JP2009074074A - Organic compound, polymer compound, crosslinking type polymer compound, composition for organic electroluminescence element, and electroluminescence element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an organic electroluminescence element, which has high luminescent efficacy and high driving stability, by using a polymer compound suitable for a wet film-forming method, the polymer compound being capable of being dissolved under mild conditions; and excellent in positive hole transporting ability, thermal and electrochemical stability, and storage stability. <P>SOLUTION: The polymer compound comprises a repeating unit represented by following formula (II). Formula (II) is -[-N(Ar1)-A1-N(-A2-G1-Z)-Q-]-, wherein Z is a cationic polymerizing group. G1 is a divalent group formed by connecting 1-30 groups selected from an -O- group, -S- group, -C(=O)- group, -S(=O)2- group, -SiH2- group or -CH2- group, or is a direct bond. Ar1 is an aromatic hydrocarbon group which may have a substituent group or an aromatic heterocyclic group which may have a substituent group. A1 and A2 are divalent groups represented by -Ar2-(-G2-Ar3-)n-, wherein G2 has the same meaning as G1, and Ar2 and Ar3 are aromatic hydrocarbon groups which may have a substituent group. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an organic compound having a cation polymerizable group, a polymer compound having a cation polymerizable group, a crosslinked polymer compound obtained by crosslinking the polymer compound, and an organic electric field containing the polymer compound. The present invention relates to an organic electroluminescence device having a composition for a light emitting device and an organic layer containing the polymer compound or a cross-linked polymer compound, having 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 can be laminated, it has an advantage that the charge injection from the anode and / or the cathode is improved and the exciton light-emitting layer can be easily contained.

On the other hand, the wet film formation method does not require a vacuum process, is easy to increase in area, and can be easily mixed with a plurality of materials having various functions in one layer (coating liquid). There is.
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 the lamination by the wet film forming method, Patent Document 1 and Non-Patent Document 1 propose a compound having a cationic polymerizable group as described below, and use an organic solvent. Lamination is disclosed.

  However, in order to achieve insolubilization with a compound having a low molecular weight as described above, since it is necessary to have a three-dimensional network structure from a one-dimensional point, insolubilization may not be sufficient.

  In order to achieve insolubilization more easily, Non-Patent Document 2 proposes a polymer compound having the following cationic polymerizable group.

  In order to achieve insolubilization with the above-described polymer compound, a three-dimensional network structure may be formed from a two-dimensional line, and insolubilization can be considered easier than a compound having a small molecular weight.

However, in the polymer compound as described above, since two cationic polymerizable groups exist in one repeating unit, the cationic polymerizable groups in the same repeating unit do not form a bond. There is a risk that it is difficult to form the original network structure. In order to efficiently form a three-dimensional network structure, it is preferable that the cationic polymerizable group is dispersed in the polymer chain. However, in the polymer compound as described above, two cationic polymerization groups are always present. Since the functional groups are present at very close positions, the efficiency of insolubilization is poor, and it is highly possible that the cationic polymerizable group remains without reacting even after the insolubilization treatment.
International Publication No. WO2005 / 083812 Pamphlet Applied Physics Letters 2005, 86, 221102 Macromolecules 2006, 39, 8911

The present invention is obtained by crosslinking a polymer compound that can be insolubilized under mild conditions, excellent in hole transportability, excellent in thermal and electrochemical stability, and excellent in storage stability. It is an object of the present invention to provide a crosslinkable polymer compound and a composition for an organic electroluminescence device containing the polymer compound. Another object of the present invention is to provide an organic compound having cationic polymerizability useful for obtaining the polymer compound.
Another object of the present invention is to provide an organic electroluminescent device having a long life and high driving stability, using the polymer compound or a crosslinked polymer compound obtained by crosslinking the polymer compound. .

As a result of intensive studies to solve the above problems, the present inventors have found that a polymer compound having a cation polymerizable group having the following specific structure can be insolubilized under mild conditions and has excellent hole transportability. The present inventors have found that the compound is excellent in thermal and electrochemical stability, excellent in storage stability, and suitable for a wet film-forming method.
That is, the gist of the present invention is as follows.

〔式（Ｉ）中、Ｚは、カチオン重合性基を表す。
Ｇ^１は、−Ｏ−基、−Ｓ−基、−Ｃ（＝Ｏ）−基、−Ｓ（＝Ｏ）_２−基、−ＳｉＨ_２−基または−ＣＨ_２−基から選ばれる基を１〜３０個連結してなる２価の基或いは直接結合を表す。−ＳｉＨ_２−基および−ＣＨ_２−基は置換基を有していてもよい。
Ａｒ^１は、置換基を有していてもよい芳香族炭化水素基または置換基を有していてもよい芳香族複素環基を表す。Ａ^１およびＡ^２は、それぞれ独立に、下記式（Ｉ−１）で表される２価の基を表す。

（式（Ｉ−１）中、Ａｒ^２およびＡｒ^３は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素基を表す。Ｇ^２は、上記Ｇ^１と同義である。ｎは、０〜４の整数を表す。）〕 [1] An organic compound represented by the following formula (I).

[In formula (I), Z represents a cationically polymerizable group.
G ¹ represents a group selected from an —O— group, —S— group, —C (═O) — group, —S (═O) ₂ — group, —SiH ₂ — group, or —CH ₂ — group. Represents a divalent group or a direct bond formed by linking 30 units. The —SiH ₂ — group and the —CH ₂ — group may have a substituent.
Ar ¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. A ¹ and A ² each independently represent a divalent group represented by the following formula (I-1).

(In Formula (I-1), Ar ² and Ar ³ each independently represent an aromatic hydrocarbon group which may have a substituent. G ² has the same meaning as G ¹ above. N Represents an integer of 0 to 4.)]

[2] The organic compound according to [1], wherein the cationically polymerizable group is a cyclic ether group or a vinyl ether group.

〔式(II)中、Ｚは、カチオン重合性基を表す。
Ｇ^１は、−Ｏ−基、−Ｓ−基、−Ｃ（＝Ｏ）−基、−Ｓ（＝Ｏ）_２−基、−ＳｉＨ_２−基または−ＣＨ_２−基から選ばれる基を１〜３０個連結してなる２価の基或いは直接結合を表す。−ＳｉＨ_２−基および−ＣＨ_２−基は置換基を有していてもよい。
Ａｒ^１は、置換基を有していてもよい芳香族炭化水素基または置換基を有していてもよい芳香族複素環基を表す。Ａ^１およびＡ^２は、それぞれ独立に、下記式（Ｉ−１）で表される２価の基を表す。

（式（Ｉ−１）中、Ａｒ^２およびＡｒ^３は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素基を表す。Ｇ^２は、上記Ｇ^１と同義である。ｎは、０〜４の整数を表す。）
Ｑは連結基を表す。〕 [3] A polymer compound containing a repeating unit represented by the following formula (II).

[In formula (II), Z represents a cationically polymerizable group.
G ¹ represents a group selected from an —O— group, —S— group, —C (═O) — group, —S (═O) ₂ — group, —SiH ₂ — group, or —CH ₂ — group. Represents a divalent group or a direct bond formed by linking 30 units. The —SiH ₂ — group and the —CH ₂ — group may have a substituent.
Ar ¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. A ¹ and A ² each independently represent a divalent group represented by the following formula (I-1).

(In Formula (I-1), Ar ² and Ar ³ each independently represent an aromatic hydrocarbon group which may have a substituent. G ² has the same meaning as G ¹ above. N Represents an integer of 0 to 4.)
Q represents a linking group. ]

[4] The polymer compound according to [3], wherein the cationically polymerizable group is a cyclic ether group or a vinyl ether group.

[5] A crosslinked polymer compound obtained by crosslinking the polymer compound according to [3] or [4].

[6] A composition for an organic electroluminescent device comprising the polymer compound according to [3] or [4].

[7] In an organic electroluminescent element having an anode, a cathode, and one or more organic layers between the anode and the cathode on a substrate, at least one of the organic layers is [3] or The organic electroluminescent element containing the high molecular compound as described in [4].

[8] The organic electroluminescence device according to [7], wherein the layer containing the polymer compound is a hole injection layer or a hole transport layer.

[9] In an organic electroluminescence device having an anode, a cathode, and one or more organic layers between the anode and the cathode on a substrate, at least one of the organic layers is The organic electroluminescent element containing the crosslinking type high molecular compound of description.

[10] The organic electroluminescence device according to [9], wherein the layer containing the crosslinked polymer compound is a hole injection layer or a hole transport layer.

[11] 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 forming method. Thru | or the organic electroluminescent element in any one of [10].

[12] An organic EL display using the organic electroluminescence device according to any one of [7] to [11].

  The polymer compound of the present invention can be insolubilized under mild conditions, has excellent hole transportability, excellent thermal and electrochemical stability, and excellent storage stability. Further, this polymer compound is suitable for a wet film formation method, and it becomes possible to form an organic electroluminescent element by laminating the organic layer of the organic electroluminescent element by a wet film formation method using this polymer compound.

Moreover, the organic electroluminescent element formed by the wet film-forming method using the composition for organic electroluminescent elements containing this high molecular compound can be enlarged.
It is also possible to form an organic thin film insoluble in an organic solvent using the composition for an organic electroluminescent device containing the polymer compound, and it is easy to stack the organic electroluminescent device by a wet film forming method. Become.

Furthermore, according to the organic electroluminescent device comprising the polymer compound of the present invention or a crosslinked polymer compound obtained by crosslinking this polymer compound, it becomes possible to emit light with high efficiency, and the stability of the device, In particular, driving stability is improved.
In addition, the polymer compound of the present invention has a hole injection material, a hole transport material, a light emitting material, and a host material in accordance with the layer structure of the element because of excellent film forming property, charge transport property, light emitting property, and heat resistance. It can also be applied as an electron injection material, an electron transport material and the like.

  The organic compound of the present invention is useful as a production raw material for producing such a polymer compound of the present invention.

An organic electroluminescent device containing the polymer compound of the present invention or a crosslinked polymer compound obtained by crosslinking this polymer compound is a flat panel display (for example, for OA computers or wall-mounted televisions), an in-vehicle display device, a mobile phone. It can be applied to light sources (for example, light sources for copiers, liquid crystal displays and instrument backlights), display boards, and sign lamps that take advantage of the characteristics of displays and surface light emitters, and have great technical value. It is.
The polymer compound of the present invention or the crosslinked polymer compound obtained by crosslinking this polymer compound has an excellent oxidation-reduction stability, and is not limited to an organic electroluminescent device. It is also useful for photographic photoreceptors.

  In the following, embodiments of the organic compound, polymer compound, cross-linked polymer compound, composition for organic electroluminescence device and organic electroluminescence device of the present invention will be described in detail. It is an example (representative example) of the embodiment of the present invention, and the present invention is not specified by these contents unless it exceeds the gist.

[Organic compounds]
The organic compound of the present invention is represented by the following formula (I).

〔式（Ｉ）中、Ｚは、カチオン重合性基を表す。
Ｇ^１は、−Ｏ−基、−Ｓ−基、−Ｃ（＝Ｏ）−基、−Ｓ（＝Ｏ）_２−基、−ＳｉＨ_２−基または−ＣＨ_２−基から選ばれる基を１〜３０個連結してなる２価の基或いは直接結合を表す。−ＳｉＨ_２−基および−ＣＨ_２−基は置換基を有していてもよい。
Ａｒ^１は、置換基を有していてもよい芳香族炭化水素基または置換基を有していてもよい芳香族複素環基を表す。Ａ^１およびＡ^２は、それぞれ独立に、下記式（Ｉ−１）で表される２価の基を表す。

（式（Ｉ−１）中、Ａｒ^２およびＡｒ^３は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素基を表す。Ｇ^２は、上記Ｇ^１と同義である。ｎは、０〜４の整数を表す。）〕

[In formula (I), Z represents a cationically polymerizable group.
G ¹ represents a group selected from an —O— group, —S— group, —C (═O) — group, —S (═O) ₂ — group, —SiH ₂ — group, or —CH ₂ — group. Represents a divalent group or a direct bond formed by linking 30 units. The —SiH ₂ — group and the —CH ₂ — group may have a substituent.
Ar ¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. A ¹ and A ² each independently represent a divalent group represented by the following formula (I-1).

