JP2017069324A - Organic electronics material, organic layer, organic electronics element, organic electroluminescent element, display element, luminaire, and display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic electronics material and an organic electronics element which are superior in life characteristic.SOLUTION: An organic electronics material comprises a charge-transporting material having an aromatic ring substituted by a monovalent unsaturated group at a terminal. The monovalent unsaturated group includes an aliphatic organic group including at least one carbon-carbon double bond, and the number of carbon atoms of the aliphatic organic group is 6 or more.SELECTED DRAWING: None

Description

  Embodiments described herein relate generally to an organic electronic material, 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.

  The organic EL element is attracting attention as a large-area solid-state light source application that can replace, for example, an incandescent lamp or a gas-filled lamp. It is also attracting attention as the most powerful self-luminous display that can replace the liquid crystal display (LCD) in the flat panel display (FPD) field, and its commercialization is progressing.

  Organic EL elements are roughly classified into two types, low molecular organic EL elements and polymer organic EL elements, from the organic materials used. In the polymer organic EL element, a polymer compound is used as an organic material, and in the low molecular organic EL element, a low molecular compound is used. On the other hand, the manufacturing method of the organic EL element includes a dry process in which film formation is mainly performed in a vacuum system, and a wet process in which film formation is performed by plate printing such as relief printing and intaglio printing, and plateless printing such as inkjet. It is roughly divided into two. Since simple film formation is possible, the wet process is expected as an indispensable method for future large-screen organic EL displays.

  For this reason, the development of materials suitable for wet processes has been underway, and for example, studies have been made to form a multilayer structure using a compound having a polymerizable group (for example, Patent Document 1 and Non-Patent Documents). 1).

JP 2006-279007 A

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

  An organic EL element manufactured using a wet process has a feature that cost reduction and area increase are easy. However, further improvement is desired for the characteristics of the organic EL element.

  In view of the above, an object of an embodiment of the present invention is to provide an organic electronic material having excellent life characteristics, and an organic layer using the same. Another object of the present invention is to provide an organic electronics element, an organic EL element having excellent lifetime characteristics, and a display element, an illumination device, and a display device using the same.

  As a result of intensive studies, the present inventors have found that an organic electronics material containing at least a charge transporting material having a specific structure and a polymerization initiator is effective in improving the lifetime characteristics of organic electronics elements and organic EL elements. As a result, the present invention has been completed.

  That is, an embodiment of the present invention is an organic electronics material containing a charge transporting material having an aromatic ring substituted with a monovalent unsaturated group at the end, wherein the monovalent unsaturated group is a carbon- The present invention relates to an organic electronic material comprising an aliphatic organic group containing at least one carbon double bond, wherein the total number of carbon atoms of the aliphatic organic group is 6 or more.

  In one embodiment, the carbon-carbon double bond is located at the end of the monovalent unsaturated group.

  In one embodiment, the monovalent unsaturated group includes a vinyl group and / or a vinyl ether group.

  In one embodiment, the charge transport material is hole transportable.

  In one embodiment, the charge transporting material is a charge transporting polymer including a charge transporting structural unit and an aromatic ring substituted with the monovalent unsaturated group.

  In one embodiment, the organic electronic material further includes a polymerization initiator.

  In one embodiment, the polymerization initiator includes a cationic polymerization initiator.

  In one embodiment, the cationic polymerization initiator is an onium salt.

  In one embodiment, the charge transport material is selected from the group consisting of an aromatic amine compound, a carbazole compound, and a thiophene compound.

  Other embodiment of this invention is related with the organic layer formed with one of the said organic electronics materials.

  Another embodiment of the invention relates to an organic electronic device comprising the organic layer.

  Other embodiment of this invention is related with the organic electroluminescent element containing the said organic layer.

  In one embodiment, the organic electroluminescent element has a light emitting layer containing a phosphorescent material.

  In one embodiment, the organic electroluminescent element has a light emitting layer containing a delayed fluorescent material.

  In one embodiment, the organic electroluminescent device further includes a flexible substrate.

  In one Embodiment, the said organic electroluminescent element further has a resin film board | substrate.

  Other embodiment of this invention is related with the display element provided with one of the said organic electroluminescent elements.

  Other embodiment of this invention is related with the illuminating device provided with one of the said organic electroluminescent elements.

  Other embodiment of this invention is related with the display apparatus provided with the said illuminating device and the liquid crystal element as a display means.

  According to the embodiments of the present invention, it is possible to provide an organic electronic material capable of improving life characteristics and an organic layer using the same. Moreover, according to other embodiment of this invention, the organic electronics element which is excellent in a lifetime characteristic, an organic EL element, a display element using the same, an illuminating device, and a display apparatus can be provided.

FIG. 1 is a schematic diagram illustrating an example of an organic EL element according to an embodiment of the present invention.

An embodiment of the present invention will be described.
<Organic electronics materials>
An organic electronic material according to an embodiment of the present invention is an organic electronic material containing a charge transporting material having an aromatic ring substituted with a monovalent unsaturated group at the end, wherein the monovalent unsaturated group is An organic electronic material comprising an aliphatic organic group containing at least one carbon-carbon double bond, wherein the total number of carbon atoms of the aliphatic organic group is 6 or more.
[Charge transport material]

  The charge transport material in the present invention will be described in detail.

  The charge transport material in an embodiment of the present invention is a charge transport material having an aromatic ring substituted with a monovalent unsaturated group at the end, and the monovalent unsaturated group is a carbon-carbon double group. An aliphatic organic group containing at least one bond is included, and the total number of carbon atoms of the aliphatic organic group is 6 or more. Hereinafter, this monovalent unsaturated group may be referred to as “monovalent unsaturated group X”. The aromatic ring substituted by the monovalent unsaturated group X may be at least at one end of the charge transporting material.

“Aromatic ring” refers to a ring exhibiting aromaticity. The aromatic ring may have a monocyclic structure such as benzene, or may have a condensed ring structure in which the rings are condensed with each other, such as naphthalene.
The aromatic ring may be an aromatic hydrocarbon such as benzene, naphthalene, anthracene, tetracene, fluorene, or phenanthrene, for example, pyridine, pyrazine, quinoline, isoquinoline, acridine, phenanthroline, furan, pyrrole, thiophene, carbazole, It may be an aromatic heterocycle such as oxazole, oxadiazole, thiadiazole, triazole, benzoxazole, benzooxadiazole, benzothiadiazole, benzotriazole, and benzothiophene.
The aromatic ring may have a structure in which two or more selected from independent single rings and condensed rings are bonded, such as biphenyl, terphenyl, and triphenylbenzene.

  The aromatic ring substituted with the monovalent unsaturated group X is preferably benzene substituted with the monovalent unsaturated group X.

