JP6536809B2 - 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 device, an organic electroluminescent device (also referred to as “organic EL device”), a display device, a lighting device, and a display device.

  Organic EL devices are attracting attention as large-area solid-state light source applications, for example, as alternatives to incandescent lamps, gas-filled lamps and the like. In addition, it is attracting attention as a leading self-luminous display to replace liquid crystal displays (LCDs) in the flat panel display (FPD) field, and its commercialization is in progress.

  Organic EL elements are roughly classified into low molecular weight organic EL elements and high molecular weight organic EL elements from the organic materials used. In a high molecular weight organic EL device, a high molecular weight compound is used as an organic material, and in a low molecular weight organic EL device, a low molecular weight compound is used. On the other hand, the method of manufacturing an 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, plateless printing such as inkjet It is divided roughly into two. Since simple film formation is possible, a wet process is expected as an essential method for future large screen organic EL displays (see, for example, Patent Document 1 and Non-Patent Document 1).

Unexamined-Japanese-Patent No. 2006-279007

Kensuke Hirose, Daisuke Kumaki, Nobuaki Koike, Kei Kuriyama, Seiichiro Ikehata, Shizutoshi Tokito, The 53rd Joint Conference on Applied Physics, 26p-ZK-4 (2006)

  The organic EL element produced using a wet process has the feature that cost reduction and area enlargement are easy. However, regarding the characteristics of the organic EL element, further improvement is desired in the organic EL element including the organic layer produced using a wet process.

  In view of the above, embodiments of the present invention aim to provide an organic electronic material and an ink composition suitable for a wet process and for improving the life characteristics of an organic electronic device. Another object of the present invention is to provide an organic layer suitable for improving the life characteristics of an organic electronic device. Furthermore, another embodiment of the present invention aims to provide an organic electronic device, an organic EL device, a display device, 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, an embodiment of the present invention is an organic electronic material containing a charge transportable polymer, wherein the charge transportable polymer has a cyclic site which is unsubstituted or has a substituent at at least one end. And the cyclic moiety which is unsubstituted or has a substituent contains 7 or more of sp ² carbons, has 2 or more of aromatic rings, and includes a fused ring in which three or more benzene rings are adjacently condensed Not related to organic electronics materials.

  In one embodiment, the charge transporting polymer has three or more ends. Preferably, the charge transporting polymer has the cyclic site at 25% or more of the ends based on the total number of ends.

  In one embodiment, the unsubstituted or substituted cyclic moiety contains 2 to 6 aromatic rings. Preferably, the unsubstituted or substituted cyclic moiety is unsubstituted or has a substituent, naphthalene moiety, acenaphthylene moiety, fluorene moiety, spirobifluorene moiety, carbazole moiety, acridine moiety, xanthene It is selected from the group consisting of a site, a dibenzofuran site, an indole site, an isoindole site, a benzimidazole site, a quinoline site, an isoquinoline site, a quinoxaline site, a diphenylbenzene site, and a triphenylethenylbenzene site.

  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 of the organic electronic materials described above and a solvent.

  In addition, another embodiment of the present invention relates to an organic layer formed using any of the above-mentioned organic electronic materials or the above-mentioned ink composition.

  In addition, another embodiment of the present invention relates to an organic electronic device and an organic electroluminescent device 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.

  Furthermore, another embodiment of the present invention relates to a display device and a lighting device provided with any one of the organic electroluminescent devices, and a display device provided with the lighting device and a liquid crystal device as a display means.

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

Embodiments of the present invention will be described.
<Organic electronics materials>
The organic electronic material which is an embodiment of the present invention contains a charge transporting polymer. The charge transporting polymer has a cyclic moiety which is unsubstituted or has a substituent at at least one end, and the cyclic moiety which is unsubstituted or has a substituent contains 7 or more sp ² carbons And having two or more aromatic rings and not including a fused ring in which three or more benzene rings are condensed adjacent to each other (hereinafter, the cyclic portion is also simply referred to as a “cyclic portion”). The organic electronic material may contain only one type of charge transporting polymer, or may contain two or more types. The charge transporting polymer is preferable in that the film forming property in the wet process is excellent as compared with the low molecular weight compound.

[Charge transporting polymer]
Charge transport polymers have the ability to transport charge. Holes are preferred as the charge to be transported. The polymer chain of the charge transporting polymer contains structural units having the ability to transport the charge. 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, for example, the block property It may be a carried random copolymer. In one embodiment, the structural unit means a monomeric unit. Examples of structural units having the ability to transport charges include structural units 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 "end" refers to the end of the polymer chain. The charge transporting polymer has a cyclic site at at least one end.

(Cyclic part)
The charge transporting polymer has “a cyclic site which is unsubstituted or has a substituent” at at least one end. The “unsubstituted or substituted cyclic moiety” contains 7 or more sp ² carbons, has 2 or more aromatic rings, and does not contain a fused ring in which three or more benzene rings are condensed adjacently . The charge transporting polymer may have only one type of cyclic moiety or may have two or more types of cyclic moieties. The charge transporting polymer is considered to improve the electron transportability by including a cyclic site at the end. In particular, when the charge transportable polymer has a structural unit having hole transportability and a cyclic site at the end, the charge transportable polymer has stability against electrons while maintaining the hole transportability. It is thought that as a result, high performance as an organic electronic material can be exhibited to improve.

  The cyclic moiety may be substituted or unsubstituted. Examples of the substituent include alkyl, alkenyl, alkoxy, phenyl, phenyl-substituted alkyl, phenyl-substituted alkenyl, and phenyl-containing substituents such as phenyl-substituted alkoxy. Be The carbon number of the alkyl group, the alkenyl group and the alkoxy group is preferably 1 to 20, more preferably 1 to 15, and further preferably 1 to 10. The alkyl group, the alkenyl group and the alkoxy group may be linear, branched or cyclic. When it has a substituent, a substituent containing an alkyl group and a phenyl group is preferable from the viewpoint of excellent solubility, stability and the like or from the viewpoint of improving the characteristics. The number of substituents is one or more, and two or more substituents may be combined with each other to form a ring.

