JP4883032B2 - Organic electroluminescent device and display medium - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescent element which is excellent in thermal stability and preservation stability in light emission, has long element service life and is easily manufactured. <P>SOLUTION: The organic electroluminescent element contains at least one charge transporting polyester consisting of a repeating unit containing a constitutional unit of thiazolothiazole condensed ring and aromatic amine as a partial structure. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an organic electroluminescent device and a display medium using the same.

  An electroluminescent element is a self-luminous all-solid-state element, has high visibility and is resistant to impact, and thus is widely expected to be applied. At present, those using inorganic phosphors are the mainstream and widely used, and an AC voltage of 200 V or more and 50 Hz to 1000 Hz is required for driving. On the other hand, research on electroluminescent devices using organic compounds began with a single crystal such as anthracene. The film thickness was about 1 mm and a driving voltage of 100 V or higher was required. (For example, refer nonpatent literature 1).

  The light emission of these elements is such that electrons are injected from one of the electrodes and holes are injected from the other electrode, so that the light emitting material in the element is excited to a high energy level, and the excited illuminant becomes the base. This is a phenomenon in which excess energy for returning to the state is emitted as light.

  As organic electroluminescent devices, research and development have recently been conducted on electroluminescent devices using polymer materials instead of low molecular compounds, and conductive polymer devices such as poly (p-phenylene vinylene) (for example, patent documents). 1 or non-patent document 2), a polymer element in which triphenylamine is introduced into the side chain of polyphosphazene (see, for example, non-patent document 3), an electron transport material and a fluorescent dye in a hole transporting polyvinyl carbazole. A mixed element (for example, see Non-Patent Document 4) has been proposed.

  In addition, as an organic electroluminescent device that is easy to produce, has sufficient luminance, and has excellent durability, a hole transporting polyester comprising a repeating unit containing at least one selected from a specific amine structure as a partial structure is organically used. A technique for forming a compound layer is disclosed (for example, see Patent Document 2).

Further, in the manufacturing method, a coating method is desirable from the viewpoint of simplification of manufacturing, workability, large area, cost, and the like, and it has been reported that an element can be obtained by a casting method (for example, Non-Patent Document 5). And 6).
Japanese Patent Laid-Open No. 10-92576 JP 2002-43066 A Thin Solid Films, 94, 171 (1982) Nature, 357, 477 (1992) 42nd Polymer Symposium Proceedings 20J21 (1993) Proceedings of the 38th Joint Conference on Applied Physics 31p-G-12 (1991) Proceedings of the 50th Japan Society of Applied Physics, 29p-ZP-5 (1989) Proceedings of the 51st Japan Society of Applied Physics, 28a-PB-7 (1990)

  An object of the present invention is to provide an organic electroluminescent device having a longer device lifetime than an organic electroluminescent device using polyvinylcarbazole and a display medium using the same.

The above-mentioned subject is achieved by the following present invention.
That is, the invention according to claim 1 of the present invention includes a pair of electrodes composed of an anode and a cathode, at least one of which is transparent or translucent,
One or more organic compound layers sandwiched between the pair of electrodes, at least one layer containing one or more charge transporting polyesters represented by the following general formula (I-1) or (I-2);
It is an organic electroluminescent element.

In the general formulas (I-1) and (I-2), A ₁ represents at least one selected from the structures represented by the following general formulas (II-1) and (II-2), and R ₁ represents A substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, a substituted or unsubstituted monovalent condensed aromatic hydrocarbon group having 2 to 10 aromatic rings, or a group having 1 to 6 carbon atoms It represents a monovalent linear hydrocarbon group, a monovalent branched hydrocarbon group having 2 to 10 carbon atoms, or a hydroxyl group. Y ₁ represents a divalent alcohol residue, Z ₁ represents a divalent carboxylic acid residue, m represents an integer of 1 to 5, and p represents an integer of 5 to 5000. B and B ′ are groups represented by —O— (Y ₁ —O) m—H or —O— (Y ₁ —O) m—CO—Z ₁ —CO—OR ₂ (wherein Y ₁ , Z ₁ and m are as defined above, and R ₂ represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group.

  In the general formulas (II-1) and (II-2), Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted or unsubstituted Represents a monovalent condensed aromatic hydrocarbon having 2 to 10 substituted aromatic rings or a substituted or unsubstituted monovalent aromatic heterocyclic ring, j represents 0 or 1, and T represents 2 having 1 to 6 carbon atoms. Represents a valent linear hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and X represents a group represented by the following formula (III).

In general formula (III), Ar ₁ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted or unsubstituted aromatic ring having 2 to 10 represents a divalent condensed aromatic hydrocarbon or a substituted or unsubstituted divalent aromatic heterocyclic ring.

  In the invention according to claim 2, the organic compound layer includes a light emitting layer and at least one layer of an electron transport layer and an electron injection layer, and at least one layer selected from the light emitting layer, the electron transport layer, and the electron injection layer. The organic electroluminescent device according to claim 1, comprising at least one charge transporting polyester represented by the general formula (I-1) or (I-2).

  In the invention according to claim 3, the organic compound layer includes a light emitting layer and at least one of a hole transport layer and a hole injection layer, and is selected from the light emitting layer, the hole transport layer, and the hole injection layer. 2. The organic electroluminescent device according to claim 1, wherein at least one layer contains at least one type of charge transporting polyester represented by the general formula (I-1) or (I-2).

  The invention according to claim 4 is characterized in that the organic compound layer includes a light emitting layer, at least one layer of a hole transport layer and a hole injection layer, and at least one layer of an electron transport layer and an electron injection layer, At least one layer selected from a hole transport layer, a hole injection layer, an electron transport layer and an electron injection layer is one or more kinds of the charge transporting polyester represented by the general formula (I-1) or (I-2). It is an organic electroluminescent element of Claim 1 contained.

  The invention according to claim 5 is such that the organic compound layer is composed only of a light emitting layer having a charge transporting function, and the light emitting layer having the charge transporting function is represented by the general formula (I-1) or (I-2). It is an organic electroluminescent element of Claim 1 containing 1 or more types of charge transport polyester shown by these.

The invention according to claim 6 has a pair of electrodes, at least one of which is transparent, and an organic compound layer sandwiched between the pair of electrodes and composed of one or more layers, and the organic compound An organic electroluminescence device in which at least one layer constituting the layer contains one or more kinds of the charge transporting polyester according to claim 1 and arranged in at least one of a matrix shape and a segment shape;
And a driving means for driving the organic electroluminescent elements arranged in at least one of a matrix shape and a segment shape.

According to the first aspect of the present invention, an organic electroluminescent element having a longer element lifetime than an organic electroluminescent element using polyvinyl carbazole can be obtained.
According to the invention which concerns on Claim 2, compared with the case where it does not have this structure, an organic electroluminescent element with high luminous efficiency is obtained.
According to the third aspect of the present invention, an organic electroluminescent element having high durability can be obtained as compared with the case where this configuration is not provided.
According to the invention which concerns on Claim 4, compared with the case where it does not have this structure, the organic electroluminescent element driven by a lower voltage is obtained.
According to the invention which concerns on Claim 5, compared with the case where it does not have this structure, the organic electroluminescent element with a simple layer structure is obtained.
According to the invention which concerns on Claim 6, compared with the organic electroluminescent element using polyvinyl carbazole, the display medium excellent in a display characteristic is obtained.

Hereinafter, embodiments of the present invention will be described in detail.
<Organic electroluminescent device>
The organic electroluminescent element of the present embodiment (hereinafter, sometimes referred to as “organic EL element”) is sandwiched between a pair of electrodes each consisting of an anode and a cathode, at least one of which is transparent or translucent, and the pair of electrodes. And at least one layer has one or a plurality of organic compound layers containing one or more charge transporting polyesters represented by the following general formula (I-1) or (I-2).

In the general formulas (I-1) and (I-2), A ₁ represents at least one selected from the structures represented by the following general formulas (II-1) and (II-2), and R ₁ is a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, a substituted or unsubstituted monovalent condensed aromatic hydrocarbon group having 2 to 10 aromatic rings, and 1 to 6 monovalent linear hydrocarbon groups, monovalent branched hydrocarbon groups having 2 to 10 carbon atoms, and hydroxyl groups. Y ₁ represents a divalent alcohol residue, Z ₁ represents a divalent carboxylic acid residue, m represents an integer of 1 to 5, preferably 1, and p represents an integer of 5 to 5000. B and B ′ are groups represented by —O— (Y ₁ —O) m—H or —O— (Y ₁ —O) m—CO—Z ₁ —CO—OR ₂ (wherein Y ₁ , Z ₁ and m are as defined above, and R ₂ represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group. Y ₁ (divalent alcohol residue) and Z ₁ (divalent carboxylic acid residue) are, for example, charge transporting monomers represented by structural formulas (VI-1) and (VI-2). For example, it is produced by polymerization by a method described later.

  In the general formulas (II-1) and (II-2), Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted or unsubstituted Represents a substituted monovalent condensed aromatic hydrocarbon having 2 to 10 substituted aromatic rings or a substituted or unsubstituted monovalent aromatic heterocyclic ring, j represents 0 or 1, preferably 1, T represents 1 carbon atom Represents a divalent linear hydrocarbon group having 6 to 6 carbon atoms or a divalent branched hydrocarbon group having 2 to 10 carbon atoms, and X represents a group represented by the following formula (III).

In general formula (III), Ar ₁ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted or unsubstituted aromatic ring having 2 to 10 represents a divalent condensed aromatic hydrocarbon or a substituted or unsubstituted divalent aromatic heterocyclic ring.

