JP2009196982A - Crosslinkable organic compound, composition for organic electroluminescent device, organic electroluminescent device, and organic el(electroluminescent) display - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic compound for electroluminescent devices suitable to wet film-forming method with easy lamination, a crosslinked polymeric compound obtained by crosslinking the above organic compound, a composition for electroluminescent devices containing the above organic compound, particularly a positive-hole-transportable organic compound and a composition each excellent in electrochemical stability, and an organic electroluminescent device high in emission efficiency and high in drive stability. <P>SOLUTION: The organic compound is provided, which has a crosslinkable group and is characterized by having in the molecule a divalent pyrene ring optionally bearing substituent(s). <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic compound having a crosslinkable group that can be formed by a wet film forming method, a composition for an organic electroluminescent device containing the organic compound, and a network polymer obtained by crosslinking the organic compound. The present invention relates to an organic electroluminescent element and an organic EL display having an organic layer containing a compound, high luminous efficiency, and excellent driving stability.

In recent years, an electroluminescent element (organic electroluminescent element) using an organic thin film has been developed. Examples of the method for forming the organic thin film in the organic electroluminescence device include a vacuum deposition method and a wet film formation method.
Since the vacuum deposition method is easy to stack, it has an advantage that the charge injection from the anode and / or the cathode is improved, and the exciton light-emitting layer is easily contained. The wet film formation method does not require a vacuum process, is easy to increase in area, and has an advantage that it is easy to mix a plurality of materials having various functions into one layer (coating liquid). .

However, since the wet film forming method is difficult to stack, the driving stability is inferior to that of the element by the vacuum vapor deposition method, and the present state is that it has not reached a practical level except for a part. In particular, the layering by the wet film forming method can be performed by stacking two layers by using an organic solvent and an aqueous solvent, but it is difficult to stack three or more layers.
In order to solve such problems in lamination, Non-Patent Document 1 and Non-Patent Document 2 propose a compound having a crosslinkable group as described below, and the lamination is made insoluble in an organic solvent by crosslinking. Is disclosed.

However, since the compound having only a benzene ring as an aromatic ring as described above has insufficient electrochemical stability, the driving stability of the device is insufficient.
Non-Patent Document 3 discloses a compound having a crosslinkable group in the pyrene ring as described below.

  However, it cannot be said that the above-mentioned compounds have sufficient electrochemical stability, and the resulting organic thin film was not sufficiently insoluble in organic solvents.

Applied Physics Letters 2005, 86, 221102 Macromolecules 2006, 39, 8911 Polymeric Materials Science and Engineering 1999, 80, 122

The present invention relates to an organic compound for an organic electroluminescent device suitable for a wet film-forming method that can be easily laminated, a crosslinked polymer compound obtained by crosslinking the organic compound, and an organic electroluminescent device containing the organic compound. It is an object of the present invention to provide a composition, in particular, a hole transporting organic compound and a composition excellent in electrochemical stability.
Another object of the present invention is to provide an organic electroluminescence device and an organic EL display having high luminous efficiency and high driving stability.

  As a result of intensive studies to solve the above problems, the present inventors have found that an organic compound having a specific structure and a crosslinkable group has high electrochemical stability and high hole transporting ability, The present inventors have found that the present invention is suitable for a wet film forming method that can be easily laminated. That is, the present invention is a compound having a crosslinkable group, an organic compound having a divalent pyrene ring in the molecule which may have a substituent, a composition for an organic electroluminescent device comprising the same, an organic It exists in an electroluminescent element and an organic EL display.

The organic compound of the present invention can be easily laminated, is suitable for a wet film formation method, and is excellent in electrochemical stability.
Moreover, the organic electroluminescent element formed by the wet film-forming method using the composition for organic electroluminescent elements containing this organic compound can be enlarged.
Moreover, it is possible to form an organic thin film insoluble in an organic solvent using the composition for an organic electroluminescent device containing the organic compound, and the organic electroluminescent device can be easily laminated by a wet film forming method. .

In addition, according to the organic electroluminescent device having an organic layer containing a network polymer compound obtained by crosslinking the organic compound of the present invention, it is possible to emit light with high efficiency, and the stability of the device, In particular, driving stability is improved.
Furthermore, the organic compound of the present invention has a hole injection material, a hole transport material, an excellent electrochemical stability, film formability, charge transport ability, light emission characteristics, and heat resistance according to the layer structure of the device. It can also be applied as a light emitting material, a host material, an electron injection material, an electron transport material and the like.

  An organic electroluminescent device having an organic layer containing a network polymer compound obtained by crosslinking the organic compound of the present invention is a flat panel display (for example, for OA computers or wall-mounted televisions), an in-vehicle display device, a mobile phone display. It can be applied to light sources (for example, light sources for copiers, backlight sources for liquid crystal displays and instruments), display panels, and marker lamps that make use of the characteristics of surface light emitters. is there.

  In addition, since the organic compound of this invention has the oxidation-reduction stability which was excellent essentially, it is useful not only for an organic electroluminescent element but for organic devices in general, such as an electrophotographic photoreceptor and an organic solar cell.

It is sectional drawing which shows typically an example of the structure of the organic electroluminescent element of this invention.

Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. It is not specified in the contents.
[Organic compounds]
The organic compound of the present invention is a compound having a crosslinkable group and having a divalent pyrene ring in the molecule which may have a substituent.

[Structural features]
Since the organic compound of the present invention contains a pyrene ring having at least two substituents, it is excellent in electrochemical stability. Moreover, since it has a crosslinkable group, a film formed by a wet film-forming method can be insoluble in an organic solvent under mild conditions.
[Crosslinkable group]
The organic compound of the present invention has at least one crosslinkable group, and preferably has two or more crosslinkable groups from the viewpoint of easy insolubilization. This is because, after coating, the crosslinkable group reacts to form a network structure, the solubility is lowered, and lamination becomes possible.

Examples of the crosslinkable group include groups shown in the following crosslinkable group T in that they are easily insolubilized in an organic solvent.
<Crosslinkable group T>

(In the formula, R ^{1 to} R ⁶ each independently represent a hydrogen atom or an alkyl group. Ar ¹¹ may have an aromatic hydrocarbon group or a substituent which may have a substituent. Represents an aromatic heterocyclic group.)
Among them, as the crosslinkable group, for example, a group that undergoes a crosslinking reaction by cationic polymerization such as a cyclic ether group such as an epoxy group or an oxetane group or a vinyl ether group is preferable in terms of high reactivity and easy insolubilization. Among these, an oxetane group is particularly preferable from the viewpoint that the rate of cationic polymerization can be easily controlled, and a vinyl ether group is preferable from the viewpoint that a hydroxyl group that may cause deterioration of the device during the cationic polymerization is hardly generated.

A group that undergoes a cycloaddition reaction such as an arylvinylcarbonyl group such as a cinnamoyl group or a monovalent group derived from a benzocyclobutene ring is preferred from the viewpoint of further improving electrochemical stability.
Among them, a group derived from a benzocyclobutene ring is particularly preferable in that crosslinking is performed quickly and the structure after crosslinking is particularly stable.
In the molecule, the crosslinkable group may be directly bonded to the aromatic hydrocarbon group or aromatic heterocyclic group in the molecule, but the —O— group, —C (═O) — group or (having a substituent group). It may be bonded to an aromatic hydrocarbon group or an aromatic heterocyclic group via a divalent group formed by linking 1 to 30 groups selected from —CH ₂ — groups in any order. It is preferable. Specific examples of the crosslinkable group via these divalent groups, that is, groups containing a crosslinkable group are as shown in the following group U containing a crosslinkable group, but are not limited thereto.

  <Group U containing crosslinkable group>

[Linking position of pyrene ring]
The organic compound of the present invention contains a divalent pyrene ring which may have a substituent, and the electrochemical stability is further improved. Therefore, the coupling position is represented by the following formula (I-1). 1 to be done
, 6-position, or 1,8-position as represented by the following formula (I-2) is preferable.

When the organic compound contains two or more divalent pyrene rings which may have a substituent, the connecting positions thereof may be the same or different. In addition to the linking site, examples of the substituent that the pyrene ring may have include groups described later as <specific examples of substituents for Ar ¹ and Ar ² >.
The substitution position of the divalent pyrene ring which may have a substituent is the p-position of the linking position (if the 1-position is a linking position, the 5-position and the 6-position) are electrochemically durable. Is preferable because of further improvement.

[Additional divalent groups]
The organic compound of the present invention preferably contains a divalent group represented by the following formula (II) from the viewpoint of further improving the charge transport ability.

(In the formula, Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.)
Ar ¹ and Ar ² represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
Examples of the aromatic hydrocarbon group which may have a substituent include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, and an acenaphthene ring. , A group derived from a 5- or 6-membered monocyclic ring or a 2-5 condensed ring, such as a fluorene ring and a fluoranthene ring.

  Examples of the aromatic heterocyclic group which may have a substituent include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring. , Pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine A group derived from a 5- or 6-membered monocyclic ring or a 2-4 condensed ring, such as a ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a sinoline ring, a quinoxaline ring, a benzimidazole ring, a perimidine ring, or a quinazoline ring. Can be mentioned.

From the viewpoint of the electrochemical stability of the resulting organic compound, Ar ¹ and Ar ² are each independently
A group derived from a ring selected from the group consisting of a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring and fluorene ring is preferred. Ar ¹ and Ar ² are preferably a group in which one or two or more rings selected from the above group are connected by a direct bond, and more preferably a biphenylene group or a terphenylene group.

Furthermore, the substituent that the aromatic hydrocarbon group or aromatic heterocyclic group in Ar ¹ and Ar ² may have is not particularly limited, but for example, the following <Ar ¹ and Ar ² substituents Specific group> is selected. Ar ¹ and Ar ² may have one substituent or two or more. When it has two or more, you may have one type and may have two or more types by arbitrary combinations and arbitrary ratios.
Ar ¹ or Ar ² may be a group containing a divalent pyrene ring which may have a substituent.

<Specific Examples of Substituents for Ar ¹ and Ar ² >
An alkyl group (preferably a linear or branched alkyl group having 1 to 8 carbon atoms, for example, methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group) Etc.)
Alkenyl group (preferably an alkenyl group having 2 to 9 carbon atoms, such as vinyl, allyl, 1-butenyl group, etc.)
Alkynyl group (preferably an alkynyl group having 2 to 9 carbon atoms, such as ethynyl and propargyl groups).
Aralkyl group (preferably an aralkyl group having 7 to 15 carbon atoms, such as benzyl group)
Alkoxy group (preferably an alkoxy group having 1 to 8 carbon atoms, such as methoxy, ethoxy and butoxy groups).
Aryloxy group (preferably having an aromatic hydrocarbon group having 6 to 12 carbon atoms, such as phenyloxy, 1-naphthyloxy, 2-naphthyloxy group, etc.)
Heteroaryloxy group (preferably having a 5- or 6-membered aromatic heterocyclic group, such as pyridyloxy and thienyloxy groups)
Acyl group (preferably an acyl group having 2 to 10 carbon atoms, such as formyl, acetyl, benzoyl group, etc.)
Alkoxycarbonyl group (preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl groups).
An aryloxycarbonyl group (preferably an aryloxycarbonyl group having 7 to 13 carbon atoms, such as a phenoxycarbonyl group).
An alkylcarbonyloxy group (preferably an alkylcarbonyloxy group having 2 to 10 carbon atoms, such as an acetoxy group).
Halogen atoms (especially fluorine or chlorine atoms),
Carboxy group
Cyano group
Hydroxyl group
Mercapto group
An alkylthio group (preferably an alkylthio group having 1 to 8 carbon atoms, such as a methylthio group and an ethylthio group).
An arylthio group (preferably an arylthio group having 6 to 12 carbon atoms, such as a phenylthio group and a 1-naphthylthio group).
A sulfonyl group (for example, a mesyl group, a tosyl group, etc.)
Silyl group (for example, trimethylsilyl group, triphenylsilyl group, etc.)
Boryl group (for example, dimesitylboryl group)
Phosphino group (for example, diphenylphosphino group)
Aromatic hydrocarbon group (for example, benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, fluoranthene ring, etc. Or a monovalent group derived from 2 to 5 condensed rings.)
Aromatic heterocyclic groups (eg furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole Ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, And monovalent groups derived from a 5- or 6-membered monocyclic ring or a 2-4 condensed ring such as an isoquinoline ring, a sinoline ring, a quinoxaline ring, a benzimidazole ring, a perimidine ring, and a quinazoline ring.
Amino group [Preferably, an alkylamino group having one or more alkyl groups having 1 to 8 carbon atoms which may have a substituent (for example, methylamino, dimethylamino, diethylamino, dibenzylamino group, etc.). ), An arylamino group having an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent (for example, phenylamino, diphenylamino, ditolylamino group, etc.)]
Moreover, the said substituent may have a substituent further and the said exemplary substituent is mentioned as the further substituent.

The substituent that Ar ¹ and Ar ² may have may be the crosslinkable group described in the crosslinkable group T or the group U including the crosslinkable group.
In addition, the organic compound of the present invention has a substituent because Ar ¹ or Ar ^{2 in} formula (II) is a group containing a divalent pyrene ring which may have a substituent. Alternatively, an organic compound containing a divalent pyrene ring and a divalent group represented by the formula (II) may be used.

The organic compound of the present invention may be a molecule having a single molecular weight or a polymer compound having a molecular weight distribution.
[Molecular weight single molecule]
The organic compound of the present invention is preferably a molecule having a single molecular weight in that it can be easily purified and the fluctuation in performance can be reduced. In the case of a molecule having a single molecular weight, it may be any molecule having a divalent pyrene ring which may have a substituent, and preferably has a divalent group represented by the formula (II). Further, a divalent pyrene ring which may have a substituent and a structure other than that represented by the formula (II) may be included. In addition, each independently, a divalent pyrene ring which may have two or more different substituents and a structure represented by the formula (II) may be included in one molecule.

[1] Molecular weight range
When the organic compound of the present invention is a molecule having a single molecular weight, the molecular weight is usually 300 or more, preferably 500 or more, more preferably 2000 or more, usually 20000 or less, preferably 10,000 or less, more preferably 5000 or less. . If the molecular weight exceeds this upper limit, the synthesis route becomes complicated and it may be difficult to achieve high purity, and purification may also be difficult due to high molecular weight impurities. On the other hand, if the molecular weight is below this lower limit, the film formability may be lowered, and the glass transition temperature, melting point and vaporization temperature will be lowered, so that the heat resistance may be significantly impaired.

[2] Ratio of Crosslinkable Group When the organic compound of the present invention is a molecule having a single molecular weight, the ratio of molecular weight / number of crosslinkable groups is usually 200 or more, preferably 300 or more, most preferably 500 or more, Usually, it is 4000 or less, preferably 3500 or less, and most preferably 3000 or less. Below this lower limit, unreacted crosslinkable groups remain and the electrical durability of the formed film decreases, the degree of crosslinking increases too much, cracking of the film occurs, and charge transport ability is reduced. There is a risk of lowering the excitation level. Moreover, when this upper limit is exceeded, there exists a possibility that a film | membrane may become difficult to insolubilize or heat resistance may fall.

