JP7255194B2 - organic electronic materials - Google Patents

Description

TECHNICAL FIELD Embodiments of the present invention relate to organic electronic materials and organic thin films using the materials. Further, another embodiment of the present invention relates to an organic electronic element and an organic electroluminescence element containing the above organic thin film, and a display element, a lighting device, and a display device using these.

An organic electronic element is an element that performs electrical operation using an organic substance, and is expected to exhibit features such as energy saving, low cost, and flexibility. Therefore, it is attracting attention as a technology to replace conventional inorganic semiconductors mainly composed of silicon.

Examples of organic electronic elements include organic electroluminescence elements (hereinafter also referred to as “organic EL elements”), organic photoelectric conversion elements, organic transistors, and the like.
Among organic electronic devices, organic EL devices have attracted attention as large area solid state light source applications, for example, replacing incandescent lamps or gas-filled lamps. In addition, it is attracting attention as the most powerful self-luminous display to replace the liquid crystal display (LCD) in the flat panel display (FPD) field, and commercialization is progressing.

Organic EL elements are roughly classified into low-molecular-weight organic EL elements and high-molecular-weight organic EL elements according to the organic materials used. Polymeric organic EL devices use polymer compounds as organic materials, and low-molecular-weight organic EL devices use low-molecular-weight compounds. On the other hand, the manufacturing method of organic EL elements is mainly a dry process in which films are formed in a vacuum system, a wet process in which films are formed by plate printing such as letterpress printing and intaglio printing, and plateless printing such as inkjet. and Since the wet process enables simple film formation, it is expected to be an indispensable method for realizing large-screen organic EL displays in the future.

Therefore, in recent years, efforts have been made to develop materials suitable for wet processes. For example, studies have been made to produce an organic EL device having a multilayer structure using a polymer compound having a polymerizable functional group (see, for example, Patent Document 1 and Non-Patent Document 1).

Japanese Patent Application Laid-Open No. 2006-279007

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

An organic EL element manufactured by a wet process using a polymer compound has the advantage that it can be easily manufactured at a low cost and in a large area. However, organic EL elements manufactured using conventional polymer compounds are desired to be further improved in various characteristics of the organic EL elements such as driving voltage, luminous efficiency, and life characteristics.

In addition, when a polymer compound having a polymerizable functional group is used to produce an organic EL element with a multilayer structure, in order to improve mass productivity and yield, a stable ink composition that does not easily generate insoluble matter and precipitates is used. is desirable.

In view of the above, an embodiment of the present invention provides an organic electronic material that can exhibit excellent charge transportability and is suitable as an ink composition, and an organic thin film that uses the material and has excellent charge transportability. aim. Another object of the present invention is to provide an organic electronic device and an organic EL device containing the organic thin film, and a display device, lighting device, and display device using these.

As a result of intensive studies on organic electronic materials containing charge-transporting polymer compounds, the present inventors have found that a super Bronsted acid compound, a charge-transporting compound, a Group 15 element of the IUPAC periodic table of elements, or the IUPAC element period an organic electronic material comprising a compound having an element of Group 16 of the Periodic Table of the Elements and a solvent having neither an element of Group 15 of the IUPAC Periodic Table of the Elements nor a solvent of Group 16 of the IUPAC Periodic Table of Elements; , an organic electronic material comprising a super Bronsted acid compound, a charge-transporting compound and a solvent having an IUPAC Group 15 element of the Periodic Table of the Elements or an element of the IUPAC Group 16 of the Periodic Table of the Elements is preferably found that it can be used. Furthermore, the inventors have found that an organic thin film formed using the above organic electronic material is effective in improving the charge transport property of an organic EL device, and have completed the present invention. That is, embodiments of the present invention relate to:

Embodiments of the present invention relate to organic electronic materials, one aspect of which is a charge-transporting compound, a super Bronsted acid compound, and a Group 15 element of the IUPAC Periodic Table of the Elements or an element of the IUPAC Periodic Table of the Elements. It relates to an organic electronic material comprising a compound having a Group 16 element and a solvent having neither the IUPAC Group 15 elements nor the IUPAC Group 16 elements.
Another aspect of the organic electronic material of the embodiment of the present invention is a charge-transporting compound, a super Bronsted acid compound, and a Group 15 element of the IUPAC Periodic Table of Elements or an element of the IUPAC Periodic Table of Elements. and a solvent having Group 16 elements.
In the organic electronic material, the charge-transporting compound preferably contains a polymer compound.
In the organic electronic material, the charge-transporting compound preferably has at least one polymerizable functional group.

Another embodiment of the present invention relates to an organic thin film formed using the organic electronic material of any one of the above embodiments.

Another embodiment of the present invention relates to an organic electronic device comprising the organic thin film of the above embodiments.

Another embodiment of the present invention relates to an organic electroluminescent device including the organic thin film of the above embodiment. The organic thin film of the above embodiment is preferably at least one of a hole injection layer and a hole transport layer.
Preferably, the organic electroluminescence element further has a flexible substrate or a resin film substrate.

Another embodiment of the present invention relates to a display device comprising the organic electroluminescence device of the above embodiment.

Another embodiment of the present invention relates to a lighting device including the organic electroluminescence element of the above embodiment.

Another embodiment of the present invention relates to a display device including the illumination device of the above embodiment and a liquid crystal element as display means.

According to the embodiments of the present invention, it is possible to provide an organic electronic material that can exhibit excellent charge transportability and is suitable as an ink composition, and an organic thin film that uses the material and has excellent charge transportability. Further, according to another embodiment of the present invention, an organic electronic element and an organic EL element including an organic thin film formed using an organic electronic material, and a display element, lighting device, and display using the same Equipment can be provided.

FIG. 1 is a schematic diagram showing an example of an organic EL device that is one embodiment of the present invention. FIG. 2 is a schematic diagram showing an example of an organic EL element that is one embodiment of the present invention. 3 is a graph of voltage-current density curves when a voltage is applied to each hole-only device obtained in Example 30 and Comparative Example 10. FIG.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of the present invention will be described in detail.

<Organic electronic materials>
One aspect of the organic electronic material that is an embodiment of the present invention includes a charge-transporting compound, a super Bronsted acid compound, and the IUPAC Periodic Table of the Elements (version date 1 June 2012). The same applies hereinafter.) Group 15 elements (hereinafter, sometimes simply referred to as "Group 15 elements") or Group 16 elements of the IUPAC periodic table of elements (hereinafter simply referred to as "16th group elements") (sometimes referred to as "group elements"), and solvents that do not have either group 15 or group 16 elements. Hereinafter, this organic electronic material may be referred to as "organic electronic material I".
Another aspect of the organic electronic material, which is an embodiment of the present invention, includes a charge-transporting compound, a super Bronsted acid compound, and a solvent having a Group 15 element or Group 16 element. Hereinafter, this organic electronic material may be referred to as "organic electronic material II".
Both of the above organic electronic materials I and II can be preferably used as an ink composition. Also, an organic thin film having excellent charge transport ability can be formed. Therefore, by using such organic electronic materials and organic thin films, it is possible to easily improve various device characteristics including emission lifetime.

<<Organic electronics material I>>
Any of a charge-transporting compound, a super Bronsted acid compound, a compound containing a Group 15 element or a Group 16 element, and a Group 15 element or a Group 16 element, which are one of the embodiments of the present invention An organic electronic material (organic electronic material I) containing a solvent that does not have a solvent will be described.

[Charge-transporting compound]
The charge-transporting compound is not particularly limited as long as it is a compound capable of transporting charges. From the viewpoint of ease of compound synthesis/purification, low-molecular-weight compounds having only one structural unit are preferred, and from the viewpoints of solvent solubility and film-forming properties, high-molecular-weight compounds having a plurality of structural units are preferred. Hereinafter, a low-molecular-weight compound having charge-transporting properties may be referred to as a "charge-transporting low-molecular-weight compound". Also, a polymer compound having a charge-transporting property is sometimes referred to as a "charge-transporting polymer".