“Contains 7 or more sp ² carbons” means that among carbon atoms contained in the cyclic moiety, 7 or more carbon atoms have sp ² hybrid orbitals. If the annular portion has a substituent, including the number of sp ² carbon of the aromatic ring contained in the substituent, sp ² number of carbons may be at 7 or more. If the number of sp ² carbons contained in the cyclic portion is less than 7, the effect of improving the life characteristics can not be obtained. The number of sp ² carbons is preferably 10 or more, 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 still more preferably 30 or less from the viewpoint of preventing formation of a rigid skeleton and enhancing solubility. .

  The cyclic portion which is unsubstituted or has a substituent contains two or more aromatic rings. The "aromatic ring" as used herein refers to one ring exhibiting aromaticity. When the cyclic moiety has a substituent, the number of aromatic rings may be two or more, including the number of aromatic rings contained in the substituent. The number of aromatic rings is preferably 3 or more. Examples of the "aromatic ring" include benzene ring, pyridine ring, pyrrole ring, furan ring, imidazole ring, pyrazole ring, oxazole ring, pyrazine ring, pyrimidine ring, pyridazine ring, phosphole ring and the like. From the viewpoint of enhancing the life characteristics, it is preferably a benzene ring. When the cyclic moiety contains two or more benzene rings, the luminous efficiency and the luminous life tend to be improved as compared to the case where the cyclic site does not contain a benzene ring or the case where only one benzene ring is contained.

  The number of aromatic rings is preferably 8 or less, more preferably 7 or less, and still more preferably 6 or less, from the viewpoint of maintaining good hole transportability. If the number of aromatic rings is one, the effect of improving the life characteristics can not be obtained.

  Two or more aromatic rings may contain fused rings fused to one another or may contain a single ring. Examples of the two or more aromatic rings include a fused ring which is unsubstituted; a fused ring which has a substituent; and a single ring which has a substituent including a phenyl group. However, a fused ring (eg, anthracene, phenanthrene, pyrene, perylene, etc.) in which three or more benzene rings are condensed adjacent to each other in a cyclic portion is not included. If a fused ring in which three or more benzene rings are fused adjacently is contained, good performance can not be obtained because a low energy level is locally generated by the conjugated system.

  In a preferred embodiment, the cyclic moiety is selected from fused rings that are unsubstituted or have substituents. The fused ring is preferably a naphthalene site, acenaphthylene site, fluorene site, spirobifluorene site, carbazole site, carboline site, acridine site, carbazine site, indenocarbazole site, indolocarbazole site, xanthene site, dibenzofuran site, fluorenone It is selected from the group consisting of an anthraquinone site, a cyanthrene site, a dibenzothiophene site, an indole site, an isoindole site, a benzimidazole site, a quinoline site, an isoquinoline site, and a quinoxaline site, more preferably a naphthalene site, acenaphthylene site, fluorene Site, spirobifluorene site, carbazole site, acridine site, xanthene site, dibenzofuran site, indole site, isoindole site, Down zone imidazole sites, quinoline site is selected isoquinoline site, and from the group consisting of quinoxaline site. The fused ring is more preferably a naphthalene moiety, a fluorene moiety, a spirobifluorene moiety, a carbazole moiety, an acridine moiety, and a dibenzofuran from the viewpoint that it is easy to obtain excellent durability although it is not particularly limited. It is selected from the group consisting of sites.

  In another preferred embodiment, the cyclic moiety is selected from a single ring having a substituent comprising a phenyl group. As a substituent containing a phenyl group, a phenyl group and a phenyl substituted alkenyl group are preferable. Preferably, a single ring having a substituent containing a phenyl group is selected from a phenylbenzene site, a diphenylbenzene site (o-diphenylbenzene site, m-diphenylbenzene site, p-diphenylbenzene site), and a triphenylethenylbenzene site Are selected from the group consisting of Although not particularly limited, the cyclic moiety is more preferably a diphenylbenzene moiety (o-diphenylbenzene moiety, m-diphenylbenzene moiety, p-diphenyl moiety, from the viewpoint that it is easy to obtain excellent durability. It is selected from the group consisting of benzene site) and triphenylethenylbenzene site.

  According to one embodiment, the cyclic site preferably has a fused 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, from the viewpoint of obtaining excellent luminous efficiency and luminous lifetime, the cyclic moiety has a benzene ring having a substituent containing a phenyl group such as diphenylbenzene or triphenylethenylbenzene. Is preferred.

As a cyclic | annular site | part, the following cyclic | annular site | part t1 is mentioned, for example.
<Circular part t1>

In the formula, Ar ¹ represents a fused ring or monocyclic ring that is unsubstituted or has a substituent, and the fused ring or monocyclic ring that is unsubstituted or has a substituent has 7 or more sp ² carbon atoms And has a structure having two or more aromatic rings and no fused ring in which three or more benzene rings are adjacently fused. Examples of the substituent include an alkyl group; an alkenyl group; an alkoxy group; a substituent containing a phenyl group such as a phenyl group, a phenyl-substituted alkyl group, a phenyl-substituted alkenyl group, and a phenyl-substituted alkoxy group.

Preferred specific examples of the cyclic moiety are listed below.

(Other end sites)
In one embodiment, the charge transporting polymer has at a terminal a site other than the cyclic site (hereinafter, the site is also referred to as “other terminal site”). The charge transporting polymer may have only one type of other terminal site or may have two or more types. Other terminal sites are not particularly limited. For example, a portion having an aromatic hydrocarbon structure or an aromatic heterocyclic structure can be mentioned. Examples of the site having an aromatic hydrocarbon structure or an aromatic heterocyclic structure include the terminal site t2 shown below. The end site t2 is different from the cyclic site t1.

<End site t2>

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

  From the viewpoint of improving the properties of the organic electronic device, the proportion of the “cyclic moiety” at all the ends of the charge transporting polymer is 25 mol% or more, more preferably 30 mol% or more, still more preferably 35 mol based on the total number of terminals. % Or more. The upper limit is not particularly limited, and is 100 mol% or less.

