JP5343832B2 - Arylamine polymer, organic electroluminescent element material, composition for organic electroluminescent element, organic electroluminescent element, organic EL display and organic EL lighting - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an arylamine polymer with the excellent positive hole transportation ability and electrochemical stability. <P>SOLUTION: The arylamine polymer has a repeating unit represented by formula (1) and a repeating unit represented by formula (2), wherein Ar<SP>1</SP>to Ar<SP>3</SP>represent an aromatic hydrocarbon group or an aromatic heterocycle group. Ar<SP>2</SP>and/or Ar<SP>3</SP>have a crosslinkable group as a substituent. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to an arylamine polymer, and in particular, an arylamine polymer useful as a hole injection layer and a hole transport layer of an organic electroluminescent device, an organic electroluminescent device material containing the arylamine polymer, and a composition for an organic electroluminescent device The present invention relates to an object, an organic electroluminescent element, and an organic EL display and an organic EL illumination including the organic electroluminescent element.

  In recent years, electroluminescent devices using organic thin films (that is, organic electroluminescent devices) have 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.

  The wet film formation method does not require a vacuum process, is easy to increase in area, and has an advantage that it is easy to mix a plurality of materials having various functions in one layer and a coating liquid for forming the layer. is there. However, the wet film formation method is difficult to stack. For this reason, compared with the element manufactured by the vacuum evaporation method, the element manufactured by the wet film-forming method is inferior in driving stability, and has not reached a practical level except for a part. In particular, in the wet film forming method, two layers can be stacked by using an organic solvent and an aqueous solvent, but it is difficult to stack three or more layers.

  In order to solve such problems in lamination, Patent Document 1 and Patent Document 2 propose arylamine polymers (Q-1) and (Q-2) having the following fluorene rings and crosslinkable groups. And the structure which laminates | stacks using the network polymer obtained when these crosslinkable groups react becomes insoluble in an organic solvent is disclosed.

  Patent Document 3 proposes introducing a fluorene ring into the side chain of an arylamine polymer. However, Patent Document 3 does not describe introducing a crosslinkable group into an arylamine polymer.

International Publication No. 2008-032843 Pamphlet International Publication No. 2008-038747 Pamphlet International Publication No. 2004-014985 Pamphlet

  The fluorene ring is a planar ring, and HOMO (highest occupied molecular orbital) or LUMO (lowest unoccupied molecular orbital) extends throughout the ring. For this reason, an arylamine polymer having a fluorene ring is usually excellent in charge transport ability. Therefore, it is speculated that the arylamine polymers (Q-1) and (Q-2) described in Patent Documents 1 and 2 also have charge transporting ability. However, in the arylamine polymers (Q-1) and (Q-2), since the fluorene ring is present only in the main chain, it is considered that most of the charge is transported through the main chain.

  On the other hand, when the arylamine polymers (Q-1) and (Q-2) become a network polymer by cross-linking, the main chain structure is twisted or twisted, and the spread of HOMO and LUMO in the main chain is inhibited. For this reason, even if the arylamine polymers (Q-1) and (Q-2) have a charge transport ability, the network polymer after crosslinking does not necessarily have a sufficient charge transport ability. Rather, since the arylamine polymers (Q-1) and (Q-2) have a molecular structure that the main chain should bear most of charge transport, the arylamine polymers (Q-1) and (Q- The charge transport ability of the network polymer cross-linked 2) tends to be extremely small. For this reason, the drive voltage of the organic electroluminescent element obtained by the techniques described in Patent Documents 1 and 2 is high, the light emission efficiency is low, and the drive life is short.

  Furthermore, Patent Document 3 exemplifies an arylamine polymer having a fluorene ring in the side chain, but there is no description of a crosslinkable group or the like for making it insoluble after coating. Lamination by the method was difficult.

The present invention was devised in view of the above-described problems, and has excellent hole transport ability and electrochemical stability, can be laminated, can hardly be decomposed by energization, and can provide a uniform film quality. An object of the present invention is to provide an arylamine polymer, an organic electroluminescent element material containing the arylamine polymer, and a composition for an organic electroluminescent element.
Another object of the present invention is to provide an organic electroluminescent element, an organic EL display including the same, and an organic EL illumination that can be driven at a low voltage, have high luminous efficiency, and high driving stability.

  As a result of intensive studies to solve the above problems, the present inventors have found that an arylamine polymer having a specific structure having a fluorene ring in a side chain and a crosslinkable group is crosslinked to an organic solvent. Even after making it insoluble, it was found that it has high hole transport ability and electrochemical stability, and the present invention was completed.

（式（１）及び式（２）中、Ａｒ^１〜Ａｒ^３は、各々独立に、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表し、Ｒ^１〜Ｒ^４は、各々独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有してもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表し、Ｒ^５Ａは、直接結合、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表し、ｍ及びｎは、各々独立に、１以上の整数を表す。） That is, the gist of the present invention is an arylamine polymer having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), wherein Ar ² and / or Ar ³ have a substituent. As an arylamine polymer characterized by having a crosslinkable group .

(In Formula (1) and Formula (2), Ar ^{1 to} Ar ³ are each independently an aromatic hydrocarbon group which may have a substituent or an aromatic heterocycle which may have a substituent. R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or a substituent. R ^5A represents a direct bond, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. , M and n each independently represents an integer of 1 or more.)

At this time, the arylamine polymer of the present invention has a weight average molecular weight (Mw) of 20,000 or more and a dispersity (Mw / Mn; Mn represents a number average molecular weight) of 2.5 or less. preferable.
The crosslinkable group is preferably a group selected from the following crosslinkable group group T.

（前記式中、Ｒ^５〜Ｒ^９は、各々独立に、水素原子又はアルキル基を表し、Ａｒ^４は置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表す。）

(In said formula, R < ⁵ > -R < ⁹ > respectively independently represents a hydrogen atom or an alkyl group, Ar < ⁴ > may have the aromatic hydrocarbon group or substituent which may have a substituent. Represents a good aromatic heterocyclic group.)

  Another gist of the present invention resides in an organic electroluminescent element material comprising the arylamine polymer of the present invention.

  Still another subject matter of the present invention lies in an organic electroluminescent composition comprising the arylamine polymer of the present invention.

Still another subject matter of the present invention is an organic electroluminescent device comprising a substrate, an anode, one or more organic layers, and a cathode in this order, wherein at least one of the organic layers is the arylamine of the present invention. The present invention resides in an organic electroluminescence device comprising a network polymer crosslinked with a polymer.
Moreover, in the organic electroluminescent element of this invention, it is preferable that the layer which has the said network polymer is a positive hole injection layer or a positive hole transport layer.
Furthermore, the organic electroluminescent device of the present invention includes the hole injection layer, the hole transport layer, and the light emitting layer, and the hole injection layer, the hole transport layer, and the light emitting layer are all formed by a wet film formation method. Preferably it is formed.

  Still another subject matter of the present invention lies in an organic EL display comprising the organic electroluminescent element of the present invention.

  Furthermore, another gist of the present invention resides in an organic EL illumination comprising the organic electroluminescent element of the present invention.

According to the arylamine polymer, the organic electroluminescent device material, and the organic electroluminescent device composition of the present invention, the hole transport ability and the electrochemical stability are excellent, lamination is possible, and decomposition is caused by energization. It is difficult to form a film having a uniform film quality.
The organic electroluminescent element, the organic EL display and the organic EL illumination of the present invention can be driven with a low voltage, can achieve excellent performance such as high luminous efficiency and high driving stability.

It is sectional drawing which shows typically the layer structure of the organic electroluminescent element as one Embodiment of this invention. It is sectional drawing which shows typically the layer structure of the element for a measurement produced in the Example and comparative example of this invention. It is a figure which shows the current-voltage characteristic measured in Example 5 and Comparative Example 4 of this invention. The vertical axis represents current density [A / cm ² ], and the horizontal axis represents voltage [V].

  Hereinafter, the present invention will be described in detail with reference to embodiments and examples, but the present invention is not limited to the following embodiments and examples, and may be arbitrarily modified without departing from the gist of the present invention. Can be implemented.

（式（１）及び式（２）中、Ａｒ^１〜Ａｒ^３は、各々独立に、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表し、Ｒ^１〜Ｒ^４は、各々独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有してもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表し、Ｒ^５Ａは、直接結合、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表し、ｍ及びｎは、各々独立に、１以上の整数を表す。） [1. Configuration of arylamine polymer]
The arylamine polymer of the present invention comprises at least a repeating unit represented by the following formula (1) (hereinafter referred to as “repeating unit (1)” as appropriate) and a repeating unit represented by the following formula (2) (hereinafter referred to as appropriate). Arylamine polymer having “repeating unit (2)”, and having a crosslinkable group as a substituent at Ar ² and / or Ar ³ .

(In Formula (1) and Formula (2), Ar ^{1 to} Ar ³ are each independently an aromatic hydrocarbon group which may have a substituent or an aromatic heterocycle which may have a substituent. R ^{1 to} R ⁴ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or a substituent. R ^5A represents a direct bond, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. , M and n each independently represents an integer of 1 or more.)

  The repeating unit (1) has a fluorene ring in the side chain. By having the fluorene ring in the side chain as described above, the spread of HOMO and LUMO of the fluorene ring is not inhibited even after the arylamine polymer is crosslinked, and the charge transport ability of the film can be maintained high. Specifically, the charge mobility can be kept at a high value. For this reason, when a layer is formed of a network polymer obtained by crosslinking an arylamine polymer, the layer can pass a current even at a low voltage.

  On the other hand, the repeating unit (2) has a crosslinkable group in its main chain and / or side chain. This allows the arylamine polymer to crosslink. Since the crosslinked network polymer is hardly dissolved in a solvent, lamination by a wet film forming method is facilitated. Further, if the repeating unit having a fluorene ring in the main chain and / or side chain has a crosslinkable group, the spread of HOMO and LUMO of the fluorene ring may be inhibited. By having the repeating unit (1) having a fluorene ring in the side chain separately from the repeating unit (2) having, it is possible to prevent the HOMO and LUMO spreading of the fluorene ring present in the side chain from being inhibited by crosslinking. . For this reason, when a layer is formed of a network polymer obtained by crosslinking an arylamine polymer, an arbitrary layer can be easily laminated on the layer, and a current can be stably passed through the layer even at a low potential. .

* Description of Ar ^{1 to} Ar ^{3 In} Formula (1) and Formula (2), Ar ^{1 to} Ar ³ each independently have an aromatic hydrocarbon group or substituent which may have a substituent. Represents an aromatic heterocyclic group which may be present.

Examples of the aromatic hydrocarbon group which may have a substituent constituting Ar ^{1 to} Ar ³ include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, and a benzpyrene ring. , A group derived from a 6-membered monocyclic ring or a 2-5 condensed ring, such as a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, a fluorene ring, and a biphenyl group and a terphenyl group.

Examples of the aromatic heterocyclic group that may have a substituent constituting Ar ^{1 to} Ar ³ include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and an oxacin group. Diazole ring, indole ring, carbazole ring, pyrroloimidazole 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, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene Such as, include groups derived from monocyclic or 2-4 fused ring of 5 or 6-membered ring.

Among them, Ar ^{1 to} Ar ³ are selected from the group consisting of a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a triphenylene ring, a pyrene ring, a thiophene ring, a pyridine ring, and a fluorene ring from the viewpoints of solubility and heat resistance. Ring-derived groups are preferred.

Furthermore, the aromatic hydrocarbon group or aromatic heterocyclic group in Ar ¹ may have, and the aromatic hydrocarbon group or aromatic heterocyclic group in Ar ² and / or Ar ³ may have. The substituent other than the crosslinkable group is not particularly limited, and examples thereof include a group selected from the following substituent group Z. Ar ^{1 to} Ar ³ may have one substituent or may have two or more. When it has two or more, you may have one type and may have two or more types by arbitrary combinations and arbitrary ratios.

(Substituent group Z)
For example, an alkyl group, such as a methyl group or an ethyl group, having usually 1 or more carbon atoms and usually 24 or less, preferably 12 or less;
An alkenyl group having usually 2 or more carbon atoms and usually 24 or less, preferably 12 or less, such as a vinyl group;
An alkynyl group such as an ethynyl group, which usually has 2 or more carbon atoms and is usually 24 or less, preferably 12 or less;
For example, an alkoxy group having a carbon number of usually 1 or more and usually 24 or less, preferably 12 or less, such as a methoxy group or an ethoxy group;
For example, an aryloxy group having usually 4 or more, preferably 5 or more, and usually 36 or less, preferably 24 or less, such as a phenoxy group, a naphthoxy group, or a pyridyloxy group;
For example, an alkoxycarbonyl group having 2 or more carbon atoms, usually 24 or less, preferably 12 or less, such as a methoxycarbonyl group or an ethoxycarbonyl group;
For example, a dialkylamino group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less, such as a dimethylamino group or a diethylamino group;
For example, a diarylamino group having a carbon number of usually 10 or more, preferably 12 or more, usually 36 or less, preferably 24 or less, such as a diphenylamino group, a ditolylamino group, or an N-carbazolyl group;
An arylalkylamino group having usually 7 or more carbon atoms, usually 36 or less, preferably 24 or less, such as a phenylmethylamino group;
For example, an acetyl group, a benzoyl group, etc., an acyl group having usually 2 or more carbon atoms and usually 24 or less, preferably 12 or less;
For example, a halogen atom such as a fluorine atom or a chlorine atom;
A haloalkyl group having usually 1 or more and usually 12 or less, preferably 6 or less, such as a trifluoromethyl group;
For example, an alkylthio group having a carbon number of usually 1 or more and usually 24 or less, preferably 12 or less, such as a methylthio group or an ethylthio group;
For example, an arylthio group having a carbon number of usually 4 or more, preferably 5 or more, usually 36 or less, preferably 24 or less, such as a phenylthio group, a naphthylthio group, or a pyridylthio group;
For example, a silyl group having a carbon number of usually 2 or more, preferably 3 or more, usually 36 or less, preferably 24 or less, such as a trimethylsilyl group or a triphenylsilyl group;
For example, a siloxy group having 2 or more, preferably 3 or more, usually 36 or less, preferably 24 or less, such as trimethylsiloxy group or triphenylsiloxy group;
A cyano group;
For example, an aromatic hydrocarbon ring group having usually 6 or more carbon atoms and usually 36 or less, preferably 24 or less, such as a phenyl group or a naphthyl group;
For example, an aromatic heterocyclic group having 3 or more, preferably 4 or more, usually 36 or less, preferably 24 or less, such as thienyl group or pyridyl group.

Among these substituents, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms are preferable from the viewpoint of solubility.
Moreover, each said substituent may have a substituent further, The group illustrated to the said substituent group Z is mentioned as the example.
The formula weight of the substituents for Ar ^{1 to} Ar ³ is preferably 500 or less, more preferably 250 or less, including further substituted substituents. If the formula weight of the substituent is too large, the charge transport ability may be reduced.

When m and n are 2 or more, the repeating unit (1) and the repeating unit (2) each have two or more Ar ¹ and Ar ³ . In that case, Ar ¹ and Ar ³ may be the same or different. Further, Ar ¹ and Ar ³ may be bonded to each other directly or via a linking group to form a cyclic structure.

-Explanation of m and n In the formula (1), m represents the number of repetitions of Ar ¹ . In the formula (2), n represents the number of Ar ³ repetitions. Specifically, m and n are 1 or more, and usually represent an integer of 6 or less, preferably 5 or less, more preferably 4 or less. If m and n are too large, the charge transport ability may be reduced. Note that m and n may be the same or different.

Particularly preferred specific examples of-(Ar ¹ ) _m- in the above formula (1) and-(Ar ³ ) _n- in the above formula (2) are shown below, but-(Ar ¹ ) _m- in the present invention and -(Ar ³ ) _n- is not limited thereto.

（Ｒ^２１〜Ｒ^２４は、各々独立に、置換基を有していてもよいアルキル基を示す。） <Example group>

(R ^{21 to} R ²⁴ each independently represents an alkyl group which may have a substituent.)

Ar ¹ and Ar ³ are particularly preferably p-phenylene groups because of excellent durability. Moreover, Ar ¹ and Ar ³ are particularly preferably 9,9-dialkyl-2,7-fluorene because of excellent solubility before crosslinking.

(S-1), (S-2), and (S-5) are preferable, and (S-1) is more preferable from the viewpoint that the ionization potential becomes shallow and the charge injection ability from the anode is excellent. Further, from the viewpoint of increasing the molecular orbital spread and excellent charge transport ability, (S-3), (S-4) and (S-6) are preferable, and (S-3) is more preferable.
Further,-(Ar ¹ ) _m- and-(Ar ³ ) _n- have the same structure in that the synthesis is simple, the energy levels of the respective repeating units are about the same, and the charge transport ability is high. It is preferable.

The arylamine polymer of the present invention may have two or more types of repeating units represented by the formula (1) and two or more types of repeating units represented by the formula (2). In the arylamine polymer of the present invention, two or more different (Ar ¹ ) _m can be alternately arranged in the polymer main chain. For example, when the repeating unit represented by the formula (1) where m = 1 and the repeating unit represented by the formula (1) where m = 2 are alternately arranged, the following formula can be expressed. .

For example, by having a structure such as the above formula, repeating units having different characteristics can coexist without losing the regularity of the polymer. Accordingly, when the arylamine polymer has two types of repeating units represented by the formula (1) and two types of repeating units represented by the formula (2), the repeating unit represented by the formula (1) and 2 It is preferable to arrange alternately the repeating unit represented by the seed formula (2).
Among these, from the viewpoint of easy synthesis, when the arylamine polymer has two types of repeating units represented by the formula (1) and two types of repeating units represented by the formula (2), they are randomly selected. It is preferable to arrange.

Description of R ^{1 to} R ^{4 In} formula (1), R ^{1 to} R ⁴ are each independently a hydrogen atom, an alkyl group that may have a substituent, or an aromatic carbon that may have a substituent. It represents an aromatic heterocyclic group which may have a hydrogen group or a substituent.

As an alkyl group which may have a substituent constituting R ^{1 to} R ⁴ , for example, a methyl group, an ethyl group, or the like, usually has 1 or more carbon atoms, usually 24 or less, preferably 12 or less. A certain alkyl group etc. are mentioned.

Examples of the aromatic hydrocarbon group which may have a substituent constituting R ^{1 to} R ⁴ include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, and a benzpyrene ring. , A monovalent group derived from a 6-membered monocyclic ring or a 2-5 condensed ring, such as a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, or a fluorene ring.

Examples of the aromatic heterocyclic group which may have a substituent constituting R ^{1 to} R ⁴ include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, and an oxacin group. Diazole ring, indole ring, carbazole ring, pyrroloimidazole 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, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. And a monovalent group derived from a monocyclic or 2-4 fused ring of 5 or 6-membered ring.

Especially, as R < ¹ > and R < ² >, a hydrogen atom is preferable at a point with high charge transport property. Moreover, as R < ³ > and R < ⁴ >, an alkyl group is preferable at the point which the solubility before insolubilization by bridge | crosslinking and oxidation-reduction stability are improved.

The substituent that the alkyl group, aromatic hydrocarbon group, and aromatic heterocyclic group in R ^{1 to} R ⁴ may have has the aromatic hydrocarbon or aromatic heterocyclic ring in Ar ^{1 to} Ar ³ . It is the same as the substituent which may be substituted (except for the crosslinkable group in Ar ² and / or Ar ³ ).

Further, regarding the formula weight, the formula weight of R ^{1 to} R ⁴ is usually 1 or more, usually 500 or less, preferably 250 or less, more preferably 100 or less. If the formula weights of R ^{1 to} R ⁴ are too large, the charge transport ability may be lowered.

R ¹ and R ² , and R ³ and R ⁴ may be bonded to each other directly or via a linking group to form a cyclic structure.
R ¹ , R ² , R ³ and R ⁴ may be the same as or different from each other.

・ Description of R ^5A
In Formula (1), R ^5A represents a direct bond, an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. Among them, R ^5A is preferably a direct bond, but when R ^5A is an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, Specific examples and preferred examples thereof are the same as those of Ar ^{1 to} Ar ^3.

Arylamine polymer of the description of the invention The crosslinking groups, having a crosslinkable group in Ar ² and / or Ar ^3. Here, the “crosslinkable group” refers to a group that reacts with the same or different group of another molecule located in the vicinity to generate a new chemical bond. For example, the group which reacts with the same or different group of the other molecule | numerator located in the vicinity by irradiation of a heat | fever and / or active energy ray, and produces | generates a novel chemical bond is mentioned. Examples of the crosslinkable group include groups shown in the following crosslinkable group group T.

（式中、Ｒ^５〜Ｒ^９は、それぞれ独立に、水素原子又はアルキル基を表す。Ａｒ^４は置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表す。なお、アルキル基、芳香族炭化水素基、芳香族複素環基及び置換基としては、例えば、Ｒ^１〜Ｒ^４において説明したものと同様のものが挙げられる。） [Crosslinkable group T]

(In formula, R < ⁵ > -R < ⁹ > represents a hydrogen atom or an alkyl group each independently. Ar < ⁴ > may have the aromatic hydrocarbon group or substituent which may have a substituent. Represents an aromatic heterocyclic group, and examples of the alkyl group, the aromatic hydrocarbon group, the aromatic heterocyclic group and the substituent include the same as those described for R ^{1 to} R ⁴ .