The monovalent unsaturated group X includes an aliphatic organic group containing at least one carbon-carbon double bond.
The aliphatic organic group may be linear, branched, alicyclic, or a combination thereof.
Hereinafter, an aliphatic organic group containing at least one carbon-carbon double bond contained in the monovalent unsaturated group X may be referred to as “aliphatic organic group Y”. In addition, the carbon-carbon double bond contained in the aliphatic organic group Y may be referred to as “carbon-carbon double bond y”.
The monovalent unsaturated group X may contain an aromatic ring, but the total carbon number of the aliphatic organic group Y does not include the carbon number of this aromatic ring. As an example in which the monovalent unsaturated group X includes an aromatic ring, the monovalent unsaturated group X includes an aliphatic organic group Y and an aromatic ring or a group including an aromatic ring, or an aliphatic organic group. In the group Y, the case where two carbon atoms are connected via an aromatic ring, and the like can be mentioned. However, when two carbon atoms are connected via an aromatic ring in the aliphatic organic group Y, the carbon number of the aromatic ring is not included in the total number of carbon atoms of the aliphatic organic group Y.

  The aliphatic organic group Y may contain a hydrogen atom, a halogen atom, and / or a hetero element (S, N, O, P) or the like. For example, the aliphatic organic group Y may include a single bond (for example, an ether bond) and / or a multiple bond between a carbon atom and a hetero atom.

  The monovalent unsaturated group X may be either linear or branched, but is preferably linear from the viewpoint of easy monomer availability.

  The carbon-carbon double bond y is a carbon-carbon double bond other than an aromatic ring and is not particularly limited. In the monovalent unsaturated group X, the carbon-carbon double bond y is, for example, an acryloyl group, It may be contained in acryloyloxy group, acryloylamino group, methacryloyl group, methacryloyloxy group, methacryloylamino group, vinyloxy group, vinylamino group, styryl group, butenyl group, vinyl group, norbornenyl group, etc. From the viewpoint of excellent lifetime characteristics, it is preferably contained in a vinyl group, vinyloxy group, acryloyl group, methacryloyl group, styryl group, or norbornenyl.

From the viewpoint of excellent curability, the carbon-carbon double bond y is preferably located at the end of the monovalent unsaturated group X. For example, the carbon-carbon double bond y is linear. You may be located in the terminal part of the monovalent unsaturated group X.
As an example in which the carbon-carbon double bond y is located at the end of the monovalent unsaturated group X, when the vinyl group is located at the end of the monovalent unsaturated group X, monovalent unsaturated And the like when the norbornenyl group is located at the terminal of the group X.
The monovalent unsaturated group X has a vinyl group, a vinyloxy group, an acryloyl group, a methacryloyl group, a styryl group, or a norbornenyl group at the end of the linear structure, but is preferably a structure.

  Specific examples of the monovalent unsaturated group X in the present invention are shown below, but the monovalent unsaturated group X is not limited to the following specific examples. In the specific examples of monovalent unsaturated groups shown below, “*” represents a bonding site with an aromatic ring.

  The charge transporting material in the present invention is not particularly limited as long as it has an aromatic ring substituted with a monovalent unsaturated group X at the terminal and has an ability to transport charges. Holes are preferred as the charge to be transported. The charge transporting material may be a commercially available material or a material synthesized by a method known to those skilled in the art, and is not particularly limited. If it is a hole transporting compound, it can be used as, for example, a hole injection layer or a hole transport layer of an organic EL device, and if it is an electron transporting compound, it can be used as an electron transport layer or an electron injection layer. it can. In addition, any compound that transports both holes and electrons can be used as a material for the light emitting layer.

  The charge transporting material has one or more structural units having a charge transporting property. Specific examples and preferred ranges of the structural unit having charge transportability are the same as the specific examples and preferred ranges of the structural unit D of the “charge transporting polymer” described later.

  The charge transporting material may be either a low molecular compound having one structural unit or a high molecular compound having a plurality of structural units (meaning “polymer or oligomer”). From the viewpoint of easily obtaining a high purity material, a low molecular weight compound is preferable. From the viewpoint of easy production of the composition and excellent film formability, a polymer compound is preferable. Furthermore, it is also possible to use a mixture of a low molecular compound and a high molecular compound from the viewpoint of obtaining the advantages of both.

[Low molecular charge transport materials]
A low molecular weight compound (hereinafter also referred to as “low molecular charge transporting material”), which is an embodiment of a charge transporting material, has an aromatic ring substituted with a monovalent unsaturated group X at the end. And a low molecular weight compound having charge transporting properties. The low-molecular charge transporting material has a partial structure having charge transporting properties. Specific examples and preferred examples of the partial structure having charge transporting properties include specific examples of the structural unit D of “charge transporting polymer or oligomer” described later. Examples and preferred ranges are given.

[Charge transporting polymer]
The charge transporting material may be a polymer or an oligomer (hereinafter collectively referred to as “charge transporting polymer”).
The charge transporting polymer has an aromatic ring substituted with a monovalent unsaturated group X at the terminal and has an ability to transport charges. The charge transporting polymer may be linear or have a branched structure. The charge transporting polymer preferably includes at least a divalent structural unit L having charge transporting properties and a monovalent structural unit T constituting a terminal portion, and a trivalent or higher structural unit B constituting a branched portion. Further, it may be included. The charge transporting polymer may contain only one type of each structural unit, or may contain a plurality of types. In the charge transporting polymer, each structural unit is bonded to each other at a binding site of “monovalent” to “trivalent or higher”.

(Construction)
Examples of the partial structure contained in the charge transporting polymer include the following. The charge transporting polymer is not limited to a 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 L may be the same structural unit or different structural units. The same applies to T and B.

Linear charge transporting polymer

Charge transporting polymer having a branched structure

(Structural unit L)
The structural unit L is a divalent structural unit having charge transportability. The structural unit L is not particularly limited as long as it contains an atomic group having the ability to transport 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, 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 A thiophene structure, a benzoxazole structure, a benzooxadiazole structure, a benzothiazole structure, a benzothiadiazole structure, a benzotriazole structure, and one or more of these 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 includes a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, pyrrole structure, and these from the viewpoint of obtaining excellent hole transport properties. Preferably, it is selected from a structure containing one or more of these, and is selected from a substituted or unsubstituted aromatic amine structure, carbazole structure, and a structure containing one or more of these Is more preferable. In another embodiment, from the viewpoint of obtaining excellent electron transport properties, the structural unit L is a substituted or unsubstituted fluorene structure, benzene structure, phenanthrene structure, pyridine structure, quinoline structure, and one or two of these. It is preferably selected from structures containing more than one species.

  Specific examples of the structural unit L include the following. The structural unit L is not limited to the following.