  When the charge transporting polymer has “other end site” at the end, the proportion of “other end site” at all ends is preferably 75 based on the total number of ends from the viewpoint of improving the characteristics of the organic electronic device. It is at most mol%, more preferably at most 70 mol%, further preferably at most 65 mol%. The lower limit is not particularly limited, but can be, for example, 5 mol% or more in consideration of introduction of a polymerizable functional group described later, introduction of a substituent for improving film forming properties, wettability, and the like.

The proportions of "cyclic site" and "other terminal site" may be determined using the amounts of the monomer having a cyclic site and the monomer having a site other than a cyclic site, which were used to synthesize the charge transport polymer. it can. In addition, the proportions of the “cyclic site” and the “other terminal site” can be calculated as an average value by using the integral value of the spectrum derived from each site in the ¹ H NMR spectrum of the charge transporting polymer. In the case where the preparation amount is clear, it is preferable to adopt a value determined using the preparation amount because it is simple.

(Construction)
The charge transporting polymer preferably includes at least a divalent structural unit L having charge transportability, and more preferably a divalent structural unit L having charge transportability and a monovalent structural unit T constituting an end portion. including. The charge transporting polymer may further include a trivalent or more structural unit B constituting a branch. The structural unit T includes at least a structural unit having a cyclic site (the structural unit is also referred to as “structural unit T1”). The charge transporting polymer may contain only one type of each structural unit, or may contain multiple types of each. In the charge transporting polymer, each structural unit is bonded to each other at a “monovalent” to “trivalent or higher” bonding site.

  The following is mentioned as an example of the partial structure contained in a charge transportable polymer. The charge transporting polymer is not limited to the polymer having the following partial structure. In the partial structure, “L” represents a structural unit L, “T” represents a structural unit T, and “B” represents a structural unit B. "*" Represents a binding site to another structural unit. In the following partial structures, a plurality of L may be the same structural unit as one another or structural units different from one another. The same applies to T and B.

Linear charge transporting polymer

Charge transporting polymer having branched structure

(Structural unit L)
The structural unit L is a divalent structural unit having charge transportability. The structural unit L should just contain the atomic group which has the ability to transport an electric charge, and it is not specifically limited. For example, the structural unit L may be substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, biphenylene structure, terphenylene structure, naphthalene structure, anthracene structure, anthracene structure, tetracene structure, phenanthrene structure, dihydro 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 Thiophene structure, benzoxazole structure, benzoxadiazole structure, benzothiazole structure, benzothiadiazole structure, benzotriazole structure, and one of these or It is selected from a structure including more species. 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, a carbazole structure, a thiophene structure, a fluorene structure, a benzene structure, a pyrrole structure, and these, from the viewpoint of obtaining excellent hole transportability. It is preferable to be selected from the structure containing one or two or more kinds, and selected from a substituted or unsubstituted aromatic amine structure, a carbazole structure, and a structure containing one or more of them. Is more preferred. 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 them, from the viewpoint of obtaining excellent electron transportability. It is preferable to select from the structure containing a species or more.

As specific examples of the structural unit L, the following may be mentioned. The structural unit L is not limited to the following.

Each R independently represents a hydrogen atom or a substituent. Preferably, R's each independently represent -R ¹ , -OR ² , -SR ³ , -OCOR ⁴ , -COOR ⁵ , -SiR ⁶ R ⁷ R ⁸ , a halogen atom, and a polymerizable functional group described later It is 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 or heteroaryl group having 2 to 30 carbon atoms. The alkyl group may be further substituted by an aryl group or heteroaryl group having 2 to 20 carbon atoms, and the aryl group or heteroaryl group is further preferably a linear, cyclic or branched group having 1 to 22 carbon atoms. It may be substituted by 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 heteroarylene group having 2 to 30 carbon atoms. Ar is preferably an arylene group, more preferably a phenylene group.

  In the present specification, an 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. An 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 2 hydrogen atoms from an aromatic heterocycle. The aromatic hydrocarbon includes a single ring, a condensed ring, or a polycyclic ring in which two or more selected from a single ring and a condensed ring are bonded via a single bond. The aromatic heterocyclic ring includes a single ring, a condensed ring, or a polycyclic ring in which two or more selected from a single ring and a condensed ring are bonded via a single bond.

(Structural unit T)
The structural unit T is a monovalent structural unit constituting an end 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 structural unit T includes at least a structural unit having a cyclic site (the structural unit is also referred to as “structural unit T1”).

The following structural unit t1 is mentioned as a specific example of structural unit T1. Structural unit T1 is not limited to the following.
<Structural unit t1>

In the formula, T ¹ represents a “cyclic site”, preferably a cyclic site t 1. Ar represents an arylene group or heteroarylene group having 2 to 30 carbon atoms, and n represents 0 or 1.

  In one embodiment, the charge transporting polymer has a structural unit other than the structural unit T1 (hereinafter, the structural unit is also referred to as “structural unit T2”) at the end. 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, structural units having an aromatic hydrocarbon structure or an aromatic heterocyclic structure can be mentioned. Examples of structural units having an aromatic hydrocarbon structure or aromatic heterocyclic structure include structural units t2 shown below. The structural unit t2 has a structure different from that of the structural unit t1.

<Structural unit t2>

Wherein, T ² represents the "other-end portion", preferably an end portion t2. Ar represents an arylene group or heteroarylene group having 2 to 30 carbon atoms, and n represents 0 or 1.

(Structural unit B)
The structural unit B is a trivalent or higher structural unit constituting a branched portion when the charge transporting polymer has a branched structure. The structural unit B is preferably hexavalent or less, more preferably trivalent or tetravalent, from the viewpoint of improving the durability of the organic electronic device. The structural unit B is preferably a unit having charge transportability. For example, the structural unit B may be a substituted or unsubstituted aromatic amine structure, a carbazole structure, a fused polycyclic aromatic hydrocarbon structure, and one or two of them from the viewpoint of improving the durability of the organic electronic device. It is selected from structures containing more than 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 a different structure. You may have.