Among them, the crosslinkable group is preferably a group that crosslinks by cationic polymerization such as a cyclic ether group such as an epoxy group or an oxetane group, or a vinyl ether group. This is because the reactivity is high and insolubilization is easy. Among them, an oxetane group is particularly preferable in terms of easy control of the rate of cationic polymerization, and a vinyl group is bonded via an oxygen atom in that it is difficult to generate hydroxyl groups that may cause deterioration of the device during cationic polymerization. Particularly preferred are vinyl ether groups.
Further, for example, an arylvinylcarbonyl group such as a cinnamoyl group or a group that undergoes a cycloaddition reaction such as a group derived from a benzocyclobutene ring is preferable in terms of further improving electrochemical stability.

  In addition, the kind of crosslinkable group which the arylamine polymer of this invention has may be one type, and two or more types may be used together in arbitrary combinations and arbitrary ratios.

In the molecule, the crosslinkable group may be directly bonded to the aromatic hydrocarbon group or aromatic heterocyclic group in Ar ² and / or Ar ³ , but is bonded via an appropriate divalent group. Also good. As the divalent group, a group selected from the group consisting of an —O— group, a —C (═O) — group or a —CH ₂ — group optionally having a substituent, in any combination, ratio and A divalent group formed by connecting 1 to 30 in order is preferable.

  Specific examples of the crosslinkable group via these divalent groups, that is, groups containing a crosslinkable group are as follows. However, the present invention is not limited to the following examples.

Among the repeating units (1) described above, a repeating unit represented by the following formula (1-1) is preferable. Moreover, the repeating unit represented by following formula (2-1) among the repeating unit (2) mentioned above is preferable.

(In Formula (1-1) and Formula (2-1), R ¹¹ and R ¹² each independently represent an alkyl group having 1 to 12 carbon atoms, and Ar ^{21 to} Ar ²³ each independently represent 1 carbon atom. Represents an aromatic hydrocarbon group which may have an alkyl group of ˜12 as a substituent or an aromatic heterocyclic group which may have an alkyl group of 1 to 12 carbon atoms as a substituent, Q is a direct bond , —O— group, —C (═O) — group, and a group selected from the group consisting of optionally substituted —CH ₂ — groups, any combination, any ratio and any In order, it represents a divalent group formed by connecting 1 to 30, and p and q each independently represent an integer of 1 to 4.)

· ^{R 11} and ^{R 12} Description formula ^{(1-1), R 11} and ^{R 12} represents an alkyl group having 1 to 12 carbon atoms. R ¹¹ and R ¹² may be the same or different.

* Description of Ar ^{21 to} Ar ^{23 In} formula (1-1) and formula (2-1), Ar ^{21 to} Ar ²³ may have an alkyl group having 1 to 12 carbon atoms as an aromatic carbon. The aromatic heterocyclic group which may have a hydrogen group or a C1-C12 alkyl group as a substituent is represented. The aromatic hydrocarbon group and the aromatic heterocyclic group are the same as Ar ^{1 to} Ar ³ described above, and preferred examples are also the same. Furthermore, the substituent that the aromatic hydrocarbon group and the aromatic heterocyclic group in Ar ^{21 to} Ar ²³ may have is an alkyl group having 1 to 12 carbon atoms, and a preferable example is also the above Ar ^{1 to} Ar ³ . Same as the case.

During · Q description formula (2-1), Q is a direct bond, -O- group, -C (= O) - group, and, optionally -CH ₂ may have a substituent - consists group It represents a divalent group formed by connecting 1 to 30 groups selected from the group in any combination, in any ratio, and in any order.

* Explanation of p and q In formula (1-1) and formula (2-1), p and q each independently represent an integer of 1 to 4.

By the way, the repeating unit represented by Formula (2-1) has a group containing a benzocyclobutene ring in its side chain. Since the group containing a benzocyclobutene ring does not necessarily require a crosslinking reaction accelerator described later when crosslinking, even if an organic layer is formed using the arylamine polymer of the present invention, the crosslinking reaction is accelerated by energization. The decomposition of the agent can be avoided.
Further, when the crosslinkable group remains in the organic layer after the organic layer is formed, other crosslinkable groups such as cationic polymerizable groups are highly polar and easily cause charge trapping or degradation. Since the group containing is small in polarity, it is estimated that there is little adverse effect on device characteristics.
When a group containing a benzocyclobutene ring is bridged, it forms a ring as a new chemical bond. Therefore, a layer formed by cross-linking the arylamine polymer of the present invention (corresponding to a cross-linked layer) is electrochemically stable, and the organic electroluminescent device having this layer has high current efficiency and long life. Is estimated to be long.

  The number of crosslinkable groups possessed by the arylamine polymer of the present invention is usually 0.01 or more, preferably 0.05 or more, and usually 3.0 or less, preferably per 1000 molecular weight of the arylamine polymer. Is 2.0 or less, more preferably 1.0 or less. When the lower limit of this range is not reached, the network polymer is insufficiently insolubilized, and consequently the layer formed by the network polymer (crosslinked layer) is insufficiently insolubilized, and a multilayer laminated structure is formed by a wet film formation method. It may not be possible. On the other hand, if the upper limit of this range is exceeded, a flat cross-linked layer cannot be obtained due to cracks, the cross-link density becomes too high, or the number of unreacted cross-linkable groups increases in the cross-linked layer, thereby producing an element May affect the life of the product.

  Here, the number of crosslinkable groups per 1000 molecular weight of the arylamine polymer can be calculated from the molar ratio of charged monomers at the time of synthesis and the structural formula, excluding the end groups from the arylamine polymer. For example, in the case of the arylamine polymer (H1) used in Example 1 described later, the total formula amount of the repeating units (1) and (2) excluding the terminal group is 468.87, and the number of crosslinkable groups Is 0.2 on average per molecule. When this is calculated by simple proportion, the number of crosslinkable groups per 1000 molecular weight is calculated to be 0.43.

-Example of repeating unit (1) Hereinafter, the example of a repeating unit (1) is shown. However, the present invention is not limited to the following examples.

-Example of repeating unit (2) Examples of the repeating unit (2) are shown below. However, the present invention is not limited to the following examples.

Specific examples of the arylamine polymer of the present invention Specific examples of the arylamine polymer of the present invention are shown below. However, the present invention is not limited to the following examples.

  Furthermore, specific examples of the arylamine polymer of the present invention include [I. And arylamine polymers described in the section “Synthesis of Polymer”.

-Other matter regarding arylamine polymer In the arylamine polymer of this invention, 2 or more types of repeating units (1) and repeating units (2) may exist respectively. In this case, the repeating units (1) and the repeating units (2) are different from each other by, for example, any one or all of Ar ^{1 to} Ar ³ , R ^{1 to} R ⁴ , m, and n being different. It may be.

In the arylamine polymer of the present invention, the ratio of the repeating unit (1) to the repeating unit (2) may be appropriately determined so that the number of crosslinkable groups is within the above range. The ratio represented by “number of (1)” / {total number of repeating units (1), repeating units (2), and other repeating units} is usually 0.01 or more, preferably 0.1 or more. Preferably it is 0.2 or more, usually 0.995 or less, preferably 0.99 or less, more preferably 0.98 or less. This is because if the amount of the repeating unit (1) is too small, the excellent charge transporting characteristic of the arylamine polymer of the present invention may not be obtained.
On the other hand, the ratio represented by “number of repeating units (2)” / {total number of repeating units (1), repeating units (2) and other repeating units} is usually 0.005 or more, preferably 0.8. It is 01 or more, more preferably 0.02 or more, usually 0.9 or less, preferably 0.6 or less, more preferably 0.4 or less. If the number of the repeating units (2) is too small, the ratio including the number of crosslinkable groups is decreased, the insolubility of the crosslinked layer in the organic solvent is reduced, and there is a possibility that lamination cannot be performed. If the number of repeating units (2) is too large, too many crosslinkable groups will cause cracks and a flat film will not be formed, or the network polymer in the crosslinked layer will remarkably aggregate to reduce charge transport ability. In other words, the crosslink density becomes too high and the number of unreacted crosslinkable groups in the crosslink layer increases, thereby reducing the redox stability and affecting the life of the device to be manufactured.

  The arylamine polymer of the present invention usually has only the repeating unit (1) and the repeating unit (2) as repeating units. However, the repeating unit (1) and repeating unit (2) are not used unless the effects of the present invention are significantly impaired. It may have repeating units other than). However, from the viewpoint of exhibiting the effect of the present invention more remarkably, it is preferable that the amount of the repeating unit other than the repeating unit (1) and the repeating unit (2) contained in the arylamine polymer of the present invention is small. Specifically, the ratio represented by “the number of other repeating units” / {total number of repeating units (1), repeating units (2), other repeating units} may be 0.7 or less. Preferably, it is 0.5 or less.

  The weight average molecular weight Mw of the arylamine polymer of the present invention is usually 10,000 or more, preferably 20,000 or more, and usually 2,000,000 or less, preferably 1,000,000 or less. In addition, the number average molecular weight Mn of the arylamine polymer of the present invention is usually 3000 or more, preferably 6000 or more, and usually 1000000 or less, preferably 500000 or less. If the weight average molecular weight or number average molecular weight is below the lower limit of this range, the insolubility of the crosslinked layer in the organic solvent may be reduced, and lamination may not be possible, and the glass transition temperature may be reduced and heat resistance may be impaired. There is sex. If the upper limit of this range is exceeded, there is a possibility that a flat film cannot be obtained without dissolving in the organic solvent even before crosslinking.

  Furthermore, the dispersity (Mw / Mn) in the arylamine polymer of the present invention is usually 3.5 or less, preferably 2.5 or less, more preferably 2.0 or less. If the degree of dispersion of the arylamine polymer exceeds the upper limit of this range, purification may be difficult, solvent solubility may be reduced, and charge transport capability may be reduced. In addition, although there is no restriction | limiting in the minimum of dispersity, it is 1.0 or more normally, Preferably it is 1.1 or more, More preferably, it is 1.2 or more.

  The weight average molecular weight and number average molecular weight of the arylamine polymer are usually determined by SEC (size exclusion chromatography) measurement. In SEC measurement, the elution time is shorter for the higher molecular weight component, and the elution time is longer for the lower molecular weight component. As a specific measurement method, the weight average molecular weight and the number average molecular weight can be measured by converting the elution time of the sample into the molecular weight using a calibration curve calculated from the elution time of polystyrene (standard sample) having a known molecular weight. .

  The ionization potential of the arylamine polymer of the present invention is usually 4.7 eV or more, preferably 5.0 eV in terms of excellent charge transport ability, excellent charge injection from the anode side, and excellent charge injection to the cathode side. In addition, it is usually 5.8 eV or less, preferably 5.5 eV or less.

-Advantages of the arylamine polymer of the present invention The arylamine polymer of the present invention has a repeating unit (1) having a fluorene group in the side chain as shown in the formula (1), so that charge transfer is higher than before. Have excellent hole transportability. Furthermore, the arylamine polymer of the present invention has little influence on the charge mobility even if the number of crosslinkable groups per 1000 molecular weight is increased.
Moreover, in the state before bridge | crosslinking, it has high solubility with respect to a solvent, is excellent in the surface flatness at the time of film-forming, and can form into a film with uniform film quality.
Furthermore, since it becomes difficult to dissolve in an organic solvent after crosslinking, lamination is possible. In addition, since the intermolecular bonds are strengthened by crosslinking, the electrical stability of the network polymer is good, and decomposition due to energization hardly occurs.

Because of such excellent properties, the arylamine polymer of the present invention is suitable for use as an organic electroluminescent element material.
The arylamine polymer of the present invention is not limited to organic electroluminescent devices, but can be effectively used for other electrophotographic photoreceptors, organic electroluminescent devices, photoelectric conversion devices, organic solar cells, organic rectifying devices, and the like. be able to.

[2. Method for producing arylamine polymer]
The method for producing the arylamine polymer of the present invention is not particularly limited, and is arbitrary as long as the arylamine polymer of the present invention is obtained. For example, it can be produced by a polymerization method by Suzuki reaction, a polymerization method by Grignard reaction, a polymerization method by Yamamoto polymerization method, a polymerization method by Ullmann reaction, a polymerization method by Buchwald-Hartwig reaction, or the like.

In the case of the polymerization method by the Ullmann reaction and the polymerization method by the Buchwald-Hartwig reaction, for example, the fluorenamine represented by the formula (1a) and the arylaniline represented by the formula (2a) are converted into (Ar ¹ ) _m -X ₂ and The aryl halides represented by (Ar ³ ) _n —X ₂ ( _where X represents a halogen atom such as I, Br, Cl, F, etc.) are reacted. Thereby, the secondary amine compound represented by Formula (1b) or Formula (2b) is obtained. And the arylamine polymer of this invention is manufactured by making the secondary amine compound represented by the obtained Formula (1b) or Formula (2b) react further.
In the following reaction formula, each compound and reaction in the case where R ^5A is a direct bond are described. However, R ^5A has an aromatic hydrocarbon group or substituent which may have a substituent. Even if it is the aromatic heterocyclic group which may be carried out, the arylamine polymer of this invention can be manufactured by reaction similar to the reaction shown below.

When (Ar ¹ ) _m and (Ar ³ ) _n are the same, they are synthesized in one step as in the following formula.

式中、Ｚ^２−ＮＨ_２は前記式（１ａ）及び（１ｂ）を表し、Ｚ^３、Ｚ^４は（Ａｒ^１）_ｍを表し、Ｚ^３、Ｚ^４は互いに異なる） Further, as shown in the following formula, two different (Ar ¹ ) _m can be alternately arranged in the polymer main chain.

In the formula, Z ² —NH ₂ represents the above formulas (1a) and (1b), Z ³ and Z ⁴ represent (Ar ¹ ) _m , and Z ³ and Z ⁴ are different from each other)

In the above polymerization method, the reaction to form N—Ar ¹ bond, N—Ar ² bond, and N—Ar ³ bond in each step is usually a base such as potassium carbonate, tert-butoxy sodium, triethylamine, etc. In the presence. Moreover, it can also carry out in presence of transition metal catalysts, such as copper and a palladium complex, as needed.

In the case of a polymerization method using a Suzuki reaction, for example, fluorenamine represented by the formula (1a) and arylaniline represented by the formula (2a) are added to Ar—X ₂ (where X is I, Br, Cl, F, etc.). Are reacted with each other. Thereby, the secondary amine compound represented by Formula (1c) or Formula (2c) is obtained. The obtained secondary amine compound is a boron derivative such as Z- (BR) ₂ (where R is an arbitrary substituent, and usually represents a hydroxyl group or an alkoxy group that may form a ring, Represents the partial structure of (Ar ¹ ) _m or (Ar ³ ) _n ) to synthesize the arylamine polymer of the present invention.
In the following reaction formula, each compound and reaction in the case where R ^5A is a direct bond are described. However, R ^5A has an aromatic hydrocarbon group or substituent which may have a substituent. Even if it is the aromatic heterocyclic group which may be carried out, the arylamine polymer of this invention can be manufactured by reaction similar to the reaction shown below.

  In the above polymerization method, the reaction step with the halide is usually carried out in the presence of a base such as potassium carbonate, tert-butoxy sodium, triethylamine or the like. Moreover, it can also carry out in presence of transition metal catalysts, such as copper and a palladium complex, as needed. Furthermore, the reaction step with a boron derivative can be performed in the presence of a base such as quaternary ammonium salt, potassium carbonate, tert-butoxy sodium, triethylamine, and a transition metal catalyst such as copper or palladium complex.

[3. Composition for Organic Electroluminescent Device]
As described above, the arylamine polymer of the present invention can be used as a material for a layer constituting an organic electroluminescent element. In this case, usually, a composition for an organic electroluminescence device containing at least the arylamine polymer of the present invention (hereinafter referred to as “the composition for an organic electroluminescence device of the present invention” as appropriate) is prepared, and this organic electric field is prepared. Film formation is performed using the composition for a light-emitting element.

The organic electroluminescent element composition of the present invention is usually used as a composition for forming an organic layer by a wet film forming method in an organic electroluminescent element having an organic layer disposed between an anode and a cathode. It is done. Among them, the composition for an organic electroluminescence device of the present invention is preferably used for forming a hole injection layer or a hole transport layer in the organic layer, and used for forming a hole transport layer. Is more preferable.
Here, when there is one layer between the anode and the light emitting layer in the organic electroluminescent element, this layer is referred to as a “hole transport layer”, and when there are two or more layers, The layers in contact with each other are referred to as “hole injection layers”, and the other layers are collectively referred to as “hole transport layers”. In addition, layers provided between the anode and the light emitting layer may be collectively referred to as a “hole injection / transport layer”.

-Arylamine polymer The composition for organic electroluminescent elements of the present invention contains at least one arylamine polymer of the present invention. In addition, the composition for organic electroluminescent elements of the present invention may contain one kind of the arylamine polymer of the present invention, or may contain two or more kinds in any combination and in any ratio. Also good.

  The amount of the arylamine polymer of the present invention contained in the composition for organic electroluminescence device of the present invention is usually 0.01% by weight or more, preferably 0.05% by weight or more, more preferably 0.1% by weight or more. It is usually 50% by weight or less, preferably 20% by weight or less, more preferably 10% by weight or less. If the amount of the arylamine polymer of the present invention is too small, it may be difficult to obtain a preferable film thickness as the charge transport layer of the organic electroluminescent device. If the amount is too large, the viscosity of the composition for the organic electroluminescent device significantly increases. It may be difficult to handle.

-Solvent The composition for organic electroluminescent elements of the present invention usually contains a solvent. This solvent is preferably one that dissolves the arylamine polymer of the present invention. Specifically, a solvent in which the arylamine polymer of the present invention is usually 0.05% by weight or more, preferably 0.5% by weight or more, and more preferably 1% by weight or more is suitable.

  Examples of solvents include: aromatic solvents such as toluene, xylene, methicylene, cyclohexylbenzene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene, o-dichlorobenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene Aliphatic ethers such as glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, Ether solvents such as aromatic ethers such as 2,3-dimethylanisole and 2,4-dimethylanisole; aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate; phenyl acetate, propylene And organic solvents such as; phenyl phosphate, methyl benzoate, ethyl benzoate, isopropyl benzoate, propyl benzoate, ester solvents such as aromatic esters such as benzoic acid n- butyl. In addition, 1 type may be used for a solvent and it may use 2 or more types together by arbitrary combinations and arbitrary ratios.

Among them, as a solvent contained in the composition for organic electroluminescent elements of the present invention, a solvent having a surface tension at 20 ° C. of usually less than 40 dyn / cm, preferably 36 dyn / cm or less, more preferably 33 dyn / cm or less. Is preferred.
In the case of forming a layer by crosslinking the arylamine polymer after applying the composition for organic electroluminescent elements of the present invention, it is preferable that the affinity with the base is high. This is because the uniformity of the film quality greatly affects the uniformity and stability of light emission of the organic electroluminescence device. Therefore, the composition for organic electroluminescent elements used in the wet film-forming method is required to have a low surface tension so as to form a uniform coating film with higher leveling properties. Therefore, it is preferable that a uniform layer containing the arylamine polymer of the present invention can be formed by using a solvent having a low surface tension as described above, and thus a uniform crosslinked layer can be formed. It is.

  Specific examples of the 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, trifluoromethoxyanisole, penta Examples include fluoromethoxybenzene, 3- (trifluoromethyl) anisole, ethyl (pentafluorobenzoate), and the like.

On the other hand, as a solvent contained in the composition for organic electroluminescent elements of the present invention, a solvent having a vapor pressure at 25 ° C. of usually 10 mmHg or less, preferably 5 mmHg or less, and usually 0.1 mmHg or more is preferable. . By using such a solvent, it is possible to prepare a composition for an organic electroluminescent device suitable for a process for producing an organic electroluminescent device by a wet film forming method and suitable for the properties of the arylamine polymer of the present invention. Because it can.
Specific examples of such a solvent include the above-described aromatic solvents such as toluene, xylene, and methicylene, ether solvents, and ester solvents.

  By the way, moisture may cause deterioration of the performance of the organic electroluminescent element, and in particular, may promote a decrease in luminance during continuous driving. Therefore, in order to reduce moisture remaining during wet film formation as much as possible, among the above solvents, those having a water solubility at 25 ° C. of preferably 1% by weight or less are preferred, and solvents having a water content of 0.1% by weight or less Is more preferable.

  The concentration of the solvent contained in the composition for organic electroluminescent elements of the present invention is usually 10% by weight or more, preferably 30% by weight or more, more preferably 50% by weight or more, and particularly preferably 80% by weight or more. Thereby, the flatness and uniformity of the formed layer can be improved.