(In Formula (I-1), Ar ² and Ar ³ each independently represent an aromatic hydrocarbon group which may have a substituent. G ² has the same meaning as G ¹ above. N Represents an integer of 0 to 4.)]

[1] Molecular Weight of Organic Compound The molecular weight of the organic compound of the present invention is usually 5000 or less, preferably 2000 or less. If the molecular weight exceeds this upper limit, purification may become difficult due to the high molecular weight of impurities.

[2] Ar ^{1 to} Ar ³
Ar ¹ in the above formula (I) represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent.
Ar ² and Ar ³ in the above formula (I-1) each independently represent an aromatic hydrocarbon group which may have a substituent.

  Examples of the aromatic hydrocarbon group which may have a substituent include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring and fluorene ring. , A group derived from a 5- or 6-membered monocyclic ring or a 2-5 condensed ring, such as a fluoranthene ring, or a group in which these rings are linked by a direct bond.

  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 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, a quinazoline ring, Straighten these rings Group linked by bonds.

Ar ^{1 to} Ar ³ are each independently selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and a fluorene ring from the viewpoint of the electrochemical stability of the resulting polymer compound. Ring-derived groups are preferred. Ar ² and Ar ³ are preferably a divalent group in which one or two or more rings selected from the above groups are connected by a direct bond, and more preferably a biphenylene group or a terphenylene group.

Although there is no restriction | limiting in particular as a substituent which the aromatic hydrocarbon group of Ar < ¹ > -Ar < ³ > and an aromatic heterocyclic group may have, The following are mentioned.

<Specific Examples of Substituents for Ar ^{1 to} Ar ³ >
An alkyl group which may have a substituent (preferably a linear or branched alkyl group having 1 to 8 carbon atoms which may have a substituent, such as methyl, ethyl, n-propyl, 2- And propyl, n-butyl, isobutyl, tert-butyl group, etc.).
An alkenyl group which may have a substituent (preferably an alkenyl group having 2 to 9 carbon atoms which may have a substituent, such as vinyl, allyl and 1-butenyl groups).
An alkynyl group which may have a substituent (preferably an alkynyl group having 2 to 9 carbon atoms which may have a substituent, such as ethynyl and propargyl groups).
Aralkyl group which may have a substituent (preferably an aralkyl group having 7 to 15 carbon atoms which may have a substituent, such as a benzyl group).
An alkoxy group which may have a substituent (preferably an alkoxy group having 1 to 8 carbon atoms which may have a substituent, such as methoxy, ethoxy and butoxy groups).
An aryloxy group which may have a substituent (preferably an aromatic hydrocarbon group having 6 to 12 carbon atoms which may have a substituent, such as phenyloxy, 1-naphthyloxy, And 2-naphthyloxy group.
Heteroaryloxy group which may have a substituent (preferably one having a 5- or 6-membered aromatic heterocyclic group which may have a substituent, such as pyridyloxy, thienyloxy group, etc. Can be mentioned.)
An acyl group which may have a substituent (preferably an acyl group having 1 to 10 carbon atoms which may have a substituent, such as formyl, acetyl and benzoyl groups).
An alkoxycarbonyl group which may have a substituent (preferably an alkoxycarbonyl group having 2 to 10 carbon atoms which may have a substituent, such as methoxycarbonyl and ethoxycarbonyl groups).
An aryloxycarbonyl group which may have a substituent (preferably an aryloxycarbonyl group having 7 to 13 carbon atoms which may have a substituent, such as a phenoxycarbonyl group).
An alkylcarbonyloxy group which may have a substituent (preferably an alkylcarbonyloxy group having 2 to 10 carbon atoms which may have a substituent, such as an acetoxy group).
Halogen atom (preferably a fluorine atom or a chlorine atom)
Carboxy group Cyano group Hydroxyl mercapto group Alkylthio group which may have a substituent (preferably an alkylthio group having 1 to 8 carbons which may have a substituent, such as methylthio group, ethylthio group, etc. Can be mentioned.)
An arylthio group which may have a substituent (preferably an arylthio group having 6 to 12 carbon atoms which may have a substituent, such as a phenylthio group and a 1-naphthylthio group).
A sulfonyl group which may have a substituent (for example, a mesyl group, a tosyl group, etc.).
A silyl group which may have a substituent (for example, a trimethylsilyl group, a triphenylsilyl group, etc.).
An optionally substituted boryl group (eg, a dimesitylboryl group).
A phosphino group which may have a substituent (for example, a diphenylphosphino group).
An aromatic hydrocarbon group which may have a substituent (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. And monovalent groups derived from 5- or 6-membered monocyclic rings or 2 to 5 condensed rings.)
An aromatic heterocyclic group which may have a substituent (for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring, pyrrolo) Imidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, A monovalent group derived from a 5- or 6-membered monocyclic ring or a 2-4 condensed ring such as 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.)
An amino group which may have a substituent [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, A dibenzylamino group, etc.), and 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, when the said substituent further has a substituent, the said exemplary substituent is mentioned as the substituent.

[3] Z
Z in the above formula (I) represents a cationically polymerizable group.
The cationically polymerizable group is a group that polymerizes in a chain manner when an initiator that gives a cation is present.

  As the cationic polymerizable group, a cyclic ether group such as an epoxy group or an oxetane group is preferable. In particular, an oxetane group is particularly preferable because the rate of cationic polymerization can be easily controlled. In addition, a vinyl ether group is particularly preferable because a hydroxyl group that may cause deterioration of the device during cationic polymerization is hardly generated.

  Further, the cationically polymerizable group is preferably a group selected from the following group W because it is easily insolubilized.

（式中、Ｒ^１〜Ｒ^３は、各々独立に、水素原子またはアルキル基を表す。
該アルキル基としては、通常炭素数１以上、好ましくは１２以下、より好ましくは６以下のアルキル基が挙げられる。） <Group W>

(In formula, R < ¹ > -R < ³ > represents a hydrogen atom or an alkyl group each independently.
Examples of the alkyl group include alkyl groups having usually 1 or more carbon atoms, preferably 12 or less, more preferably 6 or less. )

[4] G ¹ , G ²
G ^{1 in} the above formula (I) and G ² in the above formula (I-1) are each independently —O— group, —S— group, —C (═O) — group, —S (═O). ₂ - group, -SiH ₂ - group or a -CH ₂ - represents a divalent group or a direct bond formed by 1-30 linking group selected from the group. Here, the —SiH ₂ — group and the —CH ₂ — group may have a substituent.
Specific examples of the substituent that the —CH ₂ — and —SiH ₂ — group may have include those exemplified as the specific examples of the substituents of Ar ^{1 to} Ar ³ , but are linear or branched. A C1-C20 alkyl group and an alkoxy group are preferable.

G ¹ is the point of promoting insolubilization, from the viewpoint of excellent electrochemical stability, -CH ₂ - and 2-12 groups - divalent group formed by a group linked 2 to 15, -CH ₂ A divalent group formed by linking 1 to 3 non-continuous —O— groups is preferable. In particular, the group connected to the aromatic amine moiety (A ¹ , A ² ) is preferably an —O— group from the viewpoint of excellent electrochemical stability and hole transportability.

G ² represents a direct bond, an —O— group, an optionally substituted —O— (CH ₂ ) _m —O— group, because the resulting polymer compound has excellent electrochemical stability; or it may have a substituent group - _{(CH 2) m} - group is preferably (m is an integer of 2-6). As a substituent of the —O— (CH ₂ ) _m —O— group or — (CH ₂ ) _m — group, a linear or branched alkyl group having 1 to 20 carbon atoms is preferable.
G ² is particularly preferably an —O— group or a direct bond from the viewpoint of further improving the hole transport ability of the resulting polymer compound and excellent heat resistance.
G ² is preferably an —O— (CH ₂ ) _m —O— group or an optionally substituted — (CH ₂ ) _m — group from the viewpoint that the resulting polymer compound is excellent in solubility. (M represents an integer of 2 to 6) is particularly preferable.

[5] n
N in the above formula (I-1) represents an integer of 0 to 4.
It is preferable that n = 0 because the obtained polymer compound is easy to move, the crosslinking reaction is promoted, and it is easily insolubilized.
It is preferable that n is an integer of 1 to 4 because the hole transport property is further improved.

[6] Specific Examples Preferred specific examples of the organic compound of the present invention are shown below, but the organic compound of the present invention is not limited thereto.

〔式(II)中、Ｚ、Ｇ^１、Ａｒ^１、Ａ^１およびＡ^２は、それぞれ独立に、式（Ｉ）におけるものと同義である。Ｑは連結基を表す。〕 [Polymer compound]
The polymer compound of the present invention contains a repeating unit represented by the following formula (II).

[In formula (II), Z, G ¹ , Ar ¹ , A ¹ and A ² are each independently the same as defined in formula (I). Q represents a linking group. ]

[1] Structural features Since the polymer compound of the present invention has one cation polymerizable group in one repeating unit, the cation polymerizable groups in one polymer chain form a bond with each other. Therefore, it is possible to form a three-dimensional network structure efficiently. In addition, since an efficient three-dimensional network structure is formed, the amount of unreacted cationic polymerizable groups that can cause deterioration of the device can be reduced.

[2] Molecular Weight of Polymer Compound The weight average molecular weight of the polymer compound of the present invention is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 500,000 or less, and usually 1 5,000 or more, preferably 2,500 or more, more preferably 5,000 or more.

  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. The weight average molecular weight is calculated by conversion.

  If the molecular weight exceeds this upper limit, purification may become difficult due to the high molecular weight of impurities, and if the molecular weight falls below this lower limit, the glass transition temperature, melting point, vaporization temperature, etc. will decrease. There is a risk that the properties are significantly impaired.

[3] Q
Q in the above formula (II) represents a divalent linking group.

Q is not particularly limited as long as Q is a divalent group, but an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent is preferable. Specific examples and preferred examples of the aromatic hydrocarbon group, the aromatic heterocyclic group, and the substituent that may be included are the same as those of Ar ² or Ar ³ described above.

Q is preferably used by linking one or more divalent groups selected from an aromatic hydrocarbon group and an aromatic heterocyclic group via a direct bond or a linking group. Examples of the linking group include those similar to G ¹ described above and amino groups.

[4] Examples of repeating units Specific examples of the repeating unit of the polymer compound of the present invention represented by the formula (II) are shown below, but the present invention is not limited thereto.

[5] Sequence and Ratio of Repeating Units, etc. The polymer compound of the present invention may have any repeating unit represented by the formula (II), and other repeating units other than those represented by the formula (II) May be included. Two or more different types of repeating units represented by formula (II) may be contained in one molecule.

  Since the repeating unit represented by the formula (II) is asymmetric, the repeating unit represented by the formula (II) (hereinafter sometimes referred to as “repeating unit (II)”) and the following formula (II) A polymer compound in which repeating units represented by ') (hereinafter sometimes referred to as "repeating units (II')") are randomly arranged is obtained. The manner of entering the repeating units (II) and (II ′) in the polymer compound may be regular or random, but is preferably random from the viewpoint of solubility.