[Charge transporting low molecular compound]
The charge-transporting low-molecular-weight compound is preferably a compound containing, as a partial structure, a structure exemplified as an example of the structural unit L of the charge-transporting polymer described later.

[Charge-transporting polymer]
The charge-transporting polymer may be linear or have a structure branched in three or more directions (branched structure). From the viewpoint of easy control of the molecular weight, a linear polymer is preferable, and from the viewpoint of high charge transportability and heat resistance, it is preferable to have a branched structure in three or more directions.

The charge-transporting polymer preferably contains at least a divalent structural unit L having a charge-transporting property and a monovalent structural unit T constituting a terminal portion, and a trivalent or higher structural unit B constituting a branched portion. may further include: The charge-transporting polymer may contain only one type of each structural unit, or may contain a plurality of types of each structural unit. Each structural unit is bonded to each other at a “monovalent” to “trivalent or higher” binding site.

(structure)
Examples of partial structures contained in the charge-transporting polymer include the following. The charge-transporting polymer is not limited to polymers having the following partial structures. In the partial structure, "B" represents structural unit B, "L" represents structural unit L, and "T" represents structural unit T. "*" represents a binding site with another structural unit. In the partial structures below, a plurality of L's may be the same structural unit or different structural units. The same is true for "T" and "B".

Linear charge-transporting polymer

Charge-transporting polymer with branched structure

Each structural unit will be described in more detail below.

(structural unit L)
Structural unit L is a divalent structural unit having charge transport properties. Structural unit L is not particularly limited as long as it contains an atomic group capable of transporting charge. For example, the structural unit L is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, biphenyl structure, terphenyl 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 It is selected from a thiophene structure, a benzoxazole structure, a benzoxadiazole structure, a benzothiazole structure, a benzothiadiazole structure, a benzotriazole structure, and structures containing one or more of these.
The aromatic amine structure is preferably a triarylamine structure, more preferably a triphenylamine structure.

In one embodiment, the structural unit L is a substituted or unsubstituted aromatic amine structure, carbazole structure, thiophene structure, fluorene structure, benzene structure, pyrrole structure, and these, from the viewpoint of obtaining excellent hole transport properties. is preferably selected from structures containing one or more of the substituted or unsubstituted aromatic amine structures, carbazole structures, and structures containing one or more of these is more preferred.

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

Each R independently represents a hydrogen atom or a substituent. Preferably, R each 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. is selected from the group consisting of groups comprising R ¹ to R ⁸ each independently represent a hydrogen atom; a linear, cyclic or branched alkyl group having 1 to 22 carbon atoms; or an aryl or heteroaryl group having 2 to 30 carbon atoms. An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon. A heteroaryl group is an atomic group in which one hydrogen atom is removed from an aromatic heterocycle. 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 may be further substituted by a linear, cyclic or branched group having 1 to 22 carbon atoms. It may be substituted with an alkyl group. R is preferably a hydrogen atom, an alkyl group, an aryl group or an alkyl-substituted aryl group. Ar represents an arylene group or 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.

The aromatic hydrocarbon includes a single ring, a condensed ring, or a polycyclic ring in which two or more selected from a single ring and a condensed ring are bonded via a single bond. The aromatic heterocycle includes a single ring, a condensed ring, or a polycyclic ring in which two or more rings selected from a single ring and a condensed ring are bonded via a single bond.

(structural unit T)
Structural unit T is a monovalent structural unit that constitutes a terminal portion of the charge-transporting polymer. The structural unit T is not particularly limited, and is selected from, for example, substituted or unsubstituted aromatic hydrocarbon structures, aromatic heterocyclic structures, and structures containing one or more of these. Structural unit T may have the same structure as 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 reducing charge transportability, and substituted or unsubstituted benzene A structure is more preferred. In another embodiment, as will be described later, when the charge-transporting polymer has a polymerizable functional group at its terminal, the structural unit T is a polymerizable structure (for example, a polymerizable functional group such as a pyrrol-yl group ).

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

R is the same as R in structural unit L. When the charge-transporting polymer has a polymerizable functional group at its terminal, at least one of R is preferably a group containing a polymerizable functional group.

(Structural unit B)
Structural unit B is a trivalent or higher valent structural unit that constitutes a branched portion when the charge-transporting polymer has a branched structure. From the viewpoint of improving the durability of the organic electronic device, the structural unit B preferably has a valence of 6 or less, more preferably a valence of 3 or 4. Structural unit B is preferably a unit having charge transport properties. For example, from the viewpoint of improving the durability of the organic electronic device, the structural unit B may be a substituted or unsubstituted aromatic amine structure, a carbazole structure, a condensed polycyclic aromatic hydrocarbon structure, and one or two of these. It is selected from structures containing more than one species.

Specific examples of structural unit B include the following. 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. An arenetriyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic hydrocarbon. A heteroarenetriyl group is an atomic group obtained by removing three hydrogen atoms from an aromatic heterocyclic ring. Each Ar independently represents a divalent linking group, for example, each independently represents an arylene group having 2 to 30 carbon atoms or a heteroarylene group. Ar is preferably an arylene group, more preferably a phenylene group. Y represents a divalent linking group, for example, a group having one or more hydrogen atoms among R (excluding groups containing a polymerizable functional group) in the structural unit L, and further one hydrogen atom and divalent groups other than Z represents either a carbon atom, a silicon atom, or a phosphorus atom.

In the above structural unit, the benzene ring and Ar may have one or more substituents R. The substituents R each independently include -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: R ¹ to R ⁸ are the same as R ¹ to R ⁸ of R in structural unit L (except when R ¹ is a hydrogen atom). Substituent R is preferably an alkyl group, an aryl group, or an alkyl-substituted aryl group.

(Polymerizable functional group)
In one embodiment, the charge-transporting polymer preferably has at least one polymerizable functional group from the viewpoint of curing by a polymerization reaction and changing solubility in a solvent. "Polymerizable functional groups" refer to functional groups that can form bonds with each other by the application of heat and/or light.

As the polymerizable functional group, a group having a carbon-carbon multiple bond (e.g., vinyl group, allyl group, butenyl group, ethynyl group, acryloyl group, acryloyloxy group, acryloylamino group, methacryloyl group, methacryloyloxy group, methacryloylamino groups, vinyloxy groups, vinylamino groups, etc.), groups having small rings (e.g., cyclic alkyl groups such as cyclopropyl groups and cyclobutyl groups; epoxy groups (oxiranyl groups), cyclic ether groups such as oxetane groups (oxetanyl groups) ; diketene group; episulfide group; lactone group; These may have a substituent, and examples of the substituent include an alkyl group, and an alkyl group having 1 to 10 carbon atoms is preferable. As the polymerizable functional group, a vinyl group, an acryloyl group, a methacryloyl group, an epoxy group, and an oxetane group are particularly preferable, and from the viewpoint of reactivity and properties of the organic electronic device, a vinyl group, an oxetane group, or an epoxy group is more preferable. preferable.

From the viewpoint of increasing the degree of freedom of the polymerizable functional group and facilitating the polymerization reaction, it is preferable that the main skeleton of the charge-transporting polymer and the polymerizable functional group are linked by an alkylene chain. Further, for example, when an organic layer is formed on an electrode, from the viewpoint of improving the affinity with a hydrophilic electrode such as ITO, it is preferable that the organic layer is linked by a hydrophilic chain such as an ethylene glycol chain or a diethylene glycol chain. preferable. Furthermore, from the viewpoint of facilitating the preparation of the monomer used for introducing the polymerizable functional group, the charge-transporting polymer should be the end portion of the alkylene chain and/or the hydrophilic chain, that is, polymerized with these chains. An ether bond or an ester bond may be present at the linking portion with the functional group and/or at the linking portion between these chains and the skeleton of the charge-transporting polymer. The aforementioned "group containing a polymerizable functional group" means a polymerizable functional group itself or a group in which a polymerizable functional group and an alkylene chain or the like are combined. As a group containing a polymerizable functional group, for example, groups exemplified in International Publication No. WO2010/140553 can be preferably used.