-Other component The composition for organic electroluminescent elements of this invention may contain other components other than the arylamine polymer and solvent of this invention, unless the effect of this invention is impaired remarkably.

Examples of other components include additives, and examples of additives include additives (crosslinking accelerators) for promoting crosslinking.
Specific examples of additives that promote crosslinking include polymerization initiators or polymerization accelerators such as alkylphenone compounds, acylphosphine oxide compounds, metallocene compounds, oxime ester compounds, azo compounds, onium salts; condensed polycyclic hydrocarbons, Examples thereof include photosensitizers such as porphyrin compounds and diaryl ketone compounds. In addition, these may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

  Moreover, when it contains an additive, as the solvent, both the arylamine polymer of the present invention and the additive are usually 0.05% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more. It is preferable to use a solvent that can be dissolved. This is to prevent the arylamine polymer and additives from precipitating during storage.

Furthermore, the composition for an organic electroluminescent device of the present invention comprises a polymer other than the arylamine polymer of the present invention, a light emitting material, a hole transporting compound, an electron transporting compound, depending on the type of the organic layer to be formed. Further, it may contain an electron accepting compound.
In addition, the composition for organic electroluminescent elements of this invention may contain only 1 type of other components, and may contain 2 or more types by arbitrary combinations and arbitrary ratios.

-Film-forming method The composition for organic electroluminescent elements of the present invention is usually applied to a predetermined application target surface by a wet film-forming method, and then the arylamine polymer is crosslinked to form a desired organic layer as a crosslinked layer. Form.

  As the application target surface, for example, it is applied to the surface of a layer corresponding to the lower layer of the organic layer to be formed, such as a substrate or another layer (surface). Since the organic layer formed using the composition for organic electroluminescent elements of the present invention is preferably a hole transport layer, this organic layer is usually formed on the hole injection layer or on the anode. Formed. Hereinafter, the case where the hole transport layer is formed will be described as an example.

  Examples of wet deposition methods include spin coating, dip coating, die coating, bar coating, blade coating, roll coating, spray coating, capillary coating, ink jet, screen printing, and gravure printing. This method is a method of applying using a solvent-containing ink (corresponding to a composition for an organic electroluminescent element), such as a method, a flexographic printing method, and offset printing. Among these, a die coating method, a roll coating method, a spray coating method, an ink jet method, or a flexographic printing method is preferable from the viewpoint of easy patterning. Of these, spin coating, spray coating, and ink jet are preferred. This is because the liquid property unique to the wet film-forming composition used in the organic electroluminescence device is met.

  After applying the composition for organic electroluminescent elements of the present invention, the arylamine polymer in the applied film is usually crosslinked. This is for preventing the component of the film | membrane apply | coated using the composition for organic electroluminescent elements of this invention from melt | dissolving in the layer formed on it. Specifically, when a hole transport layer is formed using the composition for organic electroluminescent elements of the present invention, and a light emitting layer is formed on the hole transport layer, a coating composition for coating the light emitting layer is used. This is to prevent the formed hole transport layer from being dissolved in the product. For this reason, after apply | coating the composition for organic electroluminescent elements of this invention, it is preferable to raise | generate crosslinking to the arylamine polymer of this invention, and to reduce the solubility of a film | membrane.

  In order to cause the crosslinking, for example, heating or irradiation with electromagnetic energy such as light may be performed. These heating and electromagnetic energy irradiation may be carried out independently or in any combination of a plurality of means. When performing in combination, the order of implementation is not particularly limited. It is also possible to combine heating and electromagnetic energy irradiation.

When cross-linking is caused by heating, the heating conditions are not particularly limited as long as the cross-linking proceeds, but the heating temperature is usually 120 ° C. or higher, preferably 150 ° C. or higher, and usually 400 ° C. or lower, preferably 300 ° C. or lower. Next, the layer formed using the composition for organic electroluminescent elements of the present invention is heated. If the temperature is too low, the crosslinking may not proceed, and if the temperature is too high, the element may be deteriorated.
The heating time is usually 1 minute or longer, preferably 5 minutes or longer, and is usually 24 hours or shorter, preferably 3 hours or shorter. If the time is too short, the crosslinking may not proceed sufficiently, and if it is too long, the cost may increase.
Although it does not specifically limit as a heating means, Means, such as mounting the laminated body which has the formed layer, for example on a hotplate, or heating in oven, is used.
As specific heating conditions, for example, conditions such as heating on a hot plate at 120 ° C. or more for 1 minute or more can be used.

In addition, when crosslinking is caused by irradiation with electromagnetic energy such as light, the irradiation conditions are not particularly limited as long as the crosslinking proceeds.
As an irradiation method of electromagnetic energy, when irradiating light, for example, a method of directly using an ultraviolet / visible / infrared light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a halogen lamp, an infrared lamp; And a method of irradiating using a mask aligner having a built-in light source, a conveyor-type light irradiator, and the like. Moreover, when performing electromagnetic energy irradiation other than light, the method of irradiating using the apparatus (what is called a microwave oven) which irradiates the microwave generated with the magnetron, etc. are mentioned, for example.
As the irradiation time, it is preferable to set conditions necessary for lowering the solubility of the film, usually 0.1 seconds or more, preferably 1 minute or more, and usually 10 hours or less, preferably 1 hour or less. To do. If the time is too short, the crosslinking may not proceed sufficiently, and if it is too long, the cost may increase.

  In order to reduce the amount of moisture contained in the organic layer obtained after implementation and / or the amount of moisture adsorbed on the surface, the heating and electromagnetic energy irradiation described above are performed in an atmosphere not containing moisture, such as a nitrogen gas atmosphere. Preferably it is done. For the same purpose, when combined heating and / or electromagnetic energy irradiation is performed, 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.

[4. Organic electroluminescent device]
The organic electroluminescent device of the present invention comprises a substrate, an anode, one or more organic layers, and a cathode in this order, and at least one of the organic layers is a network in which the arylamine polymer of the present invention is crosslinked. A layer containing a polymer, that is, a crosslinked layer.

  Examples of the organic layer include a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron transport layer, and an electron injection layer. The organic electroluminescent device of the present invention preferably contains a network polymer obtained by crosslinking the arylamine polymer of the present invention in the hole injection layer and / or the hole transport layer among these organic layers. More preferably, the layer contains a network polymer obtained by crosslinking the arylamine polymer of the present invention. Thereby, an organic electroluminescent element having a long life, low voltage, and high power efficiency can be realized.

  Moreover, the organic electroluminescent element of this invention has a positive hole injection layer, a positive hole transport layer, and a light emitting layer at least, and it is preferable that all these are formed by the wet film-forming method. This is because the layer containing the network polymer cross-linked with the arylamine polymer of the present invention can be easily laminated by utilizing the excellent insolubility with respect to the organic solvent. In such an organic electroluminescent device, when the organic layer between the anode and the cathode is formed by a wet film forming method, the material for each layer described later is dispersed or dissolved in a solvent to form a wet film forming composition. (The above-mentioned composition for an organic electroluminescent element corresponds to this) and a film may be formed using this wet film-forming composition.

Hereinafter, with reference to the drawings, a layer structure and a general formation method thereof will be described for one embodiment of the organic electroluminescence device of the present invention. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented without departing from the gist of the present invention.
FIG. 1 is a cross-sectional view schematically showing the layer structure of the organic electroluminescent element of this embodiment. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is a hole blocking layer, 7 is an electron transport layer, 8 is an electron injection layer, 9 represents each cathode.

(Substrate 1)
The substrate 1 serves as a support for the organic electroluminescent element.
Although the material of the board | substrate 1 is not restrict | limited, For example, quartz, glass, a metal, a plastic etc. are mentioned. Any one of these materials may be used, or two or more of these materials may be used in any combination and ratio.

Although the shape of the board | substrate 1 is not restrict | limited, As an example, the shape etc. which combined a board | plate, a sheet | seat, a film, foil, etc. or these 2 types or more are mentioned.
Among them, the substrate 1 is preferably a glass substrate or a transparent synthetic resin substrate such as polyester, polymethacrylate, polycarbonate, or polysulfone.

  However, it is desirable to pay attention to gas barrier properties when using a synthetic resin substrate. This is because if the gas barrier property of the substrate 1 is too small, the organic electroluminescence element may be deteriorated by the outside air that has passed through the substrate 1. For this reason, it is preferable to ensure gas barrier properties by providing, for example, a dense silicon oxide film on at least one surface of the synthetic resin substrate.

The thickness of the substrate 1 is not limited, but is usually in the range of 1 μm or more, preferably 50 μm or more, and usually 50 mm or less, preferably 3 mm or less. If the substrate 1 is too thin, the mechanical strength may be low, and if it is too thick, the weight of the element may increase excessively.
In addition, although the board | substrate 1 is good also as a structure which consists of a single layer, it is good also as a structure where several layers were laminated | stacked. In the latter case, the plurality of layers may be layers made of the same material, but may be layers made of different materials.

(Anode 2)
An anode 2 is formed on the substrate 1. The anode 2 plays a role of hole injection into the layer on the light emitting layer 5 side (usually, the hole injection layer 3 or the hole transport layer 4).

  The material of the anode 2 is arbitrary as long as it is a conductive material. For example, a metal such as aluminum, gold, silver, nickel, palladium, or platinum; a metal oxide such as an oxide of indium and / or tin; Metal halides such as copper iodide; carbon black; conductive polymers such as poly (3-methylthiophene), polypyrrole, and polyaniline; In addition, these materials may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

  In general, the anode 2 is often formed by a sputtering method, a vacuum deposition method, or the like. Further, for example, when forming the anode 2 using conductive particles such as fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, and conductive polymer fine powder, The anode 2 can also be formed by dispersing these in a suitable binder resin solution and applying the solution onto the substrate 1. Furthermore, 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 (Appl. Phys). Lett., 60, 2711, 1992).

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

The anode 2 usually has a single-layer structure, but it can also have a laminated structure made of a plurality of materials if desired.
Furthermore, the anode 2 may be formed integrally with the substrate 1 described above, and the anode 2 may also serve as the substrate 1.

  Further, for the purpose of removing impurities adhering to the anode 2 and adjusting the ionization potential to improve the hole injection property, the surface of the anode 2 is subjected to ultraviolet (UV) treatment, ozone treatment, plasma treatment, etc. It is preferable to perform treatment (for example, oxygen plasma treatment or argon plasma treatment).

(Hole injection layer 3)
A hole injection layer 3 is usually formed on the anode 2. The hole injection layer 3 is a layer having a function of transporting holes from the anode 2 to the light emitting layer 5.
In order to express this function, the hole injection layer 3 is preferably a layer containing a network polymer obtained by crosslinking the arylamine polymer of the present invention.

The method for forming the hole injection layer 3 is not particularly limited, but is preferably formed by a wet film formation method from the viewpoint of reducing dark spots. In addition, the wet film forming method provides a thin film that is homogeneous and free of defects as compared with the conventional vacuum vapor deposition method, has a short time for formation, and is industrially superior.
When the hole injection layer 3 is formed by a wet film formation method, the material for the hole injection layer 3 is usually mixed with an appropriate solvent (a solvent for the hole injection layer) to form a film forming composition (hole (Injection layer composition) is prepared, and this hole injection layer composition is applied onto a layer corresponding to the lower layer of the hole injection layer 3 (usually the anode 2) by an appropriate technique and dried. Thus, the hole injection layer 3 is formed. Furthermore, when the composition for positive hole injection layers contains the arylamine polymer of this invention, it is made to bridge | crosslink after application | coating.

-Hole transport compound As described above, the hole injection layer 3 preferably contains a network polymer obtained by crosslinking the arylamine polymer of the present invention. In this case, the network polymer functions as a hole transporting compound. Moreover, the composition for hole injection layers used in this case is a composition containing the arylamine polymer of the present invention (that is, the composition for organic electroluminescent elements of the present invention).

Further, in order to form the hole injection layer 3, it is possible to use a hole transporting compound other than the arylamine polymer of the present invention. In this case, as the hole transporting compound, a low molecular compound or a polymer compound may be used as long as it has a hole transporting ability.
The hole transporting compound is preferably a compound having an ionization potential of 4.5 eV or more and 6.0 eV or less from the viewpoint of a charge injection barrier from the anode 2 to the hole injection layer 3. From this point of view, examples of hole transporting compounds include aromatic amine compounds, phthalocyanine derivatives, porphyrin derivatives, oligothiophene derivatives, polythiophene derivatives, benzylphenyl compounds, compounds in which tertiary amines are linked by a fluorene group, hydrazone compounds, Examples include silazane compounds, silanamine derivatives, phosphamine derivatives, quinacridone compounds, and phthalocyanine derivatives.

  Among these, an aromatic amine compound is preferable from the viewpoint of being amorphous and a visible light transmittance, and an aromatic tertiary amine compound is particularly preferable. Here, the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine. The kind of the aromatic tertiary amine compound is not particularly limited, but from the viewpoint of uniform light emission due to the surface smoothing effect, a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less (a polymer in which repeating units are linked) is more preferable.

Preferable examples of the aromatic tertiary amine polymer compound include a polymer compound having a repeating unit represented by the following formula (3).

(In Formula (3), Ar ⁵ and Ar ⁶ each independently represent an aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group that may have a substituent. .Ar ⁷ to Ar ⁹ representing are each independently, optionally substituted aromatic hydrocarbon group, or .X ¹ representing an aromatic heterocyclic group which may have a substituent Represents a linking group selected from the following group of linking groups, and among Ar ^{5 to} Ar ⁹ , two groups bonded to the same N atom may be bonded to each other to form a ring. )

(In the above formulas, Ar ^{10 to} Ar ¹⁴ and Ar ^{16 to} Ar ¹⁹ are each independently an aromatic hydrocarbon group which may have a substituent, or an aromatic which may have a substituent. Represents a heterocyclic group, and Ar ¹⁵ and Ar ²⁰ each independently represents an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. R ¹⁰ and R ¹¹ each independently represents a hydrogen atom or an arbitrary substituent.)

Ar ^{5 to} Ar ²⁰ each independently represents an aromatic hydrocarbon group which may have a substituent, or an aromatic heterocyclic group which may have a substituent. These may be the same or different from each other. Moreover, these groups may further have a substituent. The molecular weight of the substituent is usually 400 or less, and preferably 250 or less.

Ar ⁵ and Ar ⁶ are each independently a benzene ring, naphthalene ring, phenanthrene ring, thiophene ring, pyridine, from the viewpoint of the solubility, heat resistance, hole injection / transport properties of the aromatic tertiary amine polymer compound A group derived from a ring is preferable, and a phenyl group (a group derived from a benzene ring) and a naphthyl group (a group derived from a naphthalene ring) are more preferable.

Moreover, as Ar < ⁷ > -Ar < ⁹ >, the group derived from a benzene ring, a naphthalene ring, a triphenylene ring, and a phenanthrene ring is preferable each independently from the point of hole injection | pouring and transport property including heat resistance and oxidation-reduction potential, A phenylene group (a group derived from a benzene ring), a biphenylene group (a group derived from a benzene ring), and a naphthylene group (a group derived from a naphthalene ring) are more preferable.

Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by the formula (3) include those described in WO 2005/089024 pamphlet.
In addition, the hole transportable compound may contain any 1 type and may contain 2 or more types. In the case of containing two or more kinds of hole transporting compounds, the combination is arbitrary, but one or more kinds of aromatic tertiary amine polymer compounds and one or two kinds of other hole transporting compounds. It is preferable to use the above in combination.

  The concentration of the hole transporting compound (including the arylamine polymer of the present invention) in the composition for a hole injection layer is arbitrary as long as the effects of the present invention are not significantly impaired, but the film thickness is uniform. In general, it is 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.5% by weight or more, and usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight. It is as follows. If the concentration is too low, defects may occur in the hole injection layer 3 to be formed, and if the concentration is too high, film thickness unevenness may occur.

-Electron-accepting compound It is preferable that the positive hole injection layer 3 contains an electron-accepting compound, Therefore, it is preferable that the composition for positive hole injection layers also contains an electron-accepting compound. As the electron-accepting compound, a compound having an oxidizing power and an ability to accept one electron from the above-described hole-transporting compound is preferable. Specifically, a compound having an electron affinity of 4 eV or more is preferable, and a compound of 5 eV or more is more preferable.

  Examples of the electron-accepting compound include a triaryl boron compound, a metal halide, a Lewis acid, an organic acid, an onium salt, a salt of an arylamine and a metal halide, and a salt of an arylamine and a Lewis acid. 1 type, or 2 or more types of compounds etc. chosen from are mentioned. More specifically, an onium salt substituted with an organic group such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate or triphenylsulfonium tetrafluoroborate (WO 2005/089024) High-valent inorganic compounds such as iron (III) chloride (Japanese Patent Laid-Open No. 11-251067) and ammonium peroxodisulfate; cyano compounds such as tetracyanoethylene, tris (pendafluorophenyl) borane (Japanese Patent Laid-Open No. 2003-31365) Aromatic boron compounds; fullerene derivatives; iodine and the like. In addition, only 1 type may be used for an electron-accepting compound, and 2 or more types may be used together by arbitrary combinations and arbitrary ratios.

Since these electron accepting compounds oxidize the hole transporting compound, the conductivity of the hole injection layer 3 can be improved.
The content of the electron-accepting compound with respect to the hole-transporting 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.

Solvent At least one of the solvents contained in the composition for the hole injection layer is preferably a solvent that can dissolve the material of the hole injection layer 3.
Moreover, the boiling point of a solvent is 110 degreeC or more normally, Preferably it is 140 degreeC or more, More preferably, it is 200 degreeC or more, and is 400 degrees C or less normally, Preferably it is 300 degrees C or less. If the boiling point of the solvent is too low, the drying rate of the formed film is high and the film quality may deteriorate. Moreover, when the boiling point of the solvent is too high, the temperature of the drying process increases, which may adversely affect other layers and the substrate 1 (for example, a glass substrate).

  Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents and the like. Specifically, examples of the ether solvent include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3- And aromatic ethers such as dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, and 2,4-dimethylanisole. Examples of the ester solvent include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate. Further, examples of the aromatic hydrocarbon solvent include toluene, xylene, cyclohexylbenzene, 3-iropropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, and methylnaphthalene. Etc. Examples of the amide solvent include N, N-dimethylformamide, N, N-dimethylacetamide, and the like. In addition, dimethyl sulfoxide and the like can also be used as a solvent.

Among the solvents described above, a solvent having a high ability to dissolve the material of the hole injection layer 3 (dissolution ability) or a high affinity with the material is preferable. This is because a composition having a concentration excellent in the efficiency of the film forming process can be prepared by arbitrarily setting the concentration of the composition for the hole injection layer.
In addition, 1 type may be used for a solvent and it may use 2 or more types together by arbitrary combinations and arbitrary ratios.

-Other components As a material of the positive hole injection layer 3, as long as the effect of this invention is not impaired remarkably, you may contain another component other than a positive hole transport compound and an electron-accepting compound. Examples of other components include various light emitting materials, electron transporting compounds, binder resins, and coating property improving agents. In addition, 1 type may be used for another component and it may use 2 or more types together by arbitrary combinations and arbitrary ratios.

-Film-forming method After preparing the composition for positive hole injection layers, this composition is apply | coated on the layer (usually anode 2) applicable to the lower layer of the positive hole injection layer 3 with a wet film-forming method, and it dries. Thus, the hole injection layer 3 is formed. After the application, it is usually dried by heating or the like. The heating means used in the heating step is not limited as long as the effects of the present invention are not significantly impaired. Examples of the heating means include a clean oven, a hot plate, infrared rays, a halogen heater, and microwave irradiation. Among them, a clean oven and a hot plate are preferable in order to uniformly apply heat to the entire film. However, when the composition for hole injection layers contains the arylamine polymer of the present invention, crosslinking is performed after coating.

In the case of forming a layer by a vacuum deposition method, first, one or more materials (hole transporting compound, electron accepting compound, etc.) are put in a crucible installed in a vacuum vessel (two or more types). When using the material, put it in each crucible) and evacuate the inside of the vacuum vessel to about 10 ⁻⁴ Pa with a suitable vacuum pump. Then, the crucible is heated (each crucible is heated when two or more materials are used), and the evaporation amount is controlled to evaporate (when two or more materials are used, the evaporation amount is controlled independently). The hole injection layer 3 is formed on the anode of the substrate placed facing the crucible. When two or more kinds of materials are used, a mixture thereof can be put in a crucible, heated and evaporated to be used for forming the hole injection layer 3.

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. If the film thickness is too thin, the hole injection ability may be insufficient, and if it is too thick, the resistance may be increased.
The hole injection layer 3 may have a single layer structure, or may have a structure in which a plurality of layers are stacked. In the latter case, the plurality of layers may be layers made of the same material or layers made of different materials.