  Although the preferable example in case the organic compound of this invention is a molecule | numerator with a single molecular weight is shown below, this invention is not limited to these.

[Polymer compound]
The organic compound of the present invention is preferably a polymer compound having a molecular weight distribution from the viewpoint of excellent film formability.
[1] Molecular weight of polymer compound
When the organic compound of the present invention is a polymer compound, the weight average molecular weight of the polymer compound is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 500,000 or less, Usually, it is 1,000 or more, preferably 2,000 or more, more preferably 5,000 or more.

The number average molecular weight is usually 2,500,000 or less, preferably 750,000 or less, more preferably 400,000 or less, and usually 500 or more, preferably 1,500 or more, more preferably 3,000. That's it.
Usually, this weight average molecular weight is determined by SEC (size exclusion chromatography) measurement. In SEC measurement, the elution time is shorter for higher molecular weight components and the elution time is longer for lower molecular weight components, but using the calibration curve calculated from the elution time of polystyrene (standard sample) with a known molecular weight, the elution time of the sample is changed to the molecular weight. By converting, the weight average molecular weight and the number average molecular weight are calculated. If the molecular weight exceeds this upper limit, purification may become difficult due to the high molecular weight of impurities. On the other hand, if the molecular weight is below this lower limit, the film formability may be lowered, and the glass transition temperature, melting point and vaporization temperature will be lowered, and the heat resistance may be significantly impaired.

The organic compound of the present invention is preferably an organic compound having a divalent group represented by the formula (II).
This means that when the organic compound of the present invention is a polymer compound, it includes a repeating unit having a structure represented by the formula (II).
Since the structure represented by the formula (II) is a repeating unit having a conjugated structure, the charge transporting ability is excellent. Furthermore, since the glass transition temperature is high and it is amorphous, it is easy to form a crosslinked layer. For this reason, it is presumed that the surface flatness during film formation is maintained, which is preferable.
Further, when the organic compound of the present invention is a polymer compound, Ar ¹ or Ar ² in the formula (II) is a divalent pyrene ring which may have a substituent, whereby the substituent is changed. It is good also as a high molecular compound containing the bivalent pyrene ring which may have and the repeating unit which has a structure represented by Formula (II).

[2] Crosslinkable group
When the organic compound of the present invention is a polymer compound, the crosslinkable group may be in a divalent pyrene ring which may have a substituent, and includes a structure represented by the formula (II). It may be contained in a repeating unit, and may be contained in another repeating unit other than the repeating unit containing a divalent pyrene ring which may have a substituent and a structure represented by the formula (II). Also good. Moreover, you may have in parts other than a repeating unit. The crosslinkable group contained in one polymer chain is preferably an average of 1 or more, more preferably an average of 2 or more, and preferably 200 or less, more preferably 100 or less.

Further, when the organic compound of the present invention is a polymer compound, when the number of crosslinkable groups possessed by the polymer compound is represented by the number per 1000 molecular weight, usually 3.0 or less per 1000 molecular weight, preferably Is 2.0 or less, more preferably 1.0 or less, and usually 0.01 or more, preferably 0.05 or more.
If this upper limit is exceeded, a flat film cannot be obtained due to cracks, or the crosslink density becomes too high, increasing the number of unreacted crosslinkable groups in the crosslinked layer, affecting the life of the resulting device. There is a fear. On the other hand, when the lower limit is not reached, insolubilization of the layer obtained by crosslinking the organic compound of the present invention becomes insufficient, and a multilayer laminated structure may not be formed by a wet film forming method.

Here, the number of crosslinkable groups per 1000 molecular weight of the polymer compound is calculated from the molar ratio of the charged monomers at the time of synthesis and the structural formula, excluding the terminal group from the polymer compound.
For example, the case of the target 1 synthesized in Synthesis Example 1 described later will be described.

目的物１において、末端基を除いた分子量は５６５．６であり、また架橋性基は、１分子当たり平均０．１個である。これを単純比例により計算すると、分子量１０００あたりの架橋性基の数は、０．１７個と算出される。

In the target product 1, the molecular weight excluding terminal groups is 565.6, and the average number of crosslinkable groups is 0.1 per molecule. When this is calculated by simple proportion, the number of crosslinkable groups per 1000 molecular weight is calculated to be 0.17.

[3] Linking position of pyrene ring
When the organic compound of the present invention is a polymer compound, the compound represented by the formula (I-1) 1,
It is preferable that both a 6-position substitution product and a 1,8-position substitution product represented by the formula (I-2) are included in order to improve solubility and film formability.
Moreover, the preferable ratio of Formula (I-1) and Formula (I-2) is 1: 9-9: 1. Outside this range, the effect of improving solubility and film formability may not be sufficient.

[4] Sequence and ratio of repeating units
When the organic compound of the present invention is a polymer compound, it may be any one having a divalent pyrene ring which may have a substituent in the repeating unit, and further a repeating unit having a conjugated structure. Therefore, it is preferable to have a repeating unit including a structure represented by the formula (II) from the viewpoint of excellent charge transport ability. Moreover, other repeating units other than the repeating unit containing the structure represented by the bivalent pyrene ring which may have a substituent, and Formula (II) may be contained. Independently, a divalent pyrene ring which may have two or more different substituents and a repeating unit containing a structure represented by the formula (II) may be contained in one molecule. Good.

Further, the ratio of the structure represented by the formula (II) to the divalent pyrene ring which may have a substituent is 0.1 times to 5 in terms of excellent charge transporting ability and excellent reduction durability. Double is preferred.
When the organic compound of the present invention is a polymer compound, the content of the divalent pyrene ring which may have a substituent in the polymer compound is usually 0 in all monomers in terms of monomer as a raw material. .1 mol% or more, preferably 1 mol% or more, more preferably 10 mol% or more.

[Synthesis method]
The organic compound of the present invention can be synthesized by selecting a raw material according to the structure of the target compound and using a known method.
[1] Polymer compound
When the organic compound of the present invention is a polymer compound, for example, only the halide represented by the general formula (IIIa) as in the following formula is sequentially polymerized by a reaction that forms an Ar—Ar bond. The polymer compound can be obtained. The reaction is usually performed in the presence of a transition metal catalyst such as copper, palladium, or nickel complex.

(In the formula, X represents a halogen atom or a sulfonate group such as a CF ₃ SO ₂ O— group, and Ar ^a has an optionally substituted aromatic hydrocarbon group or substituent. An aromatic heterocyclic group that may be present.
In the above formula, Ar ^a represents a group containing a divalent pyrene ring which may have a substituent, and a preferred specific example in the case of the synthesis method may have a <substituent described later. Divalent group A>, <divalent group B which may have a substituent>, <divalent group C which may have a substituent> and <having a substituent Divalent group D> which may be included. A plurality of Ar ^a present in the polymer compound may be the same or different.

By the above method, the organic compound of the present invention can be synthesized by appropriately selecting the polymer compound so that a divalent pyrene ring and a crosslinkable group are contained.
For example, the polymer compound is appropriately selected so as to include a divalent pyrene ring and a crosslinkable group as follows.
Polymer compound, to include a divalent pyrene ring, for example, have a Ar ^a is below the <divalent may have a substituent Group A> and <substituent group Any group selected from good divalent group B> may be used.

Similarly, to include a crosslinkable group, Ar ^a is <substituent optionally Divalent Groups which may B have> and <2 may have a substituent divalent groups as described below Any group selected from the group D> may be used.
Thus, for example, Ar ^a is selected from <a divalent group group A optionally having substituents> and <a divalent group group C optionally having substituents>. The organic compound of the present invention can be synthesized by copolymerizing these with a selected group.

When the organic compound of the present invention is a polymer compound in which Ar ¹ or Ar ² in the formula (II) is a group containing a divalent pyrene ring which may have a substituent, for example, the general formula A halide represented by (IIIa) and a secondary amine compound represented by the general formula (IIIb);
It is obtained by sequential polymerization by a reaction that forms an Ar bond (for example, Buchwald-Hartwing coupling, Ullmann coupling). The reaction for forming the N—Ar bond is carried out in the presence of a base such as potassium carbonate, tert-butoxy sodium, triethylamine or the like, and can be carried out in the presence of a transition metal catalyst such as copper or a palladium complex as necessary.

(In the formula, X represents a halogen atom or a sulfonic acid ester group such as a CF ₃ SO ₂ O— group, and Ar ^d and Ar ^e are each independently an aromatic hydrocarbon which may have a substituent. An aromatic heterocyclic group which may have a group or a substituent, Ar ^a and Ar ^b each independently have a divalent aromatic hydrocarbon group or a substituent which may have a substituent; At least one .Ar ^a and formula shows also be divalent aromatic heterocyclic group (IIIb) has a good pyrene ring which may have a bivalent substituent, Ar ^a and the formula (At least one of (IIIb) has a crosslinkable group.)
Ar ^a , Ar ^b , Ar ^d, and Ar ^e each independently represent an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent. In the case of the above synthesis method, preferred specific examples of Ar ^a include the below-described <divalent group A which may have a substituent> and <divalent group which may have a substituent. B>, <divalent group C which may have a substituent> and <divalent group D which may have a substituent>. Specific examples of Ar ^b , Ar ^d, and Ar ^e include general formula (IIIb), and preferred examples thereof include <specific example F>, <specific example G>, <specific example H>, and < Specific example I> is given.

Furthermore, Ar ^d and Ar ^e are preferably exemplified as <monovalent group E which may have a substituent> and <monovalent group F which may have a substituent>. .
A plurality of Ar ^a , Ar ^b , Ar ^d, and Ar ^e present in the polymer compound may be the same or different.
The organic compound of the present invention can be synthesized by appropriately selecting Ar ^a , Ar ^b , Ar ^d and Ar ^e so that the polymer compound contains a divalent pyrene ring and a crosslinkable group.

At least one of Ar ^a and the general formula (IIIb) has a divalent pyrene ring means that, for example, Ar ^a has the following <divalent group A that may have a substituent> and < It is a group selected from the divalent group B which may have a substituent, or the general formula (IIIb) is a group selected from <Specific Example F> and <Specific Example G> described later. Means that.
Similarly, at least one of Ar ^a and the general formula (IIIb) has a crosslinkable group, for example, Ar ^a has a <divalent group group B optionally having substituents> described below and It is a group selected from <divalent group D which may have a substituent>, or a group selected from general examples (IIIb) selected from <specific example G> and <specific example I> described later. It means that there is.

Thus, for example, Ar ^a is a group selected from <divalent group A which may have a substituent>, and General Formula (IIIb) is a group selected from <Specific Example I>. The organic compound of the present invention can be synthesized.
Examples of the aromatic hydrocarbon group which may have a substituent for Ar ^a and Ar ^b or the aromatic heterocyclic group which may have a substituent include the aromatic carbon groups mentioned in the above Ar ¹ and Ar ² A hydrogen group, an aromatic heterocyclic group, and its substituent are mentioned. The preferable ones are also the same.

When the organic compound of the present invention is a polymer compound having a repeating unit, for example, a halide represented by the general formula (IIIa) and a boron compound represented by the general formula (IIIc) are combined with an Ar—Ar bond. Can be obtained by sequential polymerization by a reaction that forms (eg, Suzuki coupling). The reaction for forming an Ar—Ar bond is performed in the presence of a base such as potassium carbonate, tert-butoxy sodium, triethylamine, and the like.
It can also be performed in the presence of a transition metal catalyst such as copper or palladium complex.

(In the formula, X represents a halogen atom or a sulfonate group such as a CF ₃ SO ₂ O— group, R ′ represents a hydroxy group or an alkoxy group that may be bonded to each other to form a ring;
Ar ^a and Ar ^c each independently represent a divalent aromatic hydrocarbon group which may have a substituent or a divalent aromatic heterocyclic group which may have a substituent, at least one of which is substituted A divalent pyrene ring optionally having a group, at least one having a crosslinkable group)
Ar ^a and Ar ^c each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. In the case of the synthesis method described above, preferred specific examples of Ar ^a and Ar ^c include the following <divalent group group A optionally having substituents A> and <divalent optionally having substituents. Group B>, <divalent group C which may have a substituent> and <divalent group D which may have a substituent>.

In the polymer compound, by performing the selection of the appropriate Ar ^a and Ar ^c as to include divalent pyrene ring and a crosslinkable group, capable of synthesizing an organic compound of the present invention.
A plurality of Ar ^a and Ar ^c present in the polymer compound may be the same or different.
In the polymer compound, by performing the selection of the appropriate Ar ^a and Ar ^c as to include divalent pyrene ring and a crosslinkable group, capable of synthesizing an organic compound of the present invention.

That at least one of Ar ^a and Ar ^c has a divalent pyrene ring means that, for example, Ar ^a or Ar ^c has the following <divalent group group A optionally having substituents> and < It means a group selected from the divalent group B> which may have a substituent.
Similarly, at least one of Ar ^a and Ar ^c has a crosslinkable group, for example, Ar ^a or Ar ^c is a <divalent group group B optionally having substituents> described below and It means a group selected from <divalent group D which may have a substituent>.

Thus, for example, Ar ^a is a group selected from the <divalent group A that may have a substituent>, and Ar ^c may be <a divalent group that may have a substituent. By being a group selected from D>, the organic compound of the present invention can be synthesized.
In the case where Ar ^a , Ar ^b and Ar ^c are a group containing a divalent pyrene ring which may have a substituent and do not contain a crosslinkable group, preferred examples thereof are <having a substituent. However, the present invention is not limited thereto.

<Divalent group A which may have a substituent>
(When Ar ^a , Ar ^b and Ar ^c are at the end, a hydrogen atom is bonded to one of the linking sites.)

In the case where Ar ^a , Ar ^b and Ar ^c are a group containing a divalent pyrene ring which may have a substituent and a crosslinkable group, preferred examples thereof may be <having a substituent. Although it is as shown in the good divalent group B>, it is not limited to these.
(When Ar ^a , Ar ^b and Ar ^c are at the ends, a hydrogen atom is bonded to one of the linking sites.)
<Divalent group B which may have a substituent>

Preferred examples in the case where Ar ^a , Ar ^b and Ar ^c do not have a group containing a divalent pyrene ring which may have a substituent include the following <divalent which may have a substituent However, the present invention is not limited to these groups.
<Divalent group C which may have a substituent>
(When Ar ^a , Ar ^b and Ar ^c are at the end, a hydrogen atom is bonded to one of the linking sites.)