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

From the viewpoint of contributing to the change in solubility, it is preferable that the charge-transporting polymer contain a large amount of the polymerizable functional group. On the other hand, from the viewpoint of not interfering with the charge-transporting property, it is preferable that the amount contained in the charge-transporting polymer is as small as possible. The content of the polymerizable functional group can be appropriately set in consideration of these factors.

For example, the number of polymerizable functional groups per molecule of the charge-transporting polymer is preferably 1 or more, more preferably 2 or more, and even more preferably 3 or more, from the viewpoint of obtaining a sufficient change in solubility. Moreover, the number of polymerizable functional groups is preferably 1,000 or less, more preferably 700 or less, and even more preferably 500 or less, from the viewpoint of maintaining charge transportability.

The number of polymerizable functional groups per charge-transporting polymer molecule is determined by the amount of polymerizable functional groups charged (for example, the amount of monomers having polymerizable functional groups charged) used to synthesize the charge-transporting polymer, each structure It can be determined as an average value using the charged amount of the monomer corresponding to the unit, the weight average molecular weight of the charge-transporting polymer, and the like. Further, the number of polymerizable functional groups is the ratio of the integrated value of the signal derived from the polymerizable functional group in the ¹ H NMR (nuclear magnetic resonance) spectrum of the charge-transporting polymer to the integrated value of the entire spectrum. It can be calculated as an average value using the weight average molecular weight of For convenience, when the charge amount is known, the value obtained using the charge amount is preferably adopted.

(Ratio of structural units B, L, and T)
When the charge-transporting polymer contains the structural unit B, the ratio of the structural unit B contained in the charge-transporting polymer is preferably 1 mol% or more based on the total structural units, from the viewpoint of improving the durability of the organic electronic device. , more preferably 5 mol % or more, and still more preferably 10 mol % or more. In addition, the proportion of the structural unit B is preferably 50 mol % or less, and 40 mol % or less, from the viewpoint of suppressing the increase in the viscosity and synthesizing the charge-transporting polymer well, or from the viewpoint of obtaining sufficient charge-transporting properties. is more preferable, and 30 mol % or less is even more preferable. The above ratio means the total amount of the structural unit B including the structural unit B1.

From the viewpoint of obtaining sufficient charge-transporting properties, the proportion of the structural unit L contained in the charge-transporting polymer is preferably 10 mol% or more, more preferably 20 mol% or more, and 30 mol% or more, based on all structural units. is more preferred. The ratio of the structural unit L is preferably 95 mol% or less, more preferably 90 mol% or less, and even more preferably 85 mol% or less, considering the structural unit T and the structural unit B introduced as necessary. When the charge-transporting polymer contains the structural unit L1, the above ratio means the total amount including the structural unit L1.

The ratio of the structural unit T contained in the charge-transporting polymer is based on the total structural units from the viewpoint of improving the characteristics of the organic electronic device, or from the viewpoint of suppressing an increase in viscosity and performing good synthesis of the charge-transporting polymer. , is preferably 5 mol % or more, more preferably 10 mol % or more, and even more preferably 15 mol % or more. Moreover, from the viewpoint of obtaining sufficient charge transportability, the proportion of the structural unit T is preferably 60 mol % or less, more preferably 55 mol % or less, and even more preferably 50 mol % or less. When the charge-transporting polymer contains the structural unit T1, the above ratio means the total amount including the structural unit T1.

When the charge-transporting polymer has a polymerizable functional group, the proportion of the polymerizable functional group is preferably 0.1 mol % or more based on all structural units, from the viewpoint of efficiently curing the charge-transporting polymer. 1 mol % or more is more preferable, and 3 mol % or more is even more preferable. In addition, the proportion of the polymerizable functional group is preferably 70 mol % or less, more preferably 60 mol % or less, and even more preferably 50 mol % or less, from the viewpoint of obtaining good charge transport properties. In addition, the "percentage of the polymerizable functional group" as used herein refers to the percentage of structural units having a polymerizable functional group.

Considering the balance of charge transport properties, durability, productivity, etc., the ratio (molar ratio) of the structural unit L and the structural unit T is preferably L:T=100:70 to 1, more preferably 100:50 to 3. Preferably, 100:30-5 is more preferable. Further, when the charge-transporting polymer contains the structural unit B, the ratio (molar ratio) of the structural unit L, the structural unit T, and the structural unit B is L:T:B=100:10 to 200:10 to 100. 100:20 to 180:20 to 90 is more preferred, and 100:40 to 160:30 to 80 is even more preferred.

The ratio of structural units can be determined using the amount of charged monomer corresponding to each structural unit used to synthesize the charge-transporting polymer. Also, the ratio of the structural units can be calculated as an average value using the integrated value of the spectrum derived from each structural unit in the ¹ H NMR spectrum of the charge-transporting polymer. For convenience, when the charge amount is known, the value obtained using the charge 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 solvents, film-forming properties, and the like. The number average molecular weight is preferably 500 or more, more preferably 1,000 or more, and even more preferably 2,000 or more, from the viewpoint of excellent charge transportability. In addition, the number average molecular weight is preferably 1,000,000 or less, more preferably 100,000 or less, more preferably 50,000, from the viewpoint of maintaining good solubility in a solvent and facilitating preparation of the ink composition. More preferred are:

(Weight average molecular weight)
The weight-average molecular weight of the charge-transporting polymer can be appropriately adjusted in consideration of solubility in solvents, film-forming properties, and the like. The weight average molecular weight is preferably 1,000 or more, more preferably 5,000 or more, and even more preferably 10,000 or more, from the viewpoint of excellent charge transportability. In addition, the weight average molecular weight is preferably 1,000,000 or less, more preferably 700,000 or less, more preferably 400,000, from the viewpoint of maintaining good solubility in the solvent and facilitating preparation of the ink composition. More preferred are:

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

(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, and Buchwald-Hartwig coupling can be used. Suzuki coupling causes a cross-coupling reaction between an aromatic boronic acid derivative and an aromatic halide using a Pd catalyst. According to Suzuki coupling, a charge-transporting polymer can be easily produced by bonding desired aromatic rings.

In the coupling reaction, for example, a Pd(0) compound, a Pd(II) compound, a Ni compound or the like is used as a catalyst. In addition, a catalyst species generated by mixing a phosphine ligand with a precursor such as tris(dibenzylideneacetone)dipalladium(0) or palladium(II) acetate can also be used. For the method for synthesizing the charge-transporting polymer, reference can be made to, for example, International Publication No. WO2010/140553.

[Super Bronsted acid compound]
The organic electronic material I contains super Bronsted acid compounds. The super Bronsted acid compound preferably has a perfluorinated sulfonyl group.

A perfluorinated sulfonyl group is preferably a group represented by R ^f SO ₂ —. R ^f represents a perfluorinated organic group, and examples of R ^f include linear, branched or cyclic perfluoroalkyl groups, perfluoroalkylsulfonyl groups, perfluoroalkylsulfonyl groups and perfluoroalkylsulfonyl groups having 1 to 20 carbon atoms and optionally containing heteroatoms. fluoroalkyloxysulfonyl group, perfluoroarylsulfonyl group, perfluoroaryloxysulfonyl group, perfluoroacyl group, perfluoroalkoxycarbonyl group, perfluoroacyloxy group, perfluoroaryloxycarbonyl group, perfluoroalkenyl group, perfluoroalkynyl group and the like, and those represented by the following structural formula group (1) are preferred, but are not limited thereto.