Each R independently represents a hydrogen atom or a substituent. Preferably, each R independently represents —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. Selected from the group consisting of containing groups. R ^{1 to} R ⁸ each independently represents 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 aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is an atomic group obtained by removing one hydrogen atom from an aromatic heterocyclic ring. 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 linear, cyclic or branched 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 heteroarylene group having 2 to 30 carbon atoms. An arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon. A heteroarylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic heterocycle. Ar is preferably an arylene group, more preferably a phenylene group.

  Examples of the aromatic hydrocarbon include a single ring, a condensed ring, or a polycycle in which two or more selected from a single ring and a condensed ring are bonded via a single bond. Examples of the aromatic heterocycle include a single ring, a condensed ring, or 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 constituting the terminal portion of the charge transporting polymer.
At least one of the structural units T is an aromatic ring substituted with a monovalent unsaturated group X.
The structural unit T is not particularly limited as long as at least one of the structural units T is an aromatic ring substituted with a monovalent unsaturated group X. For example, a substituted or unsubstituted aromatic hydrocarbon structure, aromatic Selected from a group heterocyclic structure and a structure containing one or more of these. The structural unit T may have the same structure as the structural unit L. In one embodiment, the structural unit T is preferably a substituted or unsubstituted aromatic hydrocarbon structure from the viewpoint of imparting durability without deteriorating charge transportability, and is preferably a substituted or unsubstituted benzene structure. A structure is more preferable. In another embodiment, the structural unit T other than the aromatic ring substituted by the monovalent unsaturated group X may be a polymerizable structure (for example, a polymerizable functional group such as a pyrrol-yl group). Good.

Specific examples of the structural unit T include the following. The structural unit T is not limited to the following.

  R is the same as R in the structural unit L. However, in at least one of the structural units T, when the charge transporting polymer has a polymerizable functional group at the terminal portion, preferably at least one of R is a monovalent unsaturated group X.

(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. 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 element. The structural unit B is preferably a unit having charge transportability. For example, the structural unit B is a substituted or unsubstituted aromatic amine structure, carbazole structure, condensed polycyclic aromatic hydrocarbon structure, and 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.

Specific examples of the structural unit B include the following. The structural unit B is not limited to the following.

  W represents a trivalent linking group, for example, an arenetriyl group or a heteroarenetriyl group having 2 to 30 carbon atoms. The arenetriyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic hydrocarbon. The heteroarene triyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic heterocyclic ring. Ar each independently represents a divalent linking group, 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. For example, one R atom in the structural unit L (excluding a group containing a polymerizable functional group) has one more hydrogen atom from a group having one or more hydrogen atoms. And divalent groups excluding. Z represents any of 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.

(Polymerizable functional group)
In one embodiment, from the viewpoint of curing by a polymerization reaction and changing the solubility in a solvent, the charge transporting polymer is a polymerizable functional other than a structure containing a carbon-carbon double bond y of a monovalent unsaturated group X. It is preferred to have at least one group. The “polymerizable functional group” refers to a functional group that can form a bond with each other by applying heat and / or light. Hereinafter, the polymerizable functional group other than the structure including the carbon-carbon double bond y of the monovalent unsaturated group X is referred to as a polymerizable functional group z.

  As the polymerizable functional group z, 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, methacryloyl group) Amino groups, vinyloxy groups, vinylamino groups, etc.), groups having small rings (for example, cyclic alkyl groups such as cyclopropyl groups, cyclobutyl groups; cyclic ethers such as epoxy groups (oxiranyl groups), oxetane groups (oxetanyl groups), etc. Group; diketene group; episulfide group; lactone group; lactam group, etc.), heterocyclic group (for example, furan-yl group, pyrrol-yl group, thiophen-yl group, silole-yl group) and the like. As the polymerizable functional group z, in particular, a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group, and an oxetane group are preferable. From the viewpoint of reactivity and characteristics of the organic electronics element, a vinyl group, an oxetane group, or an epoxy group is preferable. More preferred.

  From the viewpoint of increasing the degree of freedom of the polymerizable functional group z and facilitating the occurrence of a polymerization reaction, the main skeleton of the charge transporting polymer and the polymerizable functional group z are preferably connected by an alkylene chain. In addition, for example, when an organic layer is formed on an electrode, it is connected with a hydrophilic chain such as an ethylene glycol chain or a diethylene glycol chain from the viewpoint of improving the affinity with a hydrophilic electrode such as ITO. preferable. Furthermore, from the viewpoint of facilitating the preparation of the monomer used for introducing the polymerizable functional group z, the charge transporting polymer has an alkylene chain and / or a hydrophilic chain end, that is, these chains and You may have an ether bond or an ester bond in the connection part with the polymerizable functional group z and / or the connection 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 obtained by combining a polymerizable functional group z and an alkylene chain. As the group containing the polymerizable functional group z, for example, a group exemplified in International Publication No. WO2010 / 140553 can be suitably used.

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

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

  For example, the number of polymerizable functional groups z per molecule of the charge transporting polymer is preferably 2 or more from the viewpoint of obtaining a sufficient change in solubility as the sum of the number of carbon-carbon double bonds y. More than the number is more preferable. In addition, the number of polymerizable functional groups is preferably 1,000 or less, more preferably 500 or less, from the viewpoint of maintaining charge transportability, as the total with the number of carbon-carbon double bonds y.

The sum of the number of polymerizable functional groups z per molecule of the charge transporting polymer and the number of carbon-carbon double bonds y is the charge of the polymerizable functional group z used to synthesize the charge transporting polymer. Corresponding to the amount (for example, the amount of monomer having a polymerizable functional group), the amount of carbon-carbon double bond y (for example, the amount of monomer having carbon-carbon double bond y), and each structural unit. The average value can be obtained by using the charged amount of monomer, the weight average molecular weight of the charge transporting polymer and the like. The total number of polymerizable functional groups z and the number of carbon-carbon double bonds y is the number of carbon-carbon double bonds y and polymerizability in the ¹ H NMR (nuclear magnetic resonance) spectrum of the charge transporting polymer. The average value can be calculated using the ratio between the integral value of the signal derived from the functional group z and the integral value of the entire spectrum, the weight average molecular weight of the charge transporting polymer, and the like. Since it is simple, when the preparation amount is clear, a value obtained by using the preparation amount is preferably adopted.

(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 formability, and the like. The number average molecular weight is preferably 500 or more, more preferably 1,000 or more, and still more preferably 2,000 or more, from the viewpoint of excellent charge transportability. 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 an 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 formability, 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. 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 preparation of an 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) under the following conditions using a standard polystyrene calibration curve.
Liquid feed pump: L-6050 Hitachi High-Technologies UV-Vis detector: L-3000 Hitachi High-Technologies columns: Gelpack (registered trademark) 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: Standard polystyrene

(Percentage of structural units)
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 the total structural unit from the viewpoint of obtaining sufficient charge transportability. Is more preferable. 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 proportion of the structural unit T contained in the charge transporting polymer is based on the total structural unit from the viewpoint of improving the characteristics of the organic electronics element or suppressing the increase in the viscosity and satisfactorily synthesizing the charge transporting 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 transport properties.