When Ar ^a , Ar ^b and Ar ^c do not have a group containing a divalent pyrene ring which may have a substituent and are a group containing a crosslinkable group, preferred examples thereof are <substituents As shown in the divalent group D> which may have, it is not limited thereto.
(When Ar ^a , Ar ^b and Ar ^c are at the ends, a hydrogen atom is bonded to one of the linking sites.)
<Divalent group D which may have a substituent>

When Ar ^d and Ar ^e do not contain a crosslinkable group, preferred specific examples are as shown in the following <monovalent group E which may have a substituent>, but are not limited thereto. It is not something.

  <Monovalent group E which may have a substituent>

When Ar ^d and Ar ^e contain a crosslinkable group, preferred specific examples are as shown in the following <monovalent group F which may have a substituent>, but the present invention is not limited thereto. Is not to be done.
<Monovalent group F which may have a substituent>

When general formula (IIIb) includes a divalent pyrene ring which may have a substituent and does not have a crosslinkable group, preferred specific examples are as shown in the following <Specific Example G>. However, the present invention is not limited to these.
<Specific example G>

In the case where the general formula (IIIb) includes a divalent pyrene ring which may have a substituent and has a crosslinkable group, preferred specific examples are as shown in the following <Specific Example H>. However, the present invention is not limited to these.
<Specific example H>

When general formula (IIIb) does not contain a divalent pyrene ring which may have a substituent and does not have a crosslinkable group, preferred specific examples are as shown in the following <Specific Example I>. However, the present invention is not limited to these.
<Specific Example I>

When general formula (IIIb) does not contain a divalent pyrene ring which may have a substituent and has a crosslinkable group, preferred specific examples are as shown in the following <Specific example J>. However, the present invention is not limited to these.
<Specific example J>

  In addition, when the organic compound of the present invention is a polymer compound having a repeating unit (that is, having a molecular weight distribution), in addition to the polymerization method described above, the polymerization method described in JP-A-2001-223084, According to the polymerization method described in Japanese Patent Application Laid-Open No. 2003-213002, the polymerization method described in Japanese Patent Application Laid-Open No. 2004-2740, radical polymerization of a compound having an unsaturated double bond, and a reaction that forms an ester bond or an amide bond. Sequential polymerization can be used.

Even when the organic compound of the present invention is a molecule having a single molecular weight, it can be synthesized using a known coupling method such as the above-described reaction for forming an N—Ar bond or the reaction for forming an Ar—Ar bond. . The synthesis method in the case of a molecule having a single molecular weight is shown below, but the present invention is not limited to these contents.
(Hereinafter, as described above, in the formula, X represents a halogen atom or a sulfonate group such as a CF ₃ SO ₂ O— group, and R ′ may be bonded to a hydroxy group or to form a ring. Ar ^d and Ar ^e each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Ar ^a , Ar ^b and Ar ^c each independently represents a good aromatic substituted hydrocarbon group or an optionally substituted aromatic heterocyclic group.)

(Ar ^a or general formula (IIIb) has a divalent pyrene ring which may have a substituent, and Ar ^a or general formula (IIIb) has a crosslinkable group.)

(One of Ar ^a , Ar ^b and Ar ^d contains an optionally substituted divalent pyrene ring, and any one of Ar ^a , Ar ^b and Ar ^d is a crosslinkable group. Have

(One of Ar ^a , Ar ^b and Ar ^d contains a divalent pyrene ring which may have a substituent, and any one of Ar ^a , Ar ^b and Ar ^d is crosslinkable. Group.)

(Ar ^a or Ar ^c includes an optionally substituted divalent pyrene ring, and Ar ^a or Ar ^c has a crosslinkable group.)

(Ar ^a or Ar ^c includes an optionally substituted divalent pyrene ring, and Ar ^a or Ar ^c has a crosslinkable group.)

(Ar ^a or Ar ^c includes an optionally substituted divalent pyrene ring, and Ar ^a or Ar ^c has a crosslinkable group.)
Methods for purifying organic compounds include "Separation and Purification Technology Handbook" (1993, edited by The Chemical Society of Japan), "Advanced separation of trace components and difficult-to-purify substances by chemical conversion method" (1988, Eye Co., Ltd.) Uses known techniques, including the methods described in the section “Separation and purification” of “Chemical Experiment Course (4th edition) 1” (1990, edited by The Chemical Society of Japan). Is possible. Specifically, extraction (including suspension washing, boiling washing, ultrasonic washing, acid-base washing), adsorption, occlusion, melting, crystallization (including recrystallization from solvent, reprecipitation), distillation (atmospheric pressure) Distillation, vacuum distillation), evaporation, sublimation (atmospheric pressure sublimation, vacuum sublimation), ion exchange, dialysis, filtration, ultrafiltration, reverse osmosis, pressure osmosis, zone lysis, electrophoresis, centrifugation, flotation separation, sedimentation separation, Magnetic separation, various chromatography (shape classification: column, paper, thin layer, capillary, mobile phase classification: gas, liquid, micelle, supercritical fluid. Separation mechanism: adsorption, distribution, ion exchange, molecular sieve, chelate, gel filtration , Exclusion, affinity) and the like.

  Product confirmation and purity analysis methods include gas chromatograph (GC), high performance liquid chromatograph (HPLC), high speed amino acid analyzer (organic compound), capillary electrophoresis measurement (CE), size exclusion chromatograph (SEC). , Gel permeation chromatography (GPC), cross-fractionation chromatography (CFC), mass spectrometry (MS, LC / MS, GC / MS, MS / MS), nuclear magnetic resonance apparatus (NMR (1HNMR, 13CNMR)), Fourier transform Infrared spectrophotometer (FT-IR), UV-visible near-infrared spectrophotometer (UV.VIS, NIR), electron spin resonance apparatus (ESR), transmission electron microscope (TEM-EDX), electron beam microanalyzer (EPMA), Metal element analysis (ion chromatography, inductively coupled plasma-emission spectroscopy (ICP-AES) atomic absorption) Analysis (AAS), fluorescent X-ray analyzer (XRF)), nonmetal element analysis, trace analysis (ICP-MS, GF-AAS, optionally a GD-MS), etc., it is applicable.

[Composition for organic electroluminescence device]
The composition for an organic electroluminescent device of the present invention comprises the organic compound of the present invention, and in an organic electroluminescent device having an organic layer disposed between an anode and a cathode, the organic layer is usually formed by a wet process. It is suitably used as a coating solution when forming by a film method.
The composition for organic electroluminescent elements of the present invention is particularly preferably used for forming a hole injection layer or a hole transport layer in the organic layer.

Here, when there is one layer between the anode and the light emitting layer in the organic electroluminescent element, this is referred to as a “hole transport layer”, and when there are two or more layers, the layer in contact with the anode is The “hole injection layer” and the other layers are collectively referred to as “hole transport layer”. In addition, layers provided between the anode and the light emitting layer may be collectively referred to as a “hole injection / transport layer”.
The composition for an organic electroluminescent device of the present invention is characterized by containing the organic compound of the present invention, and usually further contains a solvent.

The solvent is preferably a solvent that dissolves the organic compound of the present invention, and usually dissolves the organic compound of the present invention in an amount of 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more. It is.
In addition, the composition for organic electroluminescent elements of this invention may contain only 1 type of the organic compound of this invention, and may contain 2 or more types.

The composition for an organic electroluminescent device of the present invention is usually 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more, and usually 50% by weight of the organic compound of the present invention. % Or less, preferably 20% by weight or less, more preferably 10% by weight or less.
The solvent contained in the composition for organic electroluminescent elements of the present invention is not particularly limited, but it is necessary to dissolve the organic compound of the present invention, and preferably, toluene, xylene, methicylene, Aromatic compounds such as cyclohexylbenzene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene, o-dichlorobenzene; fats such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA) Ether, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole, etc. Ether solvents such as aromatic ethers; aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, isopropyl benzoate, benzoate And organic solvents such as ester solvents such as propyl acid and n-butyl benzoate. These may be used alone or in combination of two or more.

The concentration of the solvent contained in the composition for organic electroluminescent elements of the present invention in the composition is usually 40% by weight or more, preferably 60% by weight or more, more preferably 80% by weight or more.
In addition, it is widely known that moisture may promote deterioration of the performance of the organic electroluminescent element, particularly brightness reduction during continuous driving, in order to reduce moisture remaining in the coating film as much as possible. Among these solvents, those having a solubility of water at 25 ° C. of 1% by weight or less are preferable, and solvents having a solubility of 0.1% by weight or less are more preferable.

Examples of the solvent contained in the composition for organic electroluminescent elements of the present invention include a solvent having a surface tension at 20 ° C. of less than 40 dyn / cm, preferably 36 dyn / cm or less, more preferably 33 dyn / cm or less.
That is, when the layer containing the organic compound of the present invention is formed by a wet film formation method, the affinity with the base is important. The uniformity of the film quality greatly affects the uniformity and stability of the light emission of the organic electroluminescence device. Therefore, the coating solution used in the wet film-forming method has a surface that can form a uniform coating film with higher leveling properties. Low tension is required. By using such a solvent, a uniform layer containing the organic compound of the present invention can be formed.

  Specific examples of such a low surface tension solvent include the above-mentioned aromatic solvents such as toluene, xylene, methicylene, cyclohexylbenzene, ester solvents such as ethyl benzoate, ether solvents such as anisole, trifluoromethoxy, etc. Anisole, pentafluoromethoxybenzene, 3- (trifluoromethyl) anisole, ethyl (pentafluorobenzoate) and the like can be mentioned.

Examples of the solvent contained in the composition for organic electroluminescent elements of the present invention include a solvent having a vapor pressure at 25 ° C. of 10 mmHg or less, preferably 5 mmHg or less and usually 0.1 mmHg or more. By using such a solvent, it is possible to prepare a composition suitable for a process for producing an organic electroluminescent element by a wet film forming method and suitable for the properties of the organic compound of the present invention. Specific examples of such a solvent include the aromatic solvents such as toluene, xylene and methicylene, ether solvents and ester solvents described above. The concentration of these solvents in the composition is usually 10% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more.

As a solvent contained in the composition for organic electroluminescent elements of the present invention, the vapor pressure at 25 ° C. is 2 mmHg or more, preferably 3 mmHg or more, more preferably 4 mmHg or more (however, the upper limit is preferably 10 mmHg or less). And a mixed solvent of a solvent having a vapor pressure at 25 ° C. of less than 2 mmHg, preferably 1 mmHg or less, more preferably 0.5 mmHg or less. By using such a mixed solvent, a homogeneous layer containing the organic compound of the present invention and further an electron accepting compound can be formed by a wet film forming method. The concentration of such a mixed solvent in the composition is usually 10% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more.

  Since the organic electroluminescent element is formed by laminating a plurality of layers made of organic compounds, it is very important that the film quality is uniform. When a layer is formed by a wet film formation method, a known film formation method such as a coating method such as a spin coating method or a spray method, or a printing method such as an ink jet method or a screen method can be adopted depending on the material and properties of the base. . For example, since the spray method is effective for forming a uniform film on a surface with unevenness, it is preferable when a layer made of an organic compound is provided on a surface where unevenness due to a patterned electrode or a partition between pixels remains. In the case of application by a spray method, it is preferable that the droplets of the application liquid sprayed from the nozzle to the application surface are as small as possible because uniform film quality can be obtained. For that purpose, a solvent with high vapor pressure is mixed with the coating liquid, and a part of the solvent is volatilized from the sprayed coating droplet in the coating atmosphere, so that fine droplets are generated immediately before adhering to the substrate. Is preferred. In addition, in order to obtain a more uniform film quality, it is necessary to secure time for the liquid film generated on the substrate to be leveled immediately after coating. In order to achieve this purpose, a slower drying solvent, that is, vapor A technique in which a solvent having a low pressure is contained to some extent is used.

Specific examples of the solvent having a vapor pressure at 25 ° C. of 2 mmHg or more and 10 mmHg or less include organic solvents such as xylene, anisole, cyclohexanone, and toluene. Examples of the solvent having a vapor pressure of less than 2 mmHg at 25 ° C. include ethyl benzoate, methyl benzoate, tetralin, and phenetole.
The ratio of the mixed solvent is such that the solvent whose vapor pressure at 25 ° C. is 2 mmHg or more is 5% by weight or more, preferably 25% by weight or more, but less than 50% by weight, and the vapor pressure at 25 ° C. is 25% by weight. The solvent which is less than 2 mmHg is 30% by weight or more, preferably 50% by weight or more, particularly preferably 75% by weight or more, but less than 95% by weight in the total mixed solvent.

  In addition, since an organic electroluminescent element is formed by laminating a plurality of layers made of organic compounds, each layer is required to be a uniform layer. When a layer is formed by a wet film formation method, the moisture in the layer forming solution (composition) may be mixed into the coating film, which may impair the uniformity of the film. It is preferable that the water content is as low as possible. Specifically, the amount of water contained in the organic electroluminescent element composition is preferably 1% by weight or less, more preferably 0.1% by weight or less, and still more preferably 0.05% by weight or less.

In general, since organic electroluminescent elements use many materials such as cathodes that deteriorate significantly due to moisture, the presence of moisture is not preferable from the viewpoint of element degradation. Examples of the method for reducing the amount of water in the solution include nitrogen gas sealing, use of a desiccant, dehydration of the solvent in advance, use of a solvent with low water solubility, and the like. In particular, the use of a solvent having low water solubility is preferable because the phenomenon that the solution coating film absorbs moisture in the atmosphere and whitens during the coating process can be prevented.

From such a viewpoint, the composition for organic electroluminescent elements of the present invention contains, for example, a solvent having a water solubility at 25 ° C. of 1 wt% or less (preferably 0.1 wt% or less) in the composition. It is preferable to contain 10% by weight or more. The solvent satisfying the above solubility condition is more preferably 30% by weight or more, and particularly preferably 50% by weight or more.
In addition, as a solvent contained in the composition for organic electroluminescent elements to which this embodiment is applied, various other solvents may be included as necessary in addition to the above-described solvents. Examples of such other solvents include amides such as N, N-dimethylformamide and N, N-dimethylacetamide; dimethyl sulfoxide and the like.

  In addition, the composition for an organic electroluminescent device of the present invention may reduce the solubility of an electron-accepting compound and a hole transport layer described later, if necessary, and apply another layer on the hole transport layer. An additive such as an additive for accelerating the crosslinking reaction may be included, and the additive for accelerating the crosslinking reaction is added to a layer adjacent to the layer containing the organic compound of the present invention. It is also possible. In this case, a solvent that dissolves both the organic compound of the present invention and the additive in an amount of 0.1% by weight or more, preferably 0.5% by weight or more, and more preferably 1% by weight or more may be used. preferable.

  The additive that accelerates the crosslinking reaction of the organic compound of the present invention, which may be contained in the composition for organic electroluminescence device of the present invention, includes an alkylphenone compound, an acylphosphine oxide compound, a metallocene compound, an oxime ester compound, Examples include polymerization initiators such as azo compounds and onium salts, polymerization accelerators, photosensitizers such as condensed polycyclic hydrocarbons, porphyrin compounds, and diaryl ketone compounds. These may be used alone or in combination of two or more.