Structural formula group (1)

As the super Bronsted acid compound, a compound having an acidic functional group with an acid dissociation constant pKa of 2 or less is preferred.

The super Bronsted acid compound is preferably a nonionic compound from the viewpoint of increasing the solubility in nonpolar solvents. When the solubility of super Bronsted acid compounds in non-polar solvents improves, the compatibility with aromatic polymers, which are also easily soluble in non-polar solvents, tends to improve.

Here, the details of the "ionic compound" and the "nonionic compound" will be described.

The term "ionic compound" refers to a compound composed of a cation and an anion. Examples of cations include metal ions such as alkali metal ions and alkaline earth metal ions, carbocations such as triphenylcarbenium, and nitrogen compounds such as pyridinium and quinolinium. Known cations such as cations, onium cations such as iodonium, sulfonium and phosphonium can be used. However, in the present invention, hydrogen cations (also called H ⁺ or protons) are not included in the cations. Examples of the anion include known anions such as halide ions such as chloride ion and bromide ion, inorganic acid ions such as phosphate ion and sulfate ion, and organic acid ions such as acetate ion and lactate ion.

"Nonionic compound" refers to compounds not included in the definition of "ionic compound" above.

The super Bronsted acid compound is preferably represented by the following general formula (1) or (2).

In general formulas (1) and (2), Rf ¹ and Rf ² each independently represent a perfluorinated organic group, and R ¹ to R ³ each independently represent an organic group.

Examples and preferred structures of the perfluorinated organic group represented by Rf ¹ and Rf ² in the general formulas (1) and (2) are the same as the described ^Rf .

Examples of the organic groups represented by R ¹ to R ³ include alkyl groups having 1 to 20 carbon atoms, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups and the like, which further have substituents. may Specifically, the alkyl group is, for example, a linear, branched or cyclic alkyl group having usually 1 or more and 12 or less, preferably 6 or less carbon atoms. Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group and the like. Examples of alkenyl groups include those having usually 2 or more and 12 or less carbon atoms, preferably 6 or less carbon atoms. Specific examples include vinyl group, allyl group, 1-butenyl group and the like. Examples of alkynyl groups include those having usually 2 or more and 12 or less, preferably 6 or less carbon atoms. Specific examples include an ethynyl group and a propargyl group. Examples of the aryl group include groups obtained by removing one hydrogen atom from aromatic hydrocarbons having a 5- or 6-membered monocyclic ring or 2 to 5 condensed rings. Specific examples of aromatic hydrocarbons include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluorene ring and the like. The heteroaryl group includes, for example, a group obtained by removing one hydrogen atom from a 5- or 6-membered monocyclic ring or an aromatic heterocyclic ring having 2 to 4 condensed rings, and specific examples of the aromatic heterocyclic ring include , furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, triazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopiral ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, shinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like. In the case of having a substituent, examples of the substituent include a halogen atom, an amino group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an alkylcarbonyloxy group, an alkylthio group, an arylthio group, A silyl group, an alkylsulfonyl group, an arylsulfonyl group, and the like can be mentioned.

Examples of organic groups represented by R ¹ to R ³ include perfluorinated organic groups and groups represented by Rf ³ SO ₂ —. Rf ³ represents a perfluorinated organic group. Examples and preferred ranges of the perfluorinated organic group and the perfluorinated organic group represented by R ^f3 are the same as those described for R ^f .

In formula (1), at least one of R ¹ and R ² is preferably a perfluorinated organic group or a group represented by Rf ³ SO ₂ —, and at least one of R ¹ and R ² is more preferably a perfluorinated organic group selected from structural formula group (1) or a group represented by Rf ³ SO ₂ —.
In formula (1), R ¹ and R ² are preferably each independently a perfluorinated organic group or a group represented by Rf ³ SO ₂ —, and R ¹ and R ² are each independently represented by the structural formula It is more preferably a perfluorinated organic group selected from group (1) or a group represented by Rf ³ SO ₂ —.

In formula (2), R ³ is preferably a perfluorinated organic group or a group represented by Rf ³ SO ₂ —.

[Compound containing Group 15 element or Group 16 element]
Organic electronic material I preferably contains a compound having a Group 15 element or Group 16 element from the viewpoint of making an ink composition in which insoluble matter or precipitation is suppressed.

The compound containing a Group 15 element or Group 16 element preferably has a molecular weight of 800 or less, more preferably 500 or less, even more preferably 400 or less, and even more preferably 300 or less.

A compound having a Group 15 element or a Group 16 element preferably has at least one element selected from the group consisting of nitrogen, phosphorus, oxygen, and sulfur from the viewpoint of availability. and oxygen. A compound having a group 15 element or a group 16 element may contain one or a plurality of each of one or more of these group 15 elements and group 16 elements.

Examples of nitrogen-containing compounds include aromatic amine compounds, aliphatic amine compounds, amide compounds, imide compounds, nitro compounds, heterocyclic compounds, and salt compounds such as ammonium, aminium, and pyridinium, preferably aliphatic amines. compounds, amide compounds, imide compounds, and heterocyclic compounds. More specifically, dialkylamines (dibutylamine, etc.), trialkylamines (dicyclohexylmethylamine, N,N-dimethyl-N-tetradecylamine, N-methyldioctylamine, tris(2-ethylhexyl)amine, triisoamyl amine, N,N-dimethyl-N-octadecylamine, N,N-didecyl-N-methylamine, etc.), trialkanolamine (such as triethanolamine), tribenzylamine, N,N-dimethylformamide, N,N -diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, aniline, alkylaniline (such as 4-octylaniline), N,N-dialkylaniline, N,N-dibenzylaniline, N,N-dialkyl -N-benzylamine (such as N-ethyl-N-methylbenzylamine), N-alkyl-N,N-dibenzylamine, N,N-dialkyl-N-arylamine, N-alkyl-N,N-diaryl Amine, N-alkyl-N-aryl-N-benzylamine, N,N-diaryl-N-benzylamine, N,N-dibenzyl-N-arylamine, piperidine, pyridine, pyrazine, pyrimidine, piperazine, pyridazine, pyrrole , imidazole, nitrobenzene, ethylenediamine, propylenediamine, tetramethylenediamine, pentamethylenediamine, N,N-dialkylethylenediamine, N,N,N',N'-tetraalkylethylenediamine, N,N-dialkylpropylenediamine, N,N ,N',N'-tetraalkylpropylenediamine, N,N,N',N'-tetramethyl-1,6-diaminohexane, N,N,N',N'-tetramethylnaphthalenediamine, hexamethylenediamine , cyclohexanediamine, diethylenetriamine, tridodecylamine, triethylenetetramine, tetraethylenepentamine, tetraalkylammonium iodide (tetraethylammonium iodide, etc.), trialkoxyamine (tris{(2-methoxyethoxy)ethyl}amine, etc.), Anisidine and the like, among which trialkylamines, N,N-dialkylformamides, N,N-dialkylacetamides, and N-alkyl-N-aryl-N-benzylamines from the viewpoint of solubility in the ink composition. , N,N-dialkyl-N-arylamines, N-alkyl-N,N-diarylamines, anilines and alkylenediamines are preferred.

Examples of phosphorus-containing compounds include phosphine compounds, phosphine oxide compounds, phosphonate ester compounds, phosphonium salt compounds, phosphonic acid compounds, etc., preferably phosphine compounds, phosphine oxide compounds, phosphonic acid compounds, phosphonic acid esters. is a compound. More specifically, dimethylphosphinic acid, phenylphosphinic acid, phenylphosphonic acid, arylphosphine (such as o-tolylphosphine), triarylphosphine, trialkylphosphine, triarylphosphine oxide, trialkylphosphine oxide, triarylphosphine sulfide , tetraarylphosphonium chloride, tetraalkylphosphonium bromide (tetraoctylphosphonium bromide, etc.), tetraarylphosphonium bromide, tetraarylphosphonium iodide, dimethyl phosphonate, diethyl phosphonate, dimethyl methylphosphonate, trimethyl phosphate and the like. , triarylphosphine, trialkylphosphine, triarylphosphine oxide and trialkylphosphine oxide are preferred from the viewpoint of availability and solubility.