  The charge transporting polyester in this embodiment can control the ionization potential to be low by inserting a condensed structure of two thiazole rings linked to a substituted or unsubstituted phenylene group into the molecular structure. The charge injection property from the is improved. Furthermore, the polyester structure improves the adhesion to the substrate and improves the charge injection property. In particular, in the case of inserting two thiazole condensed rings connected to the substituted or unsubstituted phenylene group, etc., it can be dissolved in solvents and resins. Excellent in compatibility and compatibility. Therefore, the organic electroluminescent element of this embodiment has sufficient luminance, high luminous efficiency, and long element lifetime because at least one of the organic compound layers contains the charge transporting polyester. Furthermore, by using the charge transporting polyester, the area is increased and an organic electroluminescent device can be easily produced.

Moreover, since the charge transporting polyester can impart both functions of hole transporting ability and electron transporting ability by selecting a structure to be described later, depending on the purpose, a hole transporting layer, a light emitting layer, It is used for any layer such as an electron transport layer. Furthermore, since the charge transporting polyester in this embodiment has a relatively high glass transition temperature and high charge mobility, it is excellent in thermal stability and storage stability during light emission.
In the present embodiment, “charge transporting polyester” means a polyester that is a semiconductor that conducts p-type or n-type charge.

(Charge transporting polyester)
Hereinafter, the charge transporting polyester in the present embodiment will be described in detail. First, the general formula is a feature of the charge-transporting polyester (I-1) and (I-2) the structure of A ₁ in explaining.
In the general formulas (II-1) and (II-2), Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted or unsubstituted It represents a monovalent condensed aromatic hydrocarbon having 2 to 10 substituted aromatic rings or a substituted or unsubstituted monovalent aromatic heterocyclic ring. The two Ar present in general formulas (II-1) and (II-2) may be the same or different, but are preferably the same from the viewpoint of ease of production. .

Here, in the general formulas (II-1) and (II-2), the number of aromatic rings constituting the polynuclear aromatic hydrocarbon and the condensed aromatic hydrocarbon selected as the structure representing Ar is further 2 to 5 In the condensed aromatic hydrocarbon, those having 2 to 4 are more preferred. In addition, the said polynuclear aromatic hydrocarbon and condensed aromatic hydrocarbon specifically mean the polycyclic aromatic defined below in this embodiment.
That is, the “polynuclear aromatic hydrocarbon” represents a hydrocarbon in which two or more aromatic rings composed of carbon and hydrogen are present, and the rings are bonded by a carbon-carbon bond. Specific examples include biphenyl and terphenyl. The “condensed aromatic hydrocarbon” means that there are two or more aromatic rings composed of carbon and hydrogen, and these aromatic rings share a pair of adjacent bonded carbon atoms. Represents a hydrocarbon compound. Specific examples include naphthalene, anthracene, pyrene, phenanthrene, perylene, and fluorene.

  Furthermore, in the general formulas (II-1) and (II-2), the “aromatic heterocycle” selected as the structure representing Ar represents an aromatic ring containing an element other than carbon and hydrogen, and its ring skeleton The number (Nr) of atoms constituting at least one of 5 and 6 is preferably used. Further, the type and number of atoms (heterogeneous atoms) other than carbon atoms constituting the ring skeleton are not particularly limited. For example, a sulfur atom, a nitrogen atom, or an oxygen atom is preferably used. One or more kinds of heteroatoms and at least one of two or more heteroatoms may be included. In particular, as a heterocyclic ring having a 5-membered ring structure, thiophene, pyrrole and furan, or a heterocyclic ring in which the 3- and 4-position carbons of the compound are replaced with nitrogen are preferably used. Pyridine is preferably used.

Furthermore, the aromatic heterocyclic ring includes both those in which the aromatic ring is substituted with a heterocyclic ring, and those in which the heterocyclic ring is substituted with an aromatic ring. Is mentioned.
These may be either all composed of a conjugated system or partly composed of a conjugated system, but those composed entirely of a conjugated system are preferred in terms of charge transportability and light emission efficiency.

  In the general formulas (II-1) and (II-2), as a substituent further substituting the phenyl group represented by Ar, the polynuclear aromatic hydrocarbon, the condensed polycyclic aromatic hydrocarbon or the aromatic heterocyclic ring, Examples include a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, an aralkyl group, a substituted amino group, or a halogen atom. The alkyl group preferably has 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, and an isopropyl group. The alkoxyl group is preferably one having 1 to 10 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, and an isopropoxy group. The aryl group preferably has 6 to 20 carbon atoms, and examples thereof include a phenyl group and a toluyl group. The aralkyl group preferably has 7 to 20 carbon atoms, such as a benzyl group and phenethyl. Groups and the like. Examples of the substituent of the substituted amino group include an alkyl group, an aryl group, and an aralkyl group, and specific examples are as described above.

In General Formulas (II-1) and (II-2), X represents a group represented by General Formula (III).
In general formula (III), Ar ₁ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, a substituted or unsubstituted aromatic ring having 2 to 10 represents a divalent condensed aromatic hydrocarbon or a substituted or unsubstituted divalent aromatic heterocyclic ring. Here, the “aromatic group containing a polynuclear aromatic hydrocarbon, condensed aromatic hydrocarbon, or aromatic heterocycle” is as described above.
In addition, two Ar _{1 which} exists in general formula (III) may be the same or different, respectively.

  In general formulas (II-1) and (II-2), T is a divalent linear hydrocarbon group having 1 to 6 carbon atoms or a divalent branched hydrocarbon group having 2 to 10 carbon atoms. It is preferably selected from a divalent linear hydrocarbon group having 2 to 6 carbon atoms and a divalent branched hydrocarbon group having 3 to 7 carbon atoms. Among these, more specifically, the divalent hydrocarbon groups shown below are particularly preferable.

At least one selected from the structures represented by the general formulas (II-1) and (II-2) described above is a charge transporting polyester represented by the general formulas (I-1) and (I-2). it is _{a 1} in.
The plurality of A ₁ present in the charge transporting polyesters represented by the general formulas (I-1) and (I-2) may have the same structure or different structures.

In general formulas (I-1) and (I-2) (including B and B ′), Y ₁ represents a divalent alcohol residue, and Z ₁ represents a divalent carboxylic acid residue. Specific examples of Y ₁ and Z ₁ include groups selected from the following formulas (IV-1) to (IV-6).

In the above formulas (IV-1) to (IV-6), R ₃ and R ₄ are each a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon atom having 1 to 4 carbon atoms. Represents an alkoxy group, a substituted or unsubstituted phenyl group or a substituted or unsubstituted aralkyl group, or a halogen atom, a to c each independently represents an integer of 1 to 10, and e represents an integer of 0 to 2. , D and f represent 0 or 1, and V represents a group represented by the following (V-1) to (V-11).

  In the above formulas (V-1), (V-10), and (V-11), g represents an integer of 1 to 20, and h represents an integer of 0 to 10.

In the general formulas (I-1) and (I-2), m represents an integer of 1 to 5, and p represents an integer of 5 to 5,000, preferably 10 to 1,000.
More specifically, the weight average molecular weight Mw of the charge transporting polyester is preferably in the range of 5,000 to 300,000, and particularly preferably in the range of 10,000 to 150,000. The weight average molecular weight Mw can be measured by the following method. That is, the weight average molecular weight was prepared by preparing a 1.0% by mass THF solution of a charge transporting polyester, using a differential refractive index detector (RI), and gel permeation chromatography (GPC), using a styrene polymer as a standard sample. Measured.

The glass transition temperature (Tg) of the charge transporting polyester is preferably 50 ° C. or higher and 300 ° C. or lower, and more preferably 90 ° C. or higher and 250 ° C. or lower.
The glass transition temperature was determined by using a differential scanning calorimeter with α-acid value aluminum (α-Al ₂ O ₃ ) as a reference, and the sample was heated to a rubber state, immersed in liquid nitrogen and rapidly cooled, The temperature can be measured again by increasing the temperature at a temperature increase rate of 10 ° C./min.

  The charge transporting polyesters represented by the general formulas (I-1) and (I-2) are, for example, charge transporting monomers represented by the following structural formulas (VI-1) and (VI-2), It can be synthesized by polymerization by a known method described in 4th edition, Experimental Chemistry Course Vol. 28 (Edited by Chemical Society of Japan, Maruzen, 1992).

In the general formulas (VI-1) and (VI-2), Ar, X, T, and j are the same as Ar, X, T, and j in the general formulas (II-1) and (II-2). A ′ represents a hydroxyl group, a halogen atom, or —O—R ₅ (R ₅ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group).

  Here, Tables 1 to 5 show specific examples of the structure represented by the general formula (VI-1). In the table below, A ′ at the end of the compound is a methoxy group (the same applies to Tables 6 to 10), and for each specific example of the charge transporting monomer with the compound number, for example, the number 5 is assigned. A specific example is referred to as “monomer compound (5)”.

  Specific examples of the structure represented by the general formula (VI-2) are shown in Tables 6 to 10 below.

  First, a method for synthesizing the charge transporting monomers represented by the general formulas (VI-1) and (VI-2) will be described. Although the synthesis method of a charge transporting monomer is illustrated below, it is not limited to this.

  In order to obtain the charge transporting monomer in this embodiment, for example, an arylamine derivative and a halogenated carboalkoxyalkylbenzene, or an aryl halide and a carboalkoxyaniline derivative are first reacted to synthesize a diarylamine. Next, a charge transporting monomer can be obtained by performing a Ullmann coupling reaction or a palladium coupling using a Pd catalyst using a halogen compound and diarylamine using copper or copper iodide as a catalyst.

In the present invention, specifically, for example, a halogen compound represented by the following general formula (VII) and an acetamide compound represented by the following general formula (VIII) are subjected to a coupling reaction with a copper catalyst, or A diarylamine represented by the following general formula (XI) can be obtained by performing a coupling reaction of the acetamide compound represented by the formula (IX) and the halogen compound represented by the following general formula (X) using a copper catalyst. it can.
Next, a charge transporting monomer can be obtained by performing a coupling reaction of diarylamine (XI) and a dihalogen compound represented by the following general formula (XII) using a copper catalyst.

In general formula (VII), R ₆ represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and G represents a bromine atom or an iodine atom. In the general formula (VIII), Ac is an acetyl group, and Ar ₁ is the same as described above.