The electron-accepting compound that may be contained in the composition for organic electroluminescent elements of the present invention includes those described later as the electron-accepting compound contained in the hole injection layer of the organic electroluminescent element of the present invention. 1 type (s) or 2 or more types can be used.
Furthermore, the composition for organic electroluminescent elements of the present invention may contain various additives such as coating improvers such as leveling agents and antifoaming agents.

[Film formation method]
As described above, since the organic electroluminescent element is formed by laminating a plurality of layers made of organic compounds, it is very important that the film quality is uniform. When a layer is formed by a wet film formation method, a known film formation method such as a coating method such as a spin coating method or a spray method, or a printing method such as an ink jet method or a screen method can be adopted depending on the material and properties of the base. .

  When using a wet film-forming method, dissolve the organic compound of the present invention and other components used as necessary (electron-accepting compounds, additives that accelerate the crosslinking reaction, coatability improvers, etc.) in an appropriate solvent. The organic electroluminescent element composition is prepared. The composition containing the organic compound of the present invention is formed by applying this composition onto a layer corresponding to the lower layer of the layer to be formed by a technique such as spin coating or dip coating, and drying.

Usually, the layer formed using the composition for organic electroluminescent elements of the present invention is used as a hole injection layer or a hole transport layer. Therefore, the hole transport layer is usually formed on the hole injection layer or on the anode. The hole injection layer is usually formed on the anode.
In addition, in order to form a light emitting layer subsequent to the layer formed using the composition for organic electroluminescent elements of the present invention, the formed hole transport layer is dissolved in the coating composition for forming the light emitting layer. Preferably not. For this reason, after coating the composition for organic electroluminescent elements of the present invention, the organic compound of the present invention undergoes a crosslinking reaction by heating and / or irradiation with active energy such as light, and the solubility of the film after the reaction in the organic solvent Is preferably reduced. Usually, a network polymer compound is obtained by this crosslinking reaction.

  Although the heating method is not particularly limited, the heating condition is that the layer formed using the composition for organic electroluminescent elements of the present invention is usually heated to 120 ° C. or higher, preferably 400 ° C. or lower. The heating time is usually 1 minute or longer, preferably 24 hours or shorter. Although it does not specifically limit as a heating means, Means, such as mounting the laminated body which has the formed layer on a hotplate, or heating in oven, is used. For example, conditions such as heating on a hot plate at 120 ° C. or more for 1 minute or more can be used.

  In the case of irradiation with active energy such as light, a method of irradiating directly using an ultraviolet / visible / infrared light source such as an ultra-high pressure mercury lamp, a high-pressure mercury lamp, a halogen lamp, an infrared lamp, or the above-mentioned light source is incorporated. Examples include a mask aligner and a method of irradiation using a conveyor type light irradiation device. In active energy irradiation other than light, for example, there is a method of irradiation using a so-called microwave oven that irradiates a microwave generated by a magnetron.

As the irradiation time, it is preferable to set conditions necessary for reducing the solubility of the film, but irradiation is usually performed for 0.1 seconds or longer, preferably 10 hours or shorter.
Heating and irradiation of active energy such as light may be performed individually or in combination. When combined, the order of implementation is not particularly limited.

  The active energy irradiation including heating and light is preferably performed in an atmosphere containing no moisture such as a nitrogen gas atmosphere in order to reduce the amount of moisture contained in the layer and / or moisture adsorbed on the surface after implementation. For the same purpose, when combined with heating and / or irradiation with active energy such as light, it is particularly preferable to perform at least the step immediately before the formation of the organic light emitting layer in an atmosphere containing no moisture such as a nitrogen gas atmosphere.

[Organic electroluminescence device]
The organic electroluminescent device of the present invention is an organic electroluminescent device having an anode, a cathode, and one or more organic layers disposed between the anode and the cathode on a substrate. At least one layer is an organic electroluminescent element which is a layer containing a network polymer compound obtained by crosslinking the organic compound of the present invention (hereinafter sometimes referred to as “crosslinked layer”).

The cross-linking layer in the present invention is preferably a hole injection layer and / or a hole transport layer described in detail below, and the hole injection layer or the hole transport layer is the composition for an organic electroluminescence device of the present invention. It is preferable to form the product by wet film formation.
Moreover, it is preferable to have a light emitting layer formed by a wet film forming method on the cathode side of the hole transport layer, and further, formed on the anode side of the hole transport layer by a wet film forming method. It is preferable to have a hole injection layer.

That is, in the organic electroluminescent element of the present invention, it is preferable that all of the hole injection layer, the hole transport layer and the light emitting layer are formed by a wet film forming method, and in particular, the light emitting layer formed by this wet film forming method. Is preferably a layer made of a low molecular material.
FIG. 1 is a cross-sectional view schematically showing an example of the structure of the organic electroluminescent element of the present invention. The organic electroluminescent device shown in FIG. 1 has an anode 2, a hole injection layer 3, a hole transport layer 4, an organic light emitting layer 5, a hole blocking layer 6, an electron injection layer 7 and a cathode 8 on a substrate 1. These are stacked in this order. In the case of this configuration, the hole injection layer 3 or the hole transport layer 4 usually corresponds to the above-described crosslinked layer in the present invention.

[1] Substrate
The substrate 1 serves as a support for the organic electroluminescent element, and a quartz or glass plate, a metal plate or a metal foil, a plastic film, a sheet, or the like is used. In particular, a glass plate or a transparent synthetic resin plate such as polyester, polymethacrylate, polycarbonate, or polysulfone is preferable. When using a synthetic resin substrate, it is necessary to pay attention to gas barrier properties. If the gas barrier property of the substrate is too small, the organic electroluminescent element may be deteriorated by the outside air that has passed through the substrate, which is not preferable. For this reason, a method of providing a gas barrier property by providing a dense silicon oxide film or the like on at least one surface of the synthetic resin substrate is also a preferable method.

[2] Anode
The anode 2 plays a role of injecting holes into a layer (hole injection layer 3 or organic light emitting layer 5 or the like) on the organic light emitting layer side described later. This anode 2 is usually a metal such as aluminum, gold, silver, nickel, palladium, platinum, a metal oxide such as an oxide of indium and / or tin, a metal halide such as copper iodide, carbon black, or A conductive polymer such as poly (3-methylthiophene), polypyrrole, or polyaniline is used. In general, the anode 2 is often formed by sputtering, vacuum deposition, or the like. Further, in the case of metal fine particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, and conductive polymer fine powders, they are dispersed in an appropriate binder resin solution and placed on the substrate 1. It is also possible to form the anode 2 by applying to. Further, in the case of a conductive polymer, a thin film can be directly formed on the substrate 1 by electrolytic polymerization, or the anode 2 can be formed by applying a conductive polymer on the substrate 1 (Applied Physics Letters, 1992). Year, Vol.60, pp.2711). The anode 2 can also be formed by stacking different materials.

  The thickness of the anode 2 varies depending on the required transparency. When transparency is required, it is desirable that the visible light transmittance is usually 60% or more, preferably 80% or more. In this case, the thickness is usually 5 nm or more, preferably 10 nm or more, Usually, it is 1000 nm or less, preferably 500 nm or less. If opaque, the anode 2 may be the same as the substrate 1. Furthermore, it is also possible to laminate different conductive materials on the anode 2 described above.

  In addition, the surface of the anode is treated with ultraviolet (UV) / ozone, oxygen plasma, or argon plasma for the purpose of removing impurities adhering to the anode and adjusting the ionization potential to improve the hole injection property. Is preferred. In addition, a known anode buffer layer is inserted between the hole injection layer 3 and the anode 2 for the purpose of further improving the efficiency of hole injection and improving the adhesion of the entire organic layer to the anode. Also good.

[3] Hole injection layer
The hole injection layer 3 is a layer that transports holes from the anode 2 to the organic light emitting layer 5. Usually, this hole injection layer 3 is formed on the anode 2. Therefore, the hole injection layer 3 is preferably configured to contain a hole injection compound and an electron accepting compound. Furthermore, the hole injection layer 3 may contain other components without departing from the spirit of the present invention.

  Examples of the method for forming the hole injection layer 3 on the anode 2 include a wet film formation method and a vacuum deposition method. As described above, a uniform and defect-free thin film can be easily obtained. The wet film-forming method is preferable from the viewpoint that the time required for the preparation is short. In addition, ITO (indium tin oxide), which is generally used as the anode 2, has a surface roughness (Ra) of about 10 nm in addition to its surface, and often has local protrusions. There was a problem that defects were easily generated. Forming the hole injection layer 3 on the anode 2 by the wet film formation method reduces the occurrence of device defects due to the unevenness of the surface of the anode 2 as compared with the case of forming by the vacuum deposition method. It also has advantages.

As the aromatic amine compound as the hole-injecting compound, a compound having a triarylamine structure is preferable, and a compound selected from compounds conventionally used as a material for forming a hole-injecting layer in an organic electroluminescent device is appropriately selected. Also good.
Examples of the polymer compound having a hole transport site in the molecule used as the hole injecting compound include a polymer compound containing an aromatic tertiary amino group as a constituent unit in the main skeleton. Specific examples thereof include a hole injecting compound having a structure represented by the following general formula (2) as a repeating unit.

(In the formula (2), Ar ^{44 to} Ar ⁴⁸ each independently represents a divalent aromatic ring group which may have a substituent, and R ^{31 to} R ³² each independently represents a substituent. And Q is selected from a direct bond or the following linking group, wherein “aromatic ring group” means “derived from an aromatic hydrocarbon ring” Including "group" and "group derived from an aromatic heterocycle")

(In formula (3), Ar ⁴⁹ represents a divalent aromatic ring group which may have a substituent, and Ar ⁵⁰ represents a monovalent aromatic ring group which may have a substituent. .)
In the general formula (2), Ar ^{44 to} Ar ⁴⁸ are each preferably a group derived from a divalent benzene ring, naphthalene ring, anthracene ring or biphenyl group which may each independently have a substituent, A group derived from a benzene ring is preferred. Examples of the substituent include a halogen atom; a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group and an ethyl group; an alkenyl group such as a vinyl group; and a C 2-7 such as a methoxycarbonyl group and an ethoxycarbonyl group. A linear or branched alkoxycarbonyl group of 1 to 6 carbon atoms such as a methoxy group or an ethoxy group; an aryloxy group of 6 to 12 carbon atoms such as a phenoxy group or a benzyloxy group; And a dialkylamino group having an alkyl chain having 1 to 6 carbon atoms such as a diisopropylamino group. Of these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is particularly preferable. Most preferably, Ar ^{44 to} Ar ⁴⁸ are each an unsubstituted aromatic ring group.

R ³¹ and R ³² are preferably each independently a phenyl group, naphthyl group, anthryl group, pyridyl group, triazyl group, pyrazyl group, quinoxalyl group, thienyl group, or biphenyl group, which may have a substituent. Preferably a phenyl group, a naphthyl group or a biphenyl group, more preferably a phenyl group. Examples of the substituent include a group in which an aromatic ring in Ar ⁴⁴ to Ar ⁴⁸ may have include the same groups as previously described.

In the general formula (3), Ar ⁴⁹ is a divalent aromatic ring group which may have a substituent, preferably an aromatic hydrocarbon ring group from the viewpoint of hole transportability. Includes an optionally substituted divalent benzene ring, naphthalene ring, anthracene ring-derived group, biphenylene group, and terphenylene group. Further, examples of the substituent include a group in which an aromatic ring may have at Ar ⁴⁴ to Ar ^48, include the same groups as previously described. Of these, an alkyl group having 1 to 3 carbon atoms is preferable, and a methyl group is particularly preferable.

Ar ⁵⁰ is an aromatic ring group which may have a substituent, preferably an aromatic hydrocarbon ring group from the viewpoint of hole transportability, and specifically, phenyl which may have a substituent. Group, naphthyl group, anthryl group, pyridyl group, triazyl group, pyrazyl group, quinoxalyl group, thienyl group, biphenyl group and the like. As this substituent, the group similar to the group mentioned above is mentioned as a group which the aromatic ring in Ar < ⁴⁴ > -Ar < ⁴⁸ > of General formula (2) may have.

In the general formula (3), it is most preferable that Ar ⁴⁹ and Ar ⁵⁰ are both unsubstituted aromatic ring groups.
Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by the formula (2) include those described in International Publication No. 2005/089024 pamphlet.

Examples of the hole injecting material made of a polymer compound further include conjugated polymers. For this purpose, polyfluorene, polypyrrole, polyaniline, polythiophene, polyparaphenylene vinylene are preferred.
Next, the electron accepting compound will be described.
Examples of the electron accepting compound contained in the hole injection layer include triaryl boron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, arylamines and Lewis acids. And one or more compounds selected from the group consisting of salts with These electron-accepting compounds are used by mixing with a hole-injecting material, and the conductivity of the hole-injecting layer can be improved by oxidizing the hole-injecting material.

  Examples of the triarylboron compound as the electron-accepting compound include boron compounds represented by the following general formula (6). The boron compound represented by the general formula (6) is preferably a Lewis acid. The electron affinity of the boron compound is usually 4 eV or more, preferably 5 eV or more.

In the general formula (6), preferably, Ar ^{101 to} Ar ¹⁰³ are each independently a monocyclic 5- or 6-membered ring such as a phenyl group, a naphthyl group, an anthryl group, or a biphenyl group that may have a substituent, Or an aromatic hydrocarbon ring group formed by condensing and / or directly bonding 2 to 3 of these; or 5 or 6 such as a thienyl group, pyridyl group, triazyl group, pyrazyl group, quinoxalyl group, etc., which may have a substituent. It represents a single-membered ring or an aromatic heterocyclic group formed by condensing 2 or 3 of these and / or directly bonding them.

Examples of the substituent that Ar ^{101 to} Ar ¹⁰³ may have include a halogen atom; an alkyl group; an alkenyl group; an alkoxycarbonyl group; an alkoxy group; an aryloxy group; an acyl group; a haloalkyl group;
In particular, at least one of Ar ^{101 to} Ar ¹⁰³ is preferably a substituent having a positive Hammett constant (σ _m and / or σ _p ), and Ar ^{101 to} Ar ¹⁰³ are all Hammet constants (σ It is particularly preferred that _m and / or σ _p ) is a substituent showing a positive value. By having such an electron-withdrawing substituent, the electron acceptability of these compounds is improved. Ar ^{101 to} Ar ¹⁰³ are more preferably an aromatic hydrocarbon group or an aromatic heterocyclic group substituted with a halogen atom.

  Although the preferable specific example of the boron compound represented by General formula (6) is shown to the following 6-1 to 6-17, it is not limited to these.

  Of these, the following compounds are particularly preferred.

  Examples of the electron-accepting compound include onium salts described in International Publication No. 2005/089024, and suitable examples thereof are the same, but the following compounds are particularly preferable.