  In the case where the repeating unit (II) and (II ′) are regularly entered in the polymer compound, for example, the repeating unit (II) and the repeating unit (II ′) are alternately connected one by one , And the like that are alternately connected in plural.

Further, -G ¹ of the repeating unit (II) (and (II ')) if it contains other repeating units other than, other repeating units, the repeating unit (II) (and (II')) A structure in which -Z is substituted with a hydrogen atom is preferred.

  Specific examples of the other repeating units include one or more selected from the following repeating unit group K.

<Repeating unit group K>

(In the formula, Ar ^{12 to} Ar ³⁹ each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar ⁶¹ to Each of Ar ⁷⁴ independently represents an aromatic hydrocarbon group which may have a substituent, an aromatic heterocyclic group which may have a substituent, or a direct bond or a linking group of these groups; Group bonded together.)

Specific examples of the aromatic hydrocarbon group and the aromatic heterocyclic group represented by Ar ^{12 to} Ar ³⁹ and Ar ^{61 to} Ar ⁷⁴ include the aromatic hydrocarbon groups exemplified as Ar ^{1 to} Ar ³ in the above formula (I), and An aromatic heterocyclic group is exemplified, and the substituent that the group may have is the same as that exemplified as the substituent for Ar ^{1 to} Ar ³ .
^As the linking group in Ar 61 ^{to Ar 74,} and the like the like or an amino group and ^{G 1} described above.

  Further, specific examples of other repeating units include the following repeating units.

  In view of ease of insolubilization, the content of the repeating unit (II) (and (II ′)) in the polymer compound is usually 0.1 mol% or more, preferably 1 mol% or more, more preferably It is 3 mol% or more. From the viewpoint of reducing unreacted cationically polymerizable groups, the content of the repeating unit (II) (and (II ′)) in the polymer compound is preferably 50 mol% or less, more preferably 30 mol% or less. It is.

  That is, in the polymer compound of the present invention, the repeating unit (II) (and (II ′)) is most preferably 3 mol% or more and 30 mol% or less.

  Next, although the specific example of the high molecular compound of this invention is given, this invention is not limited to these.

[6] Synthesis Method The organic compound and polymer compound of the present invention can be synthesized using a known method by selecting raw materials according to the structure of the target compound.

  The polymer compound of the present invention can be obtained by reacting the organic compound of the present invention with a dihalide (XQX) as shown in the following formula. The polymer compound of the present invention is obtained by reacting the organic compound of the present invention. It may be synthesized without passing through.

(In the formula, Ar ¹ , A ¹ , A ² , G ¹ , Z, Q, n are as defined in formulas (I) and (II), and X represents F, Cl, Br, or I.)

  The reaction between the aromatic secondary amine moiety of the organic compound of the present invention and the dihalide proceeds, for example, by using a palladium catalyst or a copper catalyst in the presence of a base.

  The organic compound of the present invention can be obtained, for example, by repeating the reaction of an aromatic primary amine and an aromatic halide as shown in the following reaction formula.

(In the formula, Ar ¹ , A ¹ , A ² , G ¹ and Z have the same meanings as in formulas (I) and (II), and X represents F, Cl, Br, or I.)

  The reaction between the aromatic primary amine and the aromatic halide proceeds, for example, by using a palladium catalyst or a copper catalyst in the presence of a base.

  For the production of the organic compound of the present invention, other known coupling reactions can be used. As a known coupling method, specifically, “Palladium in Heterocyclic Chemistry: A guide for the Synthetic Chemist” (second edition, 2002, Jie Jack Li and Gordon W. Gribble, Pergamon), “Transition metal Organic synthesis to open up "various reaction formats and latest results" (1997, Junjiro, Chemical Doujinsha), "Bolhard Shore Modern Organic Chemistry" (2004, KPCVollhardt, Chemical Doujinsha)) The cited ring-to-ring (coupling) reaction, such as a coupling reaction between an aryl halide and an aryl borate, can be used.

  Methods for purifying 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, IP Corporation). Issued by C.), or the methods described in the section “Separation and purification” of “Experimental Chemistry Course (4th edition) 1” (1990, edited by The Chemical Society of Japan) can be used. It is. 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 chromatograph (GPC), cross-fractionation chromatograph (CFC), mass spectrometry (MS, LC / MS, GC / MS, MS / MS), nuclear magnetic resonance apparatus (NMR ( ¹ HNMR, ¹³ CNMR)), Fourier transform infrared spectrophotometer (FT-IR), ultraviolet 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 chromatograph, inductively coupled plasma-emission spectroscopy (ICP-AES) atoms Absorption analysis (AAS), X-ray fluorescence analyzer (XRF)), non-metallic element analysis, trace component analysis (ICP-MS, GF-AAS, GD-MS), etc. can be applied as necessary.

[Crosslinked polymer compound]
The crosslinkable polymer compound of the present invention is obtained by crosslinking the polymer compound of the present invention, and this crosslinkable polymer compound is a positive hole injection layer or a positive electrode of an organic electroluminescence device as described later. It is preferably contained in the hole transport layer.
The crosslinking method will be described in the following film formation method of the composition for organic electroluminescent elements.

[Composition for organic electroluminescence device]
The composition for an organic electroluminescent device of the present invention comprises the polymer 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 wet. It is suitably used as a coating solution when forming by a film forming 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 organic electroluminescent elements of the present invention is characterized by containing the polymer compound of the present invention, but usually further contains a solvent.
The solvent preferably dissolves the polymer compound of the present invention, and usually dissolves the polymer compound of the present invention by 0.05% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more. Solvent.
In addition, the composition for organic electroluminescent elements of this invention may contain only 1 type of the high molecular compound of this invention, and may contain 2 or more types.
In the composition for organic electroluminescence device of the present invention, the polymer compound 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%. It is contained in an amount of not more than wt%, preferably not more than 20 wt%, more preferably not more than 10 wt%.

  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 cross-linking reaction that enables the reaction may be included. In this case, a solvent that dissolves both the polymer compound of the present invention and the additive by 0.05% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more is used as the solvent. Is preferred.

  Examples of the additive that accelerates the crosslinking reaction of the polymer compound of the present invention contained in the composition for organic electroluminescence device of the present invention include alkylphenone compounds, acylphosphine oxide compounds, metallocene compounds, oxime ester compounds, azo compounds, Examples thereof include polymerization initiators such as onium salts and 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.

  Moreover, as an electron-accepting compound contained in the composition for organic electroluminescent elements of this invention, it is 1 type or 2 of what was mentioned later as an electron-accepting compound contained in the positive hole injection layer of the organic electroluminescent element of this invention. More than seeds can be used.

  The solvent contained in the composition for an organic electroluminescent device of the present invention is not particularly limited, but is preferably toluene, xylene, methicylene, because it is necessary to dissolve the polymer compound of the present invention. Aromatic solvents such as cyclohexylbenzene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene, o-dichlorobenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), etc. Aliphatic ether, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethyl Anisole 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, Examples include organic solvents such as ester solvents such as aromatic esters such as propyl benzoate 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 10% by weight or more, preferably 50% 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 polymer compound of the present invention is formed by a wet film forming 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 polymer 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.

  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.

  Examples of the solvent contained in the composition for organic electroluminescence device 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 device by a wet film forming method and suitable for the properties of the polymer 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). A mixed solvent of a certain solvent and 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 polymer 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. Also, 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, a 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, it is preferable to use a solvent having low water solubility because the solution coating film can prevent whitening by absorbing moisture in the air during the coating process.
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.
Moreover, the composition for organic electroluminescent elements of this invention may contain various additives, such as coating property improving agents, such as a leveling agent and an antifoamer.

[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, depending on the material and the properties of the underlying layer, a known wet process such as a coating method such as a spin coating method, a spray method or a dip coating method, or a printing method such as an ink jet method or a screen method is used. A membrane method can be adopted.

When using the wet film-forming method, the polymer compound of the present invention and other components used as necessary (electron-accepting compounds, additives for promoting crosslinking reaction, coating property improving agents, etc.) in an appropriate solvent. Dissolve to prepare the composition for organic electroluminescence device. This composition is formed on a layer corresponding to the lower layer of the layer to be formed by a wet film forming method, and dried to form a layer containing the polymer compound of the present invention.
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 film-forming the composition for organic electroluminescent elements of the present invention, the polymer compound of the present invention undergoes a crosslinking reaction by heating and / or irradiation with electromagnetic energy such as light, so that the solubility of the film after the reaction is increased. It is preferable to reduce. Usually, the crosslinking polymer of the present invention is obtained by this crosslinking reaction.

  The heating method is not particularly limited, and examples thereof include heat drying and reduced pressure drying. As a condition in the case of heat drying, 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 electromagnetic 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 or 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 electromagnetic energy irradiation other than light, for example, there is a method of irradiation using a device that irradiates a microwave generated by a magnetron, a so-called microwave oven.

  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 electromagnetic energy such as light may be performed individually or in combination. When combined, the order of implementation is not particularly limited.

  In order to reduce the amount of moisture contained in the layer and / or moisture adsorbed on the surface after implementation, the electromagnetic energy irradiation including heating and light is preferably performed in an atmosphere containing no moisture such as a nitrogen gas atmosphere. For the same purpose, when combined with heating and / or irradiation with electromagnetic 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 containing the polymer compound of the present invention and / or the crosslinked polymer compound of the present invention.

  The layer containing the polymer compound of the present invention and / or the crosslinked polymer compound of the present invention is preferably a hole injection layer or a hole transport layer described in detail below. The transport layer is preferably formed by forming the organic electroluminescent element composition of the present invention into a film by a wet film forming method.

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 includes 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 transport layer 7, and an electron injection layer on a substrate 1. 8 and the cathode 9 are laminated in this order. In the case of this configuration, the hole injection layer 3 or the hole transport layer 4 usually corresponds to a layer containing the above-described polymer compound or cross-linked polymer compound of the present invention.

[1] Substrate The substrate 1 serves as a support for the organic electroluminescent element, and quartz or glass plates, metal plates, metal foils, plastic films, sheets, and the like are 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 the role of hole injection into a layer (hole injection layer 3 or organic light emitting layer 5) 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. As an aromatic amine compound, the binaphthyl type compound represented by following General formula (1) is mentioned, for example.

In the general formula (1), Ar ^{a to} Ar ^d are each independently a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic monocyclic group or condensed ring group which may have a substituent. Ar ^a and Ar ^b , Ar ^c and Ar ^d may be bonded to each other to form a ring. W1 and W2 each represent an integer of 0 to 4, and W1 + W2 ≧ 1. X ¹ and X ² each independently represent a direct bond or a divalent linking group. In addition, the naphthalene ring in the general formula (1) may have an arbitrary substituent in addition to-(X ¹ NAr ^a Ar ^b ) and-(X ² NAr ^c Ar ^d ).

In the general formula (1), as the monocyclic group or condensed ring group of a 5- or 6-membered aromatic hydrocarbon ring or aromatic heterocyclic ring which may have a substituent of Ar ^{a to} Ar ^d , respectively. Independently, for example, a 5- or 6-membered monocyclic ring or a 2-3 condensed ring, specifically, a group derived from an aromatic hydrocarbon ring such as a phenyl group, a naphthyl group, an anthryl group; a pyridyl group, a thienyl group A group derived from an aromatic heterocycle such as Any of these may have a substituent.

As the substituent that Ar ^{a to} Ar ^d may have, those described later as the substituent that Ar ^{e to} Ar ^l may have, and an arylamino group (that is,-(NAr ^e Ar ^f ) described later, -(Corresponding to NAr ^g Ar ^h )).