  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 electronics element. 10 mol% or more is more preferable. The proportion of the structural unit B is preferably 50 mol% or less, preferably 40 mol% or less, from the viewpoint of suppressing the increase in viscosity and satisfactorily synthesizing the charge transporting polymer or obtaining sufficient charge transportability. Is more preferable, and 30 mol% or less is still more preferable.

When the charge transporting polymer has a polymerizable functional group z, the ratio of the polymerizable functional group z is based on the total structural unit from the viewpoint of efficiently curing the charge transporting polymer. Is preferably 0.1 mol% or more, more preferably 1 mol% or more, still more preferably 3 mol% or more. In addition, the proportion of the polymerizable functional group is preferably 70 mol% or less, and preferably 60 mol% or less as the sum of the proportion of the structural units containing the carbon-carbon double bond y from the viewpoint of obtaining good charge transportability. Is more preferable, and 50 mol% or less is still more preferable. The “ratio of polymerizable functional groups” here refers to the ratio of structural units having a polymerizable functional group.
Further, when the charge transporting polymer does not have the polymerizable functional group z, the proportion of the structural unit containing the carbon-carbon double bond y is preferably 0.1 mol% or more based on the total structural unit, 1 mol% or more is more preferable, and 3 mol% or more is still more preferable. Further, the proportion of the structural unit containing the carbon-carbon double bond y is preferably 70 mol% or less, more preferably 60 mol% or less, and further preferably 50 mol% or less.

  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: 5-30 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. Preferably, 100: 20-180: 20-90 are more preferable, and 100: 40-160: 30-80 are still more preferable.

The proportion 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. Moreover, the ratio of the structural unit can be calculated as an average value using an integrated value of the spectrum derived from each structural unit in the ¹ H NMR spectrum of the charge transporting polymer. Since it is simple, when the preparation amount is clear, a value obtained by using the preparation amount is preferably adopted.

  When the charge transporting polymer is a hole transporting material, from the viewpoint of obtaining high hole injecting property and hole transporting property, a unit having an aromatic amine structure and / or a unit having a carbazole structure is used as a main structural unit. It is preferable that it is a compound which has. From this viewpoint, the ratio of the total number of units having an aromatic amine structure and / or carbazole structure to the total number of structural units in the polymer compound (excluding the terminal structural unit) is 40% or more. Preferably, 45% or more is more preferable, and 50% or more is further preferable. The ratio of the total number of units having an aromatic amine structure and / or carbazole structure may be 100%.

(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 and the like 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. In addition, a catalyst species generated by mixing tris (dibenzylideneacetone) dipalladium (0), palladium (II) acetate and the like with a phosphine ligand can also be used. For the method for synthesizing the charge transporting polymer, for example, the description of International Publication No. WO2010 / 140553 can be referred to.

[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 be added to the organic electronic material to develop a doping effect and improve the charge transport property. Doping includes p-type doping and n-type doping. In p-type doping, a substance serving as an electron acceptor is used as a dopant, and in n-type doping, a substance serving as an electron donor is used as a dopant. It is preferable to perform p-type doping for improving hole transportability and n-type doping for improving electron transportability. The dopant used in the organic electronic material may be a dopant that exhibits any effect of p-type doping or n-type doping. Further, one kind of dopant may be added alone, or plural 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, proton acids, transition metal compounds, ionic compounds, halogen compounds, and π-conjugated compounds. Specifically, as the Lewis acid, FeCl ₃ , PF ₅ , AsF ₅ , SbF ₅ , BF ₅ , BCl ₃ , BBr _{3 and the} like; as the protonic acid, HF, HCl, HBr, HNO ₅ , H ₂ SO ₄ , HClO _{4 and} other inorganic acids, 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 include FeOCl, TiCl ₄ , ZrCl ₄ , HfCl ₄ , NbF ₅ , AlCl ₃ , NbCl ₅ , TaCl ₅ , MoF ₅ ; 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) A salt having a perfluoroanion such as a salt, a salt having a conjugate base of the protonic acid as an anion; halogen compounds such as Cl ₂ , Br ₂ , I ₂ , ICl, ICl ₃ , IBr and IF; π-conjugated compounds Examples thereof include TCNE (tetracyanoethylene), TCNQ (tetracyanoquinodimethane) and the like. Moreover, it is also possible to use the electron-accepting compounds described in JP 2000-36390 A, JP 2005-75948 A, JP 2003-213002 A, 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 donating 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 include alkaline earth metal salts; metal complexes; electron-donating organic compounds.

  In order to easily change the solubility of the organic layer, it is preferable to use a compound that can act as a polymerization initiator for the polymerizable functional group as a dopant. Examples of the substance having both a function as a dopant and a function as a polymerization initiator include the ionic compounds.

[Other optional ingredients]
The organic electronic material may further contain other polymers and the like.

[Content]
The content of the charge transporting material is preferably 50% by weight or more, more preferably 70% by weight or more, and further preferably 80% by weight or more based on the total weight of the organic electronic material from the viewpoint of obtaining good charge transporting properties. preferable. It may be 100% by mass.

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

[Polymerization initiator]
The organic electronic material of the present embodiment 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 the polymerization initiator that also has a function as a dopant include the ionic compound. Examples of the ionic compound include, for example, a salt having the perfluoroanion. Examples of the ionic compound include a salt (for example, the following compound) of a perfluoroanion and an iodonium ion or an ammonium ion.

<Ink composition>
The organic electronic material may be used as an ink composition containing the organic electronic material of the above 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. Organic solvents 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, 2,4-dimethylanisole; ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate Aliphatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butyl benzoate; N, N-dimethylformamide, N, N-dimethylacetamide, etc. Amide solvents; dimethyl sulfoxide, tetrahydrofuran, acetone, chloroform, methylene chloride and the like can be mentioned. Preferred are aromatic hydrocarbons, aliphatic esters, aromatic esters, aliphatic ethers, aromatic ethers and the like.

[Additive]
The ink composition may further contain an additive as an optional component. Examples of additives include polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, antioxidants, oxidizing agents, reducing agents, surface modifiers, emulsifiers, antifoaming agents, Examples thereof include a dispersant and a surfactant.

[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. More preferred is an amount of 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 even more preferably 10% by mass or less. .

<Organic layer>
The organic layer which is embodiment of this invention is a layer formed using the organic electronics material of the said embodiment. The organic electronic material of the embodiment may be used as an ink composition. By using the ink composition, the organic layer can be favorably formed by a coating method. Examples of the coating method include spin coating method; casting method; dipping method; letterpress printing, intaglio printing, offset printing, planographic printing, letterpress inversion offset printing, screen printing, gravure printing and other plate printing methods; ink jet method, etc. A known method such as a plateless printing method may be used. When the organic layer is formed by a coating method, the organic layer (coating layer) obtained after the coating may be dried using a hot plate or an oven to remove the solvent.