The thickness of the hole injection layer 3 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
The content of the electron-accepting compound in the hole-injecting layer 3 with respect to the hole-injecting compound is usually 0.1 mol% or more, preferably 1 mol% or more. However, it is usually 100 mol% or less, preferably 40 mol% or less.

The hole injection layer 3 may be a crosslinked layer in the present invention. That is, the organic compound of the present invention may be used as a hole injecting compound.
[4] Hole transport layer
The hole transport layer 4 has a function of injecting holes injected in the order of the anode 2 and the hole injection layer 3 into the organic light emitting layer 5 and electrons are injected from the light emitting layer 5 to the anode 2 side. It has a function of suppressing a decrease in luminous efficiency.

In order to express this function, the hole transport layer 4 is preferably a cross-linked layer in the present invention. That is, the hole transport layer is preferably a layer formed by coating the organic compound of the present invention after applying the composition for organic electroluminescent elements containing the organic compound of the present invention.
Moreover, you may use compounds other than the organic compound of this invention.
Specific examples of the compound other than the organic compound of the present invention include two compounds including two or more tertiary amines represented by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl. Starburst structures such as aromatic diamines in which the above condensed aromatic rings are substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234681), 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) triphenylamine, etc. Aromatic amine compounds having the formula (J. Lumin., 72-74, 985, 1997), aromatic amine compounds consisting of tetramers of triphenylamine (Chem. Commun., 2175, 1996), Spiro compounds such as 2,2 ′, 7,7′-tetrakis- (diphenylamino) -9,9′-spirobifluorene (Synth. Metals, 91, 209, 19 1997), carbazole derivatives such as 4,4′-N, N′-dicarbazole biphenyl, and the like. These compounds may be used individually by 1 type, and may be used in mixture of multiple types as needed.

In addition to the above compounds, polyarylene ether sulfone (Polym. Adv. Tech., Which contains polyvinyl carbazole, polyvinyl triphenylamine (JP-A-7-53953), and tetraphenylbenzidine as materials for the hole transport layer. 7 (page 33, 1996).
Furthermore, the hole transport layer is preferably a layer obtained by crosslinking a crosslinkable compound by irradiation with heat and / or active energy rays (ultraviolet rays, electron beams, infrared rays, microwaves, etc.).

Although it does not specifically limit as a crosslinkable group, For example, group containing an unsaturated double bond, cyclic ether, benzocyclobutane etc. is preferable.
Examples of the crosslinkable compound include monomers, oligomers, and polymers having the crosslinkable group described above. Among them, polymers are preferable.
Specific examples of the crosslinking compound, e.g., triarylamine derivatives, carbazole derivatives, fluorene derivatives, 2,4,6-triphenyl pyridine derivatives, C ₆₀ derivatives, oligothiophene derivatives, phthalocyanine derivatives, porphyrin derivatives, condensed polycyclic An aromatic derivative, a metal complex derivative, etc. are mentioned. Among them, a compound having a partial structure of triphenylamine and a crosslinkable group is particularly preferred because of its high electrochemical stability and charge transportability.

The hole transport layer is formed by the method described in [Film Formation Method].
The film thickness is usually in the range of 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
[5] Organic light emitting layer
An organic light emitting layer 5 is usually provided on the hole transport layer 4. The organic light-emitting layer 5 includes holes injected from the anode 2 through the hole injection layer 3 and the hole transport layer 4 between the electrodes to which an electric field is applied, and an electron injection layer 7 and a hole blocking layer 6 from the cathode 8. It is a layer that is excited by recombination with electrons injected through and becomes a main light emitting source.

  The organic light emitting layer 5 contains at least a material having a light emitting property (light emitting material), and preferably a material having a hole transporting property (hole transporting material) or a material having an electron transporting property. (Electron transport material). Furthermore, the organic light emitting layer 5 may contain other components without departing from the spirit of the present invention. As these materials, from the viewpoint of forming the organic light emitting layer 5 by a wet film formation method as described later, it is preferable to use any low molecular weight materials.

Any known material can be applied as the light emitting material. For example, a fluorescent material or a phosphorescent material may be used, but a phosphorescent material is preferable from the viewpoint of internal quantum efficiency.
In order to improve the solubility in a solvent, it is also important to reduce the symmetry and rigidity of the molecules of the luminescent material, or to introduce a lipophilic substituent such as an alkyl group.

  Examples of fluorescent dyes that give blue light emission (blue fluorescent dyes) include naphthalene, perylene, pyrene, anthracene, coumarin, p-bis (2-phenylethenyl) benzene, and derivatives thereof. Examples of the dye that gives green light emission (green fluorescent dye) include quinacridone derivatives and coumarin derivatives. Examples of dyes that give yellow luminescence (yellow fluorescent dyes) include rubrene and perimidone derivatives. Fluorescent dyes that emit red light (red fluorescent dyes) include DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran) compounds, benzopyran derivatives, rhodamine derivatives, benzothioxanthene Derivatives, azabenzothioxanthene and the like.

As the phosphorescent material, for example, a long-period type periodic table (hereinafter referred to as a long-period type periodic table when referred to as “periodic table” unless otherwise specified) is selected from the seventh to eleventh groups. And an organometallic complex containing a metal.
Preferred examples of the metal selected from Groups 7 to 11 of the periodic table contained in the phosphorescent organometallic complex include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold. Preferred examples of these organometallic complexes include compounds represented by the following formula (III) or formula (IV).

ML _(q−j) L ′ _j (III)
(In the formula (III), M represents a metal, q represents a valence of the metal, L and L ′ represent a bidentate ligand, and j represents a number of 0, 1 or 2. )

(In the formula (IV), M ⁷ represents a metal, T represents a carbon atom or a nitrogen atom. R ^{92 to} R ⁹⁵ each independently represents a substituent. However, when T is a nitrogen atom, R 7 ⁹⁴ and R ⁹⁵ are not.)
Hereinafter, the compound represented by the formula (III) will be described first.
In formula (III), M represents an arbitrary metal, and specific examples of preferable ones include the metals described above as metals selected from Groups 7 to 11 of the periodic table.

  Moreover, in formula (III), the bidentate ligand L shows the ligand which has the following partial structures.

(In the partial structure of L, ring A1 represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.)
Examples of the aromatic hydrocarbon group include a 5- or 6-membered monocyclic ring or a 2-5 condensed ring. Specific examples include monovalent groups derived from a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc. Is mentioned.

  Examples of the aromatic heterocyclic group include a 5- or 6-membered monocyclic ring or a 2-4 condensed ring. Specific examples include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, Thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring , Sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, monovalent group derived from an azulene ring, and the like.

In the partial structure of L, ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent.
Examples of the nitrogen-containing aromatic heterocyclic group include groups derived from a 5- or 6-membered monocyclic ring or a 2-4 condensed ring. Specific examples include pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, furopyrrole ring, thienofuran ring, benzoisoxazole ring. , Benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone Examples thereof include a monovalent group derived from a ring.

Examples of the substituent that each of ring A1 and ring A2 may have include a halogen atom; an alkyl group; an alkenyl group; an alkoxycarbonyl group; an alkoxy group; an aryloxy group; a dialkylamino group; Acyl group; haloalkyl group; cyano group; aromatic hydrocarbon group and the like.
In the formula (III), the bidentate ligand L ′ represents a ligand having the following partial structure. However, in the following formulae, “Ph” represents a phenyl group.

  Among these, as L ′, the following ligands are preferable from the viewpoint of the stability of the complex.

More preferable examples of the compound represented by the formula (III) include compounds represented by the following formulas (IIIa), (IIIb), and (IIIc).

(In formula (IIIa), M ⁴ represents the same metal as M, w represents the valence of the metal,
A1 represents an aromatic hydrocarbon group which may have a substituent, and ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent. )

(In formula (IIIb), M ⁵ represents the same metal as M, w represents the valence of the metal,
A1 represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and ring A2 represents a nitrogen-containing aromatic heterocyclic group which may have a substituent. )

(In formula (IIIc), M ⁶ represents the same metal as M, w represents the valence of the metal, j
Represents 0, 1 or 2, and ring A1 and ring A1 ′ each independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group, and ring A2 and ring A2 Each independently represents a nitrogen-containing aromatic heterocyclic group which may have a substituent. )
In the above formulas (IIIa), (IIIb) and (IIIc), preferred examples of ring A1 and ring A1 ′ include phenyl group, biphenyl group, naphthyl group, anthryl group, thienyl group, furyl group, benzothienyl group, benzofuryl group. Group, pyridyl group, quinolyl group, isoquinolyl group, carbazolyl group and the like.

In the above formulas (IIIa) to (IIIc), preferred examples of ring A2 and ring A2 ′ include pyridyl group, pyrimidyl group, pyrazyl group, triazyl group, benzothiazole group, benzoxazole group, benzimidazole group, quinolyl group, An isoquinolyl group, a quinoxalyl group, a phenanthridyl group, and the like can be given.
Examples of the substituent that the compounds represented by the formulas (IIIa) to (IIIc) may have include a halogen atom; an alkyl group; an alkenyl group; an alkoxycarbonyl group; an alkoxy group; an aryloxy group; A diarylamino group; a carbazolyl group; an acyl group; a haloalkyl group; a cyano group, and the like.

These substituents may be connected to each other to form a ring. As a specific example, a substituent of the ring A1 and a substituent of the ring A2 are bonded, or a substituent of the ring A1 ′ and a substituent of the ring A2 ′ are bonded. Two fused rings may be formed. Examples of such a condensed ring include a 7,8-benzoquinoline group.
Among these, as a substituent for ring A1, ring A1 ′, ring A2 and ring A2 ′, an alkyl group, alkoxy group, aromatic hydrocarbon group, cyano group, halogen atom, haloalkyl group, diarylamino group, carbazolyl are more preferable. Groups.

In addition, preferable examples of M ^{4 to} M ⁶ in the formulas (IIIa) to (IIIc) include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, or gold.
Specific examples of the organometallic complexes represented by the above formulas (III) and (IIIa) to (IIIc) are shown below, but are not limited to the following compounds.

Among the organometallic complexes represented by the above formula (III), in particular, as the ligand L and / or L ′, a 2-arylpyridine-based ligand, that is, 2-arylpyridine, there is an optional substituent. The compound which has what was couple | bonded and the thing formed by arbitrary groups condensing to this is preferable.
The compounds described in International Patent Publication No. 2005/019373 pamphlet can also be used as the light emitting material.

Next, the compound represented by formula (IV) will be described.
In formula (IV), M ⁷ represents a metal. Specific examples include the metals described above as the metal selected from Groups 7 to 11 of the periodic table. Among these, ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum or gold is preferable, and divalent metals such as platinum and palladium are particularly preferable.

In the formula (IV), R ⁹² and R ⁹³ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an alkenyl group, a cyano group, an amino group, an acyl group, an alkoxycarbonyl group, a carboxyl group, Represents an alkoxy group, an alkylamino group, an aralkylamino group, a haloalkyl group, a hydroxyl group, an aryloxy group, an aromatic hydrocarbon group or an aromatic heterocyclic group;

Further, when T is carbon ^{atom, R 94} and ^{R 95} each independently ^represents a substituent represented by the same exemplary compounds and ^{R 92} and ^{R 93.} Also, if T is a nitrogen ^{atom, R 94} and ^{R 95} is not.
R ^{92 to} R ⁹⁵ may further have a substituent. When it has a substituent, there is no restriction | limiting in particular in the kind, Arbitrary groups can be made into a substituent.

Further, any two or more groups of R ^{92 to} R ⁹⁵ may be connected to each other to form a ring.
Specific examples (T-1, T-10 to T-15) of the organometallic complex represented by the formula (IV) are shown below, but are not limited to the following examples. In the following chemical formulae, Me represents a methyl group, and Et represents an ethyl group.

  In the present invention, the molecular weight of the compound used as the light emitting material is usually 10,000 or less, preferably 5000 or less, more preferably 4000 or less, still more preferably 3000 or less, and usually 100 or more, preferably 200 or more, more preferably 300 or more. More preferably, the range is 400 or more. If the molecular weight is less than 100, the heat resistance is remarkably reduced, gas is generated, the film quality is deteriorated when the film is formed, or the morphology of the organic electroluminescent element is changed due to migration or the like. There is a case to do. When the molecular weight exceeds 10,000, it may be difficult to purify the compound, or it may take time to dissolve the compound in a solvent.

The light emitting layer may contain any one of the various light emitting materials described above alone, or may contain two or more kinds in any combination and ratio.
Examples of the low molecular weight hole transporting material include various compounds exemplified as the hole transporting compound of the above-described hole transporting layer, and 4,4′-bis [N- (1-naphthyl) -N -Phenylamino] biphenyl represented by two or more tertiary amines represented by biphenyl,
Aromatic amine compounds having a starburst structure (Journal, such as aromatic diamines substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234681), 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) triphenylamine) of Luminescence, 1997, Vol. 72-74, pp. 985), aromatic amine compounds consisting of tetramers of triphenylamine (Chemical Communications, 1996, pp. 2175), 2, 2 ', 7, 7 Examples include spiro compounds (Synthetic Metals, 1997, Vol. 91, pp. 209) such as' -tetrakis- (diphenylamino) -9,9'-spirobifluorene.

  Examples of low molecular weight electron transport materials include 2,5-bis (1-naphthyl) -1,3,4-oxadiazole (BND) and 2,5-bis (6 ′-(2 ′, 2 "-bipyridyl))-1,1-dimethyl-3,4-diphenylsilole (PyPySPyPy), bathophenanthroline (BPhen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) , Bathocuproine), 2- (4-biphenylyl) -5- (p-tertiarybutylphenyl) -1,3,4-oxadiazole (tBu-PBD) and 4,4′-bis (9-carbazole) -Biphenyl (CBP) and the like.

  These hole transport materials and electron transport materials are preferably used as host materials in the light-emitting layer. Specifically, the following compounds can be used as the host materials.

Examples of the method for forming the organic light emitting layer 5 include a wet film forming method and a vacuum evaporation method. As described above, a homogeneous and defect-free thin film can be easily obtained, and the time for formation is short. The wet film-forming method is preferable from the viewpoint that the effect of insolubilization of the hole transport layer 4 by the organic compound of the present invention can be enjoyed. When the organic light emitting layer 5 is formed by a wet film forming method, the above-described material is dissolved in an appropriate solvent to prepare a coating solution, which is applied onto the hole transport layer 4 after the above-described formation.
It is formed by forming a film and drying to remove the solvent. The formation method is the same as the formation method of the hole transport layer.

The film thickness of the organic light emitting layer 5 is usually 3 nm or more, preferably 5 nm or more, and usually 200 nm or less, preferably 100 nm or less.
[6] Hole blocking layer
In FIG. 1, the hole blocking layer 6 is provided between the organic light emitting layer 5 and the electron transport layer 7, but the hole blocking layer 6 may be omitted.

