WO2014132636A1

WO2014132636A1 - Polymerizable monomer, organic-device material including polymer thereof, hole injection/transport material, organic-electroluminescent-element material, and organic electroluminescent element

Info

Publication number: WO2014132636A1
Application number: PCT/JP2014/001018
Authority: WO
Inventors: 加藤　朋希; 藤山　高広
Original assignee: 出光興産株式会社; 三井化学株式会社
Priority date: 2013-03-01
Filing date: 2014-02-26
Publication date: 2014-09-04
Also published as: JP2016119320A

Abstract

This polymerizable monomer is represented by formula (1).

Description

Polymerizable monomer, organic device material containing the polymer, hole injecting and transporting material, organic electroluminescent element material, and organic electroluminescent element

The present invention relates to a polymerizable monomer, an organic device material containing the polymer, a hole injecting and transporting material, an organic electroluminescent element material, and an organic electroluminescent element.

In recent years, displays and illumination devices using organic electroluminescence elements (hereinafter referred to as organic EL elements) have been put into practical use. For these devices, cost reduction and large screen are cited as major issues.
Therefore, the expectation from the conventional vacuum evaporation type organic EL element to the (solution) coating type organic EL element is increasing. When the coating type is used, the material utilization efficiency is high, and large-screen film formation is facilitated. Furthermore, since a vacuum system is unnecessary, the cost of the manufacturing apparatus is expected to be low.

Here, the coating type organic EL material includes a low molecular weight type and a high molecular weight type, but a high molecular weight type is preferable from the viewpoint of solubility, coating uniformity, and formation of a laminated element. In addition, it is desired to develop a polymer-based hole transport (injection) layer material that can be a common layer for displays and lighting devices.
As a polymer hole transport (injection) layer material, a polymer having a repeating unit obtained by substituting a vinyl group for a low molecular hole transport material is known.
The applicant of the present application has proposed a polymerizable monomer and a polymer useful as a coating-type organic device material (see, for example, Patent Documents 1 and 2).

JP 2012-111719 A International Publication No. 2010/103765

An object of the present invention is to provide a novel polymerizable monomer and polymer that can be used as a coating type organic device material. Another object of the present invention is to provide an organic EL element which is a coating type organic EL element and has improved element characteristics such as life and luminous efficiency.

According to one embodiment of the present invention, a polymerizable monomer represented by the following formula (1) is provided.

(In the formula, Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms. The substituents that Ar ¹ and Ar ² may have are substituted with a linear or branched alkyl group having 1 to 30 carbon atoms and a polymerizable functional group which may be substituted with a polymerizable functional group. An optionally substituted cycloalkyl group having 3 to 10 ring carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms which may be substituted with a polymerizable functional group, and a triarylsilyl group having 18 to 30 ring carbon atoms An alkylarylsilyl group having 8 to 15 carbon atoms that may be substituted with a polymerizable functional group (the ring of an aryl group that has 1 to 5 carbon atoms and may be substituted with a polymerizable functional group) The number of carbons formed is 6-14 An aryl group having 6 to 50 ring carbon atoms which may be substituted with a polymerizable functional group, a heteroaryl group having 5 to 50 ring atoms which may be substituted with a polymerizable functional group, halogen An atom or a cyano group.
R ¹ and R ² are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, substituted Or an unsubstituted trialkylsilyl group having 3 to 10 carbon atoms, a substituted or unsubstituted triarylsilyl group having 18 to 30 ring carbon atoms, a substituted or unsubstituted alkylarylsilyl group having 8 to 15 carbon atoms, substituted Alternatively, it represents an unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, a polymerizable functional group, a halogen atom, or a cyano group.
R ¹¹ and R ¹² are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, substituted Or an unsubstituted trialkylsilyl group having 3 to 10 carbon atoms, a substituted or unsubstituted triarylsilyl group having 18 to 30 ring carbon atoms, a substituted or unsubstituted alkylarylsilyl group having 8 to 15 carbon atoms, substituted Alternatively, it represents an unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, a polymerizable functional group, a halogen atom, or a cyano group.
R ³ and R ⁴ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, substituted Alternatively, it represents an unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, or a polymerizable functional group. R ³ and R ⁴ may combine with each other to form a saturated or unsaturated divalent group that forms a ring.
n ¹ and n ² each independently represents an integer of 0 to 4.
m ¹ and m ² each independently represents an integer of 0 to 3.
When n ¹ is 2 to 4, a plurality of R ¹ may be the same or different from each other, and a plurality of adjacent R ¹ are bonded to each other to form a saturated or unsaturated divalent group that forms a ring. It may be formed.
When n ² is 2 to 4, a plurality of R ² may be the same or different from each other, and a plurality of adjacent R ² are bonded to each other to form a saturated or unsaturated divalent group that forms a ring. It may be formed.
When m ¹ is 2 or 3, a plurality of R ¹¹ may be the same or different from each other, and a plurality of adjacent R ¹¹ are bonded to each other to form a saturated or unsaturated divalent group that forms a ring. It may be formed.
When m ² is 2 or 3, a plurality of R ¹² may be the same or different from each other, and a plurality of adjacent R ¹² are bonded to each other to form a saturated or unsaturated divalent group forming a ring. It may be formed.
Two or more of R ¹ to R ⁴ , R ¹¹ , R ¹² , Ar ¹ and Ar ² contain a polymerizable functional group. )

According to the present invention, a novel polymerizable monomer and a coating-type organic device material obtained by thermal polymerization or the like can be provided.
According to the present invention, it is possible to provide a coating type organic EL element having a long lifetime and high luminous efficiency.

The polymerizable monomer of the present invention is represented by the following formula (1).

The molecular structure represented by the above formula (1), that is, a structure in which a carbazole skeleton, a fluorene skeleton, and an arylamine skeleton are connected (hole transporting structure) has a high hole transporting property. Therefore, the polymerizable monomer of the present invention can be used as a material for a hole transport layer of an organic EL device, for example.
Since the polymerizable monomer of Patent Document 1 described above has a structure in which two or more hole transporting structures are connected via a linking group, there is a problem that the solubility is low. In the present invention, the solubility of the monomer can be improved by providing one hole transporting structure for one polymerizable monomer. Thereby, the film-forming property of the film | membrane obtained by polymerizing a polymerizable monomer improves.

In addition, the polymerizable monomer of the present invention includes two or more polymerizable functional groups among R ¹ to R ⁴ , R ¹¹ , R ¹² , Ar ¹ and Ar ^{2 in} the formula (1). Thereby, the heat resistance and smoothness of the film obtained by polymerizing the polymerizable monomer are improved.

In the formula (1), Ar ¹ and Ar ² are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms. Represents.
The substituent that Ar ¹ and Ar ² may have is substituted with a linear or branched alkyl group having 1 to 30 carbon atoms, which may be substituted with a polymerizable functional group, or a polymerizable functional group. A cycloalkyl group having 3 to 10 ring carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms which may be substituted with a polymerizable functional group, a triarylsilyl group having 18 to 30 ring carbon atoms, An alkylarylsilyl group having 8 to 15 carbon atoms which may be substituted with a polymerizable functional group (ring formation of an aryl group which has an alkyl group having 1 to 5 carbon atoms and may be substituted with a polymerizable functional group) The number of carbon atoms is 6 to 14.), an aryl group having 6 to 50 ring-forming carbon atoms which may be substituted with a polymerizable functional group, and 5 to 5 ring-forming atoms which may be substituted with a polymerizable functional group 50 heteroaryl groups, halogen atoms or An anode group.

R ¹ and R ² are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, substituted Or an unsubstituted trialkylsilyl group having 3 to 10 carbon atoms, a substituted or unsubstituted triarylsilyl group having 18 to 30 ring carbon atoms, a substituted or unsubstituted alkylarylsilyl group having 8 to 15 carbon atoms, substituted Alternatively, it represents an unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, a polymerizable functional group, a halogen atom, or a cyano group.

R ¹¹ and R ¹² are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, substituted Or an unsubstituted trialkylsilyl group having 3 to 10 carbon atoms, a substituted or unsubstituted triarylsilyl group having 18 to 30 ring carbon atoms, a substituted or unsubstituted alkylarylsilyl group having 8 to 15 carbon atoms, substituted Alternatively, it represents an unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, a polymerizable functional group, a halogen atom, or a cyano group.

R ³ and R ⁴ are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, substituted Alternatively, it represents an unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, or a polymerizable functional group. R ³ and R ⁴ may combine with each other to form a saturated or unsaturated divalent group that forms a ring.

R ³ and R ⁴ are each preferably a substituted or unsubstituted linear alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms. Thereby, the solubility of a polymerizable monomer improves.

n ¹ and n ² each independently represents an integer of 0 to 4.
m ¹ and m ² each independently represents an integer of 0 to 3.
When n ¹ is 2 to 4, a plurality of R ¹ may be the same or different from each other, and a plurality of adjacent R ¹ are bonded to each other to form a saturated or unsaturated divalent group that forms a ring. It may be formed.
When n ² is 2 to 4, a plurality of R ² may be the same or different from each other, and a plurality of adjacent R ² are bonded to each other to form a saturated or unsaturated divalent group that forms a ring. It may be formed.
When m ¹ is 2 or 3, a plurality of R ¹¹ may be the same or different from each other, and a plurality of adjacent R ¹¹ are bonded to each other to form a saturated or unsaturated divalent group that forms a ring. It may be formed.
When m ² is 2 or 3, a plurality of R ¹² may be the same or different from each other, and a plurality of adjacent R ¹² are bonded to each other to form a saturated or unsaturated divalent group forming a ring. It may be formed.

Two or more of R ¹ to R ⁴ , R ¹¹ , R ¹² , Ar ¹ and Ar ² contain a polymerizable functional group.
In the polymerizable monomer of the present invention, the number of polymerizable functional groups is preferably 2 to 4 because the heat resistance and smoothness of the film obtained by polymerizing the polymerizable monomer are improved.

Among the monomers represented by the above formula (1), those represented by the following formula (2) are preferable.

(In the formula, R ¹ to R ⁴ , R ¹¹ , R ¹² , Ar ¹ , Ar ² , n ¹ , n ² , m ^1, and m ² have the same meanings as those in the above formula (1).)

In the above formulas (1) and (2), it is preferable that at least one of Ar ¹ and Ar ² is a group represented by the following formula (3) or (4). Thereby, since a glass transition temperature improves by inserting a rigid structure, film | membrane stability improves. Furthermore, since reduction resistance (electron resistance) improves, durability and lifetime of an organic device, especially an organic EL element improve.

[Wherein, L ¹ represents a single bond or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
L ² is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
The substituent that L ¹ and L ² may have is substituted with a linear or branched alkyl group having 1 to 30 carbon atoms and a polymerizable functional group which may be substituted with a polymerizable functional group. An optionally substituted cycloalkyl group having 3 to 10 ring carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms which may be substituted with a polymerizable functional group, and a triarylsilyl group having 18 to 30 ring carbon atoms An alkylarylsilyl group having 8 to 15 carbon atoms that may be substituted with a polymerizable functional group (the ring of an aryl group that has 1 to 5 carbon atoms and may be substituted with a polymerizable functional group) The number of carbon atoms formed is 6 to 14.), an aryl group having 6 to 50 ring carbon atoms that may be substituted with a polymerizable functional group, and a ring atom number 5 that may be substituted with a polymerizable functional group Up to 50 heteroaryl groups, halogen atoms or An anode group.
X is a substituted or unsubstituted heteroatom.
When X is substituted, the substituent is an alkyl group having 1 to 20 carbon atoms which may be substituted with a polymerizable functional group, or a carbon group having 3 to 10 carbon atoms which may be substituted with a polymerizable functional group. A cycloalkyl group, an aryl group having 6 to 30 ring carbon atoms which may be substituted with a polymerizable functional group, an aralkyl group having 7 to 31 carbon atoms which may be substituted with a polymerizable functional group (ring of the aryl moiety) And one or more groups selected from the group consisting of heterocyclic groups having 6 to 30 carbon atoms and 3 to 30 ring-forming atoms optionally substituted with a polymerizable functional group.
R ¹³ to R ¹⁶ are each independently substituted with a polymerizable functional group, a linear or branched alkyl group having 1 to 30 carbon atoms which may be substituted with a polymerizable functional group, or a polymerizable functional group. An optionally substituted cycloalkyl group having 3 to 10 ring carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms which may be substituted with a polymerizable functional group, and a triarylsilyl group having 18 to 30 ring carbon atoms An alkylarylsilyl group having 8 to 15 carbon atoms that may be substituted with a polymerizable functional group (the ring of an aryl group that has 1 to 5 carbon atoms and may be substituted with a polymerizable functional group) The number of carbon atoms formed is 6 to 14.), an aryl group having 6 to 50 ring carbon atoms that may be substituted with a polymerizable functional group, and a ring atom number 5 that may be substituted with a polymerizable functional group ~ 50 heteroaryl groups, halogen Komata is a cyano group.
a is an integer of 0 to 3.
b to d are each independently an integer of 0 to 4. ]
As the hetero atom of X, an oxygen atom, a sulfur atom and a nitrogen atom are preferable.

The group containing the polymerizable functional group contained in the polymerizable monomer of the present invention is preferably a group containing a vinyl group, vinylidene group, vinylene group or ethynylene group represented by the following formula (i); A group containing a benzocyclobutene group represented by the following formula: a group containing an N-maleimide group represented by the following formula (iii): a group containing a norbornenyl group represented by the following formula (iv): represented by the following formula (v): A group containing an acetylenyl group; or (vi) a group having a substituted or unsubstituted norbornene skeleton other than the group represented by the formula (iv), a group having a substituted or unsubstituted epoxy group or an oxetane group, a lactone structure or a lactam Functional groups having a structure, cyclooctatetraene group, 1,5-cyclooctadiene group, 1, ω-diene group, O-divinylbenzene group, and 1, - a group containing a cyclic polymerization or ring-opening polymerizable functional group selected from the group consisting of diyne groups.

(Wherein R ₁₁ , R ₁₂ and R ₁₃ are each independently a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted ring-forming carbon number. 6 to 24 aryl groups.
L ₁₁ is a divalent linking group.
n is an integer of 0 or 1, and when n is 0, L ₁₁ is a single bond)

(In the formula, L ₁₁ is a divalent linking group.
n is an integer of 0 or 1, and when n is 0, L ₁₁ is a single bond)

Wherein R ₁₄ is a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms. .
L ₁₁ is a divalent linking group.
n is an integer of 0 or 1, and when n is 0, L ₁₁ is a single bond)

In the formulas (i) to (v), the divalent linking group of L ₁₁ is preferably —L ₁₂ —, —O—, —C (═O) —, —C (═O) O—, —OC. A divalent linkage represented by (═O) —, —C (═O) NR ₁₅ —, —NR ₁₆ C (═O) —, —NR ₁₇ —, —S—, and —C (═S) —. It includes any linking group containing any of the groups, or two or more of these linking groups bonded in any order.
L ₁₂ represents a substituted or unsubstituted arylene group having 6 to 24 ring carbon atoms, a substituted or unsubstituted divalent heterocyclic group having 3 to 24 ring atoms, a substituted or unsubstituted carbon group having 1 to 20 carbon atoms. Or a linking group selected from the group consisting of a linear or branched alkylene group, a substituted or unsubstituted vinylene group, a substituted or unsubstituted vinylidene group, and an ethynylene group, or two or more selected from the above group Each of R ₁₅ to R ₁₇ is independently a hydrogen atom, a substituted or unsubstituted linear or branched alkyl group having 1 to 20 carbon atoms, And L ₁₁ selected from the group consisting of a substituted or unsubstituted aryl group having 6 to 24 ring carbon atoms and a linking group as described above improves the solubility of the monomer in the coating solvent. ,polymerization応率 high, reduce the unreacted monomers, the organic device can