(Hole transport layer 4)
The hole transport layer 4 is usually formed on the hole injection layer 3 when the hole injection layer 3 is provided and on the anode 2 when the hole injection layer 3 is not provided. The hole transport layer 4 is preferably formed of a material having a high hole transport capability and capable of efficiently transporting injected holes. Therefore, the hole transport layer 4 has a low ionization potential, high transparency to visible light, high hole mobility, excellent stability, and trapping impurities are generated during manufacture and use. It is preferable to form with the material which is hard to carry out. Furthermore, in many cases, since the hole transport layer 4 is in contact with the light emitting layer 5, it does not quench the light emitted from the light emitting layer 5 or form an exciplex with the light emitting layer 5 to reduce the efficiency. Is preferred.

  In order to express these functions, the hole transport layer 4 preferably contains a network polymer obtained by crosslinking the arylamine polymer of the present invention. In this case, the hole transport layer 4 can be formed by applying the composition for organic electroluminescent elements of the present invention as described above and then crosslinking the arylamine polymer of the present invention.

  Moreover, the positive hole transport layer 4 can also be formed with compounds other than the arylamine polymer of this invention. Also in this case, usually, a wet film-forming method is used as in the case of using the arylamine polymer of the present invention. Specifically, the hole transport layer 4 material is mixed with an appropriate solvent (hole transport layer solvent) to prepare a film-forming composition (hole transport layer composition). The hole transport layer 4 is formed by applying the composition for the transport layer on the layer (usually the anode 2 or the hole injection layer 3) corresponding to the lower layer of the hole transport layer 4 by an appropriate technique and drying. Form. Further, after film formation, crosslinking may be performed.

In addition to the arylamine polymer of the present invention, examples of the compound serving as the material for the hole transport layer 4 include two compounds represented by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl. Aromatic diamines containing the above tertiary amines and having two or more condensed aromatic rings substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234681), 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) ) Aromatic amine compounds having a starburst structure such as triphenylamine (J. Lumin., 72-74, 985, 1997), aromatic amine compounds comprising a tetramer of triphenylamine (Chem. Commune) , 2175, 1996), spiro compounds such as 2,2 ′, 7,7′-tetrakis- (diphenylamino) -9,9′-spirobifluorene (Synth. Metals, 91, 209, 1997), and carbazole derivatives such as 4,4′-N, N′-dicarbazolebiphenyl.
Furthermore, as a compound used as the material of the hole transport layer 4, for example, polyvinyl carbazole, polyvinyl triphenylamine (JP-A-7-53953), polyarylene ether sulfone (Polym. Adv. Tech., 7, p. 33, 1996).
In addition, these compounds may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

  In addition, even when a compound other than the arylamine polymer of the present invention is used, the hole transport layer 4 can be obtained by converting the crosslinkable compound into heat and / or active energy rays (ultraviolet rays, electron beams, infrared rays, microwaves, etc.). A crosslinked layer obtained by crosslinking by irradiation or the like is preferable. In this case, the crosslinkable group is not particularly limited, but for example, a group containing an unsaturated double bond, a cyclic ether, benzocyclobutane, or the like is preferable.

Examples of the crosslinkable compound capable of crosslinking as described above include the monomers, oligomers, and polymers having the crosslinkable group described above, and among these, polymers are preferable. Specific examples of the crosslinking compound, a triarylamine derivative, a carbazole derivative, a fluorene derivative, 2,4,6-triphenyl pyridine derivatives, C ₆₀ derivatives, oligothiophene derivatives, phthalocyanine derivatives, porphyrin derivatives, condensed polycyclic aromatic Derivatives, metal complex derivatives and the like. Among these, a compound having a partial structure of triphenylamine and a crosslinkable group is particularly preferable because of its high electrochemical stability and charge transport ability.
In addition, 1 type may be used for a crosslinkable compound and it may use 2 or more types together by arbitrary combinations and arbitrary ratios.

The film formation of the hole transport layer 4 may be generally performed according to the method described as the film formation method of the composition for organic electroluminescent elements of the present invention.
The hole transport layer 4 can also be formed by a vacuum deposition method in the same manner as the hole injection layer 3.

  The thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and is usually 300 nm or less, preferably 100 nm or less. If the film thickness is too thin, the characteristics of the anode 2 may be affected, and if it is too thick, the film quality may be deteriorated.

(Light emitting layer 5)
When the hole injection layer 3 or the hole transport layer 4 is provided, the light emitting layer 5 is provided on the hole transport layer 4. The light emitting layer 5 is a layer that is excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 between the electrodes 2 and 9 to which an electric field is applied, and becomes a main light emitting source. is there.

  The light emitting layer 5 contains at least a material having a light emitting property (light emitting material) as a constituent material thereof, and preferably a compound having a hole moving property (hole transporting compound) or an electron transfer. A compound (electron transporting compound) having the following properties: Furthermore, the light emitting layer 5 may contain other components as long as the effects of the present invention are not significantly impaired. In addition, when forming the light emitting layer 5 with a wet film-forming method, it is preferable to use a low molecular weight material in any case.

-Light-emitting material There is no particular limitation on the light-emitting material, and a material that emits light at a desired light emission wavelength and has good light emission efficiency may be used. Examples thereof include fluorescent materials (also referred to as fluorescent dyes), phosphorescent materials, and the like. From the viewpoint of internal quantum efficiency, phosphorescent materials are preferred.
For the purpose of improving the solubility in a solvent, it is preferable to reduce the symmetry and rigidity of the molecules of the luminescent material, or to introduce a lipophilic substituent such as an alkyl group.

Hereinafter, although the example of a fluorescent dye is mentioned among light emitting materials, a fluorescent dye is not limited to the following illustrations.
Examples of fluorescent dyes that give blue light emission (blue fluorescent dyes) include naphthalene, perylene, pyrene, anthracene, coumarin, chrysene, p-bis (2-phenylethenyl) benzene, and derivatives thereof.
Examples of fluorescent dyes that give green light emission (green fluorescent dyes) include quinacridone derivatives, coumarin derivatives, and aluminum complexes such as Al (C ₉ H ₆ NO) ₃ .
Examples of fluorescent dyes that give yellow light (yellow fluorescent dyes) include rubrene and perimidone derivatives.
Examples of fluorescent dyes that give red luminescence (red fluorescent dyes) include DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran) compounds, benzopyran derivatives, rhodamine derivatives, benzoates. Examples thereof include thioxanthene derivatives and azabenzothioxanthene.

Examples of phosphorescent materials include long-period periodic tables (hereinafter referred to as long-period periodic tables when referred to as “periodic tables” unless otherwise specified). And an organometallic complex containing a metal selected from:
Preferred examples of the metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold.
On the other hand, as the ligand of the complex, for example, a ligand in which a (hetero) aryl group such as a (hetero) arylpyridine ligand or a (hetero) arylpyrazole ligand is linked to pyridine, pyrazole, phenanthroline, or the like is used. Particularly preferred are phenylpyridine ligands and phenylpyrazole ligands. Here, the (hetero) aryl group represents an aryl group or a heteroaryl group.

  On the other hand, phosphorescent materials include, for example, tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, tris (2- Phenylpyridine) osmium, tris (2-phenylpyridine) rhenium, octaethyl platinum porphyrin, octaphenyl platinum porphyrin, octaethyl palladium porphyrin, octaphenyl palladium porphyrin, and the like.

The molecular weight of the luminescent material is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 100 or more, preferably 200 or more, more preferably 300 or more, still more preferably 400 or more, and usually 10,000 or less, preferably 5000. Hereinafter, more preferably 4000 or less, and still more preferably 3000 or less. If the molecular weight of the luminescent material is too small, the heat resistance will be significantly reduced, gas generation will be caused, the film quality will be reduced when the film is formed, or the morphology of the organic electroluminescent element will be changed due to migration, etc. There is a possibility of coming. On the other hand, if the molecular weight of the luminescent material is too large, it tends to be difficult to purify the luminescent material, or it may take time to dissolve in the solvent.
In addition, any 1 type may be used for a luminescent material, and 2 or more types may be used together by arbitrary combinations and arbitrary ratios.

  The ratio of the light emitting material in the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.05% by weight or more, preferably 0.3% by weight or more, more preferably 0.5% by weight or more. It is usually 35% by weight or less, preferably 25% by weight or less, more preferably 20% by weight or less. If the amount of the light emitting material is too small, uneven light emission may occur. If the amount is too large, the light emission efficiency may be reduced. In addition, when using together 2 or more types of luminescent material, it is made for the total content of these to be contained in the said range.

-Hole transport compound The light emitting layer 5 may contain a hole transport compound as a constituent material thereof. Here, among the hole transporting compounds, as the polymer compound, for example, the arylamine polymer of the present invention can be used. Examples of the low molecular weight hole-transporting compound include various compounds exemplified as the hole-transporting compound in the above-described hole injection layer section, for example, 4,4′-bis [N- ( An aromatic diamine represented by 1-naphthyl) -N-phenylamino] biphenyl, which contains two or more tertiary amines and has two or more condensed aromatic rings substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234811) ), 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) triphenylamine and other aromatic amine compounds having a starburst structure (Journal of Luminescence, 1997, Vol. 72-74, pp. 985) Aromatic amine compounds consisting of tetramers of triphenylamine (Chemical Communications, 1996, pp. 217). ), 2,2 ′, 7,7′-tetrakis- (diphenylamino) -9,9′-spirobifluorene (Synthetic Metals, 1997, Vol. 91, pp. 209) and the like. .
In the light emitting layer 5, one kind of hole transporting compound may be used, or two or more kinds may be used in any combination and in any ratio.

  The ratio of the hole transporting compound in the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight. These are usually 65% by weight or less, preferably 50% by weight or less, and more preferably 40% by weight or less. If the amount of the hole transporting compound is too small, it may be easily affected by a short circuit, and if it is too large, the film thickness may be uneven. In addition, when using together 2 or more types of hole transportable compounds, it is made for the total content of these to be contained in the said range.

-Electron transporting compound The light emitting layer 5 may contain an electron transporting compound as a constituent material thereof. Here, among the electron transporting compounds, examples of low molecular weight electron transporting compounds include 2,5-bis (1-naphthyl) -1,3,4-oxadiazole (BND), 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, bathocuproin), 2- (4-biphenylyl) -5- (p-tertiarybutylphenyl) -1,3,4-oxadiazole (tBu-PBD), 4 , 4′-bis (9-carbazole) -biphenyl (CBP) and the like.

  The light emitting layer 5 may contain only one kind of electron transporting compound, but may contain two or more kinds in any combination and in any ratio.

  The ratio of the electron transporting compound in the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.1% by weight or more, preferably 0.5% by weight or more, more preferably 1% by weight or more. It is usually 65% by weight or less, preferably 50% by weight or less, more preferably 40% by weight or less. If the amount of the electron transporting compound is too small, it may be easily affected by a short circuit, and if it is too large, the film thickness may be uneven. In addition, when using together 2 or more types of electron transport compounds, it is preferable to make these total content contain in the said range.

-Formation method of the light emitting layer 5 The light emitting layer 5 is normally formed by the wet film-forming method. Even in this case, since the hole injection layer 3 and the hole transport layer 4 are difficult to dissolve in the solvent by including the network polymer obtained by crosslinking the arylamine polymer of the present invention as described above, The light emitting layer 5 can be easily laminated.

  When forming the light emitting layer 5 by a wet film-forming method, the above-mentioned material is dissolved in an appropriate solvent (light emitting layer solvent) to prepare a light emitting layer composition, and the composition is applied and dried. Moreover, you may make it bridge | crosslink after application | coating as needed. Film formation, drying, crosslinking, and the like may be performed in the same manner as the hole injection layer 3 and the hole transport layer 4.

As a solvent for forming the light emitting layer 5 by a wet film forming method, any solvent can be used as long as the light emitting layer 5 can be formed. However, those capable of dissolving the light emitting material, the hole transporting compound, and the electron transporting compound are preferable. Specifically, the solubility of the light emitting material, the hole transporting compound or the electron transporting compound is usually 0.01% by weight or more, particularly 0.05% by weight or more, particularly 0.1% at normal temperature / normal pressure. It is preferable to dissolve by weight% or more.
Suitable examples of the solvent for the light emitting layer include the same solvents as those contained in the composition for organic electroluminescent elements. In addition, the solvent for light emitting layers may use 1 type, and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

  The ratio of the solvent for the light emitting layer to the composition for the light emitting layer is arbitrary as long as the effects of the present invention are not significantly impaired, but is usually 0.01% by weight or more, preferably 0.1% by weight or more, more preferably 0.8%. It is 5% by weight or more, usually 70% by weight or less, preferably 60% by weight or less, more preferably 50% by weight or less. In addition, when mixing and using 2 or more types of solvents as a solvent for light emitting layers, it is preferable to make it the sum total of these solvents satisfy | fill this range.

In the wet film forming method, the light emitting layer 5 is usually formed by drying the coating film obtained after applying the composition for the light emitting layer and removing the solvent for the light emitting layer. The method of the wet film forming method is not limited as long as the effect of the present invention is not significantly impaired, and any of the methods described above can be used.
In addition, when forming another organic layer with the wet film-forming method based on this invention, you may use a vapor deposition method or another method for formation of the light emitting layer 5. FIG.

  The thickness of the light emitting layer 5 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 3 nm or more, preferably 5 nm or more, and usually 200 nm or less, preferably 100 nm or less. If the thickness of the light emitting layer 5 is too thin, defects may occur in the film, and if it is too thick, the driving voltage may increase.

(Hole blocking layer 6)
A hole blocking layer 6 may be provided between the light emitting layer 5 and an electron injection layer 8 described later. The hole blocking layer 6 is a layer laminated on the light emitting layer 5 so as to be in contact with the interface of the light emitting layer 5 on the cathode 9 side.
The hole blocking layer 6 has a role of blocking holes moving from the anode 2 from reaching the cathode 9 and a role of efficiently transporting electrons injected from the cathode 9 toward the light emitting layer 5. Have

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 the material for the hole blocking layer satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanolato) aluminum, and the like. Mixed ligand complexes of: metal complexes such as bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolinato) aluminum binuclear metal complexes; distyryl biphenyl derivatives Styryl compounds (JP-A-11-242996); Triazole derivatives such as 3- (4-biphenylyl) -4-phenyl-5 (4-tert-butylphenyl) -1,2,4-triazole (JP-A-7 -41759); phenanthroline derivatives such as bathocuproine (JP-A-10-79297) and the like. That. Further, a compound having at least one pyridine ring substituted at the 2,4,6-positions described in International Publication No. 2005-022962 is also preferable as a material for the hole blocking layer.
In addition, the material of the hole-blocking layer 6 may use 1 type, and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

There is no restriction | limiting in the formation method of the hole-blocking layer 6. FIG. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.
The thickness of the hole blocking layer 6 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less. If the hole blocking layer 6 is too thin, the light emission efficiency may be reduced due to insufficient hole blocking capability. If the hole blocking layer 6 is too thick, the voltage of the device may be increased.

(Electron transport layer 7)
An electron transport layer 7 may be provided between the light emitting layer 5 and an electron injection layer 8 described later.
The electron transport layer 7 has a role of further improving the light emission efficiency of the device.

The physical properties required of the material constituting the electron transport layer 7 include that electrons injected from the cathode 9 can be efficiently transported in the direction of the light emitting layer 5 between the electrodes 2 and 9 to which an electric field is applied. . Examples of the material that satisfies such conditions include an electron transporting compound. Among them, usually, a compound that has high electron injection efficiency from the cathode 9 or the electron injection layer 8 and has high electron mobility and can efficiently transport injected electrons is used. For example, a metal complex such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), a metal complex of 10-hydroxybenzo [h] quinoline, an oxadiazole derivative, a distyrylbiphenyl derivative, Silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Pat. No. 5,645,948), quinoxaline compounds (JP-A-6-207169) Publication), phenanthroline derivative (Japanese Patent Laid-Open No. 5-331459), 2-t-butyl-9,10-N, N'-dicyanoanthraquinone diimine, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, Examples include n-type zinc selenide.
In addition, the material of the electron carrying layer 7 may use 1 type, and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

There is no restriction | limiting in the formation method of the electron carrying layer 7. FIG. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.
The thickness of the electron transport layer 7 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.

(Electron injection layer 8)
The electron injection layer 8 is a layer that plays a role of efficiently injecting electrons injected from the cathode 9 into the 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. In this case, the thickness of the electron injection layer 8 is preferably 0.1 nm or more and 5 nm or less.

  Furthermore, an organic electron transport compound represented by a metal complex such as a nitrogen-containing heterocyclic compound such as bathophenanthroline or an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium, or rubidium ( (As described in JP-A-10-270171, JP-A-2002-1000047, JP-A-2002-1000048, etc.), it is possible to improve the electron injection / transport properties and achieve excellent film quality. preferable. In this case, the film thickness is usually 5 nm or more, preferably 10 nm or more, and is usually 200 nm or less, preferably 100 nm or less.

In addition, the material of the electron injection layer 8 may use 1 type, and may use 2 or more types together by arbitrary combinations and arbitrary ratios.
There is no restriction | limiting in the formation method of the electron injection layer 8. FIG. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.

(Cathode 9)
The cathode 9 plays a role of injecting electrons into a layer on the light emitting layer 5 side (such as the electron injection layer 8 or the light emitting layer 5).
The material of the cathode 9 can be the same as the material used for the anode 2, but a metal having a low work function is preferable for efficient electron injection. For example, a suitable metal such as tin, magnesium, indium, calcium, aluminum, 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.
In addition, the material of the cathode 9 may use 1 type, and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

The film thickness of the cathode 9 is usually the same as that of the anode 2.
Furthermore, for the purpose of protecting the cathode 9 made of a low work function metal, if a metal layer (not shown) having a high work function and stable to the atmosphere is further laminated thereon, the stability of the device is increased. preferable. For this purpose, for example, metals such as aluminum, silver, copper, nickel, chromium, gold and platinum are used. In addition, these materials may use 1 type and may use 2 or more types together by arbitrary combinations and arbitrary ratios.

(Other layers)
The organic electroluminescent element according to the present invention may have another configuration without departing from the gist thereof. For example, as long as the performance is not impaired, an arbitrary layer may be provided between the anode 2 and the cathode 9 in addition to the layers 3 to 8 described above, and the optional layer is omitted. May be.

  Examples of the layer that may be included include an electron blocking layer. The electron blocking layer is a layer provided between the hole injection layer 3 or the hole transport layer 4 and the light emitting layer 5. This electron blocking layer prevents electrons moving from the light emitting layer 5 from reaching the hole injection layer 3 or the hole transport layer 4, thereby recombining holes and electrons in the light emitting layer 5. It plays a role of increasing the probability and confining the generated excitons in the light emitting layer 5 and efficiently transporting holes injected from the hole injection layer 3 in the direction of the light emitting layer 5. In particular, when a phosphorescent material or a blue light emitting material is used as the light emitting material, it is effective to provide an electron blocking layer.

  The characteristics required for the material of the electron blocking layer include a high hole transport ability, a large energy gap (difference between HOMO and LUMO), and a high excited triplet level (T1). Furthermore, when the light emitting layer 5 is produced by a wet film formation method, the electron blocking layer is also required to be compatible with the wet film formation. Examples of the material used for such an electron blocking layer include a copolymer of dioctylfluorene and triphenylamine typified by F8-TFB (International Publication No. 2004/084260).

In addition, the material of an electron blocking layer may use 1 type, and may use 2 or more types together by arbitrary combinations and arbitrary ratios.
There is no restriction | limiting in the formation method of an electron blocking layer. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.

Further, at the interface between the cathode 9 and the light emitting layer 5 or the electron transport layer 7, for example, lithium fluoride (LiF), magnesium fluoride (MgF ₂ ), lithium oxide (Li ₂ O), cesium carbonate (II) (CsCO ₃ ). It is also an effective method to improve the efficiency of the device by inserting an ultrathin insulating film (thickness is usually 0.1 nm to 5 nm) formed by the method (Applied Physics Letters, 1997, Vol. 70, pp.). 152; Japanese Patent Laid-Open No. 10-74586; see IEEE Transactions on Electron Devices, 1997, Vol. 44, pp. 1245; SID 04 Digest, pp. 154, etc.).

  Moreover, in the layer structure demonstrated above, it is also possible to laminate | stack components other than the board | substrate 1 in reverse order. For example, in the case of the layer configuration of FIG. 1, the other components on the substrate 1 are the cathode 9, the electron injection layer 8, the electron transport layer 7, the hole blocking layer 6, the light emitting layer 5, the hole transport layer 4, the positive layer. The hole injection layer 3 and the anode 2 may be provided in this order.

Furthermore, the organic electroluminescent element according to the present invention can be configured by, for example, laminating components other than the substrate between two substrates, at least one of which is transparent. Further, for example, a structure in which a plurality of components (light emitting units) other than the substrate are stacked (a structure in which a plurality of light emitting units are stacked) may be used. In that case, instead of the interface layer between the steps (between the light emitting units) (in the case where the anode is ITO and the cathode is Al, these two layers), for example, a charge made of vanadium pentoxide (V ₂ O ₅ ) or the like. When a generation layer (Carrier Generation Layer: CGL) is provided, a barrier between steps is reduced, which is more preferable from the viewpoint of light emission efficiency and driving voltage.