The hole blocking layer 6 is laminated on the organic light emitting layer 5 so as to be in contact with the interface of the organic light emitting layer 5 on the cathode 8 side, but the holes moving from the anode 2 reach the cathode 8. And a compound capable of efficiently transporting electrons injected from the cathode 8 toward the organic light emitting layer 5.
The physical properties required for the material constituting the hole blocking layer 6 include high electron mobility, low hole mobility, a large energy gap (difference between HOMO and LUMO), and excited triplet level (T1). Is high.

  Examples of hole blocking materials that satisfy such conditions include bis (2-methyl-8-quinolinolato), (phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato), (triphenylsilanolato) aluminum, and the like. Mixed metal complexes such as bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolinato) aluminum binuclear metal complexes, distyrylbiphenyl derivatives, etc. Triazole derivatives such as styryl compounds (JP-A-11-242996), 3- (4-biphenylyl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazole (JP-A-7 -41759) and phenanthroline derivatives such as bathocuproine (Japanese Patent Laid-Open No. 10-79297).Furthermore, a compound having at least one pyridine ring substituted at the 2,4,6-positions described in International Publication No. 2005-022962 is also preferable as the hole blocking material.

  Specific examples include the compounds described below.

Similarly to the hole injection layer 3 and the organic light emitting layer 5, the hole blocking layer 6 can also be formed by a wet film formation method, but is usually formed by a vacuum deposition method. The details of the procedure of the vacuum deposition method are the same as those of the electron injection layer 7 described later.
The film thickness of the hole blocking layer 6 is usually 0.5 nm or more, preferably 1 nm or more, and usually 100 nm or less, preferably 50 nm or less.

[7] Electron transport layer
The electron transport layer 7 is provided between the light emitting layer 5 and the electron injection layer 8 for the purpose of further improving the light emission efficiency of the device.
The electron transport layer 7 is formed of a compound that can efficiently transport electrons injected from the cathode 9 between electrodes to which an electric field is applied in the direction of the light emitting layer 5. As the electron transporting compound used for the electron transport layer 7, the electron injection efficiency from the cathode 9 or the electron injection layer 8 is high, and the injected electrons can be efficiently transported with high electron mobility. It must be a compound.

  Materials satisfying such conditions include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), metal complexes of 10-hydroxybenzo [h] quinoline, oxadiazole derivatives, Styryl biphenyl derivative, silole derivative, 3- or 5-hydroxyflavone metal complex, benzoxazole metal complex, benzothiazole metal complex, trisbenzimidazolylbenzene (US Pat. No. 5,645,948), quinoxaline compound 6-207169), phenanthroline derivative (Japanese Patent Laid-Open No. 5-33159), 2-t-butyl-9,10-N, N′-dicyanoanthraquinonediimine, n-type hydrogenated amorphous silicon carbide, n Type zinc sulfide, n-type zinc selenide and the like.

The lower limit of the thickness of the electron transport layer 7 is usually 1 nm, preferably about 5 nm, and the upper limit is usually about 300 nm, preferably about 100 nm.
The electron transport layer 7 is formed by laminating on the hole blocking layer 6 by a wet film forming method or a vacuum vapor deposition method in the same manner as described above, but a vacuum vapor deposition method is usually used.
[8] Electron injection layer
The electron injection layer 8 plays a role of efficiently injecting electrons injected from the cathode 9 into the electron transport layer 7 or the organic light emitting layer 5.

In order to perform electron injection efficiently, the material for forming the electron injection layer 8 is preferably a metal having a low work function. Examples include alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium. The film thickness is usually preferably from 0.1 nm to 5 nm.
Further, organic electron transport materials represented by metal complexes such as nitrogen-containing heterocyclic compounds such as bathophenanthroline and aluminum complexes of 8-hydroxyquinoline described later are doped with alkali metals such as sodium, potassium, cesium, lithium and rubidium. (Described in JP-A-10-270171, JP-A 2002-1000047, JP-A 2002-1000048, and the like) makes it possible to improve electron injection / transport properties and achieve excellent film quality. Therefore, it is preferable. The film thickness in this case is usually in the range of 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.

The electron injection layer 8 is formed by laminating on the organic light emitting layer 5 or the hole blocking layer 6 thereon by a wet film formation method or a vacuum deposition method.
Details of the wet film forming method are the same as those of the hole injection layer 3 and the organic light emitting layer 5.
On the other hand, in the case of the vacuum vapor deposition method, the vapor deposition source is put into a crucible or metal boat installed in the vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 ⁻⁴ Pa with an appropriate vacuum pump, and then the crucible or metal The boat is heated and evaporated to form an electron injection layer 8 on the organic light-emitting layer 5, hole blocking layer 6 or electron transport layer 7 on the substrate placed facing the crucible or metal boat.

The alkali metal as the electron injection layer is deposited by using an alkali metal dispenser in which nichrome is filled with an alkali metal chromate and a reducing agent. By heating the dispenser in a vacuum container, the alkali metal chromate is reduced and the alkali metal is evaporated.
In the case of co-evaporating the organic electron transport material and the alkali metal, the organic electron transport material is put in a crucible installed in a vacuum vessel, and the inside of the vacuum vessel is evacuated to about 10 ⁻⁴ Pa with a suitable vacuum pump. Each crucible and dispenser are simultaneously heated and evaporated to form the electron injection layer 8 on the substrate placed facing the crucible and dispenser.

At this time, co-evaporation is uniformly performed in the film thickness direction of the electron injection layer 8, but there may be a concentration distribution in the film thickness direction.
[9] Cathode
The cathode 9 plays a role of injecting electrons into a layer (such as the electron injection layer 8 or the organic light emitting layer 5) on the organic light emitting layer 5 side. As the material of the cathode 9, the material used for the anode 2 can be used. However, in order to perform electron injection efficiently, a metal having a low work function is preferable, and tin, magnesium, indium, calcium, A suitable metal such as aluminum or silver or an alloy thereof is used. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.

The film thickness of the cathode 9 is usually the same as that of the anode 2.
For the purpose of protecting the cathode made of a low work function metal, it is preferable to further stack a metal layer having a high work function and stable to the atmosphere because the stability of the device is increased. For this purpose, metals such as aluminum, silver, copper, nickel, chromium, gold, platinum are used.
[10] Other
As described above, the organic electroluminescent element having the layer configuration shown in FIG. 1 has been mainly described. However, the organic electroluminescent element of the present invention may have another configuration without departing from the gist thereof. For example, as long as the performance is not impaired, an arbitrary layer may be provided between the anode 2 and the cathode 9 in addition to the layers described above, and an arbitrary layer may be omitted. .

In the present invention, by using the organic compound of the present invention for the hole transport layer 4, the hole injection layer 3, the hole transport layer 4 and the organic light emitting layer 5 are all laminated by a wet film formation method. be able to. This makes it possible to manufacture a large area display.
Note that the structure opposite to that shown in FIG. 1, that is, a cathode, an electron injection layer, a light emitting layer, a hole injection layer, and an anode can be laminated on the substrate 1 in this order, and at least one of them is transparent as described above. It is also possible to provide the organic electroluminescent element of the present invention between two highly functional substrates.

Further, a structure in which a plurality of layers shown in FIG. 1 are stacked (a structure in which a plurality of light emitting units are stacked) may be employed. In that case, instead of the interfacial layer (between the light emitting units) (when the anode is ITO and the cathode is Al, the two layers), for example, V ₂ O ₅ is used as the charge generation layer (CGL). This is more preferable from the viewpoint of luminous efficiency and driving voltage.
The present invention can be applied to any of an organic electroluminescent element having a single element, an element having a structure arranged in an array, and a structure having an anode and a cathode arranged in an XY matrix.

[Organic EL display]
The organic EL display of the present invention includes the organic electroluminescent element of the present invention as described above. There is no restriction | limiting in particular about the model and structure of an organic electroluminescent display, It can assemble in accordance with a conventional method using the organic electroluminescent element of this invention.
For example, the organic EL display of the present invention is formed by a method as described in “Organic EL Display” (Ohm, published on August 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata). can do.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to description of a following example, unless the summary is exceeded.
[Synthesis example]
(Synthesis Example 1)

  In a nitrogen stream, pyrene (10.11 g) and dimethoxyethane (400 ml) were added and stirred while cooling to 0 ° C. in an ice bath. Bromine (15.18 g) dissolved in 50 ml of dimethoxyethane was added dropwise to room temperature. The mixture was warmed and stirred for 8 hours, and then left overnight. The precipitated crystals were collected by filtration, washed with ethanol, and recrystallized with toluene to obtain a mixture (5.8 g) of monomers 3 and 4.

1H NMR (CDCl3, 400MHz)
1,8-dibromopyrene
δ 8.53 (s, 2H), 8.28 (d, 2H, J = 8.40), 8.05 (d, 2H, J = 8.00), 8.04 (s, 2H)
1,6-dibromopyrene
δ 8.47 (d, 2H, J = 9.60), 8.27 (d, 2H, J = 8.40), 8.13 (d, 2H, J = 9.20), 8.06 (d , 2H, J = 8.40)

In a nitrogen stream, in a solution of monomer 1 (2.407 g), monomer 2 (0.327 g), a mixture of monomer 3 and monomer 4 (1.530 g, monomer 3: monomer 4 = 33: 67), toluene (46 ml) , 20% tetraethylammonium hydroxide aqueous solution (28 m
l) was added, tetrakis (triphenylphosphine) palladium (0) (0.108 g) was added, and the mixture was stirred with heating under reflux for 8 hours. After allowing to cool, the reaction solution was added to ethanol, and the precipitated polymer 1 was collected by filtration and dried. A 20% tetraethylammonium hydroxide aqueous solution (20 ml) was added to a solution of polymer 1, bromobenzene (0.131 g), and toluene (100 ml) in a nitrogen stream, and tetrakis (triphenylphosphine) palladium (0) (0. 054 g) was added and stirred for 2 hours under reflux. Subsequently, phenylboronic acid (0.509 g) was added, and the mixture was stirred for 6 hours with heating under reflux. After allowing to cool, the reaction solution was added to ethanol, and the polymer 1 having the end-capped end residues was collected by filtration and dried, and then purified by a silica gel column using toluene and tetrahydrofuran as developing solvents. The product 1 (0.771 g) was obtained by reprecipitation, filtration and drying.

The target product 1 had a weight average molecular weight of 77,000 and a number average molecular weight of 39,000.
(Synthesis Example 2)

  Potassium hydroxide was added to 80 ml of compound 1 (10.0 g), compound 2 (16.3 g) and dimethyl sulfoxide, and the mixture was stirred at room temperature for 6 hours. Ethyl acetate (100 ml) and water (100 ml) were added to the reaction mixture, and the mixture was stirred and separated. The aqueous layer was extracted with ethyl acetate (100 ml x 2), the organic layers were combined, dried over magnesium sulfate, and concentrated. . Furthermore, the compound 3 (13.3g) was obtained by refine | purifying with silica gel column chromatography (n-hexane / ethyl acetate = 10/1).

In a nitrogen stream, compound 3 (3.0 g), compound 4 (1.44 g), sodium tert-butoxide (1.13 g) and toluene (50 ml) were stirred for 30 minutes while heating to 60 ° C., and tris ( Dibenzylidene) dipalladium (0) chloroform complex (0.09 g) and tri-tert-butylphosphine (0.07 g) were added, and the mixture was stirred for 3 hours under heating to reflux. After allowing to cool to room temperature, toluene (100 ml) and water (100 ml) were added to the reaction solution, and the mixture was stirred and separated. The aqueous layer was extracted with toluene (100 ml × 2 times), and the organic layers were combined. After drying, it was concentrated. Furthermore, silica gel column chromatography (n
Compound 5 (3.4 g) was obtained by purification with -hexane / ethyl acetate = 10/1).

  In a nitrogen stream, NBS (N-bromosuccinimide) was dissolved in 30 ml of DMF in 100 ml of Compound 5 (3.4 g) and DMF (N, N-dimethylformamide) at −5 ° C., and the mixture was stirred at this temperature for 2 hours. . Ethyl acetate (100 ml) and water (100 ml) were added to the reaction mixture, and the mixture was stirred and separated. The aqueous layer was extracted with ethyl acetate (100 ml x 2), the organic layers were combined, dried over magnesium sulfate, and concentrated. . Furthermore, the monomer 5 (2.3g) was obtained by refine | purifying with silica gel column chromatography (n-hexane / ethyl acetate = 10/1).

  In a nitrogen stream, monomer 1 (2.512 g), monomer 5 (0.302 g), monomer 6 (1.033 g), mixture of monomer 3 and monomer 4 (0.792 g, monomer 3: monomer 4 = 37: 63) To a solution of toluene (40 ml), a 20% tetraethylammonium hydroxide aqueous solution (20 ml) was added, tetrakis (triphenylphosphine) palladium (0) (0.058 g) was added, and the mixture was stirred for 8 hours while heating under reflux. After allowing to cool, the reaction solution was added to ethanol, and the precipitated polymer 2 was collected by filtration and dried. In a nitrogen stream, 20% tetraethylammonium hydroxide aqueous solution (50 ml) was added to a solution of polymer 2, bromobenzene (0.140 g), and toluene (100 ml), and tetrakis (triphenylphosphine) palladium (0) (0. 058 g) was added and the mixture was stirred for 2.5 hours under reflux with heating. Subsequently, phenylboronic acid (0.610 g) was added, and the mixture was stirred for 6 hours with heating under reflux. After allowing to cool, toluene and water are added, the organic layer is concentrated to 50 ml, ethanol is added, and the precipitated polymer 2 end-capped is collected by filtration and dried, and then toluene and tetrahydrofuran are added. The product was purified by a silica gel column as a developing solvent, reprecipitated from ethanol in tetrahydrofuran, collected by filtration, and dried to obtain the intended product 2 (2.20 g).

The target product 2 had a weight average molecular weight of 26,000 and a number average molecular weight of 13,000.
(Synthesis Example 3)

  A 500 ml four-necked flask was repeatedly heated and dried with a heat gun under reduced pressure and purged with nitrogen to create a nitrogen atmosphere. A mixture of 1,6-dibromopyrene and 1,8-dibromopyrene (7.2 g) and dry THF (150 ml) were added, and the reactor was cooled to -70 ° C in a dry ice-acetone bath. 50 ml of n-butyllithium (1.06M) was added dropwise over 30 minutes, and stirring was continued for 2 hours from the end of the addition while maintaining at -70 ° C. 17.6 ml of 2-isopropyl-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was added dropwise. Stirring was performed under cooling conditions for 30 minutes after the completion of dropping, and then the cooling bath was removed, the temperature was gradually raised to room temperature, and the mixture was allowed to stand overnight. The precipitated crystals were collected by suction filtration. This was dissolved in methylene chloride, washed with 100 ml of water, the methylene chloride layer was concentrated, and the resulting crystals were washed with a mixed solvent of THF and hexane and then dried to give monomer 7 (2.1 g). Got.