In general formula (IX), R ₆ represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted aralkyl group, and Ac represents an acetyl group.

In general formula (X), Ar ₁ and G are the same as described above. Ar ₁ and R ₆ in general formula (XI) are the same as described above. Further, G and X in the general formula (XII) are the same as described above.

In the above coupling reaction, 0.5 equivalent or more and 1.5 equivalents or less of the halogen compound represented by the general formula (VII) or the general formula (X) with respect to 1 equivalent of the acetamide compound represented by the general formula (VIII) or (IX). It is used in an equivalent amount or less, desirably 0.7 equivalent or more and 1.2 equivalent or less.
Examples of the copper catalyst used in the coupling reaction include copper powder, cuprous oxide, copper sulfate and the like, and with respect to 1 part by mass of the acetamide compound represented by the general formula (VIII) or (IX) Preferably, it is used in an amount of 0.001 to 3 parts by mass, more preferably 0.01 to 2 parts by mass.

  In the coupling reaction, a base may be used. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, or potassium carbonate can be used, and 1 equivalent of an acetamide compound represented by the general formula (VIII) or (IX) Is preferably 0.5 equivalents or more and 3 equivalents or less, more preferably 0.7 equivalents or more and 2 equivalents or less.

In the coupling reaction, a solvent may or may not be used.
In the case of using a solvent, examples of desirable solvents include high-boiling water-insoluble hydrocarbon solvents such as n-tridecane, tetralin, p-cymene, or terpinolene, and high-boiling halogens such as o-dichlorobenzene and chlorobenzene. Solvent, and 0.1 to 3 parts by weight, preferably 0.2 to 2 parts by weight, based on 1 part by weight of the acetamide compound represented by the general formula (VIII) or (IX) Used in the range of

  The coupling reaction is sufficiently performed in an atmosphere of an inert gas such as nitrogen or argon at a temperature range of 100 ° C. to 300 ° C., preferably 150 ° C. to 270 ° C., more preferably 180 ° C. to 230 ° C. It is desirable to carry out the reaction while stirring efficiently and further to remove water generated during the reaction.

After completion of the coupling reaction, after cooling as necessary, a solvent such as methanol, ethanol, n-octanol, ethylene glycol, propylene glycol, or glycerin and a base such as sodium hydroxide or potassium hydroxide are used. The hydrolysis reaction is performed.
Specifically, for example, after the first coupling reaction is performed, a solvent and a base are directly added to the reaction solution, and the reaction solution is 50 ° C. or higher in an inert gas atmosphere such as nitrogen or argon. In the temperature range below the boiling point, it is carried out with sufficiently efficient stirring.
In this case, it is desirable to use a solvent having a high boiling point of 150 ° C. or higher that can raise the reaction temperature because a carboxylate is generated and solidified by a coupling reaction. Further, in the post-treatment of the hydrolysis reaction, water-soluble ethylene glycol, propylene glycol, or in order to liberate the diarylamine compound represented by the general formula (XI) by injecting into water and then neutralizing with hydrochloric acid or the like It is particularly desirable to use glycerin or the like.

The amount of the solvent used is 0.5 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 1 part by weight of the acetamide compound represented by the general formula (VIII) or (IX). Used in a range.
The base is in the range of 0.2 to 5 parts by weight, preferably 0.3 to 3 parts by weight, based on 1 part by weight of the acetamide compound represented by the general formula (VIII) or (IX). Used in

After completion of the hydrolysis reaction, the reaction product is poured into water and neutralized with hydrochloric acid or the like to liberate the diarylamine compound represented by the general formula (XI) (post-treatment). Next, after washing thoroughly and dissolving in a suitable solvent as necessary, column purification is performed with silica gel, alumina, activated clay, activated carbon, etc., or these adsorbents are added to the solution. Processing such as adsorbing unnecessary parts is performed. Further, after recrystallization from a suitable solvent such as acetone, ethanol, ethyl acetate, or toluene, or after esterification such as methyl esterification or ethyl esterification, the same operation may be performed.
Next, the diarylamine compound represented by the general formula (XI) obtained above and the halogen compound represented by the general formula (XII) are subjected to a coupling reaction using a copper catalyst, and then methyl esterified or ethyl ester Or a diarylamine compound represented by the general formula (XI) is methylesterified or ethylesterified, and then a coupling reaction using a dihalogen compound represented by the general formula (XII) and a copper catalyst. By performing this, a diamine compound represented by the general formula (VI-1) can be obtained.

In the coupling reaction between the diarylamine compound represented by the general formula (X) and the halogen compound represented by the general formula (XII), the compound represented by the general formula (XI) as the compound represented by the general formula (XII) A dihalogen compound represented by the general formula (XII) of 1.5 equivalents or more and 5 equivalents or less, preferably 1.7 equivalents or more and 4 equivalents or less is used with respect to 1 equivalent.
Moreover, as said copper catalyst, copper powder, cuprous oxide, copper sulfate etc. can be used, for example, 0.001 mass part or more 3 with respect to 1 mass part of diarylamine compounds shown by general formula (XI). It is used in an amount of not more than part by mass, desirably not less than 0.01 part by mass and not more than 2 parts by mass.

  In the above coupling reaction, a base may be used. For example, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or the like can be used, and preferably 1 equivalent of the compound represented by the general formula (XI) is preferably used. It is used in an amount of 1 equivalent to 6 equivalents, more preferably 1.4 equivalents to 4 equivalents.

In the above coupling reaction, a solvent is used as necessary. Desirable ones include, for example, a high-boiling water-insoluble hydrocarbon solvent such as n-tridecane, tetralin, p-cymene, or terpinolene, o -High-boiling halogen solvents such as dichlorobenzene and chlorobenzene are mentioned, and 0.1 parts by weight or more and 3 parts by weight or less, preferably 0.2 parts by weight with respect to 1 part by weight of the diarylamine compound represented by the general formula (XI). It is used in the range of not less than 2 parts by mass.
The coupling reaction is sufficiently efficient at 100 ° C. to 300 ° C., desirably 150 ° C. to 270 ° C., more desirably 180 ° C. to 250 ° C. in an inert gas atmosphere such as nitrogen or argon. It is desirable to carry out the reaction while stirring and to remove the water generated during the reaction.

  After completion of the above coupling reaction, the reaction product is dissolved in a solvent such as toluene, isopar, or n-tridecane, and unnecessary substances are removed by washing or filtration as necessary. Further, silica gel, alumina, Purify the column with activated clay or activated carbon, or add these adsorbents to the solution to adsorb unnecessary components, and then use a suitable solvent such as ethanol, ethyl acetate, or toluene. Then recrystallize and purify.

In addition, the charge transporting monomers represented by the general formulas (VI-1) and (VI-2) in this embodiment can also be synthesized in an amination reaction using a palladium catalyst. That is, as a method for producing the carbazole compound represented by the general formula (I), a diarylamine compound represented by the general formula (XI) and a dihalogen compound represented by the general formula (XII) are converted into a tertiary phosphine, a palladium compound, Alternatively, it can be obtained by reacting in the presence of a base.
When the amination reaction is performed, the amount of the diarylamine represented by the general formula (XI) is, for example, 0.5 to 4.0 times in terms of molar ratio with respect to the dihalogen compound represented by the general formula (XI). The following range is desirable, and more desirably the range is 0.8 times to 2.0 times.

The tertiary phosphines are not particularly limited. For example, triphenylphosphine, tri (tertiarybutyl) phosphine, tri (p-tolyl) phosphine, tri (m-tolyl) phosphine), triisobutylphosphine, tri Tertiary alkyl phosphines such as cyclohexylphosphine or triisopropylphosphine can be mentioned, and tri (tertiarybutyl) phosphine is preferable.
Although the amount of tertiary phosphine used is not particularly limited, for example, it is preferably 0.5 mol times or more and 10 mol times or less with respect to the palladium compound, and more preferably 2.0 mol times or more with respect to the palladium compound. The range is 8.0 mole times or less.

Further, the palladium compound is not particularly limited, and for example, a divalent compound such as palladium acetate (II), palladium chloride (II), palladium bromide (II), or palladium trifluoroacetate (II). Zero-valent palladium compounds such as palladium compounds, tris (dibenzylideneacetone) dipalladium (0), (dibenzylideneacetone) dipalladium (0), tetrakis (triphenylphosphine) palladium (0), or palladium-carbon Particularly preferable are palladium acetate and trisdibenzylideneacetone dipalladium (0).
Although the usage-amount of a palladium compound is not specifically limited, It is 0.001 mol% or more and 10 mol% or less in conversion of palladium with respect to general formula (XI), More desirably, it is 0.01 mol in conversion of palladium. % Or more and 5.0 mol% or less.

The base is not particularly limited, for example, potassium carbonate, rubidium carbonate, cesium carbonate, sodium carbonate, potassium bicarbonate, sodium bicarbonate, tertiary butoxy potassium, tertiary butoxy sodium, sodium metal, potassium metal, Potassium hydride etc. are mentioned, Preferably it is a rubidium carbonate or a tertiary butoxy sodium.
The amount of these bases used is, for example, in the range of 0.5 to 4.0 times in terms of molar ratio with respect to the compound represented by the general formula (XII), and more preferably 1.0 to 2 times. The range is less than 5 times.

The amination reaction is preferably performed in an inert solvent. As the solvent that can be used, any solvent that does not significantly inhibit this reaction may be used, for example, an aromatic hydrocarbon solvent such as benzene, toluene, xylene, or mesitylene, an ether solvent such as diethyl ether, tetrahydrofuran, or dioxane, acetonitrile, Examples thereof include dimethylformamide and dimethyl sulfoxide. Of these, aromatic hydrocarbon solvents such as toluene and xylene are more desirable.
The amination reaction is carried out under an atmosphere of an inert gas such as nitrogen or argon under normal pressure, but can also be carried out under pressurized conditions. The reaction temperature is, for example, in the range of 20 ° C. to 300 ° C., and more preferably in the range of 50 ° C. to 180 ° C. Although reaction time changes with reaction conditions, what is necessary is just to select from the range of several minutes (5 minutes) or more and 20 hours or less, for example.