  The solubility of the organic layer may be changed by advancing the polymerization reaction of the charge transporting material by light irradiation, heat treatment or the like. By laminating organic layers with different solubility, it is possible to easily increase the number of organic electronics elements. For the method of forming the organic layer, for example, the description of International Publication No. WO2010 / 140553 can be referred to.

  From the viewpoint of improving the efficiency of charge transport, 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. In addition, 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 electrical resistance.

<Organic electronics elements>
The organic electronics element which is embodiment of this invention has the organic layer of the said embodiment at least. Examples of the organic electronics element include an organic EL element, an organic photoelectric conversion element, and an organic transistor. The organic electronic element preferably has a structure in which an organic layer is disposed between at least a pair of electrodes.

[Organic EL device]
The organic EL element which is embodiment of this invention has an organic layer of the said embodiment at least. The organic EL element usually includes a light emitting layer, an anode, a cathode, and a substrate, and other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, and an electron transport layer are provided as necessary. I have. Each layer may be formed by a vapor deposition method or a coating method. The organic EL element preferably has an organic layer as a light emitting layer or other 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 an organic EL element. The organic EL element of FIG. 1 is an element having a multilayer structure, and includes a substrate 8, an anode 2, a hole injection layer 3 and a hole transport layer 6 made of the organic layer of the above 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. Hereinafter, each layer will be described.
In FIG. 1, the hole injection layer 3 and the hole transport layer 6 are organic layers formed using the organic electronic material described above, but the organic EL according to the embodiment of the present invention is not limited to such a structure. The other organic layer may be an organic layer formed using the organic electronic material.

[Light emitting layer]
As a material used for the light emitting layer, a light emitting material such as a low molecular 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 thermally 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 derivatives thereof; polyfluorene, polyphenylene, polyphenylene vinylene, polyvinyl carbazole, fluorene-benzothiadiazole copolymer , Fluorene-triphenylamine copolymers, polymers thereof such as derivatives thereof; mixtures thereof and the like.

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) that emits blue light (iridium (III) bis [(4,6-difluorophenyl) -pyridinate-N, C ² ] picolinate), Ir (ppy) ₃ that emits green light. (Factris (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-formin platinum) that emits red light.

  When the light emitting layer includes a phosphorescent material, it is preferable that a host material is further included in addition to the phosphorescent material. As the host material, a low molecular compound, a polymer, or a dendrimer can be used. 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′- Bis (carbazol-9-yl) -2,2′-dimethylbiphenyl), derivatives thereof, and the like are exemplified by the organic electronic materials, polyvinyl carbazole, polyphenylene, polyfluorene, derivatives thereof, and the like of the embodiment. It is done.

  Examples of thermally activated delayed fluorescent materials 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.

[Hole transport layer, hole injection layer]
In FIG. 1, the hole injection layer 3 and the hole transport layer 6 are organic layers formed using the above-described organic electronics material, but the organic EL of the embodiment is not limited to such a structure, The organic layer may be an organic layer formed using the organic electronic material. It is preferably used as at least one of a hole transport layer and a hole injection layer formed using the organic electronic material, and more preferably used as at least a hole transport layer. For example, when the organic EL element has a layer formed using the organic electronic material as a hole transport layer and further has a hole injection layer, a known material can be used for the hole injection layer. In addition, for example, when the organic EL element has a layer formed using the organic electronic material as an organic layer as a hole injection layer and further has a hole transport layer, a known hole transport layer is used. Material can be used.
Examples of materials that can be used for the hole injection layer and the hole transport layer include aromatic amine compounds (for example, N, N′-di (naphthalen-1-yl) -N, N′-diphenyl-benzidine ( aromatic diamines such as α-NPD), phthalocyanine compounds, thiophene compounds (eg, thiophene-based conductive polymers (eg, poly (3,4-ethylenedioxythiophene): poly (4-styrenesulfonate)) (PEDOT: PSS) and the like.

[Electron transport layer, electron injection layer]
Examples of 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, condensed ring tetracarboxylic anhydrides such as naphthalene and perylene, and carbodiimides. , Fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives (e.g. 2,2 ', 2 "-(1,3,5-benzenetriyl) tris ( 1-phenyl-1H-benzimidazole) (TPBi)), quinoxaline derivatives, aluminum complexes (for example, bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum (BAlq)) and the like. Ma The organic electronic material of the embodiment can also be used.

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

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

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

  Examples of the resin film include polyethylene terephthalate, polyethylene naphthalate, polyethersulfone, polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate, cellulose triacetate, and cellulose acetate propionate. Can be mentioned.

  When using a resin film, in order to suppress permeation | transmission of water vapor | steam, oxygen, etc., you may coat and use inorganic substances, such as a silicon oxide and a silicon nitride, on a resin film.

[Luminescent 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 devices such as home lighting, interior lighting, a clock, or a liquid crystal backlight.

  As a method of forming a white organic EL element, a method of simultaneously emitting light of a plurality of emission colors using a plurality of light emitting materials and mixing the colors can be used. A 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. Is mentioned. The emission color can be controlled by adjusting the type and amount of the light emitting material.

<Display element, lighting device, display device>
The display element which is embodiment of this invention is equipped with the organic EL element of the said 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 a thin film transistor is 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 apparatus which is embodiment of this invention is equipped with the illuminating device and the liquid crystal element as a display means. For example, the display device may be a display device using a known liquid crystal element as a display unit, that is, a liquid crystal display device, using the illumination device according to the embodiment of the present invention as a backlight.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.

<Synthesis of Monomer Having Monovalent Unsaturated Group X>
[Monomer W1]
p-bromobenzyl bromide (10.9 g, 43.5 mmol), 5-hexen-1-ol (4.36 g, 43.5 mmol), tetraethylammonium bromide (0.70 g, 2.18 mmol), hexane 100 mL and saturated NaOH 50 mL of the aqueous solution was put into a three-necked flask and heated to reflux for 5 hours. After removing the aqueous layer, the organic layer was washed three times with pure water, and magnesium sulfate was added thereto and stirred for a while. After filtering the magnesium sulfate, the solvent was distilled off to obtain 11.7 g of a colorless liquid. Further drying in vacuum yielded 11.3 g (41.9 mmol) of a colorless liquid. Yield 96.3%.

[Monomer W2]
Monomer W2 was synthesized in the same manner as the synthesis of monomer W1, except that 5-hexen-1-ol in the synthesis of monomer W1 was changed to 4-vinyloxybutanol. Yield 93.2%.