Ar ^a and Ar ^b and / or Ar ^c and Ar ^d may be bonded to each other to form a ring. In this case, specific examples of the ring to be formed include a carbazole ring, a phenoxazine ring, an iminostilbene ring, a phenothiazine ring, an acridone ring, an acridine ring, an iminodibenzyl ring and the like that may have a substituent. Of these, a carbazole ring is preferred.

  In the general formula (1), W1 and W2 each represent an integer of 0 to 4, and W1 + W2 ≧ 1. Particularly preferred are W1 = 1 and W2 = 1. The arylamino groups in the case where W1 and / or W2 is 2 or more may be the same or different.

X ¹ and X ² each independently represent a direct bond or a divalent linking group. Although there is no restriction | limiting in particular as a bivalent coupling group, For example, what is shown below etc. are mentioned. A direct bond is particularly preferable as X ¹ and X ² .

In addition to — (X ¹ NAr ^a Ar ^b ) and — (X ² NAr ^c Ar ^d ), the naphthalene ring in the general formula (1) has one or more arbitrary substituents at an arbitrary position. It may be. Preferred examples of such a substituent include a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an alkenyl group which may have a substituent. , One or more substituents selected from the group consisting of optionally substituted alkoxycarbonyl groups. Of these, an alkyl group is particularly preferred.

As binaphthyl compound represented by the general formula (1), as represented by the following general formula (1-1), Ar ^a and Ar ^c is preferably binaphthyl compound substituted by further respective arylamino group .

（一般式（１−１）中、Ａｒ^ｅ〜Ａｒ^ｌは各々独立に、置換基を有していてもよい５または６員環の芳香族炭化水素環または芳香族複素環の単環基または縮合環基を表し、Ａｒ^ｅとＡｒ^ｆ、Ａｒ^ｇとＡｒ^ｈは各々結合して環を形成していてもよい。Ｗ１およびＷ２は一般式（１）におけるのと同義である。Ｘ^１およびＸ^２は一般式（１）におけるのと同義である。）

(In the general formula (1-1), Ar ^{e to} Ar ¹ each independently represents a 5- or 6-membered aromatic hydrocarbon ring or aromatic monocyclic group which may have a substituent, or Represents a condensed ring group, Ar ^e and Ar ^f , Ar ^g and Ar ^h may be bonded to each other to form a ring, W 1 and W 2 have the same meanings as in formula (1), X ¹ and X ² has the same meaning as in general formula (1).)

In the general formula (1-1), the naphthalene ring includes substituents-(X ¹ NAr ⁱ Ar ^j NAr ^f Ar ^e ) and-(X ² NAr ^k Ar ^l NAr ^g each containing an arylamino group bonded to the naphthalene ring. In addition to Ar ^h ), it may have an arbitrary substituent. In addition, these substituents — (X ¹ NA ⁱ Ar ^j NAr ^f Ar ^e ) and — (X ² NAr ^k Ar ^l NAr ^g Ar ^h ) have a substituent at any substitution position of the naphthalene ring. Also good. Especially, the binaphthyl type compound substituted to 4-position and 4'-position of the naphthalene ring in General formula (1-1) respectively is more preferable.

  Moreover, as a high molecular compound which has a positive hole transport site | part in a molecule | numerator used as a hole injectable compound, the high molecular compound which contains an aromatic tertiary amino group in a main skeleton as a structural unit is mentioned, for example. Specific examples thereof include a hole injecting compound having a structure represented by the following general formula (2) as a repeating unit.

（式（２）中、Ａｒ^４４〜Ａｒ^４８は、各々独立して置換基を有していてもよい２価の芳香族環基を示し、Ｒ^３１〜Ｒ^３２は、各々独立して置換基を有していてもよい１価の芳香族環基を示し、Ｑは直接結合、または下記の連結基から選ばれる。なお、「芳香族環基」とは、「芳香族炭化水素環由来の基」および「芳香族複素環由来の基」の両方を含む。）

（式（３）中、Ａｒ^４９は置換基を有していてもよい２価の芳香族環基を示し、Ａｒ^５０は置換基を有していてもよい１価の芳香族環基を示す。）

(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.

  Examples of the hole-injecting compound containing an aromatic tertiary amino group as a side chain include compounds having a repeating unit having a structure represented by the following general formulas (4) and (5).

（式（４）中、Ａｒ^５１は置換基を有していてもよい２価の芳香族環基を示し、Ａｒ^５２〜Ａｒ^５３は、各々独立して置換基を有していてもよい１価の芳香族環基を示し、Ｒ^３３〜Ｒ^３５は、各々独立して水素原子、ハロゲン原子、アルキル基、アルコキシ基、置換基を有していてもよい１価の芳香族環基を示す。）

(In formula (4), Ar ⁵¹ represents a divalent aromatic ring group which may have a substituent, and Ar ^{52 to} Ar ⁵³ may each independently have a substituent 1. R ^{33 to} R ³⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, or a monovalent aromatic ring group which may have a substituent. .)

（式（５）中、Ａｒ^５４〜Ａｒ^５８は、各々独立して置換基を有していてもよい２価の芳香族環基を示し、Ｒ^３６およびＲ^３７は、各々独立して置換基を有していてもよい芳香族環基を示し、Ｙは直接結合、または下記の連結基から選ばれる。）

(In the formula (5), Ar ^{54 to} Ar ⁵⁸ each independently represent a divalent aromatic ring group which may have a substituent, and R ³⁶ and R ³⁷ each independently represent a substituent. And Y is selected from a direct bond or the following linking group.)

In the general formula (4), Ar ⁵¹ is preferably a divalent benzene ring, a naphthalene ring, a group derived from an anthracene ring, or a biphenylene group each optionally having a substituent. For example, examples of the group that the aromatic ring in Ar ^{44 to} Ar ⁴⁸ in the general formula (2) described above may have include the same groups as those described above, and preferred groups are also the same.

Ar ⁵² and Ar ⁵³ are preferably each independently a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a triazyl group, a pyrazyl group, a quinoxalyl group, a thienyl group, and a biphenyl group, and these include a substituent group. May have. Examples of the substituent include the same groups as those described above as the group that the aromatic ring in Ar ^{44 to} Ar ⁴⁸ of the general formula (2) may have, and preferred groups are also the same.

R ^{33 to} R ³⁵ are preferably each independently a hydrogen atom; a halogen atom; a linear or branched alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; a carbon such as a methoxy group or an ethoxy group. A linear or branched alkoxy group of 1 to 6; a phenyl group; or a tolyl group.

In the general formula (5), Ar ^{54 to} Ar ⁵⁸ are preferably a divalent benzene ring, a naphthalene ring, a group derived from an anthracene ring, or a biphenylene group, each of which may have a substituent. A group derived from a benzene ring. Examples of the substituent include the same groups as those described above as the groups that the aromatic ring in Ar ^{44 to} Ar ⁴⁸ of formula (2) may have, and preferred groups are also the same.

R ³⁶ and R ³⁷ are each preferably a phenyl group, a naphthyl group, an anthryl group, a pyridyl group, a triazyl group, a pyrazyl group, a quinoxalyl group, a thienyl group, or a biphenyl group, each of which may have a substituent. . Examples of the substituent include the same groups as those described above as the groups that the aromatic ring in Ar ^{44 to} Ar ⁴⁸ of formula (2) may have, and preferred groups are also the same.

  Preferred examples of the structures represented by the general formulas (2) to (5) are shown below, but are not limited thereto.

  The hole injecting compound which is a polymer compound having a hole transporting site in the molecule is most preferably a homopolymer having a structure represented by any one of the general formulas (2) to (5). It may be a copolymer (copolymer) with any monomer. When it is a copolymer, it is preferable to contain 50 mol% or more, especially 70 mol% or more of the structural units represented by the general formulas (2) to (5). In addition, the hole injectable material which is a high molecular compound may contain multiple types of structures represented by the general formulas (2) to (5) in one compound. Moreover, you may use in combination of multiple types of the compound containing the structure represented by General formula (2)-(5). Of the general formulas (2) to (5), a homopolymer composed of a repeating unit represented by the general formula (2) is particularly preferable.

  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 WO2005 / 089024, and preferred examples thereof are the same, but the following compounds are particularly preferred.

  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.

  In addition, the hole injection layer 3 was formed using the composition for organic electroluminescent elements containing the polymer compound of this invention, the bridge | crosslinking type polymer compound of this invention, or containing the polymer compound of this invention. It may be a layer. That is, the polymer compound or the crosslinked polymer 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 from the light emitting layer 5 are anode 2. It has a function of suppressing a decrease in luminous efficiency caused by being injected into the side.

  In order to express this function, the hole transport layer 4 contains the polymer compound of the present invention or the crosslinked polymer compound of the present invention or a composition for an organic electroluminescent device containing the polymer compound of the present invention. It is preferable that it is the layer formed using. That is, the polymer compound of the present invention is preferably used as a hole transporting compound.

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 The 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 from the cathode 9 to the electron injection layer 8, the electron transport layer 7 and This is a layer that is excited by recombination with electrons injected through the hole blocking layer 6 and serves as 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 has a material having a hole transporting property (hole transporting compound) or an electron transporting property. Material (electron transporting compound). 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 the fluorescent material that gives blue light emission include perylene, pyrene, anthracene, coumarin, chrysene, p-bis (2-phenylethenyl) benzene, and derivatives thereof. Examples of green fluorescent materials include quinacridone derivatives and coumarin derivatives. Examples of yellow fluorescent light-emitting materials include rubrene and perimidone derivatives. Red fluorescent materials include DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran) compounds, benzopyran derivatives, rhodamine derivatives, benzothioxanthene derivatives, azabenzothioxanthene, etc. Is mentioned.

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

（式（IV）中、Ｍ^７は金属を表し、Ｔは炭素原子または窒素原子を表す。Ｒ^９２〜Ｒ^９５は、それぞれ独立に置換基を表す。但し、Ｔが窒素原子の場合は、Ｒ^９４およびＲ^９５は無い。）

(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.

（上記Ｌの部分構造において、環Ａ１は、置換基を有していてもよい、芳香族炭化水素基または芳香族複素環基を表す。） 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, a diarylamino group, and a carbazolyl 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).

（式（IIIａ）中、Ｍ^４は、Ｍと同様の金属を表し、ｗは、上記金属の価数を表し、環Ａ１は、置換基を有していてもよい芳香族炭化水素基を表し、環Ａ２は、置換基を有していてもよい含窒素芳香族複素環基を表す。）

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

（式（IIIｂ）中、Ｍ^５は、Ｍと同様の金属を表し、ｗは、上記金属の価数を表し、環Ａ１は、置換基を有していてもよい芳香族炭化水素基または芳香族複素環基を表し、環Ａ２は、置換基を有していてもよい含窒素芳香族複素環基を表す。）

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

（式（IIIｃ）中、Ｍ^６は、Ｍと同様の金属を表し、ｗは、上記金属の価数を表し、ｊは、０、１または２を表し、環Ａ１および環Ａ１′は、それぞれ独立に、置換基を有していてもよい芳香族炭化水素基または芳香族複素環基を表し、環Ａ２および環Ａ２′は、それぞれ独立に、置換基を有していてもよい含窒素芳香族複素環基を表す。）

(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 represent Independently represents an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group, and ring A2 and ring A2 ′ are each independently a nitrogen-containing aromatic optionally having a substituent. Represents a heterocyclic group.)