Examples of oxygen-containing compounds include aliphatic alcohol compounds, aromatic alcohol compounds, phenol compounds, aliphatic ether compounds, aromatic ether compounds, aliphatic ketone compounds, aromatic ketone compounds, aliphatic ester compounds, aromatic ester compounds. compounds, aliphatic carboxylic acid compounds, aromatic carboxylic acid compounds, oxonium chlorides, etc., preferably aliphatic alcohol compounds, aromatic alcohol compounds, phenol compounds, aliphatic ether compounds, aromatic ester compounds, fatty family ester compounds. More specifically, methanol, ethanol, propanol, butanol, hexanol, ethylene glycol, propylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol monopropyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoethyl ether, diethylene glycol diethyl ether, 18-crown-6, dibenzo-18-crown-6, 3-methyl-3-oxetanemethanol, benzyl alcohol, phenol, cresol, catechol, resorcinol, Anisole, phenetol, dimethyl ether, diethyl ether, diphenyl ether, dimethoxybenzene, tetramethoxymethane, cyclohexanol, methyl benzoate, ethyl benzoate, methyl formate, ethyl formate, methyl acetate, ethyl acetate, isopentyl acetate, pentyl acetate, butyl acetate, octyl acetate, methyl propionate, methyl butyrate, ethyl butyrate, methyl salicylate, and the like. Among them, cyclohexanol, benzyl alcohol, phenol, cresol, Glycol compounds, glycol monoester compounds and glycol diester compounds are preferred.

Examples of sulfur-containing compounds include aliphatic sulfonic acid compounds, aromatic sulfonic acid compounds, aliphatic sulfonic acid ester compounds, aromatic sulfonic acid ester compounds, thiophene compounds, sulfenic acid compounds, sulfone compounds, sulfide compounds, and sulfoxide compounds. , aliphatic thiol compounds, aromatic thiol compounds, sulfonium salt compounds, etc., preferably aliphatic thiol compounds, aromatic thiol compounds, thiophene compounds, sulfoxide compounds, sulfide compounds, and sulfone compounds. More specifically, methanethiol, ethanethiol, propanethiol, butanethiol, pentanethiol, hexanethiol, cyclopentanethiol, ethanedithiol, pentanedithiol, hexanedithiol, cyclohexanethiol, thiophenol, thiocresol, thioanisidine, thioanisole , thiophenetol, naphthalenethiol, benzenedithiol, thiophene, bithiophene, terthiophene, dimethylsulfoxide, diphenylsulfoxide, methylphenylsulfoxide, dimethylsulfide, diethylsulfide, ethylmethylsulfide, dimethylenesulfide, cyclopropylphenylsulfide, trimethylenesulfide , ethylphenylsulfide, diphenylsulfide, dimethylsulfone, ethylmethylsulfone, diethylsulfone, diphenylsulfone, ethylphenylsulfone, and the like. Thiol, ethanedithiol, cyclohexanethiol, thiophenol, thioanisole, thiophene, dimethylsulfide, diphenylsulfide, dimethylsulfone, diphenylsulfone, dimethylsulfoxide, diphenylsulfoxide are preferred.

[Solvent containing neither Group 15 element nor Group 16 element]
The organic electronic material I contains a solvent that does not have any group 15 elements or group 16 elements.

As the solvent containing neither Group 15 element nor Group 16 element, an organic solvent containing neither Group 15 element nor Group 16 element, or a mixed solvent thereof can be used. Examples of organic solvents containing neither group 15 elements nor group 16 elements include alkanes such as pentane, hexane and octane; cyclic alkanes such as cyclohexane; aromatic solvents such as benzene, toluene, xylene, mesitylene, tetralin and diphenylmethane. group hydrocarbon; chloroform, methylene chloride and the like. As the solvent containing neither group 15 elements nor group 16 elements, organic solvents are preferable, and aromatic hydrocarbons and the like are more preferable. When the super Bronsted acid compound is a nonionic compound, it is preferable to use a nonpolar solvent such as an aromatic hydrocarbon from the viewpoint of compatibility between the super Bronsted acid compound and the aromatic polymer.

[Additive]
The organic electronic material I may further contain additives as optional components. Additives include, for example, polymerization inhibitors, stabilizers, thickeners, gelling agents, flame retardants, antioxidants, reducing agents, oxidizing agents, reducing agents, surface modifiers, emulsifiers, antifoaming agents, Dispersants, surfactants and the like are included.

[Content]
The content of the charge-transporting compound in the organic electronic material I is, from the viewpoint of obtaining good charge-transporting properties, the total mass of the organic electronic material I, the solvent containing neither group 15 elements nor group 16 elements is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more with respect to the mass excluding the mass of On the other hand, the content of the charge-transporting compound is 90% by mass or less with respect to the total mass of the organic electronic material I minus the mass of the solvent containing neither the group 15 element nor the group 16 element. is preferable, 80% by mass or less is more preferable, and 70% by mass or less is even more preferable.
The content of the charge-transporting compound in the organic electronic material I is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, relative to the total mass of the organic electronic material I from the viewpoint of obtaining good charge-transporting properties. is more preferable, and 1% by mass or more is even more preferable. On the other hand, the content of the charge-transporting compound is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the organic electronic material I.

The content of the super Bronsted acid compound in the organic electronic material I is more preferably such that the ratio of the super Bronsted acid compound to the charge-transporting compound is 0.1% by mass or more, and is 0.2% by mass or more. more preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more. On the other hand, the content of the super Bronsted acid compound is preferably such that the ratio of the super Bronsted acid compound to the charge-transporting compound is 40% by mass or less, more preferably 20% by mass or less, and 15% by mass. % or less, and more preferably 10 mass % or less.

The content of the compound containing the Group 15 element or Group 16 element in the organic electronic material I is such that the ratio of the compound containing the Group 15 element or Group 16 element to the charge-transporting compound is 10% by mass or more. An amount of 20% by mass or more is more preferable, an amount of 30% by mass or more is even more preferable, and an amount of 40% by mass or more is even more preferable. On the other hand, the content of the compound containing a Group 15 element or Group 16 element is preferably such that the ratio of the compound containing a Group 15 element or Group 16 element to the charge-transporting compound is 90% by mass or less. , is more preferably 80% by mass or less, and more preferably 70% by mass or less.

The content of the solvent containing neither group 15 elements nor group 16 elements in the organic electronic material I can be determined in consideration of application to various coating methods. For example, the content of the solvent containing neither Group 15 elements nor Group 16 elements is such that the ratio of the charge-transporting compound to the solvent containing neither Group 15 elements nor Group 16 elements is 0. An amount of 0.1% by mass or more is preferable, an amount of 0.2% by mass or more is more preferable, and an amount of 0.5% by mass or more is even more preferable. In addition, the content of the solvent containing neither the Group 15 element nor the Group 16 element is such that the ratio of the charge-transporting compound to the solvent containing neither the Group 15 element nor the Group 16 element is , is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less.

<<Organic Electronics Material II>>
An organic electronic material (organic electronic material II) containing a charge-transporting compound, a super Bronsted acid compound, and a solvent containing a Group 15 element or Group 16 element, which is one embodiment of the present invention, will be described. do.

[component]
As the charge-transporting compound and the super Bronsted acid compound, the charge-transporting compound and the super Bronsted acid compound described in the organic electronic material I can be used, respectively, and the preferred ranges are also the same.