1H NMR (CDCl3, 400 MHz)
δ 9.1 (d, 2H, J = 9.20), 8.52 (d, 2H, J = 7.60), 8.18 (d, 2H, J = 7.60), 8.19 ( d, 2H, J = 9.2), 1.49 (s, 12H)

  In a nitrogen stream, 20% tetraethylammonium hydroxide aqueous solution (10 ml) was added to a solution of monomer 7 (1.0 g), monomer 6 (0.91 g), monomer 5 (0.133 g), and toluene (30 ml). (Triphenylphosphine) palladium (0) (0.1 g) was added, and the mixture was stirred for 8 hours with heating under reflux. After allowing to cool, the reaction solution was added to ethanol, and the precipitated polymer 3 was collected by filtration and dried. A 20% tetraethylammonium hydroxide aqueous solution (20 ml) was added to a solution of the obtained polymer 3, bromobenzene (0.073 g), and toluene (120 ml) in a nitrogen stream, and tetrakis (triphenylphosphine) palladium (0). (0.027 g) was added, and the mixture was stirred with heating under reflux for 2 hours. Subsequently, phenylboronic acid (0.3 g) was added, and the mixture was stirred for 5 hours with heating under reflux. After allowing to cool, the reaction solution was added to ethanol, and the precipitated polymer 3 end-capped end polymer 3 was collected by filtration and dried, and then purified by a silica gel column using toluene and tetrahydrofuran as developing solvents. The product 3 (100 mg) was obtained by reprecipitation, filtration and drying.

The target product 3 had a weight average molecular weight of 10,400 and a number average molecular weight of 7030.
(Synthesis Example 4)

  In a nitrogen stream, monomer 1 (3.26 g), monomer 2 (0.45 g), monomer 3 and monomer 4, mixture (1.530 g, monomer 3: monomer 4 = 33: 67), monomer 6 (1.34 g) To a solution of toluene (59 ml) in water, 20% tetraethylammonium hydroxide aqueous solution (11 ml) was added, tetrakis (triphenylphosphine) palladium (0) (0.075 g) was added, and the mixture was stirred with heating under reflux for 6 hours. After allowing to cool, the reaction solution was added to methanol, and the precipitated crude polymer 4 was collected by filtration and dried. A 20% tetraethylammonium hydroxide aqueous solution (24 ml) was added to a solution of the obtained crude polymer 4, bromobenzene (0.20 g), and toluene (100 ml) in a nitrogen stream, and tetrakis (triphenylphosphine) palladium (0). (0.451 g) was added, and the mixture was stirred with heating under reflux for 2 hours. Subsequently, phenylboronic acid (1.80 g) was added, and the mixture was stirred for 6 hours with heating under reflux. After allowing to cool, the reaction solution was added to ethanol, and the crude polymer 4 end-capped with the precipitated end residues was collected by filtration and dried, and then purified by a silica gel column using toluene and tetrahydrofuran as developing solvents. The product 4 (1.45 g) was obtained by reprecipitation, filtration and drying.

The target product 4 had a weight average molecular weight of 22,000 and a number average molecular weight of 14,000.
(Synthesis Example 5)

  In a nitrogen stream, monomer 1 (5.024 g), monomer 2 (0.885 g), monomer 8 (2.396 g), mixture of monomer 3 and monomer 4 (1.058 g, monomer 4: monomer 5 = 37: 63) To a solution of toluene (60 ml), 20% tetraethylammonium hydroxide aqueous solution (30 ml) was added, tetrakis (triphenylphosphine) palladium (0) (0.23 g) was added, and the mixture was stirred for 5 hours while heating under reflux. After allowing to cool, the reaction solution was added to ethanol, and the precipitated polymer 5 was collected by filtration and dried. A 20% tetraethylammonium hydroxide aqueous solution (30 ml) was added to a solution of the obtained polymer 5, bromobenzene (0.33 g), and toluene (60 ml) in a nitrogen stream, and tetrakis (triphenylphosphine) palladium (0). (0.12 g) was added, and the mixture was stirred with heating under reflux for 2 hours. Subsequently, phenylboronic acid (1.0 g) was added, and the mixture was stirred for 4 hours with heating under reflux. After allowing to cool, the reaction solution was added to ethanol, and the precipitated polymer having end-capped end residues was collected by filtration and dried, and then purified by a silica gel column using toluene and tetrahydrofuran as a developing solvent. The target product 5 (3.4 g) was obtained by reprecipitation, filtration and drying.

The target product 5 had a weight average molecular weight of 38600 and a number average molecular weight of 2500.
(Synthesis Example 6)

  In a nitrogen stream, compound 6 (2.04 g), compound 7 (3.26 g), toluene (90 ml) and ethanol (45 ml) were added, and the system was replaced with nitrogen by bubbling with nitrogen. After adding sodium carbonate (3.15 g) and demineralized water (45 ml), bubbling with nitrogen and replacing the system with nitrogen, tetrakistriphenylphosphine palladium (0.16 g) was added. The mixture was heated and stirred in an oil bath at 80 ° C. for 5 hours under a nitrogen stream. After allowing to cool, water was added to separate the liquid and the oil layer. After purification by silica gel column chromatography (ethyl acetate: methylene chloride = 9: 1), the crystals were reprecipitated with methylene chloride and hexane and collected by filtration. Further, the product was purified by silica gel chromatography (hexane: ethyl acetate = 4: 6) and recrystallized from ethyl acetate to obtain the target product 6 (0.73 g).

1H NMR (CDCl3, 400 MHz)
δ 8.39 (s, 4H), 8.14 (s, 4H), 7.47-7.42 (m, 6H), 4.53 (d, 2H, J = 6.0), 4.36 ( d, 2H, J = 6.0), 4.14 (t, 2H, J = 12.8), 3.58 (t, 4H, J = 12.4), 3.51 (s, 4H), 1.97-1.93 (m, 4H), 1.88-1.82 (m, 4H), 1.32 (s, 6H)
(Synthesis Example 7)

  Potassium fluoride (23.01 g) was charged into the reaction vessel, and heating and drying and nitrogen substitution were repeated under reduced pressure to create a nitrogen atmosphere in the system. 3-Nitrophenylboronic acid (6.68 g), 4-bromo-benzocyclobutene (7.32 g) and dehydrated tetrahydrofuran (50 ml) were charged and stirred. Then, tris (dibenzylideneacetone) dipalladium chloroform complex (0.21 g) was added, the inside of the system was sufficiently substituted with nitrogen, and tri-t-butylphosphine (0.47 g) was added at room temperature, and the addition was completed. Thereafter, the mixture was stirred for 1 hour. After completion of the reaction, water was added to the reaction solution and extracted with ethyl acetate. The obtained organic layer was washed with water twice, added with sodium sulfate, dehydrated and dried, and concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain Compound 8 (8.21 g).

  (Synthesis Example 8)

  Compound 8 (8.11 g), tetrahydrofuran 36 ml, ethanol 36 ml, 10% Pd / C (1.15 g) were charged, and the mixture was heated and stirred at 70 ° C. Hydrazine monohydrate (10.81 g) was slowly added dropwise thereto. After reacting for 2 hours, the mixture was allowed to cool, the reaction mixture was filtered through celite, and the filtrate was concentrated. Ethyl acetate was added to the filtrate, washed with water, and the organic layer was concentrated. The obtained crude product was purified by column chromatography (hexane / ethyl acetate) to obtain monomer 9 (4.90 g).

  (Synthesis Example 9)

  4-n-octylaniline (1.31 g, 6.4 mmol), monomer 9 obtained in Synthesis Example 8 (0.31 g, 1.6 mmol), 4,4′-dibromobiphenyl (1.25 g, 4.0 mmol) ), Sodium tert-butoxy (2.88 g, 30.0 mmol), and toluene (20 ml), and the system was sufficiently purged with nitrogen and heated to 50 ° C. (solution A). Tri-t-butylphosphine (0.129 g, 0.064 mmol) was added to a 5 ml toluene solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.09 g, 0.0088 mmol) and heated to 50 ° C. ( Solution B). In a nitrogen stream, solution B was added to solution A and heated to reflux for 1 hour. After confirming disappearance of the raw material, the target product 3 (1.305 g, 4.0 mmol) obtained in Synthesis Example 3 was further added, and the mixture was heated to reflux for 1 hour. Since it was confirmed that the polymerization started, a mixture of 1,6-dibromopyrene and 1,8-dibromopyrene (0.013 g, 0.04 mmol) was added four times every hour (total 0.52 g). Added. The whole mixture of 1,6-dibromopyrene and 1,8-dibromopyrene was added, and the mixture was further heated under reflux for 1 hour, the reaction solution was allowed to cool, and the reaction solution was added dropwise into 200 ml of methanol, whereby the crude polymer 6 was crystallized. I made it come out.

  The obtained crude polymer 6 was dissolved in 150 ml of toluene, bromobenzene (0.25 g, 1.6 mmol) and tert-butoxy sodium (0.77 g, 8 mmol) were charged, and the inside of the system was sufficiently purged with nitrogen. Warmed to ° C. (Solution C). Tri-t-butylphosphine (0.016 g, 0.008 mmol) was added to a 10 ml toluene solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.066 g, 0.0064 mmol) and heated to 50 ° C. ( Solution D). In a nitrogen stream, solution D was added to solution C, and heated to reflux for 2 hours. N, N-diphenylamine (1.35 g, 8 mmol) was added to the reaction solution, and the mixture was further heated to reflux for 4 hours. The reaction solution was allowed to cool and added dropwise to methanol to obtain a crude polymer 6 in which terminal residues were end-capped.

The crude polymer 6 end-capped with this terminal residue was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the intended product 7 (0.53 g).
The target product 7 had a weight average molecular weight of 39,700 and a number average molecular weight of 17,600.

[Production of organic electroluminescence device]
Example 1
The organic electroluminescent element shown in FIG. 1 was produced.
An indium tin oxide (ITO) transparent conductive film deposited on a glass substrate 1 with a thickness of 120 nm (manufactured by Sanyo Vacuum Co., Ltd., sputtered film product) using ordinary photolithography technology and hydrochloric acid etching Then, the anode 2 was formed by patterning into stripes having a width of 2 mm. The patterned ITO substrate is cleaned in the order of ultrasonic cleaning with an aqueous surfactant solution, water cleaning with ultrapure water, ultrasonic cleaning with ultrapure water, and water cleaning with ultrapure water, followed by drying with compressed air, and finally UV irradiation. Ozone cleaning was performed.

  First, a hole transporting polymer material having a repeating structure represented by the following structural formula (P1) (weight average molecular weight: 26500, number average molecular weight: 12000), 4-isopropyl-4′- represented by the structural formula (A1) A coating solution for forming a hole injection layer containing methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and ethyl benzoate was prepared. This coating solution was formed on the anode 2 by spin coating under the following conditions to obtain a hole injection layer 3 having a thickness of 30 nm.

<Coating liquid for hole injection layer formation>
Solvent ethyl benzoate
Coating solution concentration P1: 2.0% by weight
A1: 0.8% by weight
<Film formation conditions for hole injection layer 3>
Spinner speed 1500rpm
Spinner rotation time 30 seconds
Spin coat atmosphere In air
Heating conditions Atmosphere 230 ° C 3 hours
Subsequently, a composition for an organic electroluminescence device containing the organic compound (H1) of the present invention (target product 6 obtained in Synthesis Example 6) represented by the following structural formula was prepared, and spin coating was performed under the following conditions. A hole transport layer 4 having a film thickness of 22 nm was formed by film formation and crosslinking by heating.

<Composition for organic electroluminescence device>
Solvent Toluene
Solid content concentration 0.4% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 30 seconds
Spin coat atmosphere In nitrogen
Heating conditions In nitrogen, 230 ° C, 1 hour
Next, in forming the light emitting layer 5, the following light emitting layer forming coating solution is prepared using the organic compounds (E1), (E2), and the iridium complex (D1) shown below. Then, spin coating was performed on the hole transport layer 4 to obtain a light emitting layer 5 with a film thickness of 40 nm.

<Light emitting layer forming coating solution>
Solvent xylene
Coating solution concentration (E1): 1.0% by weight
(E2): 1.0% by weight
(D1): 0.1% by weight
<Film-forming conditions of the light emitting layer 5>
Spinner speed 1500rpm
Spinner rotation time 30 seconds
Spin coat atmosphere In nitrogen
Heating conditions Under reduced pressure (0.1 MPa), 130 ° C., 1 hour
Here, the substrate on which the hole injection layer 3, the hole transport layer 4 and the light emitting layer 5 are formed is transferred into a vacuum deposition apparatus, and after the apparatus is roughly evacuated by an oil rotary pump, the degree of vacuum in the apparatus is increased. 2.7 × 10 ⁻⁴
After evacuating using a cryopump until the pressure became Pa or lower, a compound represented by the following structural formula (E3) was laminated by a vacuum deposition method to obtain a hole blocking layer 6. The deposition rate was controlled in the range of 0.5 to 1.2 liters / second, and the hole blocking layer 6 having a film thickness of 5 nm was formed by being laminated on the light emitting layer 5.

Subsequently, tris (8-hydroxyquinolinate) aluminum was heated and evaporated to form an electron transport layer 7. The deposition rate was controlled in the range of 0.8 to 1.4 liters / second, and an electron transport layer 7 was formed by laminating a film with a thickness of 30 nm on the hole blocking layer 6.
Here, the element that has been deposited up to the electron transport layer 7 is once taken out from the vacuum deposition apparatus into the atmosphere, and a 2 mm wide striped shadow mask is used as a cathode deposition mask. The device was placed in close contact with each other so as to be orthogonal to each other, placed in another vacuum vapor deposition apparatus, and evacuated until the degree of vacuum in the apparatus was 2.0 × 10 ⁻⁴ Pa or less in the same manner as the organic layer.

  As the electron injection layer 8, lithium fluoride (LiF) is first controlled on the electron transport layer 7 with a film thickness of 0.5 nm by using a molybdenum boat and controlling the deposition rate at 0.07 to 0.1% / second. A film was formed. Next, aluminum was similarly heated by a molybdenum boat as the cathode 9, and an aluminum layer having a film thickness of 80 nm was formed by controlling the deposition rate at 0.5 to 5.5 kg / sec. The substrate temperature during the above two-layer deposition was kept at room temperature.

Subsequently, in order to prevent the element from being deteriorated by moisture in the atmosphere during storage, a sealing process was performed by the method described below.
In a nitrogen glove box connected to a vacuum deposition apparatus, a photocurable resin (30Y-437 manufactured by ThreeBond Co., Ltd.) with a width of about 1 mm is applied to the outer periphery of a 23 mm × 23 mm size glass plate, and moisture is applied to the center. A getter sheet (manufactured by Dynic) was installed. On this, the board | substrate which complete | finished cathode formation was bonded together so that the vapor-deposited surface might oppose a desiccant sheet. Then, only the area | region where the photocurable resin was apply | coated was irradiated with ultraviolet light, and resin was hardened.