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 linked 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 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. This is not preferable. If the molecular weight exceeds 10,000, it is not preferable because it is difficult to purify the organic compound or it takes time to dissolve the organic 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 compound include various compounds exemplified as the hole transporting compound of the hole transporting layer, and 4,4′-bis [N- (1-naphthyl)- N-phenylamino] biphenyl, an aromatic diamine containing two or more tertiary amines and having two or more condensed aromatic rings substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234811), 4,4 An aromatic amine compound having a starburst structure such as', 4 "-tris (1-naphthylphenylamino) triphenylamine (Journal of Luminescence, 1997, Vol.72-74, pp.985), Spiro compounds such as aromatic amine compounds comprising tetramers (Chemical Communications, 1996, pp. 2175), 2,2 ′, 7,7′-tetrakis- (diphenylamino) -9,9′-spirobifluorene (Synthetic Metals, 1 997, Vol.91, pp.209).

  Examples of low molecular weight electron transport compounds 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), 4,4′-bis (9-carbazole) ) -Biphenyl (CBP) and the like.

  These hole transporting compounds and electron transporting compounds are preferably used as host materials in the light-emitting layer, but specifically, the following compounds can be used as 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 formation method, the above-described material is dissolved in an appropriate solvent to prepare a coating solution, which is applied and formed on the hole transport layer 4 after the above formation. 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 9 side, but the holes moving from the anode 2 reach the cathode 9. And a compound capable of efficiently transporting electrons injected from the cathode 9 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, compounds having at least one pyridine ring substituted at the 2,4,6-position described in International Publication No. 2005-022962 are 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 8 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 No. 207169), phenanthroline derivatives (Japanese Patent Laid-Open No. 5-331459), 2-t-butyl-9,10-N, N′-dicyanoanthraquinonediimine, n-type hydrogenated amorphous silicon carbide, n-type sulfide Examples include zinc and n-type zinc selenide.

  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.

  Furthermore, organic metal 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] Others While the organic electroluminescent element having the layer structure shown in FIG. 1 has been mainly described above, the organic electroluminescent element of the present invention has another structure without departing from the gist thereof. Also good. 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 polymer 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. can do. 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 uses the above-described organic electroluminescent element of the present invention. There is no restriction | limiting in particular about the model and structure of the organic electroluminescent display of this invention, 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 According to Example]
Synthesis examples of the organic compound and polymer compound of the present invention are shown below.

(Synthesis Example 1)

  To a four-necked flask equipped with a dropping funnel and a condenser tube, a mixed solution of 50 wt% aqueous sodium hydroxide (300 g) and hexane (250 mL) was added, and tetra-n-butylammonium bromide (4.98 g, 15.5 mmol) was added. Was added. After cooling this mixture to 5 ° C., a mixture of methyl oxetane methanol (31 g) and 1,4-dibromobutane (200 g) was added dropwise with vigorous stirring. After completion of the dropwise addition, the mixture was stirred at room temperature for 15 minutes, further stirred for 15 minutes under reflux, and stirred for 15 minutes while cooling to room temperature. The organic layer is separated, the organic layer is washed with water and dried over magnesium sulfate, the solvent is removed under reduced pressure, and 3- (4-bromobutoxymethyl) -3- is obtained by distillation under reduced pressure (0.42 mmHg, 72 ° C.). Methyl oxetane (52.2 g) was obtained.

  In a nitrogen stream, pulverized potassium hydroxide (8.98 g) was added to a solution of dimethyl sulfoxide (50 ml), m-bromophenol (6.92 g) was added, and the mixture was stirred for 30 minutes, and then 3- (4-bromobutoxymethyl). ) -3-Methyloxetane (12.33 g) was added and stirred at room temperature for 6 hours. The precipitate was collected by filtration, extracted with methylene chloride, the oil layer was concentrated, and purified by silica gel chromatography (hexane / methylene chloride mixed solution) to obtain the desired product 1 (11.4 g).

(Synthesis Example 2)

  To a solution of tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.647 g), bis (diphenylphosphino) ferrocene (1.40 g), and toluene (313 ml) in a nitrogen stream, 4,4′- Diaminodiphenyl ether (25.0 g), bromobenzene (19.6 g), and tert-butoxy sodium (13.2 g) were added at 60 ° C. in a nitrogen atmosphere, and the mixture was further heated to 90 ° C. and stirred for 5.5 hours. After allowing to cool, the reaction mixture was filtered with suction, the filtrate was concentrated, and purified twice by silica gel chromatography (n-hexane / ethyl acetate mixture) to give the intended product 2 (9.38 g).

  In a stream of nitrogen, tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.075 g), bis (diphenylphosphino) ferrocene (0.16 g), and toluene (45 ml) were added to the target compound 2 (4 0.0 g), target product 1 (4.8 g), and tert-butoxy sodium (1.5 g) were added at 60 ° C. under a nitrogen atmosphere, and the mixture was further heated to 90 ° C. and stirred for 5.5 hours. After allowing to cool, the reaction mixture was filtered through Celite, the filtrate was concentrated, and purified twice by silica gel chromatography (methylene chloride / ethyl acetate mixture) to give the desired product 3 (6.2 g).

(Synthesis Example 3)

  In a nitrogen stream, 1-bromohexane (28.1 ml) and 3-bromophenol (36.3 g) were sequentially added to a mixed solution of potassium hydroxide (49.4 g) and dimethyl sulfoxide (220 ml) at room temperature. Stir for hours. A solution obtained by adding 350 ml of water to the reaction solution was extracted with methylene chloride (450 ml), and the extract was washed twice with brine, dried over anhydrous magnesium sulfate, and concentrated. This was purified by silica gel column chromatography (hexane) to obtain the desired product 4 (44.3 g) as a colorless liquid.

  In a nitrogen stream, tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.673 g), bis (diphenylphosphino) ferrocene (0.708 g), and toluene (455 ml) were stirred at room temperature for 10 minutes. To the obtained solution, 3,4'-diaminodiphenyl ether (13.02 g), target product 4 (33.10 g), and tert-butoxy sodium (14.99 g) were sequentially added, and in an oil bath at 90 ° C. for 6 hours. Stir. After standing to cool, 1 liter of ethyl acetate and 500 ml of brine were added and shaken. The organic layer was dried over anhydrous magnesium sulfate and concentrated. From silica gel column chromatography (hexane / methylene chloride mixture) and methylene chloride / methanol. Was purified by recrystallization to obtain a white solid (21.44 g) of the target product 5.

(Synthesis Example 4)

  To a solution of tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.52 g), bis (diphenylphosphino) ferrocene (1.12 g), and toluene (200 ml) in a nitrogen stream, 3,4′- Diaminodiphenyl ether (20.0 g), bromobenzene (32.2 g), and tert-butoxy sodium (21.7 g) were added at 60 ° C. under a nitrogen atmosphere, and the mixture was further heated to 90 ° C. and stirred for 5.5 hours. After allowing to cool, the reaction solution is suction filtered, the filtrate is concentrated, purified by silica gel chromatography (methylene chloride / n-hexane mixture), re-solidified with methylene chloride, and the desired product 6 (26.3 g). Got.

(Synthesis Example 5)

  In a nitrogen stream, potassium carbonate (6.47 g) was added to a solution of 3-bromophenol (8.5 g) and 1,6-dibromohexane (5.71 g) in N, N-dimethylformamide (50 ml) at room temperature. The mixture was stirred for 2 hours at 60 ° C. for 2 hours and then at 80 ° C. for 5 hours. Water was added to the reaction solution, extracted with ethyl acetate, and the organic layer was washed with water. The organic layer was concentrated, purified by silica gel chromatography (n-hexane / methylene chloride mixed solution), and washed with methanol to obtain the desired product 7 (6.81 g) as a white solid.

(Synthesis Example 6)

To a methylene chloride (35 ml) solution of 2,6-dihydroxynaphthalene (2.48 g) in a nitrogen stream, trifluoromethanesulfonic anhydride (9.18 g) was added, and pyridine (2.57 g) was added dropwise. The mixture was stirred at room temperature for 4 hours, water was added for liquid separation, and the organic layer was washed with water and then with dilute hydrochloric acid. The organic layer was concentrated and purified by silica gel chromatography (n-hexane / methylene chloride mixed solution) to obtain a ditriflate (5.85 g) as a white solid.
To a solution of the obtained ditriflate (5.5 g), aniline (2.41 g), sodium tert-butoxy (2.74 g), and toluene (50 ml) in a nitrogen stream, tris (dibenzylideneacetone) dipalladium ( 0) A solution prepared by stirring chloroform complex (0.268 g), bis (diphenylphosphino) ferrocene (0.577 g), and toluene (25 ml) at 60 ° C. for 15 minutes under a nitrogen atmosphere was added, and 85 ° C. The mixture was stirred for 6 hours under heating. After allowing to cool, the mixture was filtered through Celite, and the filtrate was concentrated and suspended (n-hexane / methanol mixture, hexane / methylene chloride mixture) to obtain the target product 8 (0.80 g).

(Synthesis Example 7)

  In a nitrogen stream, a solution of 3-bromophenol (12.3 g) and 2-chloroethyl vinyl ether (8.0 g) in N, N-dimethylformamide (90 ml) was added with potassium carbonate (20.7 g) and potassium iodide (0 0.2 g) was added, the temperature was raised to 100 ° C., and the mixture was stirred for 5 hours. After allowing to cool, water was added to the reaction solution, extracted with ethyl acetate, and the organic layer was washed with water. The organic layer was concentrated and purified by silica gel chromatography (n-hexane / methylene chloride mixture) to give the intended product 9 (12.1 g).

  In a nitrogen stream, a solution of target 2 (4.0 g), target 9 (3.72 g), sodium tert-butoxy (1.67 g), and toluene (42 ml) was added to tris (dibenzylideneacetone) dipalladium ( 0) A solution prepared by stirring chloroform complex (0.038 g), bis (diphenylphosphino) ferrocene (0.080 g), and toluene (5 ml) at 60 ° C. for 15 minutes under a nitrogen atmosphere was added, The mixture was stirred for 2.5 hours under heating. After allowing to cool, the mixture was filtered through Celite, and the filtrate was concentrated and purified by silica gel chromatography (hexane / methylene chloride mixed solution) to obtain the desired product 10 (5.69 g).

(Synthesis Example 8)

  To a solution of tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.52 g), bis (diphenylphosphino) ferrocene (1.12 g), and toluene (200 ml) in a nitrogen stream, 3,4′- Diaminodiphenyl ether (20.0 g), 4-bromobiphenyl (23.3 g) and sodium tert-butoxy (10.6 g) were added at 60 ° C. under a nitrogen atmosphere, and the mixture was further stirred at 90 ° C. for 5.5 hours. did. After allowing to cool, the reaction mixture was filtered with suction, and the filtrate was concentrated and purified by silica gel chromatography (methylene chloride / n-hexane mixture) to give the intended product 11 (8.9 g).

  To a solution of tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.52 g), bis (diphenylphosphino) ferrocene (1.12 g), and toluene (200 ml) in a nitrogen stream, the target compound 11 (8 0.8 g), the target compound 1 (8.2 g), and tert-butoxy sodium (2.6 g) were added at 60 ° C. under a nitrogen atmosphere, and the mixture was further heated to 90 ° C. and stirred for 5.5 hours. After allowing to cool, the reaction mixture was filtered with suction, the filtrate was concentrated, and purified twice by silica gel chromatography (methylene chloride / ethyl acetate mixture) to give the intended product 12 (12.6 g).