The organic electronic material II preferably contains a solvent containing a Group 15 element or Group 16 element from the viewpoint of obtaining an ink composition in which insoluble matter or precipitation is suppressed.
Solvents containing Group 15 elements or Group 16 elements include alcohols such as methanol, ethanol and isopropyl alcohol; aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether and propylene glycol-1-monomethyl ether acetate; ,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and other aromatic ethers ; aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate; aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate and n-butyl benzoate esters; amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide; organic solvents such as dimethylsulfoxide, tetrahydrofuran, and acetone; and mixed solvents thereof.
Examples of the solvent containing a Group 15 element or Group 16 element include those that can be used as a solvent, among those listed as examples of compounds containing a Group 15 element or Group 16 element. be done.

As the solvent containing a Group 15 element or Group 16 element, a solvent containing oxygen is preferable, and aliphatic esters, aromatic esters, aliphatic ethers, aromatic ethers and the like are more preferable.

The organic electronic material II may include a solvent having a Group 15 element or a Group 16 element as well as a solvent having neither Group 15 nor Group 16 elements. As the solvent that does not have either the Group 15 element or the Group 16 element, a solvent that does not have either the Group 15 element or the Group 16 element described in the organic electronic material I described above is used. and the preferred range is also the same.

Organic electronic material II may further contain additives as optional components. As the additive, for example, those described in the organic electronic material I can be used.

[Content]
The content of the charge-transporting compound in the organic electronic material II is preferably 0.1% by mass or more, preferably 0.5% by mass or more, based on the total mass of the organic electronic material II, from the viewpoint of obtaining good charge-transporting properties. is more preferable, and 1% by mass or more is even more preferable. On the other hand, the content of the charge-transporting compound is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less, relative to the total mass of the organic electronic material II.

The content of the super Bronsted acid compound in the organic electronic material II is preferably such that the ratio of the super Bronsted acid compound to the charge-transporting compound is 0.1% by mass or more, and is 0.2% by mass or more. More preferably, the amount is 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 2% by mass or more. On the other hand, the content of the super Bronsted acid compound is preferably such that the ratio of the super Bronsted acid compound to the charge-transporting compound is 40% by mass or less, more preferably 20% by mass or less, and 15% by mass. % or less, and more preferably 10 mass % or less.

The content of the solvent containing the Group 15 element or Group 16 element in the organic electronic material II is such that the ratio of the solvent containing the Group 15 element or Group 16 element to the charge-transporting compound is 10% by mass or more. An amount of 20% by mass or more is more preferable, and an amount of 40% by mass or more is even more preferable. On the other hand, the content of the solvent containing the Group 15 element or Group 16 element is preferably such that the ratio of the compound containing the Group 15 element or Group 16 element to the charge-transporting compound is 90% by mass or less. , is more preferably 80% by mass or less, and more preferably 70% by mass or less.

The content of the solvent containing the Group 15 element or Group 16 element in the organic electronic material II 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 compound to the solvent is 0.1% by mass or more, more preferably 0.2% by mass or more, and 0.5% by mass or more. is more preferable. The content of the solvent is preferably such that the ratio of the charge-transporting compound 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 thin film (organic layer)>
An organic thin film (hereinafter sometimes referred to as an “organic layer”) that is an embodiment of the present invention is a layer formed using any of the organic electronic materials of the above embodiments. Since both the organic electronic materials I and II of the above embodiment contain a solvent, they can be used as an ink composition. Therefore, the organic layer can be satisfactorily formed by a coating method.
Therefore, the organic layer, which is an embodiment of the present invention, can be produced by a production method including, for example, a step of applying an ink composition (organic electronic material).
The coating method includes, for example, a spin coating method; a casting method; an immersion method; A known method such as a plateless printing method can be used.
The above production method includes drying the organic layer obtained after coating (i.e., the coating layer) using a hot plate or an oven to remove the solvent, and performing any steps such as curing the coating layer. It may contain further.

When the charge-transporting polymer has a polymerizable functional group, the polymerization reaction of the charge-transporting polymer can be advanced by light irradiation, heat treatment, or the like, and the solubility of the organic layer can be changed. By stacking organic layers with different solubilities, it is possible to easily form a multi-layered organic electronic element. For the method of forming the organic layer, for example, reference can be made to the description in International Publication No. WO2010/140553.

The thickness of the organic layer after drying or curing is preferably 0.1 nm or more, more preferably 1 nm or more, and still more preferably 3 nm or more, from the viewpoint of improving charge transport efficiency. Moreover, 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 element>
An organic electronic device that is an embodiment of the present invention has at least the organic layer of the above embodiment. Organic electronic elements include, for example, organic EL elements, organic photoelectric conversion elements, organic transistors, organic light emitting diodes (OLEDs), and the like. The organic electronic device preferably has a structure in which an organic layer is arranged between at least a pair of electrodes.

[Organic EL element]
An organic EL element that is an embodiment of the present invention has at least the organic layer of the above embodiment. An organic EL device usually comprises a light-emitting layer, an anode, a cathode, and a substrate, and optionally other functional layers such as a hole injection layer, an electron injection layer, a hole transport layer, an electron transport layer, and the like. I have. Each layer may be formed by a vapor deposition method, or may be formed by a coating method. The organic EL device preferably has an organic layer as a light emitting layer or other functional layer, more preferably as a functional layer, and even more preferably as at least one of a hole injection layer and a hole transport layer. In one embodiment, the formation of the organic layer can be successfully carried out using the ink composition described above and according to the coating method.

1 and 2 are schematic cross-sectional views showing one embodiment of the organic EL element, respectively. The organic EL element shown in FIG. 1 is an element having a multilayer structure, and has an anode 1, a hole injection layer 2, a light emitting layer 3, an electron injection layer 4, and a cathode 5 in this order on a substrate 6. . In one embodiment, the hole injection layer 2 consists of an organic layer, which is one embodiment of the invention.
The organic EL element shown in FIG. 2 is an element having a multilayer structure, and on a substrate 6, an anode 1, a hole injection layer 2, a hole transport layer 7, a light emitting layer 3, an electron transport layer 8 and an electron injection layer 4 are formed. , and the cathode 5 in this order. In one embodiment, at least one of the hole injection layer 2 and the hole transport layer 7 is composed of an organic layer that is one embodiment of the present invention. Each layer will be described below.

[Light emitting layer]
Light-emitting materials such as low-molecular-weight compounds, polymers, and dendrimers can be used as materials for the light-emitting layer. Polymers are preferred because they are highly soluble in solvents and are suitable for coating methods. Examples of light-emitting materials include fluorescent materials, phosphorescent materials, thermally activated delayed fluorescent materials (TADF), and the like.

Low-molecular-weight compounds such as perylene, coumarin, rubrene, quinacdrine, stilbene, pigments for dye lasers, aluminum complexes, and derivatives thereof; polyfluorene, polyphenylene, polyphenylenevinylene, polyvinylcarbazole, and fluorene-benzothiadiazole copolymer , fluorene-triphenylamine copolymers, derivatives thereof; and mixtures thereof.

A metal complex containing a metal such as Ir or Pt can be used as the phosphorescent material. Examples of the Ir complex include FIr(pic) (iridium (III) bis[(4,6-difluorophenyl)-pyridinate-N,C ² ]picolinate) that emits blue light, and Ir(ppy) ₃ that emits green light. (Factris(2-phenylpyridine)iridium), red-emitting (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-phorphineplatinum) that emits red light.

When the light-emitting layer contains a phosphorescent material, it preferably contains a host material in addition to the phosphorescent material. Low-molecular-weight compounds, polymers, or dendrimers can be used as host materials. Examples of low-molecular compounds 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, etc. Examples of polymers include the organic electronic materials of the above embodiments, polyvinylcarbazole, polyphenylene, polyfluorene, derivatives thereof, and the like. be done.