The following may be mentioned as specific examples of the structural unit B. 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 each independently represents a divalent linking group, and for example, each independently represents 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, from R in the structural unit L (with the exception of the group containing a polymerizable functional group), a group having one or more hydrogen atoms, and one more hydrogen atom And divalent groups other than. Z represents either 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, an arenetriyl group is a group of aromatic hydrocarbons with three hydrogen atoms removed. The heteroarene triyl 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 curing by polymerization reaction and changing the solubility in a solvent. The "polymerizable functional group" refers to a functional group that can form a bond with each other by the addition of 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, a vinyloxy group, a vinylamino group etc., a group having a small ring (eg, a cyclic alkyl group such as a cyclopropyl group, a cyclobutyl group etc .; a cyclic ether group such as an epoxy group (oxiranyl group), an oxetane group (oxetanyl group) A diketene group; an episulfide group; a lactone group; a lactam group etc., a heterocyclic group (for example, a furan-yl group, a pyrrol-yl group, a thiophene-yl group, a silole-yl group) and the like. Especially as a polymerizable functional group, a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group, and an oxetane group are preferable, and a vinyl group, an oxetane group, or an epoxy group is more preferable from the viewpoint of the reactivity and the characteristic of an organic electronic device. preferable.

  From the viewpoint of increasing the degree of freedom of the polymerizable functional group and facilitating the generation of the polymerization reaction, it is preferable that the main skeleton of the charge transporting polymer and the polymerizable functional group be linked by an alkylene chain. Also, 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 linked by a hydrophilic chain such as ethylene glycol chain or diethylene glycol chain. preferable. Furthermore, from the viewpoint of facilitating the preparation of the monomer used to introduce the polymerizable functional group, the charge transporting polymer is preferably polymerized with the end of the alkylene chain and / or the hydrophilic chain, ie, these chains The bond with the sexual functional group and / or the bond between these chain and the skeleton of the charge transport polymer may have an ether bond or an ester bond. The aforementioned “group containing a polymerizable functional group” means a polymerizable functional group itself or a group obtained by combining a polymerizable functional group with an alkylene chain or the like. As a group containing a polymerizable functional group, for example, groups exemplified in WO 2010/140553 can be suitably used.

  The polymerizable functional group may be introduced into the terminal portion (that is, the structural unit T) of the charge transporting polymer, or may be introduced into a portion other than the terminal portion (that is, the structural unit L or B). And may be introduced into both the non-terminal part. From the viewpoint of curability, it is preferably introduced to at least the terminal part, and from the viewpoint of achieving both curability and charge transportability, it is preferably introduced to only the terminal part. 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

  The polymerizable functional group is preferably contained in large amounts in the charge transporting polymer from the viewpoint of contributing to the change in solubility. On the other hand, from the viewpoint of not interfering with the charge transportability, it is preferable that the amount contained in the charge transportable polymer is 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 charge transporting polymer is preferably 2 or more, and more preferably 3 or more from the viewpoint of obtaining 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 charge transportable polymer is the charge of the polymerizable functional group used to synthesize the charge transport polymer (for example, the charge of the monomer having the polymerizable functional group), each structure It can be determined as an average value using the charged amount of the monomer corresponding to the unit, the weight average molecular weight of the charge transporting polymer, etc. Further, 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 the entire spectrum, charge transporting polymer It can be calculated as an average value using the weight average molecular weight and the like of In the case where the preparation amount is clear, it is preferable to adopt a value determined using the preparation amount because it is simple.

(Proportion of structural unit)
From the viewpoint of obtaining sufficient charge transportability, 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 more preferably 30 mol% or more, based on all structural units. Is more preferred. Further, the ratio of the structural unit L is preferably 95 mol% or less, more preferably 90 mol% or less, and still more preferably 85 mol% or less, in consideration of the structural unit T and the structural unit B introduced as necessary.

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

  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. Preferably, 10 mol% or more is more preferable. Further, the proportion of the structural unit B is preferably 50 mol% or less, and 40 mol% or less, from the viewpoint of suppressing the increase in viscosity and performing synthesis of the charge transporting polymer favorably, or from the viewpoint of obtaining sufficient charge transporting properties. Is more preferable, and 30 mol% or less is more 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 still more preferable. The ratio of the polymerizable functional group is preferably 70 mol% or less, more preferably 60 mol% or less, and still more preferably 50 mol% or less from the viewpoint of obtaining good charge transportability. In addition, "the ratio of a polymerizable functional group" here means the ratio of the structural unit which has a 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 contains 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. Preferably, 100: 20 to 180: 20 to 90 are more preferable, and 100: 40 to 160: 30 to 80 are more preferable.

The proportion of structural units can be determined using the amount of monomer corresponding to each structural unit used to synthesize the charge transporting polymer. The proportion of structural units can be calculated as an average value using the integral value of the spectrum derived from each structural unit in the ¹ H NMR spectrum of the charge transporting polymer. In the case where the preparation amount is clear, it is preferable to adopt a value determined using the preparation amount because it is simple.

  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 high hole injection property, hole transport property, etc. It is preferably a compound. The charge transporting polymer is preferably a compound having at least two or more polymerizable functional groups, from the viewpoint of facilitating the formation of a multilayer.

(Number average molecular weight)
The number average molecular weight of the charge transporting polymer can be appropriately adjusted in consideration of the solubility in a solvent, the 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 still more preferably 2,000 or more. The number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, 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 the solubility in a solvent, the film forming property and the like. The weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, and still more preferably 10,000 or more from the viewpoint of excellent charge transportability. The weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, 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 synthesis methods and is not particularly limited. A cyclic site may be introduced into a known charge transporting polymer. Examples of the synthesis method include methods using known coupling reactions such as Suzuki coupling, Negishi coupling, Sonogashira coupling, still coupling, Buchwald-Heartwig coupling and the like. Suzuki coupling causes a Pd-catalyzed cross coupling reaction to occur 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.