(Synthesis Example 9)

  To a solution of tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.10 g), bis (diphenylphosphino) ferrocene (0.56 g), and toluene (150 ml) in a nitrogen stream, 4-aminodiphenylamine ( 9.21 g), the target compound 1 (16.5 g), and tert-butoxy sodium (5.29 g) were heated to 90 ° C. under a nitrogen atmosphere and stirred for 5.5 hours. After allowing to cool, the reaction mixture was filtered with suction, the filtrate was concentrated, and purified by silica gel chromatography (methylene chloride / ethyl acetate mixture and hexane / ethyl acetate mixture) three times to obtain the target compound 13 (13.4 g). )

(Synthesis Example 10)

  In a nitrogen stream, potassium carbonate (25.34 g) was added to a solution of 4-bromophenol (17.44 g) and 4,4′-difluorobenzophenone (10.0 g) in N, N-dimethylformamide (150 ml). And stirred at 140 ° C. for 6.5 hours. The reaction solution is added to water, filtered after stirring and allowing to cool, and the resulting solid is washed by suspension (one time with heating with ethanol, one time with heating with an aqueous methanol solution, and once with chloroform). The target product 14 (16.13 g) was obtained as a white solid.

(Synthesis Example 11)

In a nitrogen stream, target 6 (5.15 g), target 3 (0.85 g), 4,4′-dibromobiphenyl (4.92 g), sodium tert-butoxy (4.85 g), and toluene (60 ml) To this solution, tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.163 g), tri-tert-butylphosphine (0.255 g), and toluene (15 ml) were added at 15 ° C. in a nitrogen atmosphere at 60 ° C. A solution prepared by stirring for 5 minutes was added, and the mixture was stirred for 4 hours under reflux with heating. Subsequently, bromobenzene (0.25 g) and toluene (2 ml) were added, and the mixture was stirred for 3 hours with heating under reflux. Subsequently, diphenylamine (0.53 g) was added, and tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.08 g), tri-tert-butylphosphine (0.13 g), and toluene (7 ml) The solution prepared by stirring for 15 minutes at 60 ° C. in a nitrogen atmosphere was added, and the mixture was stirred for 1 hour while heating under reflux. After allowing to cool, the reaction solution was added to methanol, and the precipitated solid was collected by filtration. Toluene (70 ml) was added to the obtained solid, insoluble matters were filtered off, the filtrate was concentrated, and reprecipitated in acetone. After the precipitate was collected by filtration, the solution dissolved in toluene was reprecipitated with acetone, and further toluene was added to reprecipitate in methanol. The precipitate was collected by filtration and dried under reduced pressure to give the intended product 15 (6.91 g).
The polymer compound had a weight average molecular weight (Mw) of 16,800 and a dispersity (Mw / Mn) of 1.90.

(Synthesis Example 12)

In a nitrogen stream, target 6 (3.00 g), target 5 (0.588 g), target 3 (0.558 g), 4,4′-dibromobiphenyl (3.22 g), tert-butoxy sodium (3 .27 g), and toluene (15 ml) in a solution of tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.110 g), tri-tert-butylphosphine (0.172 g), and toluene (5 ml) A solution prepared by stirring at 60 ° C. for 15 minutes in a nitrogen atmosphere was added, and the mixture was stirred for 1 hour while heating under reflux. Subsequently, 4,4′-dibromobiphenyl (0.032 g) and toluene (1 ml) were added, and the mixture was stirred for 1 hour with heating under reflux. Subsequently, 4,4′-dibromobiphenyl (0.032 g) and toluene (1 ml) were added, and the mixture was stirred for 1 hour with heating under reflux. Subsequently, 4,4′-dibromobiphenyl (0.032 g) and toluene (1 ml) were added, and the mixture was stirred for 1 hour with heating under reflux. Subsequently, bromobenzene (0.168 g) and toluene (7 ml) were added, and the mixture was stirred for 1 hour with heating under reflux. Subsequently, diphenylamine (0.53 g) and toluene (5 ml) were added, and tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.055 g), tri-tert-butylphosphine (0.086 g) And a solution prepared by stirring toluene (5 ml) at 60 ° C. for 15 minutes in a nitrogen atmosphere, and stirring for 2.5 hours under heating to reflux. After allowing to cool, the reaction solution was added to methanol, the precipitated solid was collected by filtration, toluene was added to the obtained solid, the insoluble material was filtered off, the filtrate was concentrated, and reprecipitated into acetone. After the precipitate was collected by filtration, the solution dissolved in toluene was reprecipitated in methanol, and the precipitated solid was dried under reduced pressure. In a stream of nitrogen, the obtained solid was added to a solution of diphenylamine (0.33 g), tert-butoxy sodium (0.25 g) and toluene (120 ml), and tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0 .05 g), tri-tert-butylphosphine (0.20 g), and toluene (5 ml) were added by stirring at 60 ° C. for 15 minutes under a nitrogen atmosphere, and the mixture was stirred for 2 hours under reflux with heating. . The reaction liquid was added to methanol after standing_to_cool, the depositing solid was separated by filtration, and the solid collected by filtration was washed with methanol aqueous solution, and filtered. Tetrahydrofuran and activated carbon were added to the obtained solid, and the mixture was stirred at room temperature for 30 minutes, and then filtered through celite. The filtrate was concentrated and reprecipitated with methanol. The obtained solid was dissolved in toluene, diluted hydrochloric acid treatment, water washing and alkali treatment were performed, and toluene was concentrated and reprecipitated in methanol. The collected solid was dissolved in toluene and purified by alumina chromatography (toluene solvent) to obtain the target product 16 (0.48 g).
The polymer compound had a weight average molecular weight (Mw) of 113,000.

(Synthesis Example 13)

In a nitrogen stream, in a solution of target 8 (0.80 g), target 3 (0.15 g), target 7 (1.23 g), sodium tert-butoxy (0.88 g), and toluene (9 ml), Tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.03 g), tri-tert-butylphosphine (0.05 g), and toluene (3.5 ml) were stirred at 60 ° C. for 15 minutes under a nitrogen atmosphere. The solution prepared above was added, and the mixture was stirred for 4 hours with heating under reflux. Subsequently, bromobenzene (0.05 g) and toluene (0.2 ml) were added, and the mixture was stirred for 1.5 hours with heating under reflux. Subsequently, diphenylamine (0.10 g) and toluene (0.2 ml) were added, and tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.02 g), tri-tert-butylphosphine (0. 05 g), and a solution prepared by stirring toluene (2 ml) at 60 ° C. for 15 minutes under a nitrogen atmosphere, and stirring for 1 hour while heating under reflux. The reaction liquid was added to methanol after standing_to_cool, toluene (70 ml) was added to the solid which filtered the depositing solid, it filtered by cerite, the filtrate was concentrated, and it reprecipitated with acetone. After the precipitate was collected by filtration, the solution dissolved in toluene was reprecipitated with acetone, and further toluene was added to reprecipitate in methanol. The precipitate was collected by filtration and dried under reduced pressure to give the intended product 17 (0.16 g).
This polymer compound had a weight average molecular weight (Mw) of about 50,000.

(Synthesis Example 14)

In a nitrogen stream, target 6 (3.0 g), target 5 (0.67 g), target 10 (1.07 g), 4,4′-dibromobiphenyl (3.68 g), tert-butoxy sodium (3 .74 g), and toluene (25 ml) in a solution of tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.126 g), tri-tert-butylphosphine (0.20 g), and toluene (10 ml) A solution prepared by stirring for 15 minutes at 60 ° C. in a nitrogen atmosphere was added, and the mixture was stirred for 2 hours under reflux with heating. A solution of 4,4′-dibromobiphenyl (0.38 g) in toluene (1.5 ml) was added, and the mixture was further stirred for 1 hour. Subsequently, a toluene (0.8 ml) solution of 4,4′-dibromobiphenyl (0.38 g) was added, and the mixture was further stirred for 1.5 hours. Subsequently, a solution of 4,4′-dibromobiphenyl (0.38 g) in toluene (1.5 ml) was added and stirred for 1 hour. Subsequently, bromobenzene (0.19 g) and toluene (7 ml) were added, and the mixture was stirred for 1 hour with heating under reflux. Subsequently, diphenylamine (0.41 g) and toluene (5 ml) were added, and tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.06 g), tri-tert-butylphosphine (0.1 g) And a solution prepared by stirring toluene (5 ml) at 60 ° C. for 15 minutes under a nitrogen atmosphere, and stirring for 1 hour while heating under reflux. The reaction liquid was added to methanol after standing_to_cool, the depositing solid was separated by filtration, and the solid collected by filtration was washed with methanol aqueous solution, and filtered. Toluene was added to the obtained solid and filtered through Celite. The solid on celite was extracted with tetrahydrofuran, and the extract was concentrated and reprecipitated with methanol. After the precipitate was collected by filtration, the solution dissolved in toluene was reprecipitated with acetone, and the precipitate was collected by filtration and dried under reduced pressure. In a stream of nitrogen, the obtained solid was added to a solution of diphenylamine (0.41 g), sodium tert-butoxy (1.85 g) and toluene (35 ml) in a tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0 0.06 g), tri-tert-butylphosphine (0.10 g), and toluene (5 ml) were stirred at 60 ° C. for 15 minutes under a nitrogen atmosphere, and a solution was added and heated under reflux for 4.5 hours. Stir. The reaction liquid was added to methanol after standing_to_cool, the depositing solid was separated by filtration, and the solid collected by filtration was washed with methanol aqueous solution, and filtered. Toluene was added to the obtained solid and filtered through Celite. The filtrate was concentrated and reprecipitated with methanol. The obtained solid was dissolved in toluene, treated with dilute hydrochloric acid, washed with water, and treated with alkali. Toluene was concentrated, reprecipitated in methanol, and filtered. The collected solid was dissolved in toluene and purified by silica gel chromatography to obtain the target product 18 (0.22 g).
The polymer compound had a weight average molecular weight (Mw) of 48000 and a dispersity (Mw / Mn) of 4.73.

(Synthesis Example 15)

In a nitrogen stream, target 6 (2.20 g), target 12 (3.77 g), 4,4′-dibromobiphenyl (3.90 g), tert-butoxy sodium (4.49 g), and toluene (20 ml) Into a solution of tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.142 g), tri-tert-butylphosphine (0.24 g), and toluene (10 ml) at 60 ° C. under a nitrogen atmosphere. A solution prepared by stirring for minutes was added, and the mixture was stirred for 2 hours under reflux with heating. A solution of 4,4′-dibromobiphenyl (0.38 g) in toluene (1.5 ml) was added, and the mixture was further stirred for 1 hour. Subsequently, a toluene (0.5 ml) solution of the target product 12 (0.08 g) was added, and the mixture was further stirred for 1 hour. Subsequently, a toluene (1 ml) solution of the target product 12 (0.08 g) was added and stirred for 1 hour. After cooling, the reaction solution was added to methanol, the precipitated solid was filtered off, and the collected solid was dissolved in toluene and filtered. The filtrate was concentrated and dried under reduced pressure. In a stream of nitrogen, the obtained solid was added to a solution of bromobenzene (0.79 g), sodium tert-butoxy (0.48 g) and toluene (250 ml) with tris (dibenzylideneacetone) dipalladium (0) chloroform complex ( 0.85 g), tri-tert-butylphosphine (0.19 g), and toluene (5 ml) were added by stirring at 60 ° C. for 15 minutes under a nitrogen atmosphere. The mixture was stirred for 1.5 hours under reflux with heating, diphenylamine (0.85 g) was added, and the mixture was further stirred for 2 hours. After allowing to cool, the reaction solution was added to ethanol (90% aqueous solution), the precipitated solid was filtered off, washed with an aqueous ethanol solution and filtered. Toluene was added to the solid to dissolve it, washed with dilute hydrochloric acid and brine, the extracted organic layer was concentrated by about half, and then reprecipitated in ethanol (ammonia water mixed solution), and the resulting solid was filtered off. This solid was dissolved in toluene, and the solid obtained by reprecipitation in acetone was dissolved in toluene, and purified by silica gel chromatography (toluene solvent) to obtain Target 19 (0.31 g).
The polymer compound had a weight average molecular weight (Mw) of 22,800 and a dispersity (Mw / Mn) of 2.38.