Furthermore, the organic electroluminescent element may be configured as a single organic electroluminescent element, or may be applied to a configuration in which a plurality of organic electroluminescent elements are arranged in an array, and the anode and the cathode are X- You may apply to the structure arrange | positioned at Y matrix form.
Moreover, each component 1-9 mentioned above may contain components other than having demonstrated as a material, unless the effect of this invention is impaired remarkably.

(Advantages of the organic electroluminescence device of the present invention)
Since the organic electroluminescent device of the present invention includes a layer containing a network polymer obtained by crosslinking the arylamine polymer of the present invention, it can be driven at a low voltage by taking advantage of the excellent properties of the arylamine polymer of the present invention. Various advantages such as high luminous efficiency and high driving stability can be exhibited. In general, the organic electroluminescent device of the present invention has high heat resistance, and further suppresses a decrease in light emission luminance, a voltage increase, generation of a non-light emitting portion (dark spot), a short-circuit defect, etc. during constant current driving. .

  Therefore, the organic electroluminescent device of the present invention is a flat panel display (for example, for OA computers or wall-mounted televisions), and a light source (for example, a light source of a copying machine, a liquid crystal display or an instrument) utilizing the characteristics as a surface light emitter. It can be applied to backlight light sources), display boards, and marker lamps, and its technical value is high.

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

[6. Organic EL lighting]
The organic EL lighting of the present invention includes the organic electroluminescent element of the present invention as described above. There is no restriction | limiting in particular about the model and structure of the organic EL illumination of this invention, It can assemble in accordance with a conventional method using the organic electroluminescent element of this invention.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and the present invention can be arbitrarily modified and implemented without departing from the gist thereof. In the following description, unless otherwise specified, dba represents dibenzylideneacetone, tBu represents a t-butyl group, THF represents tetrahydrofuran, Me represents a methyl group, Et represents an ethyl group, iPr represents an i-propyl group, Ph represents a phenyl group, Ac represents an acetyl group, DMSO represents dimethyl sulfoxide, TBAB represents tetrabutylammonium bromide, DME represents dimethoxyethane, and Tf ₂ O represents Represents trifluoromethanesulfonic anhydride, DMF represents dimethylformamide, dppf represents 1,1′-diphenylphosphinoferrocene, and NBS represents N-bromosuccinimide.

[I. Polymer synthesis]
(Synthesis Example 1)

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

(Synthesis Example 2)

  The target product 1 (8.11 g), 36 ml of tetrahydrofuran, 36 ml of ethanol, and 10% Pd / C (1.15 g) were charged, and the mixture was heated and stirred at 70 ° C. Hydrazine monohydrate (10.81 g) was slowly added dropwise thereto. After reacting for 2 hours, the mixture was allowed to cool, the reaction mixture was filtered through celite, and the filtrate was concentrated. Ethyl acetate was added to the filtrate, washed with water, and the organic layer was concentrated. The resulting crude product was purified by column chromatography (hexane / ethyl acetate) to obtain the desired product 2 (4.90 g).

(Synthesis Example 3)

  2-Nitrofluorene (25.0 g), 1-bromohexane (58.61 g), tetrabutylammonium bromide (7.63 g), and dimethyl sulfoxide (220 ml) were charged, and a 17M aqueous sodium hydroxide solution (35 ml) was slowly added dropwise. And allowed to react at room temperature for 3 hours. Ethyl acetate (200 ml) and water (100 ml) were added to the reaction mixture, and the mixture was stirred and separated. The aqueous layer was extracted with ethyl acetate, the organic layers were combined, dried over magnesium sulfate, and concentrated. The obtained crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to give the intended product 3 (44.0 g).

(Synthesis Example 4)

  10% Pd / C (8.6 g) was added to the target product 3 (44.0 g), tetrahydrofuran (120 ml), and ethanol (120 ml), and the mixture was heated and stirred at 50 ° C. Thereto, hydrazine monohydrate (58.0 g) was slowly added dropwise and reacted at this temperature for 3 hours. The reaction solution is allowed to cool, filtered through celite under reduced pressure, the filtrate is concentrated, the residue is added with methanol, and the crystallized crystals are collected by filtration and dried to obtain the desired product 4 (34.9 g). It was.

(Synthesis Example 5)

  Dichlorobis (acetonitrile) palladium (II) (212 mg, 0.03 equivalent) and copper iodide (104 mg, 0.02 equivalent) were put into a 200 mL four-necked flask through nitrogen, and nitrogen was bubbled beforehand. 75 mL of deaerated dioxane was added and stirred. To this solution, tri-t-butylphosphine (331 mg, 0.06 equivalent) was added and stirred at room temperature for 15 minutes. To this solution was added di-i-propylamine (3.31 g, 1.2 eq), 4-bromobenzocyclobutene 5.00 g (1.0 eq), and 20.3 g of 1,7-octadiyne (7. 0 equivalents) was added, and the mixture was allowed to react at room temperature for 9 hours. The obtained reaction mixture was distilled under a reduced pressure of 400 Pa at a bath temperature of 60 ° C. to remove light boiling components, then added with 50 mL of saturated brine and 5 mL of 1N hydrochloric acid, and extracted three times with ethyl acetate (30 mL). The ethyl acetate layer was washed twice with saturated brine (30 mL). When the ethyl acetate layer was concentrated, a crude product (7.7 g) was obtained. The crude product was purified by silica gel column chromatography (solvent: n-hexane / ethyl acetate mixed solvent) to obtain 2.78 g (48.9% yield, purity analyzed by gas chromatography 95.4%). The desired product 5 was obtained as a colorless oil.

(Synthesis Example 6)

  Nitrobenzene (3.64 g, 1.1 eq), potassium carbonate (5.06 g, 2.75 eq), copper iodide (111 mg, 0.044 eq) in a 100 mL 4-neck flask through which nitrogen was passed. ), 307 mg (0.088 equivalent) of triphenylphosphine, 623 mg of 5% Pd / C (0.022 equivalent as Pd), and dimethoxyethane / water degassed by bubbling nitrogen beforehand. 95 mL of the mixed solvent (volume ratio) was added and stirred at room temperature for 1 hour. A solution prepared by dissolving the target compound 5 (2.77 g, 1.0 equivalent) in 2 mL of dimethoxyethane was added to this solution, and the mixture was reacted by heating in a 70 ° C. bath (internal temperature 63 ° C.) for 7 hours. The resulting reaction mixture was filtered through celite, concentrated with an evaporator, 25 mL of 1N hydrochloric acid was added, and the mixture was extracted 3 times with ethyl acetate (30 mL). The resulting ethyl acetate layer was extracted 3 times with saturated brine (20 mL). Washed. The crude product obtained by concentrating the ethyl acetate layer was recrystallized from a mixed solvent of ethyl acetate-n-hexane to give 2.50 g (57.1% yield, purity 99.5% analyzed by liquid chromatography). ) Was obtained as very light yellow needle-like crystals.

(Synthesis Example 7)

  The target product 6 (2.31 g), 15 mL of tetrahydrofuran, and 15 mL of ethanol were added to a 100 mL eggplant flask and dissolved. Raney nickel 1.07 g (manufactured by Nikko Rica Co., Ltd., R-200) was added to the solution as a hydrogenation catalyst, and the mixture was replaced with hydrogen three times. The reaction solution was filtered through celite and concentrated to obtain 2.8 g of a crude product. This crude product was purified by silica gel column chromatography (solvent: n-hexane / ethyl acetate mixed solvent) to give 1.72 g (80.1% yield, purity 99.1% analyzed by liquid chromatography). The target product 7 was obtained as white needle-like crystals.

(Synthesis Example 8)

  In a nitrogen stream, 3-bromostyrene (5.0 g), 3-nitrophenylboronic acid (5.5 g), toluene: ethanol (80 ml: 40 ml), and 2M aqueous sodium carbonate solution (20 ml) were charged and heated to 60 ° C. The mixture was stirred and degassed for 30 minutes. Tetrakis (triphenylphosphine) palladium (0.95 g) was added and refluxed for 6 hours. After allowing to cool to room temperature, methylene chloride (100 ml) and water (100 ml) were added to the reaction mixture and the mixture was stirred and separated. The aqueous layer was extracted with methylene chloride, the organic layers were combined, dried over magnesium sulfate, and concentrated. did. The resulting crude product was purified by silica gel column chromatography (n-hexane / methylene chloride) to obtain the desired product 8 (5.5 g).

(Synthesis Example 9)

  In a nitrogen stream, the target product 8 (2.5 g), acetic acid (60 ml), ethanol (60 ml), 1N hydrochloric acid (2 ml), water (8 ml) and reduced iron (12.4 g) were charged and heated to reflux for 1 hour. The reaction mixture was filtered at room temperature, ethyl acetate (100 ml) and water (100 ml) were added, and the mixture was stirred and neutralized with a saturated aqueous solution of sodium hydrogen carbonate, separated, and the aqueous layer was extracted with ethyl acetate. The organic layers were combined. , Dried over magnesium sulfate and concentrated. The obtained crude product was purified by silica gel column chromatography (n-hexane / ethyl acetate) to give the intended product 9 (2.1 g).

(Synthesis Example 10)

  In a nitrogen stream, 1,2-dibromobenzene (21.0 g), 3-methoxyphenylboronic acid (29.9 g), toluene: ethanol (147 ml: 147 ml), and 2M aqueous sodium carbonate solution (295 ml) were charged at 60 ° C. The mixture was stirred and degassed for 30 minutes. Tetrakis (triphenylphosphine) palladium (6.17 g) was added and refluxed for 6 hours. After cooling to room temperature, water was added and the mixture was stirred and separated. The aqueous layer was extracted with toluene, the organic layers were combined, dried over magnesium sulfate, and concentrated. The obtained crude product was purified by silica gel column chromatography (n-hexane / methylene chloride) to obtain Intermediate 1 (15.5 g).

  Intermediate 1 (15.5 g) was dissolved in methylene chloride (70 ml) and concentrated sulfuric acid (1.4 g) was added. Iron chloride (21.6 g) was added slowly in small portions. After the reaction for 7 hours, methylene chloride (100 ml) was added and added to cold methanol, and the precipitated crystals were separated by filtration. The crude crystals were dissolved in methylene chloride (250 ml), washed with 1N hydrochloric acid (100 ml), the organic layer was filtered through celite, concentrated and washed with methanol to obtain Intermediate 2 (7.41 g). .

  Intermediate 2 (7.41 g) was dissolved in methylene chloride (110 ml), and boron tribromide (1M methylene chloride solution: 65 ml) was added under ice cooling, followed by stirring for 3 hours. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed with water, dried over magnesium sulfate, and concentrated. The precipitated crystals were washed with a methylene chloride / ethyl acetate (5/1) solution to obtain Intermediate 3 (6.58 g).

  To intermediate 3 (6.58 g) was added methylene chloride (130 ml) and trifluoromethanesulfonic anhydride (17.8 g) was added. Further, pyridine (4.4 g) was slowly added and reacted at room temperature for 5 hours. Precipitated crystals were separated by filtration, washed with water, washed with methanol, and washed twice with methylene chloride / methanol (1/9) to obtain Intermediate 4 (5.9 g).

  In a nitrogen stream, intermediate 4 (3.88 g), 4-nitrophenylboronic acid (2.72 g), toluene: ethanol (48 ml: 48 ml), and 2M aqueous sodium carbonate solution (24 ml) were charged and heated to 40 ° C. , Deaerated by stirring for 30 minutes. Tetrakis (triphenylphosphine) palladium (0.53 g) was added and refluxed for 6 hours. After cooling to room temperature, water was added and stirred, and the precipitated crystals were filtered off. Furthermore, the intermediate body 5 (2.35g) was obtained by hang-washing with ethyl acetate.

  Intermediate 5 (2.35 g) was dissolved in N, N-dimethylformamide (195 ml), 5% Pd / C (1.06 g) was charged, and the system was replaced with hydrogen, followed by 4 at 70 ° C. under hydrogen. Reacted for hours. The reaction solution was purged with nitrogen and filtered through Celite, and the filtrate was concentrated to about 30 ml and added to methanol. Further, water was added, and the crystallized crystal was separated by filtration to obtain the target product 10 (1.03 g).

(Synthesis Example 11)

The target product 10 (1.82 g), 2-bromo-9,9-dihexylfluorene (3.7 g), and tert-butoxy sodium (0.94 g) and toluene (25 ml) were charged, and the system was sufficiently filled with nitrogen. Replace and warm to 50 ° C. (solution A).
On the other hand, diphenylphosphinoferrocene (0.20 g) was added to a toluene 4 ml solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.09 g) and heated to 50 ° C. (solution B).
In a nitrogen stream, solution B was added to solution A and heated to reflux for 5 hours. After confirming the disappearance of the raw material, tetrahydrofuran was added and the mixture was filtered through Celite. The filtrate was concentrated and purified by silica gel column chromatography (n-hexane / ethyl acetate). The resulting crude crystals were n-hexane and methanol. After washing, the target product 11 (1.34 g) was obtained.

(Synthesis Example 12)

The target product 10 (0.50 g), 3- (3-bromophenyl) benzocyclobutene (0.63 g), tert-butoxy sodium (0.26 g), and toluene (15 ml) were charged, and the system was sufficiently filled with nitrogen. Replace and warm to 50 ° C. (solution A).
On the other hand, diphenylphosphinoferrocene (0.05 g) was added to a toluene 1 ml solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.02 g) and heated to 50 ° C. (solution B).
In a nitrogen stream, solution B was added to solution A and heated to reflux for 6 hours. After confirming the disappearance of the raw material, tetrahydrofuran was added and the mixture was filtered through celite. The filtrate was concentrated and purified by silica gel column chromatography (n-hexane / ethyl acetate) to obtain the desired product 12 (0.12 g). Obtained.

(Synthesis Example 13)

In a nitrogen stream, the target product 8 (2.8 g), 4-bromobenzocyclobutene (3.65 g), potassium carbonate (2.73 g), (n-C ₄ H ₉ ) ₄ Br (2.67 g), dehydration After DMF (76 ml) and palladium catalyst Pd ₂ (diphenylCl ₂ NOH) ₂ Cl ₂ 15.1 mg were reacted at 130 ° C. for 8 hours, ethyl acetate (100 ml) and water (100 ml) were added to the reaction solution at room temperature, and the mixture was stirred. The aqueous layer was extracted twice with ethyl acetate (100 ml). The organic layers were combined, dried over magnesium sulfate, and concentrated. Further, purification by silica gel column chromatography (n-hexane / ethyl acetate = 10/1) gave the target product 13 (trans, 1.7 g, LC: 98%).

(Synthesis Example 14)

  The target product 13 (1.6 g), acetic acid (30 ml), ethanol (30 ml), hydrochloric acid (1N, 1 ml), water (4 ml) and reduced iron (5.5 g) were refluxed for 2 hours in a nitrogen stream. The reaction mixture was filtered at room temperature, ethyl acetate (100 ml) and water (100 ml) were added, and the mixture was stirred and neutralized with a saturated aqueous solution of sodium hydrogen carbonate, separated, and the aqueous layer was extracted twice with ethyl acetate (50 ml). The organic layers were combined, dried over magnesium sulfate, and concentrated. Further, purification by silica gel column chromatography (n-hexane / ethyl acetate = 3/1) gave the target product 14 (1.3 g).

(Synthesis Example 15)

  3-Bromophenylboronic acid (10.0 g), m-diiodobenzene (8.21 g), sodium carbonate (15.83 g), toluene (150 mL), ethanol (150 mL) and water (75 mL) were placed in the reaction vessel. After charging and degassing under reduced pressure, tetrakis (triphenylphosphine) palladium (0) (1.726 g) was added under a nitrogen atmosphere. After stirring at 80 ° C. for about 4.5 hours, the mixture was allowed to cool to room temperature. Water was added to the reaction solution, followed by extraction with a mixed solvent of ethyl acetate-hexane, and the obtained organic layer was concentrated. The crude product was purified by silica gel column chromatography (hexane) to obtain the desired product 15 (7.39 g).

(Synthesis Example 16)

  Under a nitrogen atmosphere, p-dibromobenzene (50 g) and THF (740 mL) were charged and cooled to -78 ° C. A 1.55 M n-butyllithium hexane solution (125.7 mL) was added dropwise over about 40 minutes. After further stirring for about 1 hour, anthraquinone (15.44 g) was added. Further, after stirring for about 3 hours, the temperature was raised to room temperature over about 1 hour. After further stirring for about 3.5 hours, water (100 mL) was added, and THF was distilled off under reduced pressure. The mixture was extracted with ethyl acetate, and the organic layer was washed with water, dried over anhydrous sodium sulfate, filtered and concentrated. The obtained crude product was suspended and washed with a mixed solvent of methylene chloride-hexane, and then suspended and washed with methanol to obtain the intended product 16 (25.8 g).

(Synthesis Example 17)

  Under a nitrogen atmosphere, the target product 16 (25.7 g), acetic acid (400 mL), and zinc powder (27.4 g) were charged and heated to reflux. After 8 hours, acetic acid (190 mL) was added, and the mixture was further heated to reflux for about 8 hours. The mixture was allowed to cool to room temperature, water (400 mL) was added, and the mixture was collected by filtration and washed with water. The obtained solid was suspended in methylene chloride (2.5 L), insoluble matters were filtered off, and the filtrate was concentrated. The obtained crude product was dissolved in methylene chloride (3 L), purified by silica gel column chromatography (methylene chloride), suspended and washed with methylene chloride, and then suspended and washed with chloroform. 10.7 g) was obtained.

(Synthesis Example 18)

  Under a nitrogen atmosphere, m-dibromobenzene (25 g) and THF (370 mL) were charged and cooled to -78 ° C. A 1.6M n-butyllithium hexane solution (61 mL) was added dropwise over about 10 minutes. After further stirring for about 1 hour, anthraquinone (7.72 g) was added. Further, after stirring for about 1 hour, the temperature was raised to room temperature over about 1 hour. After further stirring for about 3.5 hours, water (150 mL) was added, and THF was distilled off under reduced pressure. The mixture was extracted with ethyl acetate, and the organic layer was washed with water, dried over anhydrous sodium sulfate, filtered and concentrated. The resulting crude product was suspended and washed with a methylene chloride-hexane mixed solvent to obtain the target product 18 (17.4 g).

(Synthesis Example 19)

  In a nitrogen atmosphere, the target product 18 (17.4 g), acetic acid (242 mL), and zinc powder (18.6 g) were charged and heated to reflux. After 10.5 hours, the mixture was allowed to cool to room temperature, water (250 mL) was added, and the mixture was filtered and washed with water. The obtained solid was suspended in methylene chloride (500 mL), insoluble matters were filtered off, the filtrate was concentrated, and suspended and washed with hexane. The obtained crude product was dissolved in methylene chloride (200 mL) and subjected to silica gel column chromatography (methylene chloride). The obtained solid was completely dissolved in 1,2-dimethoxyethane (102 mL) under heating and refluxing, slowly cooled to room temperature, and the precipitated solid was collected by filtration to obtain the intended product 19 (3.7 g). Obtained.

(Synthesis Example 20)

  In a reaction vessel, 1,3,5-tribromobenzene (22 g), 3-biphenylboronic acid (4.95 g), toluene (110 ml), and ethanol (100 ml) were charged and degassed by nitrogen bubbling for 10 minutes. It was. Sodium carbonate (7.9 g) and water (38 ml) were added to another container and deaerated by nitrogen bubbling while stirring. This aqueous solution was added to the reaction vessel, and tetrakis (triphenylphosphine) palladium (0) (866 mg) was immediately added, the temperature was raised, and the mixture was heated to reflux. After completion of the reaction, water was added to the reaction solution and extracted with toluene. Sodium sulfate was added to the obtained organic layer, dehydrated and dried, and concentrated. The crude product was purified by silica gel column chromatography (hexane / dichloromethane) to obtain the desired product 20 (7.51 g).

(Synthesis Example 21)

The target product 20 (7.0 g), bis (pinacolato) diboron (11.68 g), potassium acetate (9.71 g) and dimethylformamide (100 ml) were added, and stirring was started while nitrogen bubbling was performed. After 15 minutes, the nitrogen bubbling was changed to flow, PdCl ₂ (dppf) · CH ₂ Cl ₂ (660 mg) was added, and the temperature was raised to 80 ° C. After completion of the reaction, the reaction mixture was allowed to cool, extracted and washed with dichloromethane and water, dried over sodium sulfate and concentrated. The resulting crude product was purified by column chromatography (hexane / ethyl acetate) to obtain the desired product 21 (10 g).