  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. Alternatively, a catalyst species generated by mixing tris (dibenzylideneacetone) dipalladium (0), palladium (II) acetate or the like as a precursor with a phosphine ligand can also be used. For the synthesis method of the charge transporting polymer, for example, the description of WO 2010/140553 can be referred to.

As a monomer which can be used for a Suzuki coupling reaction, the following is mentioned, for example.
<Monomer L>

<Monomer T1>

<Monomer T2>

<Monomer B>

In the formula, L represents a structural unit L, T ¹ represents a “cyclic site”, T ² represents an “other end site”, B represents a structural unit B, Ar has 2 to 30 carbon atoms And arylene group or heteroarylene group, and n represents 0 or 1. R ^{1 to} R ⁴ each represent a functional group capable of forming a bond with each other, and preferably each independently 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 that can exhibit a doping effect by being added to the organic electronic material and can improve charge transportability. For doping, there are p-type doping and n-type doping, and in p-type doping, a substance that functions as an electron acceptor is used as a dopant, and in n-type doping, a substance that functions as an electron donor as a dopant is used. It is preferable to perform p-type doping to improve hole transportability and n-type doping to improve electron transportability. The dopant used for the organic electronic material may be a dopant that exerts any effect of p-type doping or n-type doping. Also, one dopant may be added alone, or a plurality 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, as a Lewis acid, FeCl ₃ , PF ₅ , AsF ₅ , SfF ₅ , BF ₅ , BCl ₃ , BBr ₃ etc .; As a protonic acid, HF, HCl, HBr, HNO ₅ , H ₂ SO ₄ , Inorganic acids 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 camphor sulfonic acid; transition metal compounds such as FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , AlCl ₃ , NbCl ₅ , TaCl ₅ , MoF ₅ ; ionic compounds such as tetrakis (pentafluoro acid) Phenyl) borate ion, tris (trifluoro) Methanesulfonyl) Mechidoion, bis (trifluoromethanesulfonyl) imide ion, hexafluoroantimonate ion, AsF ₆ ^- (hexafluoro arsenic acid ions), BF ₄ ^- (tetrafluoroborate), PF ₆ ^- (hexafluorophosphate) Salts with perfluorinated anions, salts with conjugated bases of the above-mentioned protonic acids as anions, etc .; halogen compounds such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr, IF etc .; π-conjugated compounds Examples of TC include TCNE (tetracyanoethylene), TCNQ (tetracyanoquinodimethane), and the like. Moreover, it is also possible to use the electron-accepting compound as described in JP-A-2000-36390, JP-A-2005-75948, JP-A-2003-213002, and the like. Preferred are Lewis acids, ionic compounds, π-conjugated compounds and the like.

The dopant used for n-type doping is an electron donative compound, for example, alkali metals such as Li and Cs; alkaline earth metals such as Mg and Ca; alkali metals such as LiF and Cs ₂ CO ₃ and / or Examples thereof include salts of alkaline earth metals; metal complexes; and 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 weight 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 good charge transporting properties. preferable. It is also possible to make it 100 mass%.

  When the dopant is contained, the content thereof is preferably 0.01% by mass or more with respect to the total mass of the organic electronic material from the viewpoint of improving the charge transportability of the organic electronic material, and 0.1% by mass or more More preferably, 0.5 mass% or more is more preferable. Moreover, from a viewpoint of keeping film-forming property favorable, 50 mass% or less is preferable with respect to the total mass of organic electronics material, 30 mass% or less is more preferable, 20 mass% or less is still more preferable.

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

[solvent]
As the solvent, water, an organic solvent, or a mixed solvent thereof can be used. 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; 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, 2,4-dimethylanisole; ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate Aliphatic esters of: phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate, and other aromatic esters; N, N-dimethylformamide, N, N-dimethylacetamide, etc. Amide solvents; 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 the function as a dopant and the function as a polymerization initiator. Such substances include, for example, the aforementioned 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 reduction inhibitor, an oxidizing agent, a reducing agent, a surface modifier, an emulsifier, an antifoamer, Dispersants, surfactants and the like can be mentioned.

[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, and more preferably 0.2% by mass or more. More preferably, In addition, 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 still more preferably 10% by mass or less .

<Organic layer>
The organic layer which is an embodiment of the present invention is a layer formed using the organic electronic material or the ink composition of the embodiment. By using the ink composition, an organic layer can be favorably formed by a coating method. Coating methods include, for example, spin coating method; cast method; immersion method; plate printing method such as letterpress printing, intaglio printing, offset printing, lithographic printing, letterpress reverse offset printing, screen printing, gravure printing, etc .; Known methods such as plateless printing can be mentioned. When forming an organic layer by the apply | coating method, the organic layer (application layer) obtained after application may be dried using a hotplate or oven, and a solvent may be removed.

  When the charge transporting polymer has a polymerizable functional group, the polymerization reaction of the charge transporting polymer can be advanced by light irradiation, heat treatment or the like to change the solubility of the organic layer. By laminating the organic layer whose solubility is changed, it is possible to easily make the organic electronic device multilayer. For the method of forming the organic layer, for example, the description of International Publication WO 2010/140553 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 still more preferably 3 nm or more, from the viewpoint of improving the charge transport efficiency. The thickness of the organic layer is preferably 300 nm or less, more preferably 200 nm or less, and still more preferably 100 nm or less, from the viewpoint of reducing the electrical resistance.

<Organic electronics device>
The organic electronic device which is an embodiment of the present invention has at least the organic layer of the above-mentioned embodiment. As an organic electronics element, an organic EL element, an organic photoelectric conversion element, an organic transistor etc. are mentioned, for example. The organic electronic device preferably has a structure in which an organic layer is disposed between at least a pair of electrodes.

[Organic EL element]
The organic EL element which is embodiment of this invention has the organic layer of the said embodiment at least. The organic EL device generally comprises a light emitting layer, an anode, a cathode, and a substrate, and as necessary, other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, an electron transport layer, etc. Have. Each layer may be formed by a vapor deposition method or may be formed by 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 still more preferably as at least one of a hole injection layer and a hole transport layer.