After the amination reaction, the reaction solution is poured into water and then stirred well. If the reaction product is a crystal, the crude product can be obtained by filtration through suction filtration. When the reaction product is an oily product, a crude product can be obtained by extraction with an appropriate solvent such as ethyl acetate or toluene.
The component organism thus obtained is subjected to column purification with silica gel, alumina, activated clay, activated carbon, or the like, or these adsorbents are added to the solution, and unnecessary components are adsorbed. Further, when the reaction product is a crystal, it is purified by recrystallization from an appropriate solvent such as hexane, methanol, acetone, ethanol, ethyl acetate, or toluene.

By polymerizing by a known method using the charge transporting monomers represented by the structural formulas (VI-1) and (VI-2) obtained as described above, the above general formula (I-1) and A charge transporting polyester represented by (I-2) is synthesized.
Specifically, it is desirable to introduce an arbitrary molecule at the terminal of the charge transporting monomer, and in this case, the following synthesis method can be mentioned.

[1] When A ′ is a hydroxyl group When A ′ is a hydroxyl group, divalent alcohols represented by HO— (Y ₁ —O) _m —H are mixed in an equivalent amount (mass ratio), and an acid catalyst is used. Polymerize. The above _{Y 1} and m are the same as _{Y 1} and m in the general formula (I-1) and (I-2).
As the acid catalyst, those used for usual esterification reaction such as sulfuric acid, toluenesulfonic acid, trifluoroacetic acid and the like can be used. It is preferably used in the range of 1/1000 parts by mass to 1/50 parts by mass. In order to remove water generated during the synthesis, it is preferable to use a solvent azeotropic with water, and toluene, chlorobenzene, 1-chloronaphthalene and the like are effective, and 1 part by mass with respect to 1 part by mass of the monomer. To 100 parts by weight, preferably 2 to 50 parts by weight. The reaction temperature can be arbitrarily set, but it is preferable to carry out the reaction at the boiling point of the solvent in order to remove water generated during the polymerization. When the solvent is not used after completion of the reaction, it is dissolved in a soluble solvent. When a solvent is used, the reaction solution is dropped as it is into a poor solvent in which a polymer such as methanol or ethanol or a polymer such as acetone is difficult to dissolve, the polymer is precipitated, and after separating the polymer, Wash thoroughly with organic solvent and dry. Further, if necessary, the reprecipitation treatment in which the polymer is precipitated by dissolving in an appropriate organic solvent and dropping in a poor solvent may be repeated. The reprecipitation treatment is preferably carried out with efficient stirring with a mechanical stirrer or the like. The solvent for dissolving the polymer in the reprecipitation treatment is used in the range of 1 to 100 parts by weight, preferably 2 to 50 parts by weight with respect to 1 part by weight of the polymer. It is used in the range of 1 part by weight to 1,000 parts by weight, preferably 10 parts by weight to 500 parts by weight with respect to 1 part by weight of the polymer.

[2] When A ′ is a halogen When A ′ is a halogen, divalent alcohols represented by HO— (Y ₁ —O) _m —H are mixed in an equivalent amount (mass ratio), and pyridine, triethylamine, etc. Polymerize using an organic basic catalyst. The above _{Y 1} and m are the same as _{Y 1} and m in the general formula (I-1) and (I-2).
The organic basic catalyst is used in an amount of 1 to 10 parts by mass, preferably 2 to 5 parts by mass with respect to 1 part by mass of the monomer. As the solvent, methylene chloride, tetrahydrofuran (THF), toluene, chlorobenzene, 1-chloronaphthalene and the like are effective, and 1 to 100 parts by weight, preferably 2 to 50 parts by weight with respect to 1 part by weight of the monomer. Used in the range of parts by mass. The reaction temperature can be arbitrarily set. After the polymerization, it can be purified by reprecipitation according to the case of [1]. In addition, when divalent alcohols with high acidity such as bisphenol are used, an interfacial polymerization method can also be used. That is, polymerization can be carried out by adding water to a dihydric alcohol, adding an equivalent (mass ratio) base and dissolving it, and then adding a monomer solution equivalent to the divalent alcohol with vigorous stirring. At this time, water is used in the range of 1 part by weight to 1,000 parts by weight, preferably 2 parts by weight to 500 parts by weight with respect to 1 part by weight of the dihydric alcohol. As the solvent for dissolving the monomer, methylene chloride, dichloroethane, trichloroethane, toluene, chlorobenzene, 1-chloronaphthalene and the like are effective. The reaction temperature can be arbitrarily set, and in order to promote the reaction, it is effective to use a phase transfer catalyst such as an ammonium salt or a sulfonium salt. The phase transfer catalyst is used in an amount of 0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight, based on 1 part by weight of the monomer.

[3] When A ′ is —O—R ₅ When A ′ is —O—R _5, an excess of a dihydric alcohol represented by HO— (Y ₁ —O) _m —H is added, and sulfuric acid is added. It can be synthesized by transesterification by heating using inorganic acid such as phosphoric acid, titanium alkoxide, acetate such as calcium and cobalt or oxide such as carbonate and zinc as a catalyst. The above _{Y 1} and m are the same as _{Y 1} and m in the general formula (I-1) and (I-2).
The dihydric alcohol is used in an amount of 2 to 100 parts by mass, preferably 3 to 50 parts by mass with respect to 1 part by mass of the monomer. The catalyst is used in a range of 1/1000 parts by weight to 1 part by weight, and preferably 1/100 parts by weight to 1/2 part by weight with respect to 1 part by weight of the monomer. The reaction is carried out at a reaction temperature of 200 ° C. to 300 ° C. After completion of the transesterification from the group —O—R ₅ to the group HO— (Y ₁ —O) _m —H, the group HO— (Y ₁ —O) _m — In order to accelerate the polymerization reaction due to elimination of H, the reaction is preferably performed under reduced pressure. Further, by using a high boiling solvent group _HO- (Y 1 _-O) m -H and capable azeotropic 1- chloronaphthalene, azeotroped group _HO- (Y 1 _-O) m -H in vacuo Let it react while removing.

  More specifically, the charge transporting polyesters represented by the general formulas (I-1) and (I-2) can be synthesized as follows. In each case of the above [1] to [3], a compound represented by the following structural formula (XIII-1) or (XIII-2) is produced by adding an excess of dihydric alcohol and reacting, This may be used as a monomer and reacted with a divalent carboxylic acid or a divalent carboxylic acid halide by the method according to the above [2], whereby a polymer is obtained.

In the general formulas (XIII-1) and (XIII-2), Ar, X, T, and j are the same as Ar, X, T, and j in the general formulas (II-1) and (II-2). , _Y 1, m is the same as _Y 1, m in the general formula (I-1) and (I-2).

  Of the synthesis methods [1] to [3], the charge transporting polyester in this embodiment is particularly preferably the synthesis method [1].

Here, specific examples of the charge transporting polyester represented by the general formulas (I-1) and (I-2) are shown in Table 11 and Table 12, but the charge transporting polyester in the present embodiment is limited to these specific examples. It is not done. In the following table, the number of columns A ₁ monomer column, the charge of the general formula (II-1) and (II-2) Examples structure number of the structure (Tables 1 to 10 Corresponding to the number of the transporting monomer). In addition, those in which the column of Z ₁ is “−” show specific examples of the charge transporting polyester represented by the general formula (I-1), and the others are the charge transporting polyesters represented by the general formula (I-2). A specific example is shown.
Hereinafter, regarding each specific example of the charge transporting polyester given a compound number in the following table, for example, a specific example given a number of 15 is referred to as “Exemplary Compound (15)”.

Next, the configuration of the organic electroluminescent element of this embodiment will be described in detail.
The organic electroluminescent element of this embodiment is composed of a pair of electrodes, at least one of which is transparent or translucent, and one or a plurality of organic compound layers sandwiched between the electrodes, and at least one of the organic compound layers The layer structure is not particularly limited as long as it contains one kind of the charge transporting polyester described above.

  In the organic electroluminescent element of this embodiment, when there is one organic compound layer, the organic compound layer means a light emitting layer having charge transporting ability, and the light emitting layer contains the charge transporting polyester. On the other hand, when there are a plurality of organic compound layers (that is, in the case of a function separation type in which each layer has a different function), at least one of the layers is a light emitting layer, and this light emitting layer is a light emitting layer having a charge transporting ability. Also good. In this case, the following (1) to (3) can be given as specific examples of the layer structure composed of the light emitting layer or the light emitting layer having the charge transporting capability and other layers.

(1) A layer configuration including a light emitting layer and at least one of an electron transport layer and an electron injection layer.
(2) A layer configuration including at least one of a hole transport layer and a hole injection layer, a light emitting layer, and at least one of an electron transport layer and an electron injection layer.
(3) A layer structure formed from at least one of a hole transport layer and a hole injection layer, and a light emitting layer.

The layers other than the light emitting layers having the layer structures (1) to (3) and the light emitting layer having a charge transporting function have a function as a charge transporting layer or a charge injection layer.
In any of the layer configurations (1) to (3), the charge transporting polyester may be contained in any one layer.

  In the organic electroluminescence device of this embodiment, the light-emitting layer, the hole transport layer, the hole injection layer, the electron transport layer, and the electron injection layer are formed of a charge transport compound (hole transport material) other than the charge transport polyester. , An electron transport material). Details of the charge transporting compound will be described later.

Hereinafter, although it demonstrates in detail, referring drawings, the organic electroluminescent element of this embodiment is not necessarily limited to these.
1 to 4 are schematic cross-sectional views for explaining the layer structure of the organic electroluminescent element of this embodiment. In the case of FIGS. 1, 2, and 3, there are a plurality of organic compound layers. FIG. 4 shows an example in which there is one organic compound layer. In FIG. 1 to FIG. 4, components having the same function are described with the same reference numerals.