Adv. Mater., 21, 4802-4906 (2009); Appl. Phys. Lett., 98, 083302 (2011); Chem. Comm., 48, 9580 (2012). Phys. Lett., 101, 093306 (2012); J. Am. Chem. Soc., 134, 14706 (2012); Chem. Comm., 48, 11392 (2012); ); Adv. Mater., 25, 3319 (2013); J. Phys. Chem. A, 117, 5607 (2013); Phys. 49, 10385 (2013); Chem. Lett., 43, 319 (2014).

[Hole Transport Layer, Hole Injection Layer]
Examples of materials that constitute the hole transport layer and the hole injection layer include organic electronic materials that are embodiments of the present invention. In one embodiment, at least one of the hole-injection layer and the hole-transport layer is preferably composed of the organic electronic materials that are embodiments of the present invention.
A material containing a polymer different from the charge-transporting polymer contained in the organic electronic material according to the embodiment of the present invention can also be used as the material constituting the hole-transporting layer and the hole-injecting layer. For example, an organic electronic material containing a charge-transporting polymer containing a trivalent or higher structural unit having a 9-phenylcarbazole structure and a structural unit having a triphenylamine structure having no alkoxy group as a substituent for the phenyl group. can also be used. Other known materials can also be used.

Examples of known materials that can be used for the hole injection layer and the hole transport layer include (aromatic amine compounds (eg, N,N'-di(naphthalene-1-yl)-N,N'-diphenyl - aromatic diamines such as benzidine (α-NPD)), phthalocyanine-based compounds, thiophene-based compounds (e.g., thiophene-based conductive polymers (e.g., poly(3,4-ethylenedioxythiophene): poly(4-styrene sulfone) acid salt) (PEDOT: PSS), etc.).

In one embodiment, when the organic EL device has a hole injection layer and a hole transport layer, the hole injection layer is formed using a known material or the above other organic electronic materials, and the hole transport layer is It is preferably composed of an organic layer formed using an organic electronic material that is an embodiment of the present invention.

[Electron transport layer, electron injection layer]
Materials used for the electron transport layer and the electron injection layer include, for example, phenanthroline derivatives, bipyridine derivatives, nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, condensed ring tetracarboxylic acid anhydrides such as naphthalene and perylene, and carbodiimides. , fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiadiazole derivatives, benzimidazole derivatives, quinoxaline derivatives, aluminum complexes and the like. In addition, the organic electronic materials of the above embodiments can also be used.

[cathode]
Metals or metal alloys such as Li, Ca, Mg, Al, In, Cs, Ba, Mg/Ag, LiF, and CsF are used as cathode materials.

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

[substrate]
Glass, plastic or the like can be used as the substrate. The substrate is preferably transparent and preferably flexible. Quartz glass, light-transmitting resin film, etc. are preferably used.

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

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

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

As a method of forming a white organic EL device, a method of simultaneously emitting a plurality of luminescent colors using a plurality of luminescent materials to mix the colors can be used. The combination of a plurality of emission colors is not particularly limited, but there are combinations containing three emission maximum wavelengths of blue, green and red, and combinations containing two emission maximum wavelengths such as blue and yellow, yellowish green and orange. mentioned. The emission color can be controlled by adjusting the type and amount of the luminescent material.

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

A lighting device according to an embodiment of the present invention includes an organic EL element according to an embodiment of the present invention. Furthermore, the display device according to the embodiment of the present invention includes a lighting device and a liquid crystal element as display means. For example, the display device can be a display device using the illumination device according to the embodiment of the present invention as a backlight and a known liquid crystal element as display means, that is, a liquid crystal display device.

[Additive]
An additive according to one embodiment of the present invention is an additive for organic electronic materials comprising a charge-transporting compound, a super Bronsted acid compound, and a solvent having neither group 15 elements nor group 16 elements. an additive comprising a compound having a group 15 element or a group 16 element.
This additive can suppress insoluble matter or precipitation in the organic electronic material containing the charge-transporting compound, the super Bronsted acid compound, and the solvent.
For the charge-transporting compound, the super Bronsted acid compound, the solvent containing neither the group 15 element nor the group 16 element, and the compound containing the group 15 element or the group 16 element, the organic Those described in the electronic material I can be used, and the preferred range is also the same. Moreover, the preferable range of the preferable content in these organic electronic materials is also the same as that of the organic electronic material I described above.

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to the following examples.

Preparation of ink composition (1)

<I> Preparation of charge-transporting polymer (Preparation of Pd catalyst)
In a glove box under a nitrogen atmosphere, at room temperature, tris(dibenzylideneacene)dipalladium (73.2 mg, 80 μmol) was weighed into a sample tube, 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 into 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 before being used as the Pd catalyst solution. All solvents were used after degassing with a nitrogen bubble for at least 30 minutes.

(Charge-transporting polymer 1)
Monomer B-1 (4.0 mmol) below, Monomer L-1 (5.0 mmol) below, Monomer T-1 (2.0 mmol) below and anisole (20 mL) below are added to a three-necked round bottom flask, and further Prepared Pd catalyst solution (7.5 mL) was added. After stirring this reaction solution for 30 minutes, 10% tetraethylammonium hydroxide aqueous solution (20 mL) was added to the above reaction solution. All raw materials were used after being degassed with nitrogen bubbles for at least 30 minutes. The mixture was heated to reflux for 2 hours. The operations up to this point were performed under a nitrogen stream.

After completion of the reaction, the organic layer was washed with water and 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 added with a metal adsorbent (“Triphenylphosphine, polymer-bound on styrene-divinylbenzene copolymer” manufactured by Strem Chemicals, 200 mg per 100 mg of precipitate). Stir overnight. After stirring was completed, the metal adsorbent and insoluble matter were removed by filtration, and the filtrate was concentrated using a rotary evaporator. After dissolving the concentrate in toluene, it was 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 dried in vacuum to obtain a charge-transporting polymer 1.
The resulting charge-transporting polymer 1 had a number average molecular weight of 9,000 and a weight average molecular weight of 36,500.

The number average molecular weight and weight average molecular weight were measured by GPC (converted to polystyrene) using tetrahydrofuran (THF) as an eluent. The measurement conditions are as follows.
Liquid sending pump: L-6050 Hitachi High-Technologies Corporation UV-Vis detector: L-3000 Hitachi High-Technologies Corporation Column: Gelpack (registered trademark) GL-A160S / GL-A150S Hitachi Chemical Co., Ltd.
Eluent: THF (for HPLC, stabilizer-free) Wako Pure Chemical Industries, Ltd.
Flow rate: 1 mL/min
Column temperature: Room temperature Molecular weight standard substance: Standard polystyrene

<II> Preparation of ink composition [Example 1]
Polymer 1 (150 mg) obtained above, super Bronsted acid compound 1 (4.5 mg) below, toluene (8.0 mL) and triamylamine (100 μL) were stirred for 5 hours to prepare an ink composition. A pale yellow ink composition was obtained.

[Example 2]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with dicyclohexylmethylamine (100 μL). A pale yellow ink composition was obtained.

[Example 3]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with cyclohexanol (100 μL). A pale yellow ink composition was obtained.

[Example 4]
An ink composition was prepared in the same manner as in Example 1, except that the triamylamine in Example 1 was replaced with triethanolamine (100 μL). A pale yellow ink composition was obtained.

[Example 5]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with N,N-dimethylformamide (100 μL). A pale yellow ink composition was obtained.

[Example 6]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with diethylene glycol monoethyl ether (100 μL). A pale yellow ink composition was obtained.

[Example 7]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with benzyl alcohol (100 μL). A pale yellow ink composition was obtained.

[Example 8]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with N-ethyl-methylbenzylamine (100 μL). A pale yellow ink composition was obtained.

