifetime in Example 9 was 1, it was 0.23 in Reference Example 4. Further, when the voltage at the luminance of 1,000 cd/m ² in Example 9 is 1, it was 1.09 in Reference Example 4.

The white organic EL device of Example 9 exhibited excellent light emission life and driving voltage.

The effects of the embodiment of the present invention have been shown by using the examples. In addition to the charge transporting polymer used in the examples, it is possible to obtain an organic EL device having a long life by using the charge transporting polymer described above, and the same excellent effect is exhibited.

1 Light-Emitting Layer 2 Anode 3 Hole Injection Layer 4 Cathode 5 Electron Injection Layer 6 Hole Transport Layer 7 Electron Transport Layer 8 Substrate

Claims (17)

Containing a charge-transporting polymer having at least one terminal a structural unit containing 7 or more sp ² carbons, 2 or more aromatic rings, and 3 or more benzene rings adjacent to each other and not containing a condensed ring Then
The charge-transporting polymer further possess the divalent structural units having charge transportability, and a polymerizable functional group,
The charge transporting polymer has 3 or more ends,
The charge-transporting polymer, the structural unit is perforated 25% or more of the terminal based on the number of all the terminal, organic electronics materials. Containing a charge-transporting polymer having at least one terminal a structural unit containing 7 or more sp ² carbons, 2 or more aromatic rings, and 3 or more benzene rings adjacent to each other and not containing a condensed ring Then
The charge transporting polymer further has a divalent structural unit having a charge transporting property and a polymerizable functional group,
The charge-transporting polymer has three or more terminal, organic electronic materials. Containing a charge-transporting polymer having at least one terminal a structural unit containing 7 or more sp ² carbons, 2 or more aromatic rings, and 3 or more benzene rings adjacent to each other and not containing a condensed ring Then
The charge transporting polymer further has a divalent structural unit having a charge transporting property and a polymerizable functional group,
The charge-transporting polymer has the structural unit, 25% or more of the terminal based on the number of all the terminal, organic electronic materials. The organic electronic material according to claim 1, wherein the structural unit contains 2 to 6 aromatic rings. Containing a charge-transporting polymer having at least one terminal a structural unit containing 7 or more sp ² carbons, 2 or more aromatic rings, and 3 or more benzene rings adjacent to each other and not containing a condensed ring Then
The charge transporting polymer further has a divalent structural unit having a charge transporting property and a polymerizable functional group,
The structural unit is a naphthalene structure, acenaphthylene structure, fluorene structure, spirobifluorene structure, carbazole structure, acridine structure, xanthene structure, dibenzofuran structure, indole structure, isoindole structure, benzimidazole structure, quinoline structure, isoquinoline structure, quinoxaline structure. comprises at least one selected terphenyl structure, and from the group consisting of tetraphenyl ethylene structure, organic electronic materials. The structural unit contains 7 or more sp ² carbons, has 2 or more aromatic rings, and has 3 benzene rings.
The organic electronic material according to any one of claims 1 to 5, which is formed by a monomer that does not include a condensed ring in which one or more are adjacently condensed. The organic electronic material according to claim 6, wherein the charge transporting polymer is a polymer of a monomer containing at least the monomer and a monomer containing a structural unit having a hole transporting property. The divalent structural unit having a charge-transporting property is a substituted or unsubstituted aromatic amine structure, a substituted or unsubstituted carbazole structure, a substituted or unsubstituted thiophene structure, a substituted or unsubstituted fluorene structure, a substituted or non-substituted Substituted benzene structure, substituted or unsubstituted biphenylene structure, substituted or unsubstituted terphenylene structure, substituted or unsubstituted naphthalene structure, substituted or unsubstituted anthracene structure, substituted or unsubstituted tetracene structure, substituted or unsubstituted Phenanthrene structure, substituted or unsubstituted dihydrophenanthrene structure, substituted or unsubstituted pyridine structure, substituted or unsubstituted pyrazine structure, substituted or unsubstituted quinoline structure, substituted or unsubstituted isoquinoline structure, substituted or unsubstituted Quinoxaline structure, substituted or unsubstituted acridine structure, substituted or unsubstituted diazaphenanthrene structure, substituted or unsubstituted furan structure, substituted or unsubstituted pyrrole structure, substituted or unsubstituted oxazole structure, substituted or unsubstituted Oxadiazole structure, substituted or unsubstituted thiazole structure, substituted or unsubstituted thiadiazole structure, substituted or unsubstituted triazole structure, substituted or unsubstituted benzothiophene structure, substituted or unsubstituted benzoxazole structure, substituted or non-substituted A substituted benzoxadiazole structure, a substituted or unsubstituted benzothiazole structure, a substituted or unsubstituted benzothiadiazole structure, a substituted or unsubstituted benzotriazole structure, and a structure containing one or more of these The organic electronic material according to claim 1, which is a structural unit selected from the group. An ink composition containing the organic electronic material according to claim 1 and a solvent. An organic layer formed by using the organic electronic material according to claim 1 or the ink composition according to claim 9. An organic electronic device comprising at least one organic layer according to claim 10. An organic electroluminescent device comprising at least one organic layer according to claim 10. The organic electroluminescent device according to claim 12, further comprising a flexible substrate. The organic electroluminescence device according to claim 12, further comprising a resin film substrate. A display device comprising the organic electroluminescence device according to claim 12. A lighting device comprising the organic electroluminescent element according to claim 12. A display device comprising: the lighting device according to claim 16; and a liquid crystal element as display means.

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