  The organic electroluminescent element shown in FIG. 1 is obtained by sequentially laminating a transparent electrode 2, a light emitting layer 4, at least one layer 5 of an electron transport layer and an electron injection layer, and a back electrode 7 on a transparent insulator substrate 1. This corresponds to the configuration (1). However, when the layer denoted by reference numeral 5 is composed of an electron transport layer and an electron injection layer, the electron transport layer, the electron injection layer, and the back electrode 7 are laminated in this order on the back electrode 7 side of the light emitting layer 4. Is done.

  The organic electroluminescent device shown in FIG. 2 has, on the transparent insulator substrate 1, at least one layer 3 of a transparent electrode 2, a hole transport layer and a hole injection layer, and at least one layer of a light emitting layer 4, an electron transport layer and an electron injection layer. 5 and the back electrode 7 are sequentially laminated and correspond to the layer structure (2). However, when the layer indicated by reference numeral 3 is composed of a hole transport layer and a hole injection layer, a hole injection layer, a hole transport layer, and a light emitting layer 4 are formed on the back electrode 7 side of the transparent electrode 2. Are stacked in this order. When the layer denoted by reference numeral 5 is composed of an electron transport layer and an electron injection layer, the electron transport layer, the electron injection layer, and the back electrode 7 are laminated in this order on the back electrode 7 side of the light emitting layer 4. Is done.

  The organic electroluminescent device shown in FIG. 3 is formed by sequentially laminating a transparent electrode 2, at least one layer 3 of a hole transport layer and a hole injection layer, a light emitting layer 4 and a back electrode 7 on a transparent insulator substrate 1. This corresponds to the layer configuration (3). However, when the layer indicated by reference numeral 3 is composed of a hole transport layer and a hole injection layer, a hole injection layer, a hole transport layer, and a light emitting layer 4 are formed on the back electrode 7 side of the transparent electrode 2. Are stacked in this order.

The organic electroluminescent element shown in FIG. 4 is obtained by sequentially laminating a transparent electrode 2, a light emitting layer 6 having a charge transporting capability, and a back electrode 7 on a transparent insulator substrate 1.
In addition, when a top emission structure or a transmissive type using both a cathode and an anode using a transparent electrode, a structure in which the layer configurations of FIGS. 1 to 4 are stacked in a plurality of stages is realized.
Each will be described in detail below.

The charge transporting polyester in the present embodiment is imparted with either a hole transporting function or an electron transporting function depending on the function of the organic compound layer contained therein.
For example, in the case of the organic electroluminescent element shown in FIG. 1, the charge transporting polyester may be contained in any one of the light emitting layer 4, at least one of the electron transporting layer and the electron injecting layer. 4 and at least one layer 5 of the electron transport layer and the electron injection layer. In addition, in the case of the layer structure of the organic electroluminescence device shown in FIG. 2, it is contained in at least one layer 3 of the hole transport layer and the hole injection layer, and at least one layer 5 of the light emitting layer 4 and the electron transport layer and the electron injection layer. Each of them functions as at least one layer 3 of the hole transport layer and the hole injection layer, and as at least one layer 5 of the light emitting layer 4, the electron transport layer, and the electron injection layer. Further, in the case of the layer configuration of the organic electroluminescent device shown in FIG. 3, it may be contained in any one of the hole transport layer and the hole injection layer 3 and the light emitting layer 4. Both act as at least one injection layer 3 and a light emitting layer 4. Furthermore, in the case of the layer structure of the organic electroluminescent element shown in FIG. 4, it is contained in the light emitting layer 6 having charge transporting ability and acts as the light emitting layer 6 having charge transporting ability.

In the case of the layer configuration of the organic electroluminescent element shown in FIGS. 1 to 4, the transparent insulator substrate 1 is preferably transparent in order to extract emitted light, and glass, plastic film, etc. are used, but not limited thereto. Absent. In addition, the said transparent means that the transmittance | permeability of the light of visible region is 10% or more, Furthermore, it is preferable that the transmittance | permeability is 75% or more. The same shall apply hereinafter.
The transparent electrode 2 is transparent or translucent for extracting light emission in accordance with the transparent insulator substrate, and preferably has a high work function for injecting holes, and has a work function of 4 eV or more. Is preferred. The translucency means that the light transmittance in the visible region is 70% or more, and the transmittance is preferably 80% or more. The same shall apply hereinafter.

  Specific examples include indium tin oxide (ITO), tin oxide (NESA), indium oxide, zinc oxide and other oxide films, and vapor deposited or sputtered gold, platinum, palladium, etc., but are not limited thereto. Absent. The sheet resistance of the electrode is desirably as low as possible, preferably several hundred Ω / □ or less, and more preferably 100 Ω / □ or less. Further, in accordance with the transparent insulator substrate, it is preferable that the light transmittance in the visible region is 10% or more, and the transmittance is 75% or more.

In the case of the layer configuration of the organic electroluminescence device shown in FIGS. 1 to 3, the electron transport layer, the hole transport layer, and the like are charged with functions (electron transport ability, hole transport ability) according to the purpose. Although the transporting polyester may be formed alone, for example, in order to adjust the hole mobility, the hole transporting material other than the charge transporting polyester is 0.1% by mass with respect to the entire material constituting the layer. It may be formed by mixing and dispersing in the range of from 50 to 50% by mass.
Examples of the hole transport material include a tetraphenylenediamine derivative, a triphenylamine derivative, a carbazole derivative, a stilbene derivative, a spirofluorene derivative, an aryl hydrazone derivative, and a porphyrin compound. Among these, a charge transporting polyester and From the viewpoint of good compatibility, tetraphenylenediamine derivatives, spirofluorene derivatives, and triphenylamine derivatives are preferable.

When adjusting the electron mobility, the electron transport material may be mixed and dispersed in the range of 0.1 mass% to 50 mass% with respect to the entire material constituting the layer.
Examples of the electron transport material include oxadiazole derivatives, nitro-substituted fluorenone derivatives, diphenoquinone derivatives, thiopyran dioxide derivatives, silole derivatives, chelate-type organometallic complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives, triazole derivatives, fluorenylidene Examples include methane derivatives.

  In addition, when both the hole mobility and the electron mobility need to be adjusted, both the hole transport material and the electron transport material may be mixed together in the charge transporting polyester.

  Furthermore, an appropriate resin (polymer) or additive may be added to improve film formability and prevent pinholes. Specific resins include polycarbonate resin, polyester resin, methacrylic resin, acrylic resin, polyvinyl chloride resin, cellulose resin, urethane resin, epoxy resin, polystyrene styrene resin, polyvinyl acetate resin, styrene butadiene copolymer, vinylidene chloride Conductive resins such as acrylonitrile copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin, poly-N-vinylcarbazole resin, polysilane resin, polythiophene, polypyrrole, and the like can be used. Moreover, as an additive, a well-known antioxidant, a ultraviolet absorber, a plasticizer, etc. can be used.

In addition, in order to improve the charge injection property, a hole injection layer or an electron injection layer may be used. As a hole injection material, a triphenylamine derivative, a phenylenediamine derivative, a phthalocyanine derivative, an indanthrene derivative, Polyalkylene dioxythiophene derivatives and the like are used. These may be mixed with a Lewis acid, a sulfonic acid, or the like. As the electron injecting material, metals such as Li, Ca, Ba, Sr, Ag and Au, metal fluorides such as LiF and MgF, and metal oxides such as MgO, Al ₂ O ₃ and LiO are used.

  Further, when the charge transporting polyester is used for a function other than the light emitting function, a light emitting compound is used as a light emitting material. As the light-emitting material, a compound that exhibits high emission quantum efficiency in a solid state is used. The light-emitting material may be either a low molecular compound or a high molecular compound. Suitable examples of organic low molecular compounds include chelate-type organometallic complexes, polynuclear or condensed aromatic ring compounds, perylene derivatives, coumarin derivatives, and styrylarylene derivatives. In the case where a silole derivative, an oxazole derivative, an oxathiazole derivative, an oxadiazole derivative or the like is a polymer, a polyparaphenylene derivative, a polyparaphenylene vinylene derivative, a polythiophene derivative, a polyacetylene derivative, or the like is used. As preferred specific examples, the following compounds (XIV-1) to (XIV-17) are used, but are not limited thereto.

In the structural formulas (XIV-13) to (XIV-17), V is the same divalent organic group as Ar _1, and n and g each independently represent an integer of 1 or more.

Further, for the purpose of improving the durability or the luminous efficiency of the organic electroluminescent element, a dye compound different from the luminescent material may be doped as a guest material in the luminescent material or the charge transport polyester. The doping ratio of the dye compound is 0.001% to 40% by weight, preferably 0.01% to 10% by weight of the target layer. As the coloring compound used for this doping, an organic compound that has good compatibility with the light emitting material and does not prevent the formation of a good thin film of the light emitting layer is used, and preferably a coumarin derivative, a DCM derivative, a quinacridone derivative, a perimidone. Derivatives, benzopyran derivatives, rhodamine derivatives, benzothioxanthene derivatives, rubrene derivatives, porphyrin derivatives, metal complex compounds such as ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold are used.
As preferred specific examples, the following compounds (XV-1) to (XV-6) are used, but are not limited thereto.

  The light emitting layer 4 may be formed of the light emitting material alone, but for the purpose of further improving electrical characteristics and light emitting characteristics, the charge transporting polyester is added to the light emitting material in an amount of 1% by mass to 50% by mass. % May be mixed and dispersed in the range of%. Alternatively, a charge transporting material other than the charge transporting polyester may be mixed and dispersed in the light emitting material in the range of 1% by mass to 50% by mass. Further, when the charge transporting polyester also has a light emitting property, it may be used as a light emitting material. In that case, for the purpose of further improving the electrical property and the light emitting property, other than the charge transporting polyester. The charge transport material may be mixed and dispersed in the range of 1% by mass to 50% by mass.