[Monomer W3]
Monomer W3 was synthesized in the same manner as the synthesis of monomer W1, except that 5-hexen-1-ol in the synthesis of monomer W1 was changed to 10-undecen-1-ol. Yield 94.9%.

[Monomer W4]
Monomer W4 was synthesized in the same manner as the synthesis of monomer W1, except that 5-hexen-1-ol in the synthesis of monomer W1 was changed to 4-hydroxybutyl acrylate. Yield 89.3%.

[Monomer W5]
Monomer W5 was synthesized in the same manner as the synthesis of monomer W1, except that 5-hexen-1-ol in the synthesis of monomer W1 was changed to 4-hexen-1-ol. Yield 92.1%.

[Monomer W6]
Monomer W6 was synthesized in the same manner as the synthesis of monomer W1, except that 5-hexen-1-ol in the synthesis of monomer W1 was changed to hydroxypropyl methacrylate. Yield 84.5%.

＜炭素−炭素二重結合を少なくとも１つ含む脂肪族有機基を有し、該脂肪族有機基の炭素数の合計が６未満であるモノマーの合成＞ [Monomer W7]
Monomer W7 was synthesized in the same manner as the synthesis of monomer W1, except that 5-hexen-1-ol in the synthesis of monomer W1 was changed to 5-norbornene-2-methanol. Yield 86.3%.

<Synthesis of a monomer having an aliphatic organic group containing at least one carbon-carbon double bond, and the total number of carbon atoms of the aliphatic organic group being less than 6>

[Monomer W8]
Monomer W8 was synthesized in the same manner as the synthesis of monomer W1, except that 5-hexen-1-ol in the synthesis of monomer W1 was changed to 3-buten-1-ol. Yield 95.0%.

[Monomer W9]
Monomer W9 was synthesized in the same manner as the synthesis of monomer W1, except that 5-hexen-1-ol in the synthesis of monomer W1 was changed to 2-propen-1-ol. Yield 91.8%.

[Monomer W10]
Monomer W10 was synthesized in the same manner as the synthesis of monomer W1, except that 5-hexen-1-ol in the synthesis of monomer W1 was changed to cinnamyl alcohol. Yield 82.6%.

<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, 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 form a catalyst. All solvents were used after being degassed with nitrogen bubbles for more than 30 minutes.

<Synthesis of hole transporting compound 1>
The following monomer A (5.0 mmol), the following monomer B1 (2.0 mmol), the monomer W1 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a 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 being degassed with nitrogen bubbles for more than 30 minutes. The mixture was heated to reflux for 2 hours. All the operations so far 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 resulting 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 for 100 mg of the precipitate) was added. Stir overnight. After completion of the stirring, the metal adsorbent and 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 resulting precipitate was collected by suction filtration and washed with methanol-acetone (8: 3). The obtained precipitate was vacuum-dried to obtain a hole transporting compound 1. The molecular weight was measured by GPC (polystyrene conversion) using THF as an eluent. The number average molecular weight of the obtained hole transporting compound 1 was 13,600, and the weight average molecular weight was 72,800. The hole transporting compound 1 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), and a monovalent unsaturated group X (at least one carbon-carbon double bond). Each having a structural unit (1c) (derived from the monomer W1) containing an aromatic ring substituted with an aliphatic organic group containing, and the aliphatic organic group having a total carbon number of 6 or more) The unit proportions were 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.

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 feed pump: L-6050 Hitachi High-Technologies UV-Vis detector: L-3000 Hitachi High-Technologies columns: Gelpack (registered trademark) 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: Standard polystyrene

<Synthesis of hole transporting compound 2>
The monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer W2 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 2 was synthesized in the same manner as the hole transporting compound 1 was synthesized. The number average molecular weight of the obtained hole transporting compound 2 was 15,600, and the weight average molecular weight was 81,500. The hole-transporting compound 2 comprises a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), and a structural unit (1c) (monomer containing a monovalent unsaturated group X). The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 3>
The monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer W3 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 3 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 3 was 7,300, and the weight average molecular weight was 15,700. The hole-transporting compound 2 comprises a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), and a structural unit (1c) (monomer containing a monovalent unsaturated group X). The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 4>
The monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer W4 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 4 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 4 was 15,000, and the weight average molecular weight was 74,600. The hole transporting compound 2 includes a structural unit (1c) containing a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), and a monovalent unsaturated group X. (Derived from monomer W4) and the proportions of the respective structural units were 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 5>
The monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer W5 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 5 was synthesized in the same manner as the hole transporting compound 1 was synthesized. The resulting hole-transporting compound 5 had a number average molecular weight of 10,600 and a weight average molecular weight of 66,700. The hole-transporting compound 2 comprises a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), and a structural unit (1c) (monomer containing a monovalent unsaturated group X). The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 6>
The monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer W6 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 6 was synthesized in the same manner as the hole transporting compound 1 was synthesized. The number average molecular weight of the obtained hole transporting compound 6 was 17,800, and the weight average molecular weight was 63,100. The hole-transporting compound 2 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), and a structural unit (1c) containing a monovalent unsaturated group X ( The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 7>
The monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer W7 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 7 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 7 was 20,400, and the weight average molecular weight was 64,100. The hole transporting compound 7 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), and a structural unit (1c) (monomer containing the monovalent unsaturated group X). The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 8>
The monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer W8 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 8 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 8 was 21,700, and the weight average molecular weight was 63,200. The hole transporting compound 8 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), and a structural unit (1c) having an unsaturated double bond (into the monomer W8). The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 9>
The monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer W9 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 9 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 9 was 13,700, and the weight average molecular weight was 48,800. The hole transporting compound 9 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), and a structural unit (1c) having an unsaturated double bond (into the monomer W9). The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 10>
The monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the monomer W10 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 10 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 10 was 14,800, and the weight average molecular weight was 57,700. The hole transporting compound 10 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), and a structural unit (1c) having an unsaturated double bond (into the monomer W10). The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 11>
The monomer A (5.0 mmol), the monomer B1 (2.0 mmol), the following monomer C2 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 11 was synthesized in the same manner as the hole transporting compound 1 was synthesized. The number average molecular weight of the obtained hole transporting compound 11 was 14,700, and the weight average molecular weight was 78,100. The hole transporting compound 11 has a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B1), and a structural unit (derived from the monomer C2) having an oxetane group, The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 12>
The monomer A (5.0 mmol), the following monomer B3 (2.0 mmol), the monomer W3 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 12 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 12 was 16,400, and the weight average molecular weight was 62,300. The hole transporting compound 12 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B3), and a structural unit (1c) (monomer containing a monovalent unsaturated group X). The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure and units having a carbazole structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 13>
The monomer A (5.0 mmol), the monomer B3 (2.0 mmol), the monomer W7 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, in the same manner as the synthesis of the hole transporting compound 1, the hole transporting compound 13 was synthesized. The number average molecular weight of the obtained hole transporting compound 13 was 17,800, and the weight average molecular weight was 63,100. The hole transporting compound 13 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B3), and a structural unit (1c) (monomer containing a monovalent unsaturated group X). The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure and units having a carbazole structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 14>
The monomer A (5.0 mmol), the monomer B3 (2.0 mmol), the monomer W9 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a Pd catalyst solution (7. 5 mL) was added. Thereafter, the hole transporting compound 14 was synthesized in the same manner as the synthesis of the hole transporting compound 1. The number average molecular weight of the obtained hole transporting compound 14 was 14,800, and the weight average molecular weight was 42,600. The hole transporting compound 14 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B3), and a structural unit (1c) having an unsaturated double bond (into the monomer W9). The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure and units having a carbazole structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 15>
The monomer A (5.0 mmol), the monomer B3 (2.0 mmol), the monomer W10 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, in the same manner as the synthesis of the hole transporting compound 1, the hole transporting compound 15 was synthesized. The number average molecular weight of the obtained hole transporting compound 15 was 17,200, and the weight average molecular weight was 60,100. The hole transporting compound 15 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B3), and a structural unit (1c) having an unsaturated double bond (into the monomer W10). The proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure and units having a carbazole structure to the total number of structural units (excluding the terminal structural unit) was 100%.