  FIG. 1 is a schematic cross-sectional view showing an embodiment of the organic EL element. The organic EL device of FIG. 1 is a device having a multilayer structure, and includes a substrate 8, an anode 2, a hole injection layer 3 and a hole transport layer 6 consisting of the organic layer of the 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.

[Emitting layer]
As materials used for the light emitting layer, light emitting materials such as low molecular weight compounds, polymers, and dendrimers can be used. The polymer is preferable because it has high solubility in a solvent and is suitable for a coating method. As the light emitting material, a fluorescent material, a phosphorescent material, a heat activated delayed fluorescent material (TADF) and the like can be mentioned.

  Fluorescent materials such as perylene, coumarin, rubrene, quinacdoline, stilbene, dyes for dye laser, aluminum complexes, low molecular weight compounds such as derivatives thereof; polyfluorene, polyphenylene, polyphenylene vinylene, polyvinylcarbazole, fluorene-benzothiadiazole copolymer And polymers such as fluorene-triphenylamine copolymer and derivatives thereof; and mixtures thereof.

As the phosphorescent material, a metal complex containing a metal such as Ir or Pt can be used. As the Ir complex, for example, FIr (pic) which emits blue light (iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate), Ir (ppy) _{3 which} emits green light (fac tris (2-phenylpyridine) iridium), and red emission _(btp) 2 Ir (acac) (bis [2- (2'-benzo [4,5-α] thienyl) pyridinato -N, ^{C 3]} Iridium (acetyl-acetonate), Ir (piq) ₃ (tris (1-phenylisoquinoline) iridium) and the like can be mentioned. Examples of the Pt complex include PtOEP (2, 3, 7, 8, 12, 13, 17, 18-octaethyl-21H, 23H-phorphine 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. As a host material, a low molecular weight compound, a polymer or a dendrimer can be used. As low molecular weight compounds, for example, 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. Examples of the polymer include the organic electronic materials of the above embodiment, polyvinylcarbazole, polyphenylene, polyfluorene, derivatives thereof, and the like. Be

  As a heat activation delayed fluorescence material, for example, 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]
Materials used for the electron transport layer and the electron injection layer include, for example, phenanthroline derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, fused ring tetracarboxylic acid anhydrides such as naphthalene and perylene, carbodiimides And fluorenylidene methane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, aluminum complexes and the like. Moreover, the organic electronic material of the said embodiment can also be used.

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

[anode]
As the anode material, for example, a metal (for example, Au) or another conductive material 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 preferably flexible. Quartz glass, a light transmitting resin film, etc. are preferably used.

  As the resin film, for example, a film composed of polyethylene terephthalate, polyethylene naphthalate, polyether sulfone, polyether imide, polyether ether ketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, cellulose acetate propionate, etc. It 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 permeation of water vapor, oxygen and the like.

[Emitting color]
The luminescent color of the organic EL element is not particularly limited. A white organic EL element is preferable because it can be used in various lighting fixtures such as home lighting, car interior lighting, watches, backlights of liquid crystals, and the like.

  As a method of forming a white organic EL element, it is possible to use a method in which a plurality of light emitting materials are used to simultaneously emit light of a plurality of light emitting colors for color mixing. The combination of plural 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 such as blue and yellow, yellow green and orange, etc. Can be mentioned. Control of the luminescent color can be performed by adjusting the type and amount of the luminescent material.

<Display element, lighting device, display device>
The display element which is an embodiment of the present invention includes the organic EL element of the 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 forming 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.

  Moreover, the illuminating device which is embodiment of this invention is equipped with the organic EL element of embodiment of this invention. Furthermore, the display device according to the embodiment of the present invention includes a lighting device and a liquid crystal element as display means. For example, the display device can be a display device using a lighting device which is an embodiment of the present invention as a backlight and a liquid crystal display device using a known liquid crystal element as a display means.

  Hereinafter, the present invention will be more specifically described by way of examples. However, the present invention is not limited to the following examples.

<Preparation of Pd catalyst>
In a glove box under a nitrogen atmosphere, tris (dibenzylideneacetone) dipalladium (73.2 mg, 80 μmol) was weighed into a sample tube at room temperature and anisole (15 mL) was added and stirred for 30 minutes. Similarly, tris (t-butyl) phosphine (129.6 mg, 640 μmol) was weighed into a sample tube, anisole (5 mL) was added and stirred for 5 minutes. The solutions were mixed and stirred at room temperature for 30 minutes to catalyze. All solvents were used after degassing with nitrogen bubbles for over 30 minutes.

<Synthesis of Charge Transport 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 further prepared Pd catalyst solution (7.5 mL) was added. After stirring for 30 minutes, 10% aqueous tetraethylammonium hydroxide solution (20 mL) was added. All solvents were used after degassing with nitrogen bubble for more than 30 minutes. The mixture was heated to reflux for 2 hours. All 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 resulting precipitate was dissolved in toluene and reprecipitated from methanol. The obtained precipitate is collected by suction filtration, dissolved in toluene, a metal adsorbent ("Triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer" manufactured by Strem Chemicals, 200 mg per 100 mg of precipitate) is added, Stir overnight. After completion of the stirring, the metal adsorbent and the insoluble matter were removed by filtration, and the filtrate was concentrated by a rotary evaporator. The concentrate was dissolved in toluene and then reprecipitated from methanol-acetone (8: 3). The resulting precipitate was collected by suction filtration and washed with methanol-acetone (8: 3). The resulting precipitate was dried under vacuum to obtain charge transporting polymer 1. The number average molecular weight of the obtained charge transporting polymer 1 was 6,900, and the weight average molecular weight was 45,700. The charge transporting polymer 1 has a structural unit L (derived from monomer L), a structural unit B (derived from monomer B-1), a cyclic moiety (derived from monomer T1-1), and a terminal moiety having an oxetane group (monomer T2 The respective ratios (molar ratios) were 45.5%, 18.2%, 18.2%, and 18.2%.