(Synthesis Example 16)

In a nitrogen stream, N, N′-diphenyl-1,4-phenylenediamine (1.90 g), target product 13 (3.16 g), target product 14 (7.50 g), tert-butoxy sodium (4.49 g) , And toluene (20 ml), tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.151 g), tri-tert-butylphosphine (0.24 g), and toluene (10 ml) in a nitrogen atmosphere Then, a solution prepared by stirring at 60 ° C. for 15 minutes was added, and the mixture was stirred for 2 hours with heating under reflux. A solution of 4,4′-dibromobiphenyl (0.38 g) in toluene (1.5 ml) was added, and the mixture was further stirred for 1 hour. Moreover, the toluene (0.5 ml) solution of the target object 14 (0.08g) was added, and also it stirred for 1 hour. Again, a solution of the target compound 14 (0.08 g) in toluene (1 ml) was added and stirred for 1 hour. Subsequently, bromobenzene (0.23 g) and toluene (3 ml) were added, and the mixture was stirred for 1 hour with heating under reflux. Subsequently, diphenylamine (0.49 g) and toluene (3 ml) were added, and the mixture was stirred for 1 hour with heating under reflux. The reaction liquid was added to ethanol aqueous solution after standing_to_cool, the solid which filtered the depositing solid was dissolved in toluene, and Celite filtration was carried out. The filtrate was concentrated and reprecipitated with acetone. After filtering the precipitate, reprecipitation of the solution dissolved in toluene with acetone was repeated twice. The precipitate was dissolved in tetrahydrofuran and reprecipitated with methanol. The target product 20 (6.63 g) was obtained by dissolving the precipitate in toluene, carrying out dilute hydrochloric acid treatment, washing with water, and alkali treatment, followed by purification by silica gel chromatography.
The polymer compound had a weight average molecular weight (Mw) of 10,000 to 50,000.

(Synthesis Example 17)

The target product 6 (8.32 g), target product 10 (1.15 g), 4,4′-dibromobiphenyl (7.86 g), tert-butoxy sodium (8.00 g), and toluene (56 ml) were charged. The interior was sufficiently purged with nitrogen and heated to 60 ° C. (solution A).
Tri-t-butylphosphine (0.4 g) was added to a 20 ml toluene solution of tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.27 g) and heated to 60 ° C. (solution B).
Tri-t-butylphosphine (0.1 g) was added to a 10 ml toluene solution of tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.13 g), and the mixture was heated to 60 ° C. (solution C).

  In a nitrogen stream, solution B was added to solution A and heated to reflux for 1 hour. 4,4′-Dibromobiphenyl (0.08 g) was added to the reaction solution three times every hour (total 0.24 g), and then bromobenzene (0.4 g) was added to the reaction solution. Then, the solution C was dripped at the reaction liquid, and also it heated and refluxed for 2 hours. The reaction solution was allowed to cool, dropped into an ethanol / water (300 ml / 50 ml) solution, and the precipitated solid was collected by filtration. The solid collected by filtration was dissolved in tetrahydrofuran, filtered through Celite, and then reprecipitated with tetrahydrofuran / acetone (twice). Filtered, dried solid (4.0 g), N, N-diphenylamine (0.44 g), sodium tert-butoxy (3.95 g) and toluene (100 ml) were charged, and the system was thoroughly purged with nitrogen. , Heated to 60 ° C. (solution D). Tri-t-butylphosphine (0.2 g) was added to a 10 ml toluene solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.14 g) and heated to 60 ° C. (solution E). In a nitrogen stream, solution E was added to solution D and heated to reflux for 6 hours. The reaction solution was allowed to cool, dropped into an ethanol / water (150 ml / 25 ml) solution, and the precipitated solid was collected by filtration. The solid collected by filtration was dissolved in tetrahydrofuran and filtered through Celite, and then the filtrate was washed with dilute hydrochloric acid and reprecipitated with ammonia-containing ethanol. The solid collected by filtration was purified by column chromatography to obtain Target 21 (2.45 g).

[Synthesis example according to comparative example]
The synthesis example which concerns on a comparative example is shown below.

(Synthesis Example 18)

  To a solution of 3,4'-diaminodiphenyl ether (2.74 g), target compound 1 (9.00 g), sodium tert-butoxy (3.69 g), and toluene (50 ml) in a nitrogen stream, tris (dibenzylideneacetone ) A solution prepared by stirring dipalladium (0) chloroform complex (0.071 g), bis (triphenylphosphino) ferrocene (0.152 g), and toluene (5 ml) at 60 ° C. for 15 minutes in a nitrogen atmosphere. In addition, the mixture was stirred at 85 ° C. for 2 hours. After allowing to cool, toluene and activated clay were added, and the mixture was stirred for 15 minutes. The insoluble material was filtered off, the filtrate was concentrated, and purified by silica gel chromatography (ethyl acetate / methylene chloride mixture) to obtain the target compound 22 (6 .52 g) was obtained.

In a nitrogen stream, target 22 (0.840 g), target 5 (6.00 g), 4,4′-dibromobiphenyl (3.76 g), tert-butoxy sodium (3.26 g), and toluene (60 ml) To this solution, tris (dibenzylideneacetone) dipalladium (0) chloroform complex (0.125 g), tri-tert-butylphosphine (0.196 g), and toluene (5 ml) were added at 15 ° C. in a nitrogen atmosphere at 60 ° C. A solution prepared by stirring for minutes was added, and the mixture was stirred for 2 hours under reflux with heating. Subsequently, bromobenzene (0.190 g) and toluene (25 ml) were added, and the mixture was stirred for 1 hour with heating under reflux. Subsequently, diphenylamine (0.410 g) was added, and the mixture was stirred for 1.5 hours with heating under reflux. After allowing to cool, toluene and activated clay were added and stirred for 15 minutes. The insoluble material was filtered off, the filtrate was concentrated, methylene chloride was added, and reprecipitation was carried out in methanol. After the precipitate was collected by filtration, activated clay was added to the solution dissolved in toluene, and the mixture was stirred for 15 minutes. The insoluble matter was filtered off, the filtrate was concentrated, methylene chloride was added, and the mixture was reprecipitated in methanol. The precipitate was collected by filtration and dried under reduced pressure to give the intended product 23 (2.74 g).
The polymer compound had a weight average molecular weight (Mw) of 158,000 and a number average molecular weight (Mn) of 31,000.

[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 following 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 condition In air 230 ° C 3 hours

  Subsequently, a composition for an organic electroluminescence device containing the polymer compound (H1) according to the present invention (target product 15 obtained in Synthesis Example 11) represented by the following structural formula was prepared, and spin was performed under the following conditions. A hole transport layer 4 having a film thickness of 8 nm was formed by forming a film by coating and crosslinking by heating.

<Composition for organic electroluminescence device>
Solvent Toluene Solid concentration 0.4 wt%

<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 30 seconds Spin coating 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 rough evacuation of the apparatus by an oil rotary pump, the degree of vacuum in the apparatus was 3.0 ×. After evacuating with a cryopump until 10 ⁻⁴ Pa or less, the compound (C5) represented by the following structural formula and the iridium complex (D1) shown below were formed by vacuum deposition, and the light emitting layer 5 was formed. Obtained. The deposition rate of (C5) is controlled in the range of 0.7 to 1.0 Å / sec, and the deposition rate of the iridium complex (D1) is controlled in the range of 0.04 to 0.06 Å / sec. A light emitting layer 5 of the film was formed. The degree of vacuum at the time of vapor deposition was 1.6 to 2.8 × 10 ⁻⁴ Pa.

Next, a hole blocking layer 6 was obtained by laminating a compound represented by the following structural formula (E1) by a vacuum deposition method. The vapor deposition rate was controlled in the range of 0.3 to 0.8 Å / second, and the hole blocking layer 6 having a film thickness of 10 nm was formed by being laminated on the light emitting layer 5. The degree of vacuum at the time of deposition was 1.3 to 2.0 × 10 ⁻⁴ Pa.

Subsequently, tris (8-hydroxyquinolinate) aluminum was heated and evaporated to form an electron transport layer 7. The degree of vacuum during deposition is 1.1 to 1.7 × 10 ⁻⁴ Pa, the deposition rate is controlled in the range of 0.5 to 1.1 Å / sec, and a film with a thickness of 30 nm is formed on the hole blocking layer 6. To form an electron transport layer 7.

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 5.6 × 10 ⁻⁴ Pa or less in the same manner as the organic layer.

As the electron injection layer 8, first, lithium fluoride (LiF) was controlled at a deposition rate of 0.03 to 0.2 liter / second and a degree of vacuum of 3.0 to 5.6 × 10 ⁻⁴ Pa using a molybdenum boat. A film having a thickness of 0.5 nm was formed on the electron transport layer 7. Next, aluminum is similarly heated by a molybdenum boat as the cathode 9 and controlled at a deposition rate of 0.5 to 6.5 liters / second and a degree of vacuum of 1.2 to 10.7 × 10 ⁻⁴ Pa to a film thickness of 80 nm. An aluminum layer was formed. 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 Co., Ltd.) 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: 8.5 [cd / A] @ 100 cd / m ²
Voltage: 4.5 [V] @ 100 cd / m ²
Luminous efficiency: 6.0 [lm / W] @ 100 cd / m ²

  The maximum wavelength of the emission spectrum of the device was 516 nm, and it was identified to be from the iridium complex (D1). The chromaticity was CIE (x, y) = (0.308, 0.624).

Table 1 shows the normalized driving life when the initial luminance of the obtained organic electroluminescent element is 2500 cd / m ² . As shown in Table 1, a device having a long lifetime was obtained by using the polymer compound of the present invention.

(Example 2)
In forming the hole transport layer 4 in Example 1, the polymer compound (H2) of the present invention (the target product 16 obtained in Synthesis Example 12) was used instead of the polymer compound (H1). The organic electroluminescent element shown in FIG. 1 was produced in the same manner as in Example 1 except that the 16 nm hole transport layer 4 was formed.

The light emission characteristics of the organic electroluminescent device obtained as described above are as follows.
Luminance / current: 8.2 [cd / A] @ 100 cd / m ²
Voltage: 4.4 [V] @ 100 cd / m ²
Luminous efficiency: 5.8 [lm / W] @ 100 cd / m ²

  The maximum wavelength of the emission spectrum of the device was 516 nm, and it was identified to be from the iridium complex (D1). The chromaticity was CIE (x, y) = (0.308, 0.623).

Table 1 shows the normalized driving life when the initial luminance of the obtained organic electroluminescent element is 2500 cd / m ² . As shown in Table 1, a device having a long lifetime was obtained by using the polymer compound of the present invention.

(Example 3)
In forming the hole transport layer 4 in Example 1, the polymer compound (H3) of the present invention (the target product 18 obtained in Synthesis Example 14) was used instead of the polymer compound (H1). The organic electroluminescent element shown in FIG. 1 was produced in the same manner as in Example 1 except that the 20 nm hole transport layer 4 was formed.

The light emission characteristics of the organic electroluminescent device obtained as described above are as follows.
Luminance / current: 16.1 [cd / A] @ 100 cd / m ²
Voltage: 5.2 [V] @ 100 cd / m ²
Luminous efficiency: 9.7 [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) = (0.303, 0.627).