(Synthesis Example 22)

  The target product 21 (5.8 g), 4-bromoiodobenzene (7.5 g), toluene (72 ml), and ethanol (72 ml) were charged into the reaction vessel and deaerated by performing nitrogen bubbling for 10 minutes. Sodium carbonate (7.6 g) and water (36 ml) were added to another container and deaerated by nitrogen bubbling while stirring. This aqueous solution was added to the reaction vessel, and tetrakis (triphenylphosphine) palladium (0) (1.0 g) was immediately added, and the temperature was raised and heated to reflux. After completion of the reaction, water was added to the reaction solution and extracted with dichloromethane. Sodium sulfate was added to the obtained organic layer, dehydrated and dried, and concentrated. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain the desired product 22 (3.9 g).

(Synthesis Example 23)

In a reaction vessel, toluene (100 ml), ethanol (50 ml), 4-bromophenylboronic acid (9.99 g), 1,3-diiodobenzene (8.41 g), sodium carbonate (8.41 g), and water 35 ml And nitrogen was blown into the system so that the atmosphere was sufficiently nitrogen and stirred. Tetrakis (triphenylphosphine) palladium (0.884g) was added there, and it heated up, and it was made to heat and reflux for 7 hours.
After completion of the reaction, water was added to the reaction solution and extracted with toluene. The obtained organic layer was washed with water twice, added with sodium sulfate, dehydrated and dried, and concentrated. The crude product was purified by silica gel column chromatography (hexane / toluene) to obtain the desired product 23 (3.54 g).

(Synthesis Example 24)

2-Bromo-9,9-dihexylfluorene (5.91 g), diphenylamine (2.37 g), tert-butoxypotassium (2.8 g), and 1,4-dioxane (100 ml) were charged, and the system was fully charged. The atmosphere was replaced with nitrogen and heated to 50 ° C. (solution A).
Meanwhile, tri-tert-butylphosphine (0.303 g) was added to a 25 ml 1,4-dioxane solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.34 g) and heated to 50 ° C. (solution B ).
In a nitrogen stream, solution B was added to solution A and heated to reflux for 3 hours. Further, 2-bromo-9,9-dihexylfluorene (1.2 g) was added, and the mixture was heated to reflux for 3 hours. The reaction solution was allowed to cool, then insoluble materials were removed by filtration, and the residue was purified by column chromatography to obtain the desired product 24 (12 g).

(Synthesis Example 25)

  The target product 24 (5.7 g) and N, N-dimethylformamide (100 ml) were charged, and the system was sufficiently purged with nitrogen and cooled to -5 ° C. In a nitrogen stream, a solution of N-bromosuccinimide (4.02 g) in N, N-dimethylformamide (40 ml) was added dropwise while keeping the temperature of the reaction solution at 0 ° C. or lower. The mixture was stirred at -5 ° C for 2.5 hours. After the reaction, ethyl acetate and water were added, and the organic layer was concentrated and purified by column chromatography to obtain the desired product 25 (6.4 g).

(Synthesis Example 26)

4-Bromo-benzocyclobutene (1.4 g), diphenylamine (1.3 g), tert-butoxy sodium (1.6 g), and toluene (50 ml) were charged, and the system was sufficiently purged with nitrogen. (Solution A).
On the other hand, tri-tert-butylphosphine (0.19 g) was added to a toluene (7 ml) solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.16 g) and heated to 50 ° C. (solution B).
In a nitrogen stream, solution B was added to solution A and heated to reflux for 8.5 hours. The reaction solution was allowed to cool, then insoluble materials were removed by filtration, and the residue was purified by column chromatography to obtain the desired product 26 (1.77 g).

(Synthesis Example 27)

  The target product 26 (1.65 g) and N, N-dimethylformamide (10 ml) were charged, and the system was sufficiently purged with nitrogen and cooled to -5 ° C. In a nitrogen stream, a solution of N-bromosuccinimide (2.16 g) in N, N-dimethylformamide (5 ml) was added dropwise while keeping the temperature of the reaction solution at 0 ° C. or lower. Stir at -5 ° C for 1 hour. After the reaction, methylene chloride and water were added, and the organic layer was concentrated and purified by column chromatography to obtain the desired product 27 (2.13 g).

(Synthesis Example 28)

  Dichloromethane (200 ml) was added to the reaction vessel under a nitrogen atmosphere to dissolve N-phenylcarbazole (2.29 g) and bis (pyridine) iodonium tetrafluoroborate (7.76 g). Next, trifluoromethanesulfonic acid (1.75 ml) was added dropwise under ice cooling, and the mixture was stirred for a whole day and night while gradually warming to room temperature. After completion of the reaction, 0.5M sodium thiosulfate aqueous solution was added to the reaction solution, and the mixture was extracted with dichloromethane. The obtained organic layer was washed with water, added with sodium sulfate, dehydrated and dried, and concentrated. Methanol was added to the crude product in dichloromethane to cause reprecipitation, and the precipitate was washed under methanol reflux conditions to obtain the desired product 28 (4.00 g).

(Synthesis Example 29)

  Add target 28 (4.00 g), p-bromophenylboronic acid (3.05 g), toluene (30 ml), ethanol (15 ml), and 2.6 M aqueous sodium carbonate solution (20 ml), and vibrate with an ultrasonic cleaner. The inside of the system was replaced with nitrogen. Tetrakis (triphenylphosphine) palladium (0.27 g) was added thereto, and the mixture was heated and stirred at 75 ° C. for 3 hours. After completion of the reaction, water was added to the reaction solution and extracted with dichloromethane. The obtained organic layer was dehydrated and dried by adding sodium sulfate and concentrated. The crude product was isolated by silica gel column chromatography (hexane / dichloromethane), and the target product 29 (2.25 g) was obtained by recrystallization purification from hot dimethoxyethane.

(Synthesis Example 30)

  Diethyl ether (100 ml) was added to the reaction vessel under a nitrogen atmosphere to dissolve 3,3′-dibromo-1,1′-biphenyl (9.00 g) and cooled to −78 ° C. A 1.6M n-butyllithium hexane solution (40 ml) was added dropwise thereto over 15 minutes, and the mixture was stirred at -78 ° C for 1 hour, then warmed to 0 ° C and further stirred for 2 hours. On the other hand, a solution prepared by dissolving trimethyl borate (33 ml) in diethyl ether (160 ml) and cooling to −78 ° C. in a separate container under a nitrogen atmosphere was added dropwise to the above mixture over 45 minutes, The solution was stirred for 4 hours while gradually returning the solution temperature to room temperature. After completion of the reaction, 3N hydrochloric acid (144 ml) was gradually added to the reaction solution at 0 ° C., and after stirring for 4 hours at room temperature, a white precipitate was recovered with a 3G glass funnel. The product was washed with water and diethyl ether and dried to give the intended product 30 (3.16 g).

(Synthesis Example 31)

  The target product 30 (2.85 g), p-iodobromobenzene (6.68 g), toluene (40 ml), ethanol (20 ml), and 2.6 M aqueous sodium carbonate solution (30 ml) were added, and vibrations were applied using an ultrasonic cleaner. The system was degassed with vacuum, and the system was replaced with nitrogen. Tetrakis (triphenylphosphine) palladium (0.41 g) was added thereto, and the mixture was heated and stirred at 75 ° C. for 6 hours. After completion of the reaction, water and toluene were added to the reaction solution, and the toluene layer was washed with 0.1N hydrochloric acid and water, sodium sulfate was added, dehydrated and dried, and concentrated. The crude product was isolated by silica gel column chromatography (hexane / chloroform) to obtain the desired product 31 (3.01 g).

(Synthesis Example 32)

Target 4 obtained in Synthesis Example 4 (3.64 g, 10.4 mmol), Target 2 obtained in Synthesis Example 2 (0.51 g, 2.6 mmol), 4,4′-dibromobiphenyl (2. 03 g, 13 mmol), sodium tert-butoxy (2.88 g, 30.0 mmol), and toluene (20 ml) were charged, the system was sufficiently purged with nitrogen, and the mixture was heated to 50 ° C. (solution A).
Meanwhile, tri-t-butylphosphine (0.210 g, 0.104 mmol) was added to a 15 ml toluene solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.148 g, 0.0143 mmol) and heated to 50 ° C. (Solution B).
In a nitrogen stream, solution B was added to solution A and heated to reflux for 1 hour. After confirming disappearance of the raw material, 4,4′-dibromobiphenyl (1.91 g, 6.1 mmol) was additionally added. Since it was confirmed that the polymerization started after heating under reflux for 1 hour, 4,4′-dibromobiphenyl (0.041 g, 0.13 mmol) was further added, and the mixture was further heated under reflux for 1 hour. The reaction solution was allowed to cool, and the reaction solution was dropped into 200 ml of methanol to crystallize the crude polymer 1.

The obtained crude polymer 1 was dissolved in 200 ml of toluene, bromobenzene (2.04 g, 13 mmol) and tert-butoxy sodium (1.50 g, 16 mmol) were charged, and the inside of the system was sufficiently purged with nitrogen. Warmed (solution C).
Meanwhile, tri-t-butylphosphine (0.026 g, 13 mmol) was added to a 10 ml toluene solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.108 g, 10.4 mmol) and heated to 50 ° C. (Solution D).
In a nitrogen stream, solution D was added to solution C, and heated to reflux for 2 hours. To this reaction solution, a toluene (2 ml) solution of N, N-diphenylamine (3.82 g, 22.6 mmol) was added, and the mixture was further heated and refluxed for 8 hours. The reaction solution was allowed to cool and added dropwise to methanol to obtain end-capped crude polymer 1.

This end-capped crude polymer 1 was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer 1 (1.01 g). In addition, it was as follows when the weight average molecular weight and the number average molecular weight of the target polymer 1 were measured.
Weight average molecular weight (Mw) = 43300
Number average molecular weight (Mn) = 26400
Dispersity (Mw / Mn) = 1.2

(Synthesis Examples 33 to 39)
According to the synthesis method of Synthesis Example 32, the monomer bodies (namely, target product 4, target product 2 and 4,4′-dibromobiphenyl) were changed to the compounds shown in Table 1 below, and target polymers 2 to 7 and A were obtained. The obtained target polymers are also summarized in Table 1.

(Synthesis Example 40)

Target 4 obtained in Synthesis Example 4 (7.5 g, 21.5 mmol), Target 2 obtained in Synthesis Example 2 (0.22 g, 1.1 mmol), 4,4′-dibromostilbene (3. 82 g, 11.3 mmol), sodium tert-butoxy (6.95 g, 72.3 mmol), and toluene (120 ml) were charged, and the system was sufficiently purged with nitrogen and heated to 50 ° C. (solution A).
Meanwhile, tri-t-butylphosphine (0.33 g, 0.45 mmol) was added to a 5 ml toluene solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.06 g, 0.06 mmol) and heated to 50 ° C. (Solution B).
In a nitrogen stream, solution B was added to solution A and heated to reflux for 3 hours. After confirming disappearance of the raw material, 4,4′-dibromobiphenyl (3.31 g, 10.6 mmol) was additionally added. Since it was confirmed that the polymerization started after heating under reflux for 1.5 hours, 4,4′-dibromobiphenyl (0.07 g, 0.2 mmol) was further added three times every 1.5 hours. did. After the total amount of 4,4′-dibromobiphenyl was added, the mixture was further heated to reflux for 1 hour, the reaction solution was allowed to cool, and the reaction solution was dropped into 300 ml of ethanol to crystallize crude polymer 8.

The obtained crude polymer 8 was dissolved in 180 ml of toluene, bromobenzene (0.71 g, 4.5 mmol) and tert-butoxy sodium (3.5 g, 36.4 mmol) were charged, and the system was sufficiently purged with nitrogen. And heated to 50 ° C. (solution C).
Meanwhile, tri-t-butylphosphine (0.18 g, 0.9 mmol) was added to a 10 ml toluene solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.12 g, 0.1 mmol) and heated to 50 ° C. (Solution D).
In a nitrogen stream, solution D was added to solution C, and heated to reflux for 2 hours. To this reaction solution, a toluene (2 ml) solution of N, N-diphenylamine (3.82 g, 22.6 mmol) was added, and the mixture was further heated and refluxed for 8 hours. The reaction solution was allowed to cool and dropped into an ethanol / water (250 ml / 50 ml) solution to obtain an end-capped crude polymer 8.

This end-capped crude polymer 8 was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer 8 (0.9 g). In addition, it was as follows when the weight average molecular weight and the number average molecular weight of the target polymer 8 were measured.
Weight average molecular weight (Mw) = 60000
Number average molecular weight (Mn) = 27000
Dispersity (Mw / Mn) = 2.2

(Synthesis Examples 41 to 46)
According to the synthesis method of Synthesis Example 40, the monomer body was changed to the compounds shown in Table 2 below, and target polymers 9 to 14 were obtained as arylamine polymers. The obtained target polymers are also summarized in Table 2.

(Synthesis Examples 47 to 56)
In the same manner as in the synthesis methods of Synthesis Examples 32 and 40, various arylamine polymer target products 15 to 24 were obtained according to the following reaction formulas and Table 3 using various monomer bodies represented by the following reaction formulas. The obtained polymers are summarized in Table 3.

(Synthesis Example 57)
In the same manner as in the synthesis methods of Synthesis Examples 32 and 40, the arylamine polymer target product 25 was obtained from various monomer bodies having the following reaction formulas according to the following reaction formulas and Table-4. The obtained polymers are summarized in Table 4.

(Synthesis Examples 58-60)
In the same manner as in the synthesis methods of Synthesis Examples 32 and 40, various monomer bodies having the following reaction formulas were obtained according to the following reaction formulas and Table-5 to obtain arylamine polymer objectives 26, B and C. The obtained polymers are summarized in Table-5.

(Synthesis Example 61)
In the same manner as in the synthesis methods of Synthesis Examples 32 and 40, various amine compounds having the following reaction formulas were obtained according to the following reaction formulas and Table-6 to obtain the arylamine polymer target product 27. The obtained polymers are summarized in Table-6.

(Synthesis Example 62)
In the same manner as in the synthesis methods of Synthesis Examples 32 and 40, various monomer bodies having the following reaction formulas were obtained according to the following reaction formulas and Table-7 to obtain the arylamine polymer target product 28. The polymers obtained are summarized in Table 7.

窒素気流中、化合物１（１０．０ｇ）、化合物２（５．０８ｇ）、トルエン：エタノール（１００ｍｌ：５０ｍｌ）及びＮａ_２ＣＯ_３（２Ｍ）３０ｍｌの混合物を、６０℃に加熱下３０分間撹拌し、Ｐｄ（ＰＰｈ_３）_４ １．５ｇを加え、６時間還流して反応させた。室温まで放冷した後、反応液に塩化メチレン（１００ｍｌ）および水（１００ｍｌ）を加え攪拌後、分液し、水層を塩化メチレン（１００ｍｌ×２回）で抽出し、有機層を合わせ、硫酸マグネシウムで乾燥後、濃縮した。さらに、シリカゲルカラムクロマトグラフィー（ｎ−ヘキサン／塩化メチレン＝１５／１）で精製することにより、淡黄色結晶の化合物３（１１．０ｇ）を得た。 (Synthesis Example 63)

In a nitrogen stream, a mixture of compound 1 (10.0 g), compound 2 (5.08 g), toluene: ethanol (100 ml: 50 ml) and Na ₂ CO ₃ (2M) 30 ml was stirred at 60 ° C. for 30 minutes with heating. , Pd (PPh ₃ ) ₄ 1.5 g was added, and the mixture was refluxed for 6 hours to be reacted. After allowing to cool to room temperature, methylene chloride (100 ml) and water (100 ml) were added to the reaction mixture, and the mixture was stirred and separated. The aqueous layer was extracted with methylene chloride (100 ml × 2 times), and the organic layers were combined. After drying with magnesium, it was concentrated. Furthermore, the compound 3 (11.0g) of the pale yellow crystal | crystallization was obtained by refine | purifying with silica gel column chromatography (n-hexane / methylene chloride = 15/1).

化合物３（１０．３ｇ）、テトラヒドロフラン（５０ｍｌ）及びエタノール（５０ｍｌ）の混合物に１０％Ｐｄ／Ｃ（４．６ｇ）を加え、さらに５０℃でＮＨ_２ＮＨ_２Ｈ_２Ｏ（１６．３ｇ）をゆっくり滴下し、この温度で３時間反応させた。室温で反応液を濾過し、濾液を濃縮し、メタノールを入れ懸濁洗浄した。そして、濾取、乾燥することにより、化合物４（８．５ｇ）を得た。 (Synthesis Example 64)

10% Pd / C (4.6 g) was added to a mixture of compound 3 (10.3 g), tetrahydrofuran (50 ml) and ethanol (50 ml), and NH ₂ NH ₂ H ₂ O (16.3 g) was added at 50 ° C. The solution was slowly added dropwise and reacted at this temperature for 3 hours. The reaction solution was filtered at room temperature, the filtrate was concentrated, and methanol was added to perform suspension washing. The compound 4 (8.5 g) was obtained by filtration and drying.

化合物４（３．８７７ｇ、９．１０９ｍｍｏｌ）、化合物５（０．２７１ｇ、１．３８８ｍｍｏｌ）、化合物６（１．６４ｇ、５．２４８ｍｍｏｌ）、ｔｅｒｔ−ブトキシナトリウム（２．９６ｇ、３０．７７ｍｍｏｌ）及びトルエン（３０ｍｌ）を仕込み、系内を十分に窒素置換して、６０℃まで加温した（溶液Ａ）。
一方、トリス（ジベンジリデンアセトン）ジパラジウムクロロホルム錯体（０．１ｇ、０．０９６ｍｍｏｌ）のトルエン２ｍｌ溶液に、トリ−ｔ−ブチルホスフィン（０．１５６ｇ、０．７７ｍｍｏｌ）を加え、６０℃まで加温した（溶液Ｂ）。
窒素気流中、溶液Ａに溶液Ｂを添加し、２．０時間、加熱還流反応させた。化合物４〜６が消失したことを確認し、化合物７（１．２４ｇ、５．２４８ｍｍｏｌ）を追添加した。４時間加熱還流し、反応液を放冷して、反応液をエタノール３００ｍｌ中に滴下し、粗ポリマーＤを晶出させた。 (Synthesis Example 65)

Compound 4 (3.877 g, 9.109 mmol), Compound 5 (0.271 g, 1.388 mmol), Compound 6 (1.64 g, 5.248 mmol), tert-butoxy sodium (2.96 g, 30.77 mmol) and Toluene (30 ml) was charged, the inside of the system was sufficiently replaced with nitrogen, and the mixture was heated to 60 ° C. (solution A).
On the other hand, tri-t-butylphosphine (0.156 g, 0.77 mmol) was added to a toluene 2 ml solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.1 g, 0.096 mmol) and heated to 60 ° C. (Solution B).
In a nitrogen stream, solution B was added to solution A and heated to reflux for 2.0 hours. After confirming disappearance of compounds 4 to 6, compound 7 (1.24 g, 5.248 mmol) was added additionally. The mixture was heated to reflux for 4 hours, the reaction solution was allowed to cool, and the reaction solution was dropped into 300 ml of ethanol to crystallize crude polymer D.

The obtained crude polymer D was dissolved in 120 ml of toluene, bromobenzene (0.33 g, 2.99 mmol) and tert-butoxy sodium (2.96 g, 33.77 mmol) were charged, and the inside of the system was sufficiently purged with nitrogen. And heated to 60 ° C. (solution C).
On the other hand, tri-t-butylphosphine (0.156 g, 0.77 mmol) was added to a 1 ml toluene solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.1 g, 0.096 mmol) and heated to 60 ° C. (Solution D).
In a nitrogen stream, solution D was added to solution C, and heated to reflux for 2 hours. To this reaction solution, a toluene (3 ml) solution of N, N-diphenylamine (2.06 g, 10.396 mmol) was added, and the mixture was further heated and refluxed for 4 hours. The reaction solution was allowed to cool and dropped into an ethanol / water (250 ml / 50 ml) solution to obtain an end-capped crude polymer D.

This end-capped crude polymer D was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer D (1.9 g).
Weight average molecular weight (Mw) = 39000
Number average molecular weight (Mn) = 21600
Dispersity (Mw / Mn) = 1.8

化合物８（１３．２ｇ）及び塩化メチレン（１２０ｍｌ）の混合物に室温で臭素（２５．０ｇ）含有の塩化メチレン４０ｍｌを滴下し、３０℃で４８時間反応させた。反応後、析出物を濾取、メタノールで懸濁洗浄した。そして、濾取、乾燥することにより、化合物９（１０．５ｇ）を得た。 (Synthesis Example 66)

To a mixture of Compound 8 (13.2 g) and methylene chloride (120 ml), 40 ml of methylene chloride containing bromine (25.0 g) was added dropwise at room temperature and reacted at 30 ° C. for 48 hours. After the reaction, the precipitate was collected by filtration and suspended and washed with methanol. The compound 9 (10.5 g) was obtained by filtration and drying.