<Synthesis of hole transporting compound 16>
The monomer A (5.0 mmol), the monomer B3 (2.0 mmol), the monomer C2 (4.0 mmol), and anisole (20 mL) were added to a three-necked round bottom flask, and a further prepared Pd catalyst solution (7. 5 mL) was added. Thereafter, in the same manner as the synthesis of the hole transporting compound 1, the hole transporting compound 16 was synthesized. The number average molecular weight of the obtained hole transporting compound 16 was 16,200, and the weight average molecular weight was 65,800. The hole transporting compound 16 includes a structural unit (1a) (derived from the monomer A), a structural unit (2b) (derived from the monomer B3), and a structural unit (1c) (derived from the monomer C2) having an oxetane group. And the proportion of each structural unit was 45.5%, 18.2%, and 36.3%. The ratio of the total number of units having an aromatic amine structure and units having a carbazole structure to the total number of structural units (excluding the terminal structural unit) was 100%.

The monomers used for the hole transporting compounds 1 to 16 are summarized in Table 1 below. The hole transporting compounds 1 to 7, 12 and 13 are charge transporting materials having an aromatic ring at the end substituted with a monovalent unsaturated group.

<Production and Evaluation of Organic EL Device>
<Organic EL device containing hole transporting compound in hole injection layer>
An organic EL device containing any of the hole transporting compounds produced above in the hole injection layer was prepared, and the performance was evaluated.
[Example 1]
In a nitrogen atmosphere, the hole transporting compound 1 (10.0 mg), the following polymerization initiator 1 (0.5 mg), and toluene (2.3 mL) were mixed to prepare an ink composition. The ink composition was spin-coated at a rotation speed of 3,000 min ⁻¹ on a glass substrate patterned with a width of 1.6 mm of ITO, and then cured by heating on a hot plate at 220 ° C. for 10 minutes to form a hole injection layer (30 nm) was formed.

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

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

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

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

[Example 5]
An organic EL device was produced in the same manner as in Example 1 except that the hole transporting compound 1 was changed to the hole transporting compound 7 in the step of forming the hole injection layer in the organic EL device of Example 1.

[Example 6]
An organic EL device was produced in the same manner as in Example 1 except that the polymerization initiator 1 was changed to the following polymerization initiator 2 in the hole injection layer forming step in the organic EL device of Example 1.

[Example 7]
An organic EL device was produced in the same manner as in Example 1 except that the polymerization initiator 1 was changed to the polymerization initiator 2 in the step of forming the hole injection layer in the organic EL device of Example 3.

[Example 8]
An organic EL device was produced in the same manner as in Example 1 except that the polymerization initiator 1 was changed to the polymerization initiator 2 in the step of forming the hole injection layer in the organic EL device of Example 5.

[Comparative Example 1]
An organic EL device was produced in the same manner as in Example 1 except that the hole transporting compound 1 was changed to the hole transporting compound 8 in the step of forming the hole injection layer in the organic EL device of Example 1.

[Comparative Example 2]
An organic EL device was produced in the same manner as in Example 1 except that the hole transporting compound 1 was changed to the hole transporting compound 10 in the step of forming the hole injection layer in the organic EL device of Example 1.

[Comparative Example 3]
In the step of forming the hole injection layer in the organic EL device of Example 1, the hole transporting compound 1 was changed to the hole transporting compound 9, and the polymerization initiator 1 was changed to the polymerization initiator 2. Thus, an organic EL element was produced.

The material used for hole injection layer formation of the organic EL element in the above Examples 1-8 and Comparative Examples 1-3 is put together in a table | surface.

When voltage was applied to the organic EL elements obtained in Examples 1 to 8 and Comparative Examples 1 to 3, green light emission was confirmed. For each element, to measure the emission luminance 1,000 cd / ^{m 2} at a light emission efficiency and an initial luminance 5,000 cd / ^{m 2} in luminance 5% decay time (LT95). Table 3 shows the measurement results. For measurement of luminance, “BM-7” manufactured by Topcon Corporation was used.

  As shown in Table 3, in Examples 1 to 8, organic EL elements having high luminous efficiency, excellent driving stability, and little initial deterioration were obtained. From Examples 1 to 8, it can be seen that, in the hole transporting compound which is a charge transporting material having a specific structure, the effect of improving the efficiency and life is obtained.

  <Organic EL device containing hole transporting compound in hole transporting layer> An organic EL device containing any of the hole transporting compounds produced above in a hole transporting layer was prepared, and its performance was evaluated.

[Example 9]
A PEDOT: PSS dispersion (AI 4083, manufactured by Heraeus Co., Ltd.) is spin-coated at 1500 min-1 on a glass substrate patterned with ITO to a width of 1.6 mm, and is heated and dried in air at 200 ° C. for 10 minutes. Thus, a hole injection layer (40 nm) was formed. Subsequent experiments were performed in a dry nitrogen environment.

The hole transporting compound 12 (10.0 mg) and toluene (1.2 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 cured by heating on a hot plate at 220 ° C. for 10 minutes to form a hole transport layer (40 nm). .

The glass substrate is transferred into a vacuum 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) was formed in this order by a vapor deposition method. Then, the sealing process was performed and the organic EL element was produced.

[Example 10]
An organic EL device was produced in the same manner as in Example 9 except that the hole transporting compound 12 was changed to the hole transporting compound 13 in the step of forming the hole transporting layer in the organic EL device of Example 9.