Table 1 shows the normalized driving life when the initial luminance of the obtained organic electroluminescent element is 2500 cd / m ² . As shown in Table 1, a device having a long lifetime was obtained by using the polymer compound of the present invention.

(Comparative Example 1)
In forming hole transport layer 4 in Example 1, instead of polymer compound (H1) of the present invention, polymer compound (H4) according to Comparative Example (target product 23 obtained in Synthesis Example 18) was used. The organic electroluminescent element shown in FIG. 1 was produced in the same manner as in Example 1 except that the hole transport layer 4 having a thickness of 20 nm was used.

The light emission characteristics of the organic electroluminescent device obtained as described above are as follows.
Luminance / current: 16.1 [cd / A] @ 100 cd / m ²
Voltage: 5.2 [V] @ 100 cd / m ²
Luminous efficiency: 9.7 [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) = (0.303, 0.627).

Table 1 shows the normalized driving life when the initial luminance of the obtained organic electroluminescent element is 2500 cd / m ² .

Example 4
In forming the hole transport layer 4 in Example 1, the polymer compound (H5) (target product 21 obtained in Synthesis Example 17) of the present invention was used instead of the polymer compound (H1). The organic electroluminescent element shown in FIG. 1 was produced in the same manner as in Example 1 except that the 18 nm hole transport layer 4 was formed.

The light emission characteristics of the organic electroluminescent device obtained as described above are as follows.
Luminance / current: 14.8 [cd / A] @ 100 cd / m ²
Voltage: 6.1 [V] @ 100 cd / m ²
Luminous efficiency: 7.6 [lm / W] @ 100 cd / m ²

  The maximum wavelength of the emission spectrum of the device was 514 nm, which was identified as from the iridium complex (D1). The chromaticity was CIE (x, y) = (0.314, 0.617).

Table 1 shows the normalized driving life when the initial luminance of the obtained organic electroluminescent element is 2500 cd / m ² . As shown in Table 1, a device having a long lifetime was obtained by using the polymer compound of the present invention.

(Example 5)
The organic electroluminescent element shown in FIG. 1 was produced.
First, in the same manner as in Example 1, an anode 2, a hole injection layer 3, and a hole transport layer 4 were formed on a glass substrate 1. However, the film thickness of the hole transport layer 4 was 15 nm.

  Next, in forming the light emitting layer 5, the following light emitting layer forming coating solution is prepared using the organic compounds (C-1), (C-2) and the iridium complex (C-3) shown below. And it spin-coated on the positive hole transport layer 4 on the conditions shown below, and obtained the light emitting layer 5 with the film thickness of 40 nm.

<Light emitting layer forming coating solution>
Solvent Xylene Coating solution concentration C-1: 1.0% by weight
C-2: 1.0% by weight
C-3: 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 condition Under reduced pressure (0.1 MPa), 130 ° C., 1 hour

Here, after 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 vapor deposition apparatus and the apparatus is roughly evacuated by an oil rotary pump, the degree of vacuum in the apparatus is increased. After evacuating using a cryopump until the pressure became 5.1 × 10 ⁻⁴ Pa or less, a compound represented by the following structural formula (C-4) was stacked by a vacuum deposition method to obtain a hole blocking layer 6. At this time, the vapor deposition rate was controlled in the range of 0.7 to 1.0 kg / 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. The degree of vacuum during deposition was 1.9 to 2.0 × 10 ⁻⁴ Pa.

Subsequently, tris (8-hydroxyquinolinate) aluminum was heated and evaporated to form an electron transport layer 7. The degree of vacuum during vapor deposition is 1.3 × 10 ⁻⁴ Pa, the vapor deposition rate is controlled in the range of 0.6 to 1.0 kg / sec, and a 30 nm thick film is laminated on the hole blocking layer 6. An electron transport layer 7 was formed.

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 2.1 × 10 ⁻⁴ Pa or less in the same manner as the organic layer.

First, lithium fluoride (LiF) was controlled as the electron injection layer 8 at a deposition rate of 0.07 to 0.17 liters / second and a degree of vacuum of 2.3 to 2.4 × 10 ⁻⁴ Pa using a molybdenum boat. A film having a thickness of 0.5 nm was formed on the electron transport layer 7. Next, aluminum is similarly heated by a molybdenum boat as the cathode 9 and controlled at a deposition rate of 0.7 to 6.1 liters / second and a degree of vacuum of 2.3 to 2.7 × 10 ⁻⁴ Pa to a film thickness of 80 nm. An aluminum layer was formed. The substrate temperature during the above two-layer deposition was kept at room temperature.

  Subsequently, sealing was performed in the same manner as in Example 1 to prevent the element from being deteriorated by moisture in the atmosphere during storage.

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: 18.7 [cd / A] @ 100 cd / m ²
Voltage: 6.1 [V] @ 100 cd / m ²
Luminous efficiency: 9.7 [lm / W] @ 100 cd / m ²

  The maximum wavelength of the emission spectrum of the device was 513 nm, which was identified as that from the iridium complex (C-3). The chromaticity was CIE (x, y) = (0.311, 0.623).

(Example 6)
The organic electroluminescent element shown in FIG. 1 was produced.
On the anode 2 formed and treated in the same manner as in Example 1, the polymer compound (H6) of the present invention (target product 20 obtained in Synthesis Example 16), 4-isopropyl- represented by the above structural formula (A1) A composition for an organic electroluminescent device containing 4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and ethyl benzoate was prepared. This coating solution was formed by spin coating on the anode 2 under the following conditions, and crosslinked by heating to obtain a hole injection layer 3 having a thickness of 25 nm.

<Composition for organic electroluminescence device>
Solvent Ethyl benzoate Coating solution concentration H6: 2.0% by weight
A1: 0.4% by weight

<Film formation conditions for hole injection layer 3>
Spinner speed 1500rpm
Spinner rotation time 30 seconds Spin coat atmosphere In air Heating condition In air 230 ° C 1 hour

  Subsequently, a coating liquid for forming a hole transport layer containing the organic compound (H7) represented by the following structural formula was prepared, and the film was formed by spin coating under the following conditions, and polymerized by heating to give a film thickness of 5 nm. The hole transport layer 4 was formed.

<Coating liquid for hole transport layer formation>
Solvent Toluene Solid content 0.1% by weight

<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 30 seconds Spin coating atmosphere In nitrogen Heating conditions In nitrogen, 230 ° C, 1 hour

  Next, in forming the light-emitting layer 5, the following organic compound (C6) and (D3) are used to prepare the following light-emitting layer-forming coating solution, and the hole transport layer 4 is subjected to the following conditions. A 40 nm-thick luminescent layer 5 was obtained by spin coating.

<Light emitting layer forming coating solution>
Solvent Toluene Coating solution concentration C6: 0.80 wt%
D3: 0.08% 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 condition Under reduced pressure (0.1 MPa) 130 ° C. 1 hour

  After forming the light emitting layer 5, the hole blocking layer 6, the electron transporting layer 7, the electron injection layer 8 and the cathode 9 were formed in the same manner as in Example 1, and sealing treatment was performed in the same manner.

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: 2.7 [cd / A] @ 100 cd / m ²
Voltage: 6.3 [V] @ 100 cd / m ²
Luminous efficiency: 1.3 [lm / W] @ 100 cd / m ²

  The maximum wavelength of the emission spectrum of the device was 465 nm, and it was identified as that from the compound (D3). The chromaticity was CIE (x, y) = (0.143, 0.187).

Table 2 shows the normalized 80% driving life in which the luminance decay time up to 80% of the initial luminance is normalized with the value of Comparative Example 2 when the initial luminance of the obtained organic electroluminescent element is 1000 cd / m ^2. Show. As shown in Table 2, a device having a long lifetime was obtained by using the polymer compound of the present invention.

(Comparative Example 2)
The organic electroluminescent element shown in FIG. 1 was produced in the same manner as in Example 6 except that the hole injection layer 3 was formed by the following method.

  A hole transporting polymer material having a repeating structure represented by the structural formula (P1) (weight average molecular weight: 26500, number average molecular weight: 12000), 4-isopropyl-4′-methyldiphenyl represented by the structural formula (A1) A coating solution for forming a hole injection layer containing iodonium 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 condition In air 230 ° C 3 hours

The light emission characteristics of the organic electroluminescent device obtained as described above are as follows.
Luminance / current: 2.2 [cd / A] @ 100 cd / m ²
Voltage: 6.0 [V] @ 100 cd / m ²
Luminous efficiency: 1.1 [lm / W] @ 100 cd / m ²

  The maximum wavelength of the emission spectrum of the device was 464 nm, which was identified as that from the compound (D3). The chromaticity was CIE (x, y) = (0.140, 0.163).

Table 2 shows the normalized 80% drive life in which the luminance decay time up to 80% of the initial luminance is normalized when the initial luminance of the obtained organic electroluminescent element is 1000 cd / m ² .

  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.

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

Explanation of symbols

DESCRIPTION OF SYMBOLS 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 represented by the following formula (I).

[In formula (I), Z represents a cationically polymerizable group.
G ¹ represents a group selected from an —O— group, —S— group, —C (═O) — group, —S (═O) ₂ — group, —SiH ₂ — group, or —CH ₂ — group. Represents a divalent group or a direct bond formed by linking 30 units. The —SiH ₂ — group and the —CH ₂ — group may have a substituent.
Ar ¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. A ¹ and A ² each independently represent a divalent group represented by the following formula (I-1).

(In Formula (I-1), Ar ² and Ar ³ each independently represent an aromatic hydrocarbon group which may have a substituent. G ² has the same meaning as G ¹ above. N Represents an integer of 0 to 4.)]   The organic compound according to claim 1, wherein the cationic polymerizable group is a cyclic ether group or a vinyl ether group. The high molecular compound containing the repeating unit represented by following formula (II).

[In formula (II), Z represents a cationically polymerizable group.
G ¹ represents a group selected from an —O— group, —S— group, —C (═O) — group, —S (═O) ₂ — group, —SiH ₂ — group, or —CH ₂ — group. Represents a divalent group or a direct bond formed by linking 30 units. The —SiH ₂ — group and the —CH ₂ — group may have a substituent.
Ar ¹ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. A ¹ and A ² each independently represent a divalent group represented by the following formula (I-1).

(In Formula (I-1), Ar ² and Ar ³ each independently represent an aromatic hydrocarbon group which may have a substituent. G ² has the same meaning as G ¹ above. N Represents an integer of 0 to 4.)
Q represents a linking group. ]   The polymer compound according to claim 3, wherein the cationic polymerizable group is a cyclic ether group or a vinyl ether group.   A crosslinked polymer compound obtained by crosslinking the polymer compound according to claim 3 or 4.   The composition for organic electroluminescent elements containing the high molecular compound of Claim 3 or 4.   5. The organic electroluminescence device having an anode, a cathode, and one or more organic layers between the anode and the cathode on a substrate, wherein at least one of the organic layers is according to claim 3 or 4. An organic electroluminescent device containing the above polymer compound.   The organic electroluminescent element according to claim 7, wherein the layer containing the polymer compound is a hole injection layer or a hole transport layer.   The organic electroluminescent device having an anode, a cathode, and one or more organic layers between the anode and the cathode on a substrate, wherein at least one of the organic layers is a cross-linking according to claim 5. Electroluminescent device containing a polymeric polymer.   The organic electroluminescent element according to claim 9, wherein the layer containing the crosslinked polymer compound is a hole injection layer 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 forming method. The organic electroluminescent element of any one.   The organic electroluminescent display using the organic electroluminescent element of any one of Claims 7 thru | or 11.

Images