In the case of the layer configuration of the organic electroluminescence device shown in FIG. 4, the light-emitting layer 6 having charge transporting capability is the charge transporting polyester provided with a function (hole transporting capability or electron transporting capability) according to the purpose. An organic electroluminescent layer in which a light emitting material (preferably, at least one selected from the light emitting materials (XIV-1) to (XIV-17)) is dispersed in an amount of 50% by mass or less. In order to adjust the balance between holes and electrons injected into the device, a charge transport material other than the charge transporting polyester may be dispersed in an amount of 10% by mass to 50% by mass.
Examples of the charge transporting material include an oxadiazole derivative, a nitro-substituted fluorenone derivative, a diphenoquinone derivative, a thiopyrandioxide derivative, and a fluorenidenemethane derivative when the electron mobility is adjusted.

  In the case of the layer structure of the organic electroluminescent element shown in FIGS. 1 to 4, the back electrode 7 is made of a metal, metal oxide, metal fluoride, or the like that can be vacuum-deposited and has a low work function for performing electron injection. Is done. Examples of the metal include magnesium, aluminum, gold, silver, indium, lithium, calcium, and alloys thereof. Examples of the metal oxide include lithium oxide, magnesium oxide, aluminum oxide, indium tin oxide, tin oxide, indium oxide, zinc oxide, and indium zinc oxide. Examples of the metal fluoride include lithium fluoride, magnesium fluoride, strontium fluoride, calcium fluoride, and aluminum fluoride.

Further, a protective layer may be provided on the back electrode 7 in order to prevent the element from being deteriorated by moisture or oxygen. Specific materials for the protective layer include metals such as In, Sn, Pb, Au, Cu, Ag, and Al, metal oxides such as MgO, SiO ₂ , and TiO ₂ , polyethylene resin, polyurea resin, and polyimide resin. Resin. For forming the protective layer, a vacuum deposition method, a sputtering method, a plasma polymerization method, a CVD method, or a coating method can be applied.

  The organic electroluminescent elements shown in FIGS. 1 to 4 are manufactured by sequentially forming individual layers on the transparent electrode 2 in accordance with the layer configuration of each organic electroluminescent element. In addition, at least one layer 3 of the hole transport layer and the hole injection layer, the light emitting layer 4, at least one layer 5 of the electron transport layer and the electron injection layer, or the light emitting layer 6 having a charge transporting capability is formed by vacuum deposition of the above materials. It is formed by a spin coating method, a casting method, a dipping method, an ink jet method or the like on the transparent electrode using the coating solution obtained by dissolving or dispersing in an appropriate organic solvent.

Since the charge transporting polyester in this embodiment has high thermal stability and excellent solubility as described above, considering the ease of forming each layer, the stability as an element, and the like, FIG. It is desirable to be used for the organic electroluminescence device having the configuration shown in FIG.
In particular, in the organic electroluminescent element having the configuration shown in FIG. 2 using the charge transporting polyester of the present embodiment, the function is shared by the layer configuration and the energy efficiency is improved.

  The film thicknesses of at least one layer 3 of the hole transport layer and the hole injection layer, the light emitting layer 4, at least one layer 5 of the electron transport layer and the electron injection layer, and the light emitting layer 6 having the charge transporting ability are each 10 μm or less. It is preferably in the range of 0.001 μm to 5 μm. The dispersion state of each of the materials (the non-conjugated polymer, the light emitting material, etc.) may be a molecular dispersion state or a particle state such as a microcrystal. In the case of a film forming method using a coating solution, it is necessary to select a dispersion solvent in consideration of the dispersibility and solubility of each material in order to obtain a molecular dispersion state. In order to disperse into particles, a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer, an ultrasonic method, or the like is used.

  Finally, in the case of the organic electroluminescent device shown in FIGS. 1 and 2, the back electrode 7 is formed on at least one layer 5 of the electron transport layer and the electron injection layer by vacuum deposition, sputtering, or the like. The organic electroluminescent element of this embodiment is obtained. In the case of the organic electroluminescent element shown in FIG. 3, the back electrode 7 is provided on the light emitting layer 4 and in the case of the organic electroluminescent element shown in FIG. The organic electroluminescent element of the present embodiment can be obtained by forming by a vacuum deposition method, a sputtering method or the like.

<Display medium>
The display medium of the present embodiment is characterized in that the organic electroluminescent elements of the present embodiment are arranged in at least one of a matrix shape and a segment shape. In the present embodiment, when organic electroluminescent elements are arranged in a matrix, only the electrodes may be arranged in a matrix, or both the electrodes and the organic compound layer may be arranged in a matrix. Good. Further, in the present embodiment, when the organic electroluminescent elements are arranged in a segment shape, the electrode may be arranged in a segment shape, or both the electrode and the organic compound layer may be arranged in a segment shape. May be.

The matrix-like or segment-like organic compound layer is easily formed by using, for example, the ink jet method described above.
As a display medium driving apparatus and driving method composed of organic electroluminescent elements arranged in a matrix and organic electroluminescent elements arranged in a segment, conventionally known ones are used.

  Hereinafter, the present invention will be described more specifically with reference to examples. However, these examples do not limit the present invention.

<Synthesis of charge transporting polyester>
(Synthesis Example 1)
In a three-necked flask, 18.5 g of 4-bromobenzaldehyde, 30.0 g of rubeanic acid and 100 ml of dimethylformamide were placed, and the mixture was refluxed and stirred for 24 hours under a nitrogen stream. After this reaction, toluene and pure water were added, then this was filtered, and the organic layer was washed with pure water. Then, 18.9 g of a halogen compound was obtained by recrystallization.

  Subsequently, acetanilide (25.0 g), methyl 4-iodophenylpropionate (64.4 g), potassium carbonate (38.3 g), copper sulfate pentahydrate (2.3 g), and n-tridecane (50 ml) were added. The mixture was placed in a 500 ml three-necked flask and heated and stirred at 230 ° C. for 20 hours under a nitrogen stream. After completion of the reaction, potassium hydroxide (15.6 g) dissolved in ethylene glycol (300 ml) was added, heated under reflux for 3.5 hours under a nitrogen stream, cooled to room temperature, and the reaction solution was diluted with 1 L of distilled water. And neutralized with hydrochloric acid to precipitate crystals. The crystals were collected by suction filtration, washed thoroughly with water, and transferred to a 1 L flask. Toluene (500 ml) was added thereto, heated to reflux, water was removed by azeotropy, then a solution of concentrated sulfuric acid (1.5 ml) in methanol (300 ml) was added, and the mixture was heated to reflux for 5 hours under a nitrogen stream. After the reaction, extraction with toluene was performed, and the organic layer was washed thoroughly with distilled water. Next, after drying over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and recrystallization from hexane gave 36.5 g of diarylamine.

  15.0 g of the obtained halogen compound, 24.9 g of diarylamine, 24.0 g of potassium carbonate, 1.2 g of copper sulfate pentahydrate and 150 ml of o-dichlorobenzene were placed in a 500 ml flask and heated for 20 hours under a nitrogen stream. Refluxed. After completion of the reaction, the reaction mixture was cooled to room temperature, dissolved in 500 ml of toluene, and unnecessary substances were filtered. The filtrate was purified by silica gel column chromatography (toluene) to obtain 8.7 g of the monomer compound (3). .

  1.0 g of the monomer compound (3), 3.0 g of ethylene glycol and 0.04 g of tetrabutoxytitanium were placed in a 100 ml three-necked eggplant flask, and the mixture was heated and stirred at 200 ° C. for 3 hours in a nitrogen stream. After confirming that the monomer compound (3) was consumed, the pressure was reduced to 0.5 mmHg and the mixture was heated to 230 ° C. while distilling off ethylene glycol, and the reaction was continued for 5 hours. Thereafter, the mixture was cooled to room temperature, dissolved in 200 ml of tetrahydrofuran, the insoluble matter was filtered through a 0.5 μm polytetrafluoroethylene (PTFE) filter, and the filtrate was added dropwise to 500 ml of methanol while stirring, and the polymer was added. Precipitated. The obtained polymer was filtered, washed with methanol, and dried to obtain 0.55 g of exemplary compound (2).

When the molecular weight of exemplary compound (2) was measured by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight (Mw) was 3.9 × 10 ⁴ (in terms of styrene). The p determined from the molecular weight of the monomer was about 56.
Moreover, the glass transition temperature (Tg) measured with the differential scanning calorimeter (the Seiko Instruments company make, Tg / DTA6200) was 151 degreeC.

(Synthesis Example 2)
Synthesis Example 1 except that 2-bromo-9,9′-dimethylmethylfluorene and 3- (4-acetylaminophenyl) propionic acid methyl ester were used in place of acetanilide and methyl 4-iodophenylpropionate in Synthesis Example 1. Synthesis was performed according to Example 1 to obtain a monomer compound (13).
Subsequently, it superposed | polymerized according to the synthesis example 1 using the monomer compound (13), and obtained the exemplary compound (7).

When the molecular weight of exemplary compound (7) was measured by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight (Mw) was 3.4 × 10 ⁴ (in terms of styrene). The p determined from the molecular weight of the monomer was about 34.
Moreover, the glass transition temperature (Tg) measured with the differential scanning calorimeter (Seiko Instruments company make, Tg / DTA6200) was 160 degreeC.

(Synthesis Example 3)
In the synthesis of the halogen compound of Synthesis Example 1, 5-bromothiophene-2-carboxaldehyde was used instead of 4-bromobenzaldehyde, and in the synthesis of diarylamine, 3-iodo instead of methyl 4-iodophenylpropionate was used. A monomer compound (24) was obtained by synthesis according to Synthesis Example 1 except that methyl phenylpropionate was used.
Subsequently, it superposed | polymerized according to the synthesis example 1 using the monomer compound (24), and obtained the exemplary compound (10).