窒素気流中、化合物９（１０．５ｇ）、化合物１０（２６．１ｇ）、ジメチルスルホキシド（２５０ｍｌ）、テトラブチルアンモニウムブロミド（２．３ｇ）に水酸化ナトリウム７．２ｇの１１ｍｌ水溶液をゆっくり滴下、その後５０℃で３時間反応した。室温まで放冷した後、反応液をろ過、ろ液に酢酸エチル（２００ｍｌ）および水（１００ｍｌ）を加え攪拌後、分液し、水層を酢酸エチル（１００ｍｌ×２回）で抽出し、有機層を合わせ、硫酸マグネシウムで乾燥後、濃縮した。さらに、シリカゲルカラムクロマトグラフィー（ｎ−ヘキサン／塩化メチレン＝１５／１）で精製することにより、淡黄色固体の化合物１１（１３．６ｇ）を得た。 (Synthesis Example 67)

In a nitrogen stream, 11 ml of an aqueous solution of 7.2 g of sodium hydroxide was slowly added dropwise to Compound 9 (10.5 g), Compound 10 (26.1 g), dimethyl sulfoxide (250 ml), and tetrabutylammonium bromide (2.3 g). The reaction was performed at 50 ° C. for 3 hours. After allowing to cool to room temperature, the reaction solution was filtered, ethyl acetate (200 ml) and water (100 ml) were added to the filtrate and stirred, then the layers were separated, and the aqueous layer was extracted with ethyl acetate (100 ml × 2 times). The layers were combined, dried over magnesium sulfate and concentrated. Furthermore, the compound 11 (13.6g) of pale yellow solid was obtained by refine | purifying with silica gel column chromatography (n-hexane / methylene chloride = 15/1).

化合物１２（１６．２ｇ、８２．９７ｍｍｏｌ）、ブロモベンゼン（１２．３８ｇ、７８．８２ｍｍｏｌ）、ｔｅｒｔ−ブトキシナトリウム（２１．５ｇ、２２４．０ｍｍｏｌ）及びトルエン（３００ｍｌ）を仕込み、系内を十分に窒素置換して、６０℃まで加温した（溶液Ａ）。
一方、トリス（ジベンジリデンアセトン）ジパラジウムクロロホルム錯体（０．２６ｇ、０．２４９ｍｍｏｌ）のトルエン５ｍｌ溶液に、１，１’−ビス（ジフェニルホスフィノ）フェロセン（０．５５ｇ、０．９９６ｍｍｏｌ）を加え、６０℃まで加温した（溶液Ｂ）。
窒素気流中、溶液Ａに溶液Ｂを添加し、３．０時間、加熱還流反応した。室温まで放冷した後、反応液に酢酸エチル（２００ｍｌ）及び水（１００ｍｌ）を加え攪拌後、分液し、水層を酢酸エチル（１００ｍｌ×２回）で抽出し、有機層を合わせ、硫酸マグネシウムで乾燥後、濃縮した。さらに、シリカゲルカラムクロマトグラフィー（ｎ−ヘキサン／塩化メチレン＝４／１）で精製することにより、淡黄色油状の化合物１３（１８．８ｇ）を得た。 (Synthesis Example 68)

Compound 12 (16.2 g, 82.97 mmol), bromobenzene (12.38 g, 78.82 mmol), sodium tert-butoxy (21.5 g, 224.0 mmol) and toluene (300 ml) were charged, and the system was thoroughly charged. The atmosphere was replaced with nitrogen and heated to 60 ° C. (solution A).
Meanwhile, 1,1′-bis (diphenylphosphino) ferrocene (0.55 g, 0.996 mmol) was added to a 5 ml toluene solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.26 g, 0.249 mmol). , Heated to 60 ° C. (solution B).
In a nitrogen stream, solution B was added to solution A, and the mixture was heated to reflux for 3.0 hours. After allowing to cool to room temperature, ethyl acetate (200 ml) and water (100 ml) were added to the reaction mixture, and the mixture was stirred and separated. The aqueous layer was extracted with ethyl acetate (100 ml × 2 times), and the organic layers were combined. After drying with magnesium, it was concentrated. Further, purification by silica gel column chromatography (n-hexane / methylene chloride = 4/1) gave pale yellow oily compound 13 (18.8 g).

化合物１１（８．８３ｇ、１７．１６ｍｍｏｌ）、化合物１３（４．８９ｇ、１８．０ｍｍｏｌ）、ｔｅｒｔ−ブトキシナトリウム（４．４５ｇ、４６．３３ｍｍｏｌ）及びトルエン（１６０ｍｌ）を仕込み、系内を十分に窒素置換して、６０℃まで加温した（溶液Ａ）。
一方、トリス（ジベンジリデンアセトン）ジパラジウムクロロホルム錯体（０．０９ｇ、０．０８６ｍｍｏｌ）のトルエン５ｍｌ溶液に、トリ−ｔ−ブチルホスフィン（０．１３９ｇ、０．６９ｍｍｏｌ）を加え、６０℃まで加温した（溶液Ｂ）。
窒素気流中、溶液Ａに溶液Ｂを添加し、３．０時間、加熱還流反応した。室温まで放冷した後、反応液に酢酸エチル（２００ｍｌ）及び水（１００ｍｌ）を加え攪拌後、分液し、水層を酢酸エチル（１００ｍｌ×２回）で抽出し、有機層を合わせ、硫酸マグネシウムで乾燥後、濃縮した。さらに、シリカゲルカラムクロマトグラフィー（ｎ−ヘキサン／塩化メチレン＝４／１）で精製することにより、淡黄色油状の化合物１４（１２．０ｇ）を得た。 (Synthesis Example 69)

Compound 11 (8.83 g, 17.16 mmol), Compound 13 (4.89 g, 18.0 mmol), sodium tert-butoxy (4.45 g, 46.33 mmol) and toluene (160 ml) were charged, and the system was fully charged. The atmosphere was replaced with nitrogen and heated to 60 ° C. (solution A).
Meanwhile, tri-t-butylphosphine (0.139 g, 0.69 mmol) was added to a 5 ml toluene solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.09 g, 0.086 mmol) and heated to 60 ° C. (Solution B).
In a nitrogen stream, solution B was added to solution A, and the mixture was heated to reflux for 3.0 hours. After allowing to cool to room temperature, ethyl acetate (200 ml) and water (100 ml) were added to the reaction mixture, and the mixture was stirred and separated. The aqueous layer was extracted with ethyl acetate (100 ml × 2 times), and the organic layers were combined. After drying with magnesium, it was concentrated. Further, purification by silica gel column chromatography (n-hexane / methylene chloride = 4/1) gave pale yellow oily compound 14 (12.0 g).

化合物１４（１２．０ｇ）、テトラヒドロフラン（６５ｍｌ）及びエタノール（６５ｍｌ）の混合物に１０％Ｐｄ／Ｃ（０．６４ｇ）を加え、５０℃に昇温した後、ＮＨ_２ＮＨ_２Ｈ_２Ｏ（９．７ｇ）をゆっくり滴下し、５０℃で８時間反応させた。室温で反応液を濾過し、濾液に酢酸エチル（２００ｍｌ）及び水（１００ｍｌ）を加え攪拌後、分液し、水層を酢酸エチル（１００ｍｌ×２回）で抽出し、有機層を合わせ、硫酸マグネシウムで乾燥後、濃縮した。さらに、シリカゲルカラムクロマトグラフィー（ｎ−ヘキサン／酢酸エチル＝９／１）で精製することにより、化合物１５（９．７ｇ）を得た。 (Synthesis Example 70)

10% Pd / C (0.64 g) was added to a mixture of compound 14 (12.0 g), tetrahydrofuran (65 ml) and ethanol (65 ml), the temperature was raised to 50 ° C., and then NH ₂ NH ₂ H ₂ O (9 0.7 g) was slowly added dropwise and reacted at 50 ° C. for 8 hours. The reaction solution was filtered at room temperature, ethyl acetate (200 ml) and water (100 ml) were added to the filtrate and the mixture was stirred and separated. The aqueous layer was extracted with ethyl acetate (100 ml × 2 times), and the organic layers were combined. After drying with magnesium, it was concentrated. Furthermore, the compound 15 (9.7g) was obtained by refine | purifying with silica gel column chromatography (n-hexane / ethyl acetate = 9/1).

化合物１１（４．８０ｇ、９．３３ｍｍｏｌ）、ジフェニルアミン（１．５８ｇ、９．３３ｍｍｏｌ）、ｔｅｒｔ−ブトキシナトリウム（１．２６ｇ、１３．１ｍｍｏｌ）及びトルエン（４５ｍｌ）を仕込み、系内を十分に窒素置換して、６０℃まで加温した（溶液Ａ）。
一方、ビス（ジベンジリデンアセトン）パラジウム（５４ｍｇ、０．０９ｍｍｏｌ）のトルエン５ｍｌ溶液に、トリ−ｔ−ブチルホスフィン（７６ｍｇ、０．３６ｍｍｏｌ）を加え、６０℃まで加温した（溶液Ｂ）。
窒素気流中、溶液Ａに溶液Ｂを添加し、６時間、加熱還流反応した。室温まで放冷した後、活性白土及びトルエンを加え攪拌した。濾液を濃縮し、シリカゲルカラムクロマトグラフィー（ｎ−ヘキサン／塩化メチレン＝４／１）で精製することにより、淡黄色油状の化合物１６（３．６３ｇ）を得た。 (Synthesis Example 71)

Compound 11 (4.80 g, 9.33 mmol), diphenylamine (1.58 g, 9.33 mmol), sodium tert-butoxy (1.26 g, 13.1 mmol) and toluene (45 ml) were charged, and the system was sufficiently nitrogen-filled. Substitution and heating to 60 ° C. (solution A).
Meanwhile, tri-t-butylphosphine (76 mg, 0.36 mmol) was added to a 5 ml toluene solution of bis (dibenzylideneacetone) palladium (54 mg, 0.09 mmol) and heated to 60 ° C. (solution B).
In a nitrogen stream, solution B was added to solution A and heated to reflux for 6 hours. After allowing to cool to room temperature, activated clay and toluene were added and stirred. The filtrate was concentrated and purified by silica gel column chromatography (n-hexane / methylene chloride = 4/1) to obtain pale yellow oily compound 16 (3.63 g).

化合物１６（３．６３ｇ）、テトラヒドロフラン（２３ｍｌ）及びエタノール（２３ｍｌ）の混合物に２０％Ｐｄ／Ｃ（０．４ｇ）を加え、５０℃に昇温した後、ＮＨ_２ＮＨ_２Ｈ_２Ｏ（６．８ｇ）をゆっくり滴下し、５０℃で４時間反応させた。室温で反応液を濾過し、シリカゲルカラムクロマトグラフィー（ｎ−ヘキサン／酢酸エチル＝９／１）で精製することにより、化合物１７（２．８５ｇ）を得た。 (Synthesis Example 72)

20% Pd / C (0.4 g) was added to a mixture of compound 16 (3.63 g), tetrahydrofuran (23 ml) and ethanol (23 ml), the temperature was raised to 50 ° C., and then NH ₂ NH ₂ H ₂ O (6 8 g) was slowly added dropwise and reacted at 50 ° C. for 4 hours. The reaction solution was filtered at room temperature and purified by silica gel column chromatography (n-hexane / ethyl acetate = 9/1) to obtain Compound 17 (2.85 g).

化合物１５（３．４０３ｇ、５．０４ｍｍｏｌ）、化合物１７（１．０ｇ、１．７４６ｍｍｏｌ）、４，４’−ジブロモビフェニル（１．０６ｇ、３．３９４ｍｍｏｌ）、ｔｅｒｔ−ブトキシナトリウム（２．１ｇ、２１．７２ｍｍｏｌ）及びトルエン（３０ｍｌ）を仕込み、系内を十分に窒素置換して、６０℃まで加温した（溶液Ａ）。
一方、トリス（ジベンジリデンアセトン）ジパラジウムクロロホルム錯体（０．０７ｇ、０．０６８ｍｍｏｌ）のトルエン２ｍｌ溶液に、トリ−ｔ−ブチルホスフィン（０．１１ｇ、０．５４３ｍｍｏｌ）を加え、６０℃まで加温した（溶液Ｂ）。
窒素気流中、溶液Ａに溶液Ｂを添加し、２．５時間、加熱還流反応した。化合物１５及び１７が消失したことを確認し、４，４’−ジブロモビフェニル（１．０３ｇ）を追添加した。３０分間加熱還流し、反応液を放冷して、反応液をエタノール３００ｍｌ中に滴下し、粗ポリマーＥを晶出させた。 (Synthesis Example 73)

Compound 15 (3.403 g, 5.04 mmol), Compound 17 (1.0 g, 1.746 mmol), 4,4′-dibromobiphenyl (1.06 g, 3.394 mmol), sodium tert-butoxy (2.1 g, 21.72 mmol) and toluene (30 ml) were charged, the inside of the system was sufficiently purged with nitrogen, and the mixture was heated to 60 ° C. (solution A).
Meanwhile, tri-t-butylphosphine (0.11 g, 0.543 mmol) was added to a toluene 2 ml solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.07 g, 0.068 mmol) and heated to 60 ° C. (Solution B).
In a nitrogen stream, solution B was added to solution A and heated to reflux for 2.5 hours. After confirming that compounds 15 and 17 had disappeared, 4,4′-dibromobiphenyl (1.03 g) was additionally added. The mixture was heated to reflux for 30 minutes, the reaction solution was allowed to cool, and the reaction solution was dropped into 300 ml of ethanol to crystallize crude polymer E.

The obtained crude polymer E was dissolved in 120 ml of toluene, bromobenzene (0.21 g) and tert-butoxy sodium (2.1 g) were charged, the inside of the system was sufficiently purged with nitrogen, and the mixture was heated to 60 ° C. ( Solution C).
Meanwhile, tri-t-butylphosphine (0.11 g) was added to a toluene 1 ml solution of tris (dibenzylideneacetone) dipalladium chloroform complex (0.07 g), and the mixture was heated to 60 ° C. (solution D).
In a nitrogen stream, solution D was added to solution C, and heated to reflux for 2 hours. To this reaction solution, a toluene (3 ml) solution of N, N-diphenylamine (1.15 g) was added, and the mixture was further heated and refluxed for 4 hours. The reaction solution was allowed to cool and dropped into an ethanol / water (250 ml / 50 ml) solution to obtain an end-capped crude polymer E.

This end-capped crude polymer E was dissolved in toluene, reprecipitated in acetone, and the precipitated polymer was separated by filtration. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain the target polymer E (2.3 g).
Weight average molecular weight (Mw) = 31900
Number average molecular weight (Mn) = 21260
Dispersity (Mw / Mn) = 1.5

(Comparative polymer)
In the same manner as in the synthesis methods of Synthesis Examples 32 and 40, various monomer bodies having the following reaction formulas were obtained in accordance with the following reaction formulas and Table-8 to obtain various comparative polymers 1 to 3. The obtained polymers are summarized in Table-8.

[II. Evaluation of organic electroluminescence device]
[Production of organic electroluminescence device]
Example 1
The organic electroluminescent element shown in FIG. 1 was produced in the manner described below.
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, an anode 2 was formed by patterning into stripes having a width of 2 mm to obtain an ITO substrate.
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.

  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′-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 hole injection layer forming coating solution was applied onto the anode 2 by spin coating under the following film forming 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>
Spinner speed 1500rpm
Spinner rotation time 30 seconds Spin coat atmosphere In air Heating condition In air 230 ° C 3 hours

  Subsequently, an organic electric field containing an arylamine polymer (H1) represented by the following structural formula (polymer having the same structural formula as the target polymer 1 synthesized in Synthesis Example 32: weight average molecular weight 43000, dispersity 1.6). A composition for a hole transport layer was prepared as a composition for a light emitting device, applied by spin coating under the following film formation conditions, and crosslinked by heating to form a hole transport layer 4 having a thickness of 20 nm.

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

<Hole transport layer deposition conditions>
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 composition for the light-emitting layer was prepared using the organic compounds (C1), (C2) and (D1) shown below. The light emitting layer 5 was obtained by spin coating on the hole transport layer 4 to a film thickness of 50 nm.

<Composition for light emitting layer>
Solvent Xylene Coating solution concentration Organic compound (C1): 1.0% by weight
Organic compound (C2): 1.0% by weight
Organic compound (D1): 0.1% by weight

<Deposition conditions for light emitting layer>
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, the substrate having the light emitting layer 5 formed thereon is transferred into a vacuum vapor deposition apparatus, exhausted until the degree of vacuum in the apparatus becomes 1.3 × 10 ⁻⁴ Pa or less, and then an organic having the structure shown below. The compound (C3) was laminated on the light emitting layer 5 by a vacuum vapor deposition method to obtain a hole blocking layer 6. The deposition rate was controlled in the range of 1.4 to 1.5 liters / second, and the film thickness was 5 nm. Moreover, the vacuum degree at the time of vapor deposition was 1.3 * 10 <^-4> Pa.

Subsequently, an organic compound (C4) having the structure shown below was heated and evaporated on the hole blocking layer 6 to form an electron transport layer 7. The degree of vacuum at the time of vapor deposition was 1.3 × 10 ⁻⁴ Pa, the vapor deposition rate was controlled in the range of 1.6 to 1.8 秒 / sec, and the film thickness was 30 nm.

Here, the element on which vapor deposition up to the electron transport layer 7 has been taken out is once taken out and placed in another vapor deposition apparatus, and a 2 mm wide striped shadow mask is orthogonal to the ITO stripe of the anode 2 as a mask for cathode vapor deposition. In this way, exhaustion was performed until the degree of vacuum in the apparatus was 2.3 × 10 ⁻⁴ Pa or less.

As the electron injection layer 8, lithium fluoride (LiF) was first formed on the electron transport layer 7 at a deposition rate of 0.1 Å / sec and a film thickness of 0.5 nm using a molybdenum boat. The degree of vacuum at the time of vapor deposition was 2.6 × 10 ⁻⁴ Pa.
Next, aluminum was similarly heated by a molybdenum boat as the cathode 9, and the deposition rate was controlled in the range of 1.0 to 4.9 kg / sec to form an aluminum layer having a thickness of 80 nm. The degree of vacuum at the time of vapor deposition was 2.6 × 10 ⁻⁴ Pa. 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, a photocurable resin (30Y-437 manufactured by ThreeBond Co., Ltd.) with a width of about 1 mm is applied to the outer periphery of a 23 mm × 23 mm glass plate, and a moisture getter sheet (Dynic Corporation) is applied to the center. Made). 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.
Voltage at 100 cd / m ² : 5.8V
Luminance at 100 cd / m ² : 17.9 cd / A
Power efficiency at 100 cd / m ² : 9.7 lm / W
The maximum wavelength of the emission spectrum of the device was 513 nm, and it was identified as that from the organic compound (D1). The chromaticity was CIE (x, y) = (0.304, 0.628).

(Example 2)
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 was formed in the following manner in Example 1.

  Organic electroluminescent device containing arylamine polymer (H2) represented by the following structural formula (polymer having the same structural formula as target polymer 2 synthesized in Synthesis Example 33: weight average molecular weight 42000, dispersity 2.5) A composition for a hole transport layer was prepared as a coating composition, applied by spin coating under the following film formation conditions, and crosslinked by heating to form a hole transport layer 4 having a thickness of 20 nm.

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

<Hole transport layer deposition conditions>
Spinner speed 1500rpm
Spinner rotation time 30 seconds Spin coating atmosphere In nitrogen Heating conditions In nitrogen, 230 ° C, 1 hour

The light emission characteristics of the organic electroluminescent element having a light emitting area portion of 2 mm × 2 mm obtained in this way are as follows.
Voltage at 100 cd / m ² : 5.1V
Luminance at 100 cd / m ² : 24.1 cd / A
Power efficiency at 100 cd / m ² : 14.9 lm / W
The maximum wavelength of the emission spectrum of the device was 513 nm, and it was identified as that from the organic compound (D1). The chromaticity was CIE (x, y) = (0.299, 0.628).

(Comparative Example 1)
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 was formed in the following manner in Example 1.

  Contains comparative polymer (H3) shown in the following structural formula (polymer having the same structural formula as comparative polymer 2 synthesized in the section (polymer for comparative example): weight average molecular weight 47000, dispersity 1.6). A composition for a hole transport layer was prepared as a composition for an organic electroluminescence device, applied by spin coating under the following film formation conditions, and crosslinked by heating to form a hole transport layer having a thickness of 20 nm.

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

<Hole transport layer deposition conditions>
Spinner speed 1500rpm
Spinner rotation time 30 seconds Spin coating atmosphere In nitrogen Heating conditions In nitrogen, 230 ° C, 1 hour

The light emission characteristics of the organic electroluminescent element having a light emitting area portion of 2 mm × 2 mm obtained in this way are as follows.
Voltage at 100 cd / m ² : 5.3V
Luminance at 100 cd / m ² : 13.0 cd / A
Power efficiency at 100 cd / m ² : 7.8 lm / W
The maximum wavelength of the emission spectrum of the device was 513 nm, and it was identified as that from the organic compound (D1). The chromaticity was CIE (x, y) = (0.304, 0.628).