[Example 11]
In the step of forming the hole transport layer in the organic EL device of Example 9, ink in which the hole transport compound 12 (10.0 mg), the polymerization initiator 1 (0.5 mg), and toluene (1.2 mL) were mixed. An organic EL device was produced in the same manner as in Example 9 except that the composition was changed.

[Example 12]
In the step of forming a hole transport layer in the organic EL device of Example 10, ink in which the hole transport compound 13 (10.0 mg), the polymerization initiator 2 (0.5 mg), and toluene (1.2 mL) were mixed. An organic EL device was produced in the same manner except that the composition was changed.

[Comparative Example 4]
An organic EL device was produced in the same manner as in Example 9 except that the hole transporting compound 12 was changed to the hole transporting compound 16 in the step of forming the hole transporting layer in the organic EL device of Example 9.

[Comparative Example 5]
An organic EL device was produced in the same manner as in Example 9 except that the hole transporting compound 12 was changed to the hole transporting compound 14 in the step of forming the hole transporting layer in the organic EL device of Example 9.

[Comparative Example 6]
An organic EL device was produced in the same manner as in Example 9 except that the hole transporting compound 12 was changed to the hole transporting compound 15 in the step of forming the hole transporting layer in the organic EL device of Example 9.

[Comparative Example 7]
In the step of forming the hole transport layer in the organic EL device of Comparative Example 4, an ink in which the hole transport compound 14 (10.0 mg), the polymerization initiator 2 (0.5 mg), and toluene (1.2 mL) are mixed. An organic EL device was produced in the same manner as in Example 9 except that the composition was changed.

  In Table 4, the structure of the positive hole transport layer of the organic EL element produced in Examples 9-12 and Comparative Examples 4-7 is shown collectively.

When voltage was applied to the organic EL elements obtained in Examples 9 to 12 and Comparative Examples 4 to 6, green light emission was confirmed. For each element, to measure the emission luminance 1,000 cd / ^{m 2} at a light emission efficiency and an initial luminance 5,000 cd / ^{m 2} in luminance 5% decay time (LT95). Table 5 shows the measurement results. For measurement of luminance, “BM-7” manufactured by Topcon Corporation was used.

  As shown in Table 5, in Examples 9 to 12, organic EL elements having high luminous efficiency, excellent driving stability, and little initial deterioration were obtained. From Examples 9 to 12, it can be seen that, in the hole transporting compound which is a charge transporting material having a specific structure, the effect of improving the light emission efficiency and the lifetime was obtained.

<Production and Evaluation of White Organic EL Element (Lighting Device)>
[Example 13]
In a nitrogen atmosphere, the hole transporting compound 1 (10.0 mg), the polymerization initiator 1 (0.5 mg), and toluene (2.3 mL) were mixed to prepare an ink composition. The ink composition was spin-coated at a rotation speed of 3,000 min ⁻¹ on a glass substrate patterned with a width of 1.6 mm of ITO, and then cured by heating on a hot plate at 220 ° C. for 10 minutes to form a hole injection layer (30 nm) was formed.

Next, the hole transporting compound 12 (20.0 mg), the polymerization initiator 1 (0.5 mg), and toluene (2.3 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 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.

Further, under nitrogen atmosphere, 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 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 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 a vapor deposition method. Then, the sealing process was performed and the white organic EL element was produced. The white organic EL element could be used as a lighting device.

[Example 14]
A white organic EL device was produced in the same manner except that the hole transporting compound 12 was changed to the hole transporting compound 15 in the step of forming the hole transporting layer in the white organic EL device of Example 13.

[Comparative Example 8]
In the step of forming the hole injection layer in the white organic EL device of Example 13, the hole transporting compound 1 was changed to the hole transporting compound 11, and in the step of forming the hole transporting layer, the hole transporting compound was changed. A white organic EL device was produced in the same manner except that 12 was changed to the hole transporting compound 16.

A voltage was applied to the white organic EL elements obtained in Examples 13 and 14 and Comparative Example 8, and a voltage at a luminance of 1,000 cd / m ² and a light emission lifetime at an initial luminance of 1,000 cd / m ² (luminance half time) Was measured. Assuming that the voltage of Example 13 was 1.0, the voltages of Example 14 and Comparative Example 8 were 1.15 and 1.05, respectively. Further, assuming that the emission lifetime of Example 13 was 1.0, the emission lifetimes of Example 14 and Comparative Example 8 were 0.88 and 0.25, respectively.

  The effects of the embodiment of the present invention have been shown using the above examples. In addition to the combination of the organic electronics materials used in the examples, it is possible to obtain an organic EL element having a long lifetime by using a combination selected from the organic electronics materials described above.

  With the organic electronic material of the present invention, an organic layer can be easily formed by a wet process, and an organic EL element having excellent lifetime characteristics can be obtained.

DESCRIPTION OF SYMBOLS 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 (19)

An organic electronic material containing a charge transporting material terminated with an aromatic ring substituted with a monovalent unsaturated group,
The monovalent unsaturated group includes an aliphatic organic group containing at least one carbon-carbon double bond, and the total number of carbon atoms of the aliphatic organic group is 6 or more. The organic electronic material according to claim 1, wherein the carbon-carbon double bond is located at a terminal of the monovalent unsaturated group. The organic electronic material according to claim 1 or 2, wherein the monovalent unsaturated group includes a vinyl group and / or a vinyl ether group. The organic electronic material according to claim 1, wherein the charge transporting material is a hole transporting material.   5. The charge transporting material according to claim 1, wherein the charge transporting material is a charge transporting polymer including a charge transporting structural unit and an aromatic ring substituted with the monovalent unsaturated group. Organic electronics materials.   Furthermore, the organic electronic material as described in any one of Claims 1-5 containing a polymerization initiator.   The organic electronic material according to claim 6, wherein the polymerization initiator includes a cationic polymerization initiator.   The organic electronic material according to claim 7, wherein the cationic polymerization initiator is an onium salt.   The organic electronic material according to any one of claims 1 to 8, wherein the charge transporting material is selected from the group consisting of an aromatic amine compound, a carbazole compound, and a thiophene compound. The organic layer formed with the organic electronics material as described in any one of Claims 1-9. An organic electronic device comprising the organic layer according to claim 10. The organic electroluminescent element containing the organic layer of Claim 10. The organic electroluminescent device according to claim 12, comprising a light emitting layer containing a phosphorescent material. The organic electroluminescent device according to claim 12, further comprising a light emitting layer containing a delayed fluorescent material. The organic electroluminescent element according to claim 12, further comprising a flexible substrate. The organic electroluminescent element according to claim 12, further comprising a resin film substrate. The display element provided with the organic electroluminescent element as described in any one of Claims 12-16. The illuminating device provided with the organic electroluminescent element as described in any one of Claims 12-16. A display device comprising the illumination device according to claim 18 and a liquid crystal element as display means.

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