When the molecular weight of exemplary compound (10) was measured by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight (Mw) was 3.5 × 10 ⁴ (in terms of styrene). The p determined from the molecular weight of the monomer was about 45.
Moreover, the glass transition temperature (Tg) measured with the differential scanning calorimeter (Seiko Instruments company make, Tg / DTA6200) was 142 degreeC.

(Synthesis Example 4)
Except that 5-bromothiophene-2-carboxaldehyde was used instead of 4-bromobenzaldehyde in the synthesis of the halogen compound of Synthesis Example 1, and p-acetoluidine was used instead of acetanilide in the synthesis of diarylamine. The monomer compound (26) was obtained by synthesis according to Synthesis Example 1.
Subsequently, it superposed | polymerized according to the synthesis example 1 using the monomer compound (26), and obtained the exemplary compound (12).

When the molecular weight of exemplary compound (12) was measured by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight (Mw) was 4.4 × 10 ⁴ (in terms of styrene). The p determined from the molecular weight of the monomer was about 54.
Moreover, the glass transition temperature (Tg) measured with the differential scanning calorimeter (the Seiko Instruments company make, Tg / DTA6200) was 148 degreeC.

(Synthesis Example 5)
A monomer compound was synthesized according to Synthesis Example 1 except that 5- (4-bromophenyl) -thiophene-2-carboxaldehyde was used instead of 4-bromobenzaldehyde in the synthesis of the halogen compound of Synthesis Example 1. (36) was obtained.
Subsequently, it superposed | polymerized according to the synthesis example 1 using the monomer compound (36), and obtained the exemplary compound (18).

When the molecular weight of exemplary compound (18) was measured by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight (Mw) was 4.2 × 10 ⁴ (in terms of styrene). The p determined from the molecular weight of the monomer was about 45.
Moreover, the glass transition temperature (Tg) measured with the differential scanning calorimeter (Seiko Instruments company make, Tg / DTA6200) was 165 degreeC.

(Synthesis Example 6)
In the synthesis of the diarylamine of Synthesis Example 1, the monomer was synthesized according to Synthesis Example 1 except that 3- (4′-iodobiphenyl) propionic acid methyl ester was used instead of methyl 4-iodophenylpropionate. Compound (52) was obtained.
Subsequently, it superposed | polymerized according to the synthesis example 1 using the monomer compound (52), and obtained the exemplary compound (25).

When the molecular weight of exemplary compound (25) was measured by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight (Mw) was 3.2 × 10 ⁴ (in terms of styrene). The p determined from the molecular weight of the monomer was about 34.
Moreover, the glass transition temperature (Tg) measured with the differential scanning calorimeter (Seiko Instruments company make, Tg / DTA6200) was 150 degreeC.

(Synthesis Example 7)
In the synthesis of the diarylamine of Synthesis Example 1, N- (9,9-dimethyl-9H-fluoren-2-yl) -formamide and 3- (4′-iodo) were used instead of acetanilide and methyl 4-iodophenylpropionate. A monomer compound (80) was obtained by synthesis according to Synthesis Example 1 except that biphenyl) propionic acid methyl ester was used.
Subsequently, it superposed | polymerized according to the synthesis example 1 using the monomer compound (80), and obtained the exemplary compound (35).

When the molecular weight of exemplary compound (35) was measured by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight (Mw) was 7.1 × 10 ⁴ (in terms of styrene). P obtained from the molecular weight of the monomer was about 27.
Moreover, although it measured with the differential scanning calorimeter (The Seiko Instruments make, Tg / DTA6200), the glass transition temperature (Tg) was not measurable.

(Synthesis Example 8)
Synthesis Example 1 except that 4-iodobiphenyl and 3- (4-acetylaminophenyl) propionic acid methyl ester were used instead of acetanilide and methyl 4-iodophenylpropionate in the synthesis of diarylamine of Synthesis Example 1. The monomer compound (7) was obtained.
Subsequently, it superposed | polymerized according to the synthesis example 1 using the monomer compound (7), and the exemplary compound (4) was obtained.

When the molecular weight of exemplary compound (4) was measured by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, HLC-8120GPC), the weight average molecular weight (Mw) was 7.5 × 10 ⁴ (in terms of styrene). The p determined from the molecular weight of the monomer was about 34.
Moreover, the glass transition temperature (Tg) measured with the differential scanning calorimeter (Seiko Instruments company make, Tg / DTA6200) was 152 degreeC.

(Synthesis Example 9)
In the synthesis of the diarylamine of Synthesis Example 1, N- (4-pyrrole-1-phenyl) formamide and 3- (4′-iodobiphenyl) propionic acid methyl ester were used instead of acetanilide and methyl 4-iodophenylpropionate. A monomer compound (83) was obtained by synthesizing according to Synthesis Example 1 except that it was used, followed by triarylation and chlorination, and further performing a homocoupling reaction of the obtained chloro compound.
Subsequently, it superposed | polymerized according to the synthesis example 1 using the monomer compound (83), and obtained the exemplary compound (37).

When the molecular weight of exemplary compound (37) was measured by gel permeation chromatography (GPC, manufactured by Tosoh Corporation, HLC-8120 GPC), the weight average molecular weight (Mw) was 9.9 × 10 ⁴ (in terms of styrene). The p determined from the molecular weight of the monomer was about 49.
Moreover, although it measured with the differential scanning calorimeter (The Seiko Instruments make, Tg / DTA6200), the glass transition temperature (Tg) was not measurable.

<Solubility of charge transporting polyester>
The solubility of each of the obtained exemplary compounds and the charge transporting polymers used in Comparative Examples 2 to 4 described later in various solvents was examined. For the solubility, in addition to dichloroethane and chlorobenzene used in Examples / Comparative Examples, the results of other solvents practically suitable for producing an organic EL device were also shown. For the solubility test, 1 g of the compound was dissolved in 100 ml of the solvent, and the situation was visually observed and judged according to the following criteria.
○: Dissolved without heating.
○ to Δ: dissolved by heating.
Δ: Partially dissolved.
The results are shown in Table 13.

<Example 1>
ITO (manufactured by Sanyo Vacuum Co., Ltd.) formed on the transparent insulating substrate was patterned by photolithography using a strip-shaped photomask and further etched to form a strip-shaped ITO electrode (width 2 mm). Next, this ITO glass substrate was washed with neutral detergent, ultra pure water, acetone (for electronics industry, manufactured by Kanto Chemical) and isopropanol (for electronics industry, manufactured by Kanto Chemical) for 5 minutes each, It was dried with a spin coater.
A 5% by mass monochlorobenzene solution of the charge transporting polyester [Exemplary Compound (2)] is prepared on the substrate as a hole transporting layer, filtered through a 0.1 μm PTFE filter, and then the thickness is reduced to 0 by the dipping method. A thin film of 0.050 μm was formed. The said exemplary compound (XIV-1) was vapor-deposited as a luminescent material, and the 0.055 micrometer-thick luminescent layer was formed. Subsequently, a metallic mask provided with strip-shaped holes was installed, and an Mg-Ag alloy was deposited by co-evaporation to form a back electrode having a width of 2 mm and a thickness of 0.15 μm so as to intersect with the ITO electrode. . The effective area of the formed organic electroluminescent element was 0.04 cm ² .

<Example 2>
A 10% by mass dichloroethane solution of 1 part by mass of the charge transporting polyester [Exemplary Compound (7)], 4 parts by mass of poly (N-vinylcarbazole) and 0.02 part by mass of the Exemplified Compound (XIV-1) was prepared. And filtered through a 0.1 μm PTFE filter. Using this solution, a strip-like ITO electrode was etched according to Example 1, washed, and a thin film having a thickness of 0.15 μm was formed on a dried glass substrate by a spin coater method. After sufficiently drying, a metal mask provided with strip-shaped holes is installed, and an Mg-Ag alloy is vapor-deposited by co-evaporation, and a back electrode having a width of 2 mm and a thickness of 0.15 μm intersects the ITO electrode. Formed as follows. The effective area of the formed organic electroluminescent element was 0.04 cm ² .

<Example 3>
A hole transport layer having a thickness of 0.050 μm is formed from the charge transporting polyester [Exemplary Compound (10)] according to Example 1 on an ITO glass substrate etched, washed and dried according to Example 1. did. Next, a mixture (mass ratio: 99/1) of the exemplary compound (XIV-1) and the exemplary compound (XV-1) as a light emitting layer is 0.065 μm in thickness, and the exemplary compound (XIV-) is used as an electron transport layer. 9) was formed with a thickness of 0.030 μm. After sufficiently drying, a metal mask provided with a strip-shaped hole is installed and the Mg-Ag alloy is co-evaporated so that the back electrode having a width of 2 mm and a thickness of 0.15 μm intersects the ITO electrode. Formed. The effective area of the formed organic electroluminescent element was 0.04 cm ² .

<Example 4>
On the ITO glass substrate etched and cleaned according to Example 1, a charge transporting polyester [Exemplary Compound (12)] having a thickness of 0.050 μm as a hole transporting layer according to Example 1 was formed by an inkjet method (piezoelectric). Inkjet method). Next, the exemplified compound (XIV-17, n = 8) containing 5% by mass of the exemplified compound (IX-5) was formed as a light emitting layer with a thickness of 0.065 μm by a spin coater method. After sufficiently drying, a back electrode having a width of 2 mm and a total thickness of 0.23 μm was formed so as to intersect the ITO electrode by vapor-depositing Ca to a thickness of 0.08 μm and Al to a thickness of 0.15 μm. The effective area of the formed organic electroluminescent element was 0.04 cm ² .

<Example 5>
An organic electroluminescent element was prepared according to Example 1 except that the charge transporting polyester [Exemplary Compound (18)] was used instead of the charge transporting polyester [Exemplary Compound (2)] used in Example 1. Produced.

<Example 6>
An organic electroluminescent element was prepared according to Example 1 except that the charge transporting polyester [Exemplary Compound (25)] was used instead of the charge transporting polyester [Exemplary Compound (2)] used in Example 1. Produced.