(Summary of Examples 1 and 2 and Comparative Example 1)
The characteristics of the organic electroluminescent elements produced in Example 1, Example 2, and Comparative Example 1, and the direct current drive test with an initial luminance of 2500 cd / m ² were performed, and the time until the luminance was reduced to half (driving life) was expressed. Summarize in -9. Note that the DC drive test is a test in which a DC current having a luminance at an initial luminance at room temperature is continuously supplied to emit light.

  From Table 1, it can be seen that the organic electroluminescent device produced according to the present invention has low voltage, high efficiency, and long life.

[III. Evaluation of charge mobility]
[Creation of charge mobility measurement device]
FIG. 2 is a cross-sectional view schematically showing the layer structure of the measurement elements produced in Examples 3 and 4 and Comparative Examples 2 and 3. As shown in FIG. 2, an ordinary indium tin oxide (ITO) transparent conductive film deposited on a glass substrate 1 to a thickness of 150 nm (manufactured by Sanyo Vacuum Co., Ltd., sputtered film product) An ITO layer was formed as an anode 2 by patterning into a stripe having a width of 2 mm using a photolithography technique and hydrochloric acid etching to obtain an ITO substrate.
The ITO substrate was 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, and then dried with compressed air.

  Next, as shown in Table-10, the material of the sample layer 10 was dissolved in toluene to prepare a coating solution, and this was applied on the anode 2 with a spinner rotation speed of 1500 rpm, a spinner rotation time of 30 seconds, and a spin. Coating atmosphere: Spin coating was performed under the condition of nitrogen, and baking was performed to form a sample layer 10 (corresponding to a hole transport layer of an organic electroluminescence device). In addition, 0.03-0.04 weight% of surface smoothing agent was added to each coating liquid with respect to toluene. As the surface smoothing agent, KF-96-10cs (manufactured by Shin-Etsu Silicone) was used.

The element on which the sample layer 10 was formed was placed in the vacuum deposition layer. At that time, a stripe shadow mask having a width of 2 mm, which is a mask for cathode vapor deposition, was brought into close contact with the element so as to be orthogonal to the ITO stripe of the anode 2. The inside of the apparatus was evacuated roughly by a scroll pump, and then evacuated by a turbo molecular pump until the degree of vacuum in the apparatus was 9.9 × 10 ⁻⁴ Pa or less.
Thereafter, aluminum is heated by a molybdenum boat, and an aluminum layer having a film thickness of 40 to 80 nm is formed on the cathode 9 by controlling the deposition rate from 0.6 to 16.0 Å / sec and the degree of vacuum from 2.0 to 25 × 10 ⁻⁴ Pa. Formed as. In addition, the substrate temperature at the time of vapor deposition of the above aluminum layer was kept at room temperature.

  Subsequently, in order to prevent the measuring element from being deteriorated by moisture in the atmosphere during storage, a sealing treatment was performed by the method described below. In a nitrogen glove box connected to a vacuum deposition apparatus, a photocurable resin (30Y-437 manufactured by ThreeBond Co., Ltd.) with a width of about 1 mm is applied to the outer periphery of a 23 mm × 23 mm size glass plate, and moisture is applied to the center. A getter sheet (manufactured by Dynic) was installed. On top of this, the measuring element was bonded so that the surface on which the cathode 9 was deposited was opposed to the 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, a measuring element having an element area of 2 mm × 2 mm was produced.

[Measurement of charge mobility]
Using the measurement elements prepared in Examples 3 and 4 and Comparative Examples 2 and 3, charge mobility was measured as follows.
As a method for measuring the charge mobility, the time of flight measurement method (ToF method) was used. An electric field strength E (V / cm) was applied so that the anode 2 side of the measuring element was at a high potential. Next, the anode 2 on the measuring element surface was irradiated with light having a wavelength of 355 nm, which is the third harmonic, for a short time using an Nd: YAG nanosecond pulse laser. The transient photocurrent generated at that time was detected, and the inflection point was _defined as the flight time t _tr (s). From this flight time t _tr and the electric field strength E (= V / d, V: potential difference between the anode 2 and the cathode 9 of the measuring element, d: film thickness of the sample layer 10 of the measuring element), By using this, the charge mobility μ _h was calculated.

Measurement was performed at a plurality of electric field strengths, and the charge mobility at which the electric field strength could be set at 160 kV / cm was calculated using the obtained charge mobility μ _h , electric field strength E, and the following Poole-Frenkel equation.

The results are shown in Table-11.

  From Table-11, when the ratio of the repeating unit containing a crosslinkable group is the same, it turns out that the arylamine polymer of this invention has a large charge mobility.

[IV. Evaluation of current-voltage characteristics]
(Example 5)
The measuring element having a single-layer structure shown in FIG. 2 was produced in the manner described below.
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, an anode 2 was formed by patterning into stripes having a width of 2 mm to obtain an ITO substrate.
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.

  An arylamine polymer (H4) represented by the following structural formula (polymer having the same structural formula as the target polymer 24 synthesized in Synthesis Example 56: weight average molecular weight 23100, dispersion degree 1.7) 2% by weight, After dissolving 0.06% by weight of 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate shown in (A1) in toluene as a solvent, PTFE (polytetrafluoroethylene) having a pore size of 0.2 μm is dissolved. It filtered using the membrane filter made, and produced the coating composition. This coating composition was spin-coated on the ITO substrate. The spin coating was performed in an air atmosphere at a temperature of 23 ° C. and a relative humidity of 60%, the spinner rotation speed was 1500 rpm, and the spinner time was 30 seconds. After spin coating, it was heated at 230 ° C. for 1 hour in an atmospheric pressure atmosphere in an oven. In this way, a sample layer (corresponding to a hole injection layer of an organic electroluminescence device) 10 was formed.

Subsequently, a stripe shadow mask having a width of 2 mm as a mask for cathode vapor deposition was brought into close contact with the element so as to be orthogonal to the ITO stripe of the anode 2. After the apparatus was roughly evacuated with an oil rotary pump, the apparatus was evacuated with a cryopump until the degree of vacuum in the apparatus was 3 × 10 ⁻⁴ Pa or less.
Aluminum was heated as a cathode 9 with a molybdenum boat, and an aluminum layer having a thickness of 80 nm was formed by controlling the deposition rate at 0.5 to 5 liters / second and the degree of vacuum at 2 to 3 × 10 ⁻⁴ Pa. The substrate temperature during the deposition of the cathode 9 was kept at room temperature.
As described above, a measuring element having an element area of 2 mm × 2 mm was obtained.

  The obtained measurement element was connected to a 2400 type source meter manufactured by Keithley, and voltage was sequentially applied to read the current value. The current-voltage characteristics of this element are shown in FIG.

(Comparative Example 4)
The arylamine polymer (H4) is represented by the following structural formula (H5) (a polymer having the same structural formula as the comparative polymer 3 synthesized in the section (polymer for comparative example): weight average molecular weight 28000, dispersity 1.7). A measuring element shown in FIG. 2 was produced in the same manner as in Example 5 except that the measuring element was replaced with the above.

  The obtained measurement element was connected to a 2400 type source meter (manufactured by Keithley), and voltage was sequentially applied to read the current value. The current-voltage characteristics of this element are shown in FIG.

(Summary of Example 5 and Comparative Example 4)
As shown in FIG. 4, the measurement element of Example 5 using the arylamine polymer of the present invention passed a current at a lower voltage than the measurement element of Comparative Example 4. From this, it is clear that the arylamine polymer of the present invention is excellent in charge transport ability.

＜正孔注入層形成用塗布液＞
溶媒 安息香酸エチル
塗布液濃度 Ｈ６：２．０重量％
Ａ１：０．４重量％
＜正孔注入層３の成膜条件＞
スピナ回転数 １５００ｒｐｍ
スピナ回転時間 ３０秒
スピンコート雰囲気 大気中
加熱条件 大気中 ２３０℃ １時間 <Production of organic electroluminescence device>
(Example 6)
The organic electroluminescent element shown in FIG. 1 was produced.
On an ITO patterning substrate prepared in the same manner as in Example 1, first, an arylamine polymer (weight average molecular weight: 60100, number average molecular weight: 34100) represented by the following structural formula (H6), represented by structural formula (A1). A coating solution for forming a hole injection layer containing 4-isopropyl-4′-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 45 nm.

<Coating liquid for hole injection layer formation>
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

＜正孔輸送層形成用塗布液＞
溶媒 シクロヘキシルベンゼン
塗布液濃度 １．４重量％
＜正孔輸送層４の成膜条件＞
スピナ回転数 １５００ｒｐｍ
スピナ回転時間 １２０秒
スピンコート雰囲気 窒素中
加熱条件 ３０℃、１時間、窒素中 Subsequently, a coating solution for forming a hole transport layer containing a polymer represented by the following structural formula (H7) (weight average molecular weight: 68000, number average molecular weight: 35000) was prepared, and a film was formed by spin coating under the following conditions. The hole transport layer 4 having a thickness of 20 nm was formed by polymerization by heating.

<Coating liquid for hole transport layer formation>
Solvent Cyclohexylbenzene Coating solution concentration 1.4% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 120 seconds Spin coating atmosphere In nitrogen Heating condition 30 ° C, 1 hour in nitrogen

＜発光層形成用塗布液＞
溶媒 シクロヘキシルベンゼン
塗布液濃度 Ｃ５：３．４０重量％
Ｄ２：０．３４重量％
＜発光層５の成膜条件＞
スピナ回転数 １２００ｒｐｍ
スピナ回転時間 １２０秒
スピンコート雰囲気 窒素中
加熱条件 １３０℃、１時間、減圧下（０．１ＭＰａ） Next, a coating solution for forming a light emitting layer containing the compounds (C5) and (D2) represented by the following structural formula is prepared, and film formation is performed by spin coating under the following conditions, followed by heating. A 40 nm light emitting layer 5 was formed.

<Light emitting layer forming coating solution>
Solvent Cyclohexylbenzene Coating solution concentration C5: 3.40% by weight
D2: 0.34% by weight
<Film-forming conditions of the light emitting layer 5>
Spinner speed 1200rpm
Spinner rotation time 120 seconds Spin coat atmosphere In nitrogen Heating condition 130 ° C., 1 hour, under reduced pressure (0.1 MPa)

電子輸送層７以降は実施例１と同様にして有機電界素子を作製した。
このようにして得られた２ｍｍ×２ｍｍサイズの発光面積部分を有する有機電界発光素子の発光特性を表−１２に示す。 Here, the substrate having the light emitting layer 5 formed thereon is transferred into a vacuum deposition apparatus, and after evacuating until the degree of vacuum in the apparatus becomes 2.0 × 10 ⁻⁴ Pa or less, an organic material having the following structure is obtained. The vapor deposition rate of the compound (C6) was controlled in the range of 0.8 to 1.2 liters / second by a vacuum vapor deposition method, and was laminated on the light emitting layer 5 to obtain a hole blocking layer 6 having a thickness of 10 nm.

After the electron transport layer 7, an organic electric field element was produced in the same manner as in Example 1.
The light emission characteristics of the organic electroluminescence device having the light emission area portion of 2 mm × 2 mm obtained in this way are shown in Table-12.

得られた素子の発光特性を表−１２に示す。 (Comparative Example 5)
Example 6 is the same as Example 6 except that the comparative polymer (H8) (weight average molecular weight: 63600, number average molecular weight: 35100) was used instead of the arylamine polymer (H6) in the composition for forming the hole injection layer in Example 6. Similarly, an organic electroluminescent element was produced.

The light emission characteristics of the obtained device are shown in Table-12.

表−１２に示すが如く、本発明のアリールアミンポリマー用いて作製した有機電界発光素子は駆動電圧が低く、電流効率が高く、更に駆動寿命が長いことが分かる。

As shown in Table-12, it can be seen that the organic electroluminescence device produced using the arylamine polymer of the present invention has a low driving voltage, a high current efficiency, and a long driving life.

＜正孔注入層形成用塗布液＞
溶媒 安息香酸エチル
塗布液濃度 Ｈ６：２．０重量％
Ａ１：０．４重量％
＜正孔注入層３の成膜条件＞
スピナ回転数 １５００ｒｐｍ
スピナ回転時間 ３０秒
スピンコート雰囲気 大気中
加熱条件 大気中 ２３０℃ １時間 (Example 7)
The organic electroluminescent element shown in FIG. 1 was produced.
On an ITO patterning substrate prepared in the same manner as in Example 1, first, an arylamine polymer (weight average molecular weight: 60100, number average molecular weight: 34100) represented by the following structural formula (H6), represented by structural formula (A1). A coating solution for forming a hole injection layer containing 4-isopropyl-4′-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 45 nm.

<Coating liquid for hole injection layer formation>
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

＜正孔輸送層形成用塗布液＞
溶媒 シクロヘキシルベンゼン
塗布液濃度 １．４重量％
＜正孔輸送層４の成膜条件＞
スピナ回転数 １５００ｒｐｍ
スピナ回転時間 １２０秒
スピンコート雰囲気 窒素中
加熱条件 ２３０℃、１時間、窒素中 Subsequently, a coating solution for forming a hole transport layer containing an arylamine polymer (weight average molecular weight: 41000, number average molecular weight: 28000) represented by the following structural formula (H9) was prepared, and spin coating was performed under the following conditions. A hole transport layer 4 having a thickness of 20 nm was formed by forming a film and polymerizing by heating.

<Coating liquid for hole transport layer formation>
Solvent Cyclohexylbenzene Coating solution concentration 1.4% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 120 seconds Spin coat atmosphere In nitrogen Heating condition 230 ° C, 1 hour in nitrogen

＜発光層形成用塗布液＞
溶媒 シクロヘキシルベンゼン
塗布液濃度 Ｃ７：３．２０重量％
Ｄ２：０．３２重量％
＜発光層５の成膜条件＞
スピナ回転数 １２００ｒｐｍ
スピナ回転時間 １２０秒
スピンコート雰囲気 窒素中
加熱条件 １３０℃、１時間、減圧下（０．１ＭＰａ） Next, a light emitting layer forming coating solution containing the compounds (C6) and (D2) shown in the following structural formula is prepared, and film formation is performed by spin coating under the following conditions, followed by heating to a film thickness of 40 nm. The light emitting layer 5 was formed.

<Light emitting layer forming coating solution>
Solvent Cyclohexylbenzene Coating solution concentration C7: 3.20% by weight
D2: 0.32% by weight
<Film-forming conditions of the light emitting layer 5>
Spinner speed 1200rpm
Spinner rotation time 120 seconds Spin coat atmosphere In nitrogen Heating condition 130 ° C., 1 hour, under reduced pressure (0.1 MPa)

After the hole blocking layer 6, an organic electric field element was produced in the same manner as in Example 6.
The light emission characteristics of the organic electroluminescence device having the light emission area portion of 2 mm × 2 mm obtained in this way are shown in Table-13.

得られた素子の発光特性を表−１３に示す。 (Comparative Example 6)
An organic electroluminescent device was produced in the same manner as in Example 6 except that the comparative polymer (H7) was used instead of the arylamine polymer (H9) in the composition for forming a hole transport layer in Example 7.

The light emitting characteristics of the obtained device are shown in Table-13.

  As shown in Table-13, it can be seen that the organic electroluminescence device produced using the arylamine polymer of the present invention has a low driving voltage and a high current efficiency.

＜正孔注入層形成用塗布液＞
溶媒 安息香酸エチル
塗布液濃度 Ｈ１０：２．０重量％
Ａ１：０．４重量％
＜正孔注入層３の成膜条件＞
スピナ回転数 １５００ｒｐｍ
スピナ回転時間 ３０秒
スピンコート雰囲気 大気中
加熱条件 大気中 ２３０℃ １時間 (Example 8)
The organic electroluminescent element shown in FIG. 1 was produced.
On an ITO patterning substrate prepared in the same manner as in Example 1, first, an arylamine polymer (weight average molecular weight: 31900, number average molecular weight: 21260) represented by the following structural formula (H10), represented by structural formula (A1). A coating solution for forming a hole injection layer containing 4-isopropyl-4′-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 35 nm.

<Coating liquid for hole injection layer formation>
Solvent Ethyl benzoate Coating solution concentration H10: 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

＜正孔輸送層形成用塗布液＞
溶媒 シクロヘキシルベンゼン
塗布液濃度 １．２重量％
＜正孔輸送層４の成膜条件＞
スピナ回転数 １５００ｒｐｍ
スピナ回転時間 １２０秒
スピンコート雰囲気 窒素中
加熱条件 ２３０℃、１時間、窒素中 Subsequently, a coating solution for forming a hole transport layer containing a polymer represented by the following structural formula (H7) (weight average molecular weight: 68000, number average molecular weight: 35000) was prepared, and a film was formed by spin coating under the following conditions. Then, the hole transport layer 4 having a film thickness of 15 nm was formed by polymerization by heating.

<Coating liquid for hole transport layer formation>
Solvent Cyclohexylbenzene Coating solution concentration 1.2% by weight
<Film formation conditions for hole transport layer 4>
Spinner speed 1500rpm
Spinner rotation time 120 seconds Spin coat atmosphere In nitrogen Heating condition 230 ° C, 1 hour in nitrogen

＜発光層形成用塗布液＞
溶媒 シクロヘキシルベンゼン
塗布液濃度 Ｃ８：３．７５重量％
Ｃ９：１．２５重量％
Ｄ３：０．２５重量％
＜発光層５の成膜条件＞
スピナ回転数 １５００ｒｐｍ
スピナ回転時間 １２０秒
スピンコート雰囲気 窒素中
加熱条件 １３０℃、１時間、減圧下（０．１ＭＰａ） Next, a coating solution for forming a light emitting layer containing the compounds (C8), (C9) and (D3) shown in the following structural formula is prepared, and film formation is performed by spin coating under the following conditions, followed by heating. A light emitting layer 5 having a thickness of 40 nm was formed.

<Light emitting layer forming coating solution>
Solvent Cyclohexylbenzene Coating solution concentration C8: 3.75% by weight
C9: 1.25% by weight
D3: 0.25% by weight
<Film formation conditions of the light emitting layer 5>
Spinner speed 1500rpm
Spinner rotation time 120 seconds Spin coat atmosphere In nitrogen Heating condition 130 ° C., 1 hour, under reduced pressure (0.1 MPa)

After the hole blocking layer 6, an organic electric field element was produced in the same manner as in Example 6.
Table-14 shows the light emission characteristics of the organic electroluminescence device having a light emitting area portion of 2 mm × 2 mm obtained in this way.

得られた素子の発光特性を表−１４に示す。 (Comparative Example 7)
An organic electroluminescent device was produced in the same manner as in Example 8, except that the comparative polymer (H8) was used instead of the arylamine polymer (H10) in the composition for forming the hole injection layer in Example 8.

The light emitting characteristics of the obtained device are shown in Table-14.

  As shown in Table-14, it can be seen that the organic electroluminescence device produced using the arylamine polymer of the present invention has a long driving life.

  The present invention relates to various fields in which organic electroluminescent elements are used, for example, flat panel displays (for example, for OA computers and wall-mounted televisions), and light sources that make use of characteristics as surface light emitters (for example, light sources for copying machines). , Liquid crystal displays and backlights for instruments), display panels, marker lamps, and the like.

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 10 Sample layer

Claims (10)

An arylamine polymer having a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2),
Arylamine polymer characterized by having a crosslinking group as the substituent on Ar ² and / or Ar ^3.

(In Formula (1) and Formula (2),
Ar ^{1 to} Ar ³ each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
R ^{1 to} R ⁴ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, or an aromatic which may have a substituent. Represents a heterocyclic group,
R ^5A represents a direct bond, an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent,
m and n each independently represents an integer of 1 or more. ) The weight average molecular weight (Mw) is 20,000 or more,
2. The arylamine polymer according to claim 1, wherein the dispersity (Mw / Mn; Mn represents a number average molecular weight) is 2.5 or less. The arylamine polymer according to claim 1 or 2, wherein the crosslinkable group is a group selected from the following crosslinkable group group T.

(In the above formula,
R ^{5 to} R ⁹ each independently represents a hydrogen atom or an alkyl group,
Ar ⁴ represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. ) An organic electroluminescent element material comprising the arylamine polymer according to any one of claims 1 to 3. The composition for organic electroluminescent elements containing the arylamine polymer as described in any one of Claims 1-3. In an organic electroluminescent device comprising a substrate, an anode, one or more organic layers, and a cathode in this order,
At least one layer of this organic layer contains the network polymer which bridge | crosslinked the arylamine polymer as described in any one of Claims 1-3, The organic electroluminescent element characterized by the above-mentioned. The organic electroluminescent device according to claim 6, wherein the layer having a network polymer is a hole injection layer or a hole transport layer. The hole injection layer and the hole transport layer, and a light emitting layer,
The organic electroluminescent device according to claim 7, wherein all of the hole injection layer, the hole transport layer, and the light emitting layer are formed by a wet film forming method. An organic EL display comprising the organic electroluminescent element according to any one of claims 6 to 8. An organic EL illumination comprising the organic electroluminescent element according to any one of claims 6 to 8.

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