As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. The light emission characteristics of this element are as follows.
Luminance / current: 17.6 [cd / A] @ 100 cd / m ²
Voltage: 8.3 [V] @ 100 cd / m ²
Luminous efficiency: 6.7 [lm / W] @ 100 cd / m ²
The maximum wavelength of the emission spectrum of the device was 513 nm, which was identified as from the iridium complex (D1). The chromaticity was CIE (x, y) = (0.310, 0.623).

The obtained organic electroluminescent element was subjected to a durability test by continuous lighting with an initial luminance of 2500 cd / m ² . Table 1 shows the time required for the luminance of the organic electroluminescent element to reach 50% of the initial luminance as a numerical value when Comparative Example 1 is 1. As shown in Table 1, it is clear that a highly durable device was obtained by using the organic compound of the present invention.
(Comparative Example 1)
In forming the hole transport layer 4 in Example 1, the same procedure as in Example 1 was performed except that the 18 nm-thick hole transport layer 4 was formed using the compound (C1) represented by the following structural formula. The organic electroluminescent element shown in 1 was produced.

<Coating liquid for hole transport layer formation>
Solvent xylene
Solid concentration 0.8% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 30 seconds
Spin coat atmosphere In nitrogen
Heating conditions In nitrogen, 130 ° C, 1 hour
The light emission characteristics of the organic electroluminescent device obtained as described above are as follows.

Luminance / current: 35.1 [cd / A] @ 100 cd / m ²
Voltage: 5.9 [V] @ 100 cd / m ²
Luminous efficiency: 18.6 [lm / W] @ 100 cd / m ²
The maximum wavelength of the emission spectrum of the device was 512 nm, which was identified as from the iridium complex (D1). The chromaticity was CIE (x, y) = (0.299, 0.626).

The obtained organic electroluminescent element was subjected to a durability test by continuous lighting with an initial luminance of 2500 cd / m ² . Table 1 shows the time required for the luminance of the organic electroluminescent element to reach 50% of the initial luminance as a numerical value when Comparative Example 1 is 1. As shown in Table 1, it can be seen that the organic electroluminescence device having a layer formed by crosslinking the organic compound of the present invention has high driving stability.

(Example 2)
In forming the hole transport layer 4 in Example 1, the hole transport layer 4 having a film thickness of 20 nm was formed using the organic compound (H2) according to the present invention (the target product 4 obtained in Synthesis Example 4). Produced the organic electroluminescent element shown in FIG. 1 in the same manner as in Example 1.

<Composition for organic electroluminescence device>
Solvent Toluene
Solid content concentration 0.4% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 30 seconds
Spin coat atmosphere In nitrogen
Heating conditions In nitrogen, 230 ° C, 1 hour
The light emission characteristics of the organic electroluminescent device obtained as described above are as follows.

Luminance / current: 23.6 [cd / A] @ 100 cd / m ²
Voltage: 7.5 [V] @ 100 cd / m ²
Luminous efficiency: 10.0 [lm / W] @ 100 cd / m ²
The maximum wavelength of the emission spectrum of the device was 513 nm, which was identified as from the iridium complex (D1). The chromaticity was CIE (x, y) = (0.314, 0.622).

The obtained organic electroluminescent element was subjected to a durability test by continuous lighting with an initial luminance of 2500 cd / m ² . Table 2 shows the time until the luminance of the organic electroluminescent element reaches 80% of the initial luminance as a numerical value when Comparative Example 2 is 1. As shown in Table 2, it can be seen that the organic electroluminescence device having a layer formed by crosslinking the organic compound of the present invention has high driving stability.

(Comparative Example 2)
In forming the hole transport layer 4 in Example 1, the hole transport layer 4 having a film thickness of 24 nm is formed using an organic compound (C2) having the following structure, and the hole blocking layer 6 is represented by the following structural formula. The organic electroluminescent element shown in FIG. 1 was prepared in the same manner as in Example 1 except that the organic compound represented by (E4) was used and vacuum deposition was used.

<Coating liquid for hole transport layer formation>
Solvent Toluene
Solid content concentration 0.4% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 30 seconds
Spin coat atmosphere In nitrogen
Heating conditions In nitrogen, 170 ° C, 0.5 hours

<Vapor deposition conditions for hole blocking layer 6>
Degree of vacuum 6.8-7.7 × 10 ⁻⁵ Pa
Deposition rate 1.0-1.2Å
Film thickness 10nm
The light emission characteristics of the organic electroluminescent device obtained as described above are as follows.

Luminance / current: 27.4 [cd / A] @ 100 cd / m ²
Voltage: 6.8 [V] @ 100 cd / m ²
Luminous efficiency: 12.4 [lm / W] @ 100 cd / m ²
The maximum wavelength of the emission spectrum of the device was 513 nm, which was identified as from the iridium complex (D1). The chromaticity was CIE (x, y) = (0.314, 0.621).

The obtained organic electroluminescent element was subjected to a durability test by continuous lighting with an initial luminance of 2500 cd / m ² . Table 2 shows the time until the luminance of the organic electroluminescent element reaches 80% of the initial luminance as a numerical value when Comparative Example 2 is 1. As shown in Table 2, it can be seen that the organic electroluminescence device having a layer formed by crosslinking the organic compound of the present invention has high driving stability.

(Example 3)
The process was the same as in Example 1 until the anode and hole injection layer were formed.
Subsequently, a composition for an organic electroluminescent device containing the organic compound (H3) of the present invention (target product 1 obtained in Synthesis Example 1) represented by the following structural formula was prepared, and spin coating was performed under the following conditions. A hole transport layer 4 having a film thickness of 22 nm was formed by film formation and crosslinking by heating.

<Composition for organic electroluminescence device>
Solvent Toluene
Solid content concentration 0.4% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 30 seconds
Spin coat atmosphere In nitrogen
Heating conditions In nitrogen, 230 ° C, 1 hour
Here, the substrate on which the hole injection layer 3 and the hole transport layer 4 were formed was transferred into a vacuum deposition apparatus, and after the apparatus was roughly evacuated by an oil rotary pump, the degree of vacuum in the apparatus was 1.3 ×. After evacuating with a cryopump until 10 ⁻⁴ Pa or less, a compound (E4) represented by the following structural formula and an iridium complex (D2) shown below were formed by vacuum deposition, and the light emitting layer 5 was formed. Obtained. The light emitting layer 5 having a film thickness of 32 nm was formed by controlling the deposition rate of (E4) to 0.5 Å / sec and the deposition rate of the iridium complex (D2) to 0.03 Å / sec.

  Next, the hole blocking layer 6 was obtained by laminating a compound (E5) represented by the following structural formula by a vacuum deposition method. The deposition rate was controlled in the range of 0.7 to 1.2 liters / second, and the hole blocking layer 6 having a film thickness of 10 nm was formed by laminating on the light emitting layer 5.

Subsequently, tris (8-hydroxyquinolinate) aluminum was heated and evaporated to form an electron transport layer 7. At this time, the deposition rate was controlled in the range of 0.7 to 1.3 liters / second, and an electron transport layer 7 was formed by laminating a film with a thickness of 30 nm on the hole blocking layer 6.
Here, the element that has been deposited up to the electron transport layer 7 is once taken out from the vacuum deposition apparatus into the atmosphere, and a 2 mm wide striped shadow mask is used as a cathode deposition mask. The device was placed in close contact with each other so as to be orthogonal to each other, placed in another vacuum deposition apparatus, and evacuated until the degree of vacuum in the apparatus was 1.3 × 10 ⁻⁴ Pa or less in the same manner as the organic layer.

  As the electron injection layer 8, first, lithium fluoride (LiF) is controlled using a molybdenum boat at a deposition rate of 0.08 to 0.13 Å / sec, and the electron transport layer 7 has a thickness of 0.5 nm. A film was formed on top. Next, aluminum was similarly heated as a cathode 9 by a molybdenum boat, and an aluminum layer having a thickness of 80 nm was formed by controlling the deposition rate within a range of 0.5 to 6.0 liters / second. The substrate temperature during the above two-layer deposition was kept at room temperature.

Subsequently, in order to prevent the element from being deteriorated by moisture in the atmosphere during storage, a sealing process was performed by the method described below.
In a nitrogen glove box connected to a vacuum vapor deposition device, a photocurable resin (30Y-437 manufactured by ThreeBond Co., Ltd.) with a width of about 1 mm is applied to the outer peripheral portion of a 23 mm × 23 mm size glass plate, and the central portion is applied. A moisture getter sheet (manufactured by Dynic) was installed. On this, the board | substrate which complete | finished cathode formation was bonded together so that the vapor-deposited surface might oppose a desiccant sheet. Then, only the area | region where the photocurable resin was apply | coated was irradiated with ultraviolet light, and resin was hardened.
As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. Table 3 shows the light emission characteristics of the device. As shown in Table 2, it is clear that a device having high luminous efficiency was obtained by using the polymer compound of the present invention.

Example 4
In forming the hole transport layer 4 in Example 3, the hole transport layer 4 having a film thickness of 20 nm was formed using the organic compound (H2) of the present invention (the target product 4 obtained in Synthesis Example 4). In the same manner as in Example 3, the organic electroluminescent element shown in FIG.

<Composition for organic electroluminescence device>
Solvent Toluene
Solid content concentration 0.4% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 30 seconds
Spin coat atmosphere In nitrogen
Heating conditions In nitrogen, 230 ° C, 1 hour
As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. Table 3 shows the light emission characteristics of the device. As shown in Table 3, it can be seen that the organic electroluminescence device having a layer formed by crosslinking the organic compound of the present invention has high luminous efficiency. The obtained organic electroluminescent element was subjected to a durability test by continuous lighting with an initial luminance of 2500 cd / m ² .

Table 3 shows the time required for the luminance of the organic electroluminescent element to reach 50% of the initial luminance as a numerical value when Comparative Example 3 is 1. As shown in Table 3, it can be seen that the organic electroluminescence device having a layer formed by crosslinking the organic compound of the present invention has high driving stability.
(Example 5)
In forming the hole transport layer 4 in Example 3, the hole transport layer 4 having a film thickness of 21 nm was formed using the organic compound (H4) of the present invention (target product 2 obtained in Synthesis Example 2). In the same manner as in Example 3, the organic electroluminescent element shown in FIG.

<Composition for organic electroluminescence device>
Solvent Toluene
Solid content concentration 0.4% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 30 seconds
Spin coat atmosphere In nitrogen
Heating conditions In nitrogen, 230 ° C, 1 hour
As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. Table 3 shows the light emission characteristics of the device. As shown in Table 3, it can be seen that the organic electroluminescence device having a layer formed by crosslinking the organic compound of the present invention has high luminous efficiency. The obtained organic electroluminescent element was subjected to a durability test by continuous lighting with an initial luminance of 2500 cd / m ² . Table 3 shows the time required for the luminance of the organic electroluminescent element to reach 50% of the initial luminance as a numerical value when Comparative Example 3 is 1. As shown in Table 3, it can be seen that the organic electroluminescence device having a layer formed by crosslinking the organic compound of the present invention has high driving stability.

(Example 6)
In forming the hole transport layer 4 in Example 3, the hole transport layer 4 having a film thickness of 20 nm was formed using the organic compound (H5) of the present invention (the target product 5 obtained in Synthesis Example 5). In the same manner as in Example 3, the organic electroluminescent element shown in FIG.

<Composition for organic electroluminescence device>
Solvent Toluene
Solid content concentration 0.4% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 30 seconds
Spin coat atmosphere In nitrogen
Heating conditions In nitrogen, 230 ° C, 1 hour
As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. Table 3 shows the light emission characteristics of the device. As shown in Table 3, it can be seen that the organic electroluminescence device having a layer formed by crosslinking the organic compound of the present invention has high luminous efficiency.

(Comparative Example 3)
In forming the hole transport layer 4 in Example 3, the same procedure as in Example 3 except that the 20 nm-thick hole transport layer 4 was formed using the compound (H7) shown in the following structural formula. The organic electroluminescent element shown in 1 was produced.

<Coating liquid for hole transport layer formation>
Solvent Toluene
Solid content concentration 0.4% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 30 seconds
Spin coat atmosphere In nitrogen
Heating conditions In nitrogen, 230 ° C, 1 hour
As described above, an organic electroluminescent element having a light emitting area portion having a size of 2 mm × 2 mm was obtained. Table 3 shows the light emission characteristics of the device.

  The present invention relates to various fields in which organic electroluminescent elements are used, for example, light sources (for example, light sources of copiers, flat panel displays (for example, for OA computers and wall-mounted televisions) and surface light emitters). It can be suitably used in the fields of liquid crystal displays and backlights of instruments), display panels, indicator lamps and the like.

1 Substrate
2 Anode
3 Hole injection layer
4 hole transport layer
5 Light emitting layer
6 Hole blocking layer
7 Electron transport layer
8 Electron injection layer
9 Cathode

Claims (12)

  An organic compound having a crosslinkable group and having a divalent pyrene ring which may have a substituent in the molecule.   The organic compound according to claim 1, which has two or more crosslinkable groups.   The organic compound according to claim 1, wherein the organic compound has a molecular weight of 2000 or more. The divalent pyrene ring which may have a substituent is represented by the following formula (I-1) or the following formula (I-2), according to any one of claims 1 to 3. The organic compound described.

(In the formulas (I-1) and (I-2), the pyrene ring may have a substituent) Furthermore, it has a bivalent group represented by following formula (II), The organic compound as described in any one of Claims 1-4 characterized by the above-mentioned.

(In Formula (II), Ar ¹ and Ar ² each independently represent an aromatic hydrocarbon group that may have a substituent or an aromatic heterocyclic group that may have a substituent.) The organic compound according to any one of claims 1 to 5, wherein the crosslinkable group is selected from the following crosslinkable group T.
<Crosslinkable group T>

(In the formula, R ^{1 to} R ⁶ each independently represent a hydrogen atom or an alkyl group. Ar ¹¹ may have an aromatic hydrocarbon group or a substituent which may have a substituent. Represents an aromatic heterocyclic group.)   The organic compound according to any one of claims 1 to 6, wherein the organic compound has a molecular weight distribution.   The composition for organic electroluminescent elements containing the organic compound as described in any one of Claims 1-7.   In the organic electroluminescent element which has an anode, a cathode, and the organic layer of 1 layer or 2 layers or more between this anode and this cathode on a board | substrate, at least 1 layer of this organic layer is any one of Claims 1-7 An organic electroluminescent device comprising a layer containing a network polymer compound obtained by crosslinking the organic compound according to claim 1.   The organic electroluminescence device according to claim 9, wherein the layer containing the network polymer compound is a hole injection layer and / or a hole transport layer.   The organic layer has a hole injection layer, a hole transport layer, and a light emitting layer, and all of the hole injection layer, the hole transport layer, and the light emitting layer are formed by a wet film formation method, The organic electroluminescent element according to claim 10.   The organic electroluminescent element using the organic electroluminescent element as described in any one of Claims 9-11 is characterized by the above-mentioned.

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