<Example 7>
An organic electroluminescent element was prepared according to Example 1 except that the charge transporting polyester [Exemplary Compound (35)] was used instead of the charge transporting polyester [Exemplary Compound (2)] used in Example 1. Produced.

<Example 8>
An organic electroluminescent device according to Example 3 was used except that the charge transporting polyester [Exemplary Compound (4)] was used instead of the charge transporting polyester [Exemplary Compound (10)] used in Example 3. Produced.

<Example 9>
An organic electroluminescent element was prepared according to Example 3 except that the charge transporting polyester [Exemplary Compound (37)] was used instead of the charge transporting polyester [Exemplary Compound (10)] used in Example 3. Produced.

<Example 10>
A 1.5 mass% dichloroethane solution of the charge transporting polyester [Exemplary Compound (2)] was prepared, and filtered through a 0.1 μm PTFE filter. Using this solution, a thin film having a thickness of 0.05 μm was formed on an ITO glass substrate etched, washed and dried according to Example 1 by an inkjet method. Next, a light emitting layer having a thickness of 0.050 μm was formed by spin coating of the exemplified compound (XIV-14, n = 8) as a light emitting material. After sufficiently drying, a back electrode having a width of 2 mm and a total thickness of 0.23 μm was formed so as to intersect the ITO electrode by vapor-depositing Ca to a thickness of 0.08 μm and Al to a thickness of 0.15 μm. The effective area of the formed organic electroluminescent element was 0.04 cm ² .

<Example 11>
On the ITO glass substrate etched, washed and dried according to Example 1, the exemplified compound (XIV-17, n = 8) was formed to a thickness of 0.050 μm as a light emitting layer. A 1.1 mass% toluene solution of the charge transporting polyester [Exemplary Compound (2)] was prepared and filtered through a 0.25 μm PTFE filter. Using this solution, an electron transport layer having a thickness of 0.065 μm was formed on the light emitting layer by a spin coater method. After sufficiently drying, a metal mask provided with a strip-shaped hole is installed and the Mg-Ag alloy is co-evaporated so that the back electrode having a width of 2 mm and a thickness of 0.15 μm intersects the ITO electrode. Formed. The effective area of the formed organic electroluminescent element was 0.04 cm ² .

<Comparative Example 1>
An organic EL device was produced according to Example 1 except that a compound represented by the following structural formula (XVI) was used instead of the charge transporting polyester [Exemplary Compound (2)] used in Example 1.

<Comparative example 2>
2 parts by mass of polyvinyl carbazole (PVK) as a charge transporting polymer, 0.1 part by mass of the exemplified compound (XIV-1) as a light emitting material, and 1 part by mass of the compound (XIV-9) as an electron transporting material A 10% by mass dichloroethane solution was prepared and filtered through a 0.1 μm PTFE filter. Using this solution, a hole-transporting layer having a thickness of 0.15 μm was formed on a glass substrate on which a 2 mm wide strip-shaped ITO electrode was formed by etching, by a dipping method. After sufficiently drying, a metal mask provided with a strip-shaped hole is placed and the Mg-Ag alloy is co-evaporated so that the back electrode having a width of 2 mm and a thickness of 0.15 μm intersects the ITO electrode. Formed. The effective area of the formed organic electroluminescent element was 0.04 cm ² .

<Comparative Example 3>
2 parts by mass of the following structural formula (XVII) as a charge transporting polymer, 0.1 part by mass of the exemplified compound (XIV-1) as a light emitting material, and 1 part by mass of the compound (XIV-9) as an electron transporting material Then, a 10% by mass dichloroethane solution was prepared and filtered through a 0.1 μm PTFE filter. Using this solution, a hole-transporting layer having a thickness of 0.15 μm was formed on a glass substrate on which a 2 mm wide strip-shaped ITO electrode was formed by etching, by a dipping method. After sufficiently drying, a metal mask provided with a strip-shaped hole is placed and the Mg-Ag alloy is co-evaporated so that the back electrode having a width of 2 mm and a thickness of 0.15 μm intersects the ITO electrode. Formed. The effective area of the formed organic electroluminescent element was 0.04 cm ² .

<Comparative example 4>
Instead of the charge transporting polyester [Exemplary Compound (2)] used in Example 1, a compound represented by the following structural formula (XVIII) (Tg: 145 ° C., weight average molecular weight: 5.1 × 10 ⁴ ) was used. Otherwise, an organic EL device was produced according to Example 1.

The organic EL element produced as described above is applied in a vacuum (133.3 × 10 ⁻³ Pa) with a positive voltage on the ITO electrode side and a negative voltage on the Mg-Ag electrode, and a direct current voltage is applied. The light emission characteristics were examined by the drive current density when the initial luminance was 1000 cd / m ² . In addition, the evaluation of the light emission lifetime was performed by using a direct current drive method (DC drive) at room temperature in dry air with an initial luminance of 1000 cd / m ^2, and the luminance of the element of Comparative Example 1 (initial luminance L ₀ : 1000 cd / m ² ). L / the relative time when the driving time when the initial luminance L ₀ = 0.5 is 1.0, and the time when the luminance of the element becomes the luminance L / initial luminance L ₀ = 0.5. The voltage was evaluated by the voltage increase (= voltage / initial driving voltage). The results are shown in Table 14.

  From the results shown in Table 14, in the organic electroluminescence devices of Examples 1 to 11 using the charge transporting polyester in this embodiment having excellent thermal stability and solubility, those using a conventional charge transporting polymer having a light emission lifetime. Better than.

It is the schematic block diagram which showed an example of the layer structure of the organic electroluminescent element of embodiment. It is the schematic block diagram which showed another example of the layer structure of the organic electroluminescent element of embodiment. It is the schematic block diagram which showed another example of the layer structure of the organic electroluminescent element of embodiment. It is the schematic block diagram which showed another example of the layer structure of the organic electroluminescent element of embodiment.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Transparent insulator substrate 2 Transparent electrode 3 At least one layer of a positive hole transport layer and a positive hole injection layer 4 Light emitting layer 5 At least one layer of an electron transport layer and an electron injection layer 6 The light emitting layer 7 which has charge transport ability 7 Back electrode

Claims (6)

A pair of electrodes consisting of an anode and a cathode, at least one of which is transparent or translucent,
One or more organic compound layers sandwiched between the pair of electrodes, at least one layer containing one or more charge transporting polyesters represented by the following general formula (I-1) or (I-2);
An organic electroluminescent device comprising:

(In the general formulas (I-1) and (I-2), A ₁ represents at least one selected from the structures represented by the following general formulas (II-1) and (II-2), and R ₁ Is a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon group having 2 to 10 aromatic rings, a substituted or unsubstituted monovalent condensed aromatic hydrocarbon group having 2 to 10 aromatic rings, and 1 to 6 carbon atoms. A monovalent linear hydrocarbon group, a monovalent branched hydrocarbon group having 2 to 10 carbon atoms, or a hydroxyl group, Y ₁ represents a divalent alcohol residue, and Z ₁ represents a divalent group. M represents an integer of 1 to 5, p represents an integer of 5 to 5000, and B and B ′ represent —O— (Y ₁ —O) m—H, or _{-O- (Y 1 -O) m-} CO-Z 1 group represented by -CO-OR _{2 (however,} Y _{1, Z 1,} m is as defined above. ₂ represents a hydrogen atom, an alkyl group, a substituted or unsubstituted aryl group, or a representative) a substituted or unsubstituted aralkyl group.)

(In the general formulas (II-1) and (II-2), Ar represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted monovalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, Represents a monovalent condensed aromatic hydrocarbon having 2 to 10 unsubstituted aromatic rings or a substituted or unsubstituted monovalent aromatic heterocyclic ring, j represents 0 or 1, and T represents 1 to 6 carbon atoms. A divalent linear hydrocarbon group or a divalent branched hydrocarbon group having 2 to 10 carbon atoms is represented, and X represents a group represented by the following formula (III).

(In the general formula (III), Ar ₁ represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent polynuclear aromatic hydrocarbon having 2 to 10 aromatic rings, or a substituted or unsubstituted aromatic ring. Represents a divalent condensed aromatic hydrocarbon of the formula 2 to 10 or a substituted or unsubstituted divalent aromatic heterocyclic ring.)   The organic compound layer includes a light emitting layer and at least one layer of an electron transport layer and an electron injection layer, and at least one layer selected from the light emitting layer, the electron transport layer, and the electron injection layer has the general formula (I-1). The organic electroluminescent element according to claim 1, wherein the organic electroluminescent element contains at least one kind of charge transporting polyester represented by (I) or (I-2).   The organic compound layer includes a light emitting layer and at least one layer of a hole transport layer and a hole injection layer, and at least one layer selected from the light emitting layer, the hole transport layer, and the hole injection layer has the general formula The organic electroluminescent element according to claim 1, comprising at least one kind of charge transporting polyester represented by (I-1) or (I-2).   The organic compound layer includes a light emitting layer, at least one layer of a hole transport layer and a hole injection layer, and at least one layer of an electron transport layer and an electron injection layer, and the light emitting layer, the hole transport layer, and the hole injection At least one layer selected from a layer, an electron transport layer, and an electron injection layer contains at least one kind of charge transporting polyester represented by the general formula (I-1) or (I-2). Item 2. The organic electroluminescent device according to Item 1.   The organic compound layer is composed only of a light emitting layer having a charge transporting function, and the light emitting layer having the charge transporting function comprises the charge transporting polyester represented by the general formula (I-1) or (I-2). The organic electroluminescent element according to claim 1, comprising at least one kind. A pair of electrodes, at least one of which is transparent, and an organic compound layer sandwiched between the pair of electrodes and composed of one or more layers, wherein at least one layer constituting the organic compound layer is An organic electroluminescent device comprising at least one charge transporting polyester according to claim 1 and arranged in at least one of a matrix and a segment;
And a driving means for driving the organic electroluminescent elements arranged in at least one of a matrix shape and a segment shape.

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