[Example 9]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with N,N,N',N'-tetramethylnaphthalenediamine (100 mg). A pale yellow ink composition was obtained.

[Example 10]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with 1-ethylpiperidine (100 μL). A pale yellow ink composition was obtained.

[Example 11]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with tetraoctylphosphonium bromide (100 mg). A pale yellow ink composition was obtained.

[Example 12]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with tetraethylammonium iodide (100 mg). A pale yellow ink composition was obtained.

[Example 13]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with N,N-dimethyl-N-tetradecylamine (100 μL). A pale yellow ink composition was obtained.

[Example 14]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with N-methyldioctylamine (100 μL). A pale yellow ink composition was obtained.

[Example 15]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with tris(2-ethylhexyl)amine (100 μL). A pale yellow ink composition was obtained.

[Example 16]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with tris{(2-methoxyethoxy)ethyl}amine (100 μL). A pale yellow ink composition was obtained.

[Example 17]
An ink composition was prepared in the same manner as in Example 1, except that triisoamylamine (100 μL) was used instead of triamylamine. A pale yellow ink composition was obtained.

[Example 18]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with N,N-dimethyl-N-octadecylamine (100 μL). A pale yellow ink composition was obtained.

[Example 19]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with N,N,N',N'-tetramethyl-1,6-diaminohexane (100 μL). A pale yellow ink composition was obtained.

[Example 20]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with 1,2-cyclohexanediamine (100 μL). A pale yellow ink composition was obtained.

[Example 21]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine (100 μL) was used instead of triamylamine. A pale yellow ink composition was obtained.

[Example 22]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with dibutylamine (100 μL). A pale yellow ink composition was obtained.

[Example 23]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with N,N-didecyl-N-methylamine (100 μL). A pale yellow ink composition was obtained.

[Example 24]
An ink composition was prepared in the same manner as in Example 1 except that the triamylamine of Example 1 was replaced with a saturated toluene solution (100 μL) of dibenzo-18-crown-6. A pale yellow ink composition was obtained.

[Example 25]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with 18-crown-6 (100 mg). A pale yellow ink composition was obtained.

[Example 26]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with o-tolylphosphine (100 mg). A pale yellow ink composition was obtained.

[Example 27]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with 4-octylaniline (100 μL). A pale yellow ink composition was obtained.

[Example 28]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with 3-methyl-3-oxetanemethanol (100 μL). A pale yellow ink composition was obtained.

[Example 29]
An ink composition was prepared in the same manner as in Example 1, except that the triamylamine of Example 1 was replaced with p-anisidine (100 mg). A pale yellow ink composition was obtained.

[Comparative Example 1]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was not included. Insoluble matter was observed, and a uniform ink composition was not obtained.

[Comparative Example 2]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with o-xylene (100 μL). Insoluble matter was generated during stirring, and a uniform ink composition was not obtained.

[Comparative Example 3]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with chlorobenzene (100 μL). Insoluble matter was observed, and a uniform ink composition was not obtained.

[Comparative Example 4]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with mesitylene (100 μL). Insoluble matter was observed, and a uniform ink composition was not obtained.

[Comparative Example 5]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with 1-phenylhexane (100 μL). Insoluble matter was observed, and a uniform ink composition was not obtained.

[Comparative Example 6]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with fluorene (100 mg). Insoluble matter was observed, and a uniform ink composition was not obtained.

[Comparative Example 7]
An ink composition was prepared in the same manner as in Example 1 except that triamylamine was replaced with tetralin (100 μL). Insoluble matter was observed, and a uniform ink composition was not obtained.

[Comparative Example 8]
An ink composition was prepared in the same manner as in Example 1, except that triamylamine in Example 1 was replaced with diphenylmethane (100 μL). Insoluble matter was observed, and a uniform ink composition was not obtained.

[Comparative Example 9]
An ink composition was prepared in the same manner as in Example 1, except that super Bronsted acid compound 1 and triamylamine were not included. A pale yellow ink composition was obtained.

<III> Preparation and Evaluation of Hole-Only Device (Evaluation of Charge Transport Property of Organic Thin Film Formed from Ink Composition)
Using the previously prepared ink composition, a hole-only device was produced as follows, and the charge transport property was evaluated from the current density characteristics.

(Example 30)
The ink composition obtained in Example 1 was spin-coated on a glass substrate patterned with ITO to a width of 1.6 mm at a rotation speed of 3,000 min ^-1 , and then heated on a hot plate at 120 ° C. for 10 minutes. The film was cured to form a hole injection layer (150 nm).
The glass substrate having the hole injection layer was transferred into a vacuum vapor deposition machine, and Al (150 nm) was deposited on the hole injection layer by a vapor deposition method. After that, a sealing treatment was performed to fabricate a hole-only device.

(Comparative Example 10)
A hole-only device was produced in the same manner as in Example 30, except that the ink composition obtained in Comparative Example 9 was used in the step of forming the hole injection layer in the hole-only device of Example 30.

FIG. 3 shows a graph of a voltage-current density curve when a voltage is applied to each hole-only device obtained in Example 30 and Comparative Example 10. In FIG.
As is clear from the graph shown in FIG. 3, Example 30 has a higher current density than Comparative Example 10 and is superior in charge transportability. As is clear from the comparison between Example 30 and Comparative Example 10, the organic thin film formed from the ink composition of the present invention exhibits excellent charge transport properties.

As described above, the effects of the embodiments of the present invention have been shown through examples. However, according to the present invention, not only the organic electronic materials used in the examples but also other organic electronic materials that do not deviate from the scope of the present invention can be used to produce organic electronic elements in the same manner. It is possible to obtain

The organic electronic material which is an embodiment of the present invention can be suitably used as an ink composition and can form an organic thin film having excellent charge transport properties.

1 anode 2 hole injection layer 3 light emitting layer 4 electron injection layer 5 cathode 6 substrate 7 hole transport layer 8 electron transport layer

Claims (15)

A charge-transporting compound, a super Bronsted acid compound, a compound containing at least one element selected from the group consisting of nitrogen, phosphorus and oxygen and having a molecular weight of 800 or less, and a compound having a molecular weight of 800 or less, and a compound having a molecular weight of 800 or less, and the IUPAC Periodic Table of Elements. and a solvent that does not have any of the Group 15 elements and Group 16 elements of the IUPAC Periodic Table of the Elements. 2. The organic electronic material according to claim 1, wherein said super Bronsted acid compound has a perfluorinated sulfonyl group. 3. The organic electronic material according to claim 1, wherein said charge-transporting compound comprises a polymer compound. 4. The organic electronic material according to any one of claims 1 to 3, wherein the charge-transporting compound has one or more polymerizable functional groups. An organic thin film formed using the organic electronic material according to any one of claims 1 to 4. An organic electronic device comprising the organic thin film according to claim 5 . An organic electroluminescence device comprising the organic thin film according to claim 5 . 8. The organic electroluminescence device according to claim 7, wherein said organic thin film is a hole injection layer. 8. The organic electroluminescence device according to claim 7, wherein said organic thin film is a hole transport layer. 10. The organic electroluminescence device according to claim 7, further comprising a flexible substrate. 10. The organic electroluminescence device according to claim 7, further comprising a resin film substrate. A display device comprising the organic electroluminescence device according to any one of claims 7 to 11. A lighting device comprising the organic electroluminescence element according to any one of claims 7 to 11. A display device comprising the lighting device according to claim 13 and a liquid crystal element as display means. Organic electronic materials comprising a charge transporting compound, a super Bronsted acid compound and a solvent that does not have any of the IUPAC Group 15 elements of the Periodic Table of the Elements and the IUPAC Group 16 elements of the Periodic Table of the Elements An additive comprising a compound having at least one element selected from the group consisting of nitrogen, phosphorus and oxygen and having a molecular weight of 800 or less .

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