The number average molecular weight and the weight average molecular weight were measured by GPC (in terms of polystyrene) using tetrahydrofuran (THF) as an eluent. The measurement conditions are as follows.
Liquid delivery pump: L-6050 Hitachi High-Technologies Corporation UV-Vis Detector: L-3000 Hitachi High-Technologies Corporation 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 Transport 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 further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transportable polymer 2 was synthesized in the same manner as the charge transportable polymer 1 was synthesized. The number average molecular weight of the obtained charge transporting polymer 2 was 17,600, and the weight average molecular weight was 47,400. The charge transporting polymer 2 has a structural unit L (derived from the monomer L), a structural unit B (derived from the monomer B-1), a cyclic moiety (derived from the monomer T1-2), and an end moiety having a oxetane group (monomer T2 -1), and the respective proportions were 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transport 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 further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transportable polymer 3 was synthesized in the same manner as the charge transportable polymer 1 was synthesized. The number average molecular weight of the obtained charge transporting polymer 3 was 5,100, and the weight average molecular weight was 40,200. The charge transporting polymer 3 has a structural unit L (derived from monomer L), a structural unit B (derived from monomer B-1), a cyclic site (derived from monomer T1-3), and a terminal site having an oxetane group (monomer T2 -1), and the respective proportions were 45.5%, 18.2%, 27.3%, and 9.1%.

<Synthesis of Charge Transport 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 further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transportable polymer 4 was synthesized in the same manner as the charge transportable polymer 1 was synthesized. The number average molecular weight of the obtained charge transporting polymer 4 was 14,400, and the weight average molecular weight was 53,100. The charge transporting polymer 4 has a structural unit L (derived from monomer L), a structural unit B (derived from monomer B-1), a cyclic site (derived from monomer T1-4), and a terminal site having an oxetane group (monomer T2 -1), and the respective proportions were 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transport 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 further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transportable polymer 5 was synthesized in the same manner as the charge transportable polymer 1 was synthesized. The number average molecular weight of the obtained charge transporting polymer 5 was 14,500, and the weight average molecular weight was 64,000. The charge transporting polymer 5 includes a structural unit L (derived from monomer L), a structural unit B (derived from monomer B-1), an end portion having an oxetane group (derived from monomer T2-1), and a terminal containing a benzene structure. There were sites (from monomer T2-2), the proportions of which were 45.5%, 18.2%, 18.2% and 18.2%, respectively.

<Synthesis of Charge Transport Polymer 6>
In a three-necked round-bottomed flask, the monomer L (5.0 mmol), the following monomer B-2 (2.0 mmol), the following monomer T1-5 (2.0 mmol), the monomer T2-1 (2.0 mmol), and anisole (20 mL) was added, and further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transportable polymer 6 was synthesized in the same manner as the charge transportable polymer 1 was synthesized. The number average molecular weight of the obtained charge transporting polymer 6 was 20,700, and the weight average molecular weight was 75,600. The charge transporting polymer 6 has a structural unit L (derived from monomer L), a structural unit B (derived from monomer B-2), a cyclic site (derived from monomer T1-5), and a terminal site having an oxetane group (monomer T2 -1), and the respective proportions were 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transport Polymer 7>
In a three-necked round-bottomed 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 further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transportable polymer 7 was synthesized in the same manner as the charge transportable polymer 1 was synthesized. The number average molecular weight of the obtained charge transporting polymer 7 was 1,500, and the weight average molecular weight was 23,200. The charge transporting polymer 7 has a structural unit L (derived from monomer L), a structural unit B (derived from monomer B-2), a cyclic site (derived from monomer T1-6), and a terminal site having an oxetane group (monomer T2 -1), and the respective proportions were 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transport Polymer 8>
In a three-necked round-bottomed 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 further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transportable polymer 8 was synthesized in the same manner as the charge transportable polymer 1 was synthesized. The number average molecular weight of the obtained charge transporting polymer 8 was 11,300, and the weight average molecular weight was 43,900. The charge transporting polymer 8 has a structural unit L (derived from monomer L), a structural unit B (derived from monomer B-2), a cyclic site (derived from monomer T1-7), and a terminal site having an oxetane group (monomer T2 -1), and the respective proportions were 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transport Polymer 9>
In a three-necked round-bottomed 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 further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transportable polymer 9 was synthesized in the same manner as the charge transportable polymer 1 was synthesized. The number average molecular weight of the obtained charge transporting polymer 9 was 15,900, and the weight average molecular weight was 64,400. The charge transporting polymer 9 has a structural unit L (derived from monomer L), a structural unit B (derived from monomer B-2), a cyclic portion (derived from monomer T1-8), and a terminal portion having an oxetane group (monomer T2 -1), and the respective proportions were 45.5%, 18.2%, 18.2%, and 18.2%.

<Synthesis of Charge Transportable Polymer 10>
In a three-necked round-bottomed 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 further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transportable polymer 10 was synthesized in the same manner as the charge transportable polymer 1 was synthesized. The number average molecular weight of the obtained charge transporting polymer 10 was 14,300, and the weight average molecular weight was 102,600. The charge transporting polymer 10 includes a structural unit L (derived from monomer L), a structural unit B (derived from monomer B-2), an end portion having an oxetane group (derived from monomer T2-1), and a terminal containing a benzene structure. There were sites (from monomer T2-3), the proportions of which were 45.5%, 18.2%, 18.2% and 18.2%, respectively.

<Synthesis of Charge Transport 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 further prepared Pd catalyst solution (7.5 mL) was added. Thereafter, the charge transportable polymer 11 was synthesized in the same manner as the charge transportable polymer 1 was synthesized. The number average molecular weight of the obtained charge transporting polymer 11 was 14,500, and the weight average molecular weight was 53,900. The charge transporting polymer 11 includes a structural unit L (derived from monomer L), a structural unit B (derived from monomer B-2), an end portion having an oxetane group (derived from monomer T2-1), and a terminal including a thiophene structure. There were sites (from monomer T2-4), the proportions of which were 45.5%, 18.2%, 18.2% and 18.2%, respectively.

<Fabrication of Organic EL Element 1>
Example 1
Under a nitrogen atmosphere, 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. The ink composition is spin-coated at a rotational speed of 3,000 min- ¹ on a glass substrate patterned to a width of 1.6 mm of ITO, and then cured by heating at 220 ° C. for 10 minutes on a hot plate. (25 nm) was formed.

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

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

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

Example 4
An organic EL device was manufactured in the same manner as 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 manufactured in the same manner as Example 1, except that the charge transporting polymer 1 was changed to the charge transporting polymer 5 in the step of forming the hole injection layer.

  The layer configurations of the organic EL elements manufactured in Examples 1 to 4 and Reference Example 1 are summarized in Table 1.

When voltage was applied to the organic EL elements 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 with high luminous efficiency and long life with excellent driving stability was obtained.

<Fabrication of Organic EL Element 2>
[Example 5]
Under a nitrogen atmosphere, 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. The ink composition is spin-coated at a rotational speed of 3,000 min- ¹ on a glass substrate patterned to a width of 1.6 mm of ITO, and then cured by heating at 220 ° C. for 10 minutes on a hot plate. (25 nm) was formed.

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

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

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

[Example 7]
An organic EL device was manufactured in the same manner as 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 manufactured in the same manner as 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 manufactured in the same manner as 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 manufactured in the same manner as 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 summarizes the layer configurations of the organic EL elements produced in Examples 5 to 8 and Reference Examples 2 and 3.

When voltage was applied to the organic EL elements 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 (Lighting Device)>
[Example 9]
Under a nitrogen atmosphere, 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. The ink composition is spin-coated at a rotational speed of 3,000 min- ¹ on a glass substrate patterned to a width of 1.6 mm of ITO, and then cured by heating at 220 ° C. for 10 minutes on a hot plate. (25 nm) was formed.

Next, 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 rotational speed of 3,000 min- ¹ and then cured by heating at 200 ° C. for 10 minutes on a hot plate to form a hole transport layer (40 nm) . The hole transport layer could be formed without dissolving the hole injection layer.

Next, 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 (dichlorobenzene) 0.5 mL) was mixed to prepare an ink composition. The ink composition was spin-coated at a rotational speed of 3,000 min- ¹ and dried by heating at 80C for 5 minutes on a hot plate 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 deposition machine, and BAlq (10 nm), TPBi (30 nm), LiF (0.5 nm), and Al (100 nm) were formed in this order on the light emitting layer by the evaporation method. Then, the sealing process was carried out and the white organic EL element was produced. 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 elements obtained in Example 9 and Reference Example 4, and the light emission lifetime (brightness half time) was measured as an initial brightness of 1,000 cd / m ² . When the light emission lifetime in Example 9 is 1, it is 0.23 in Reference Example 4. Further, when the voltage at a luminance of 1,000 cd / m ² in Example 9 is 1, it is 1.09 in Reference Example 4.

  The white organic EL element of Example 9 exhibited excellent light emission lifetime and drive voltage.

  The effects of the embodiments of the present invention have been described above using the examples. Other than the charge transporting polymer used in the examples, it is possible to obtain an organic EL device having a long lifetime by using the charge transporting polymer described above, and it exhibits the same excellent effect.

Reference Signs List 1 light emitting layer 2 anode 3 hole injecting layer 4 cathode 5 electron injecting layer 6 hole transporting layer 7 electron transporting layer 8 substrate

Claims (15)

An organic electronic material containing a charge transporting polymer,
The charge transporting polymer contains at least one selected from the following partial structures, has three or more ends, and
The charge transporting polymer has a cyclic site which is unsubstituted or has a substituent at at least one end,
The above-mentioned unsubstituted or substituted cyclic moiety contains 7 or more sp ² carbons, has 2 or more aromatic rings, and does not contain a fused ring in which three or more benzene rings are condensed adjacently, Organic electronics materials.

(In the formula, L independently represents a divalent structural unit having charge transportability, and B represents a trivalent structural unit.)

(In the formula, each L independently represents a divalent structural unit having charge transportability, and B represents a tetravalent structural unit.) The organic electronic material according to claim 1, wherein the charge transporting polymer further comprises the following partial structure .

(Wherein L represents a divalent structural unit having charge transportability, T represents a monovalent structural unit T, and the structural unit T is a cyclic group which is unsubstituted or has a substituent. Containing a structural unit T1 having a site) The organic electronic material according to claim 1, wherein the charge transporting polymer has a cyclic portion which is unsubstituted or has a substituent at 25% or more of the ends based on the total number of the ends. The cyclic moiety which is unsubstituted or has a substituent contains 2 to 6 aromatic rings.
The organic electronic material as described in any one of -3. A naphthalene moiety, an acenaphthylene moiety, a fluorene moiety, a spirobifluorene moiety, which is unsubstituted or has a substituent, in the above-mentioned unsubstituted or substituted cyclic moiety.
It is selected from the group consisting of a carbazole site, acridine site, xanthene site, dibenzofuran site, indole site, isoindole site, benzoimidazole site, benzoimidazole site, quinoline site, isoquinoline site, quinoxaline site, diphenylbenzene site, and triphenylethenylbenzene site The organic electronic material according to any one of claims 1 to 4. The organic electronic material according to any one of claims 1 to 5, wherein the charge transporting polymer further has a polymerizable functional group. The ink composition containing the organic electronics material in any one of Claims 1-6, and a solvent. An organic layer formed using the organic electronic material according to any one of claims 1 to 6 or the ink composition according to claim 7.   An organic electronic device comprising at least one organic layer according to claim 8.   An organic electroluminescent device comprising at least one organic layer according to claim 8.   The organic electroluminescent device according to claim 10, further comprising a flexible substrate.   The organic electroluminescent device according to claim 10, further comprising a resin film substrate. The display element provided with the organic electroluminescent element in any one of Claims 10-12. A lighting device comprising the organic electroluminescent device according to any one of claims 10 to 12.   The display apparatus provided with the illuminating device of Claim 14, and a liquid crystal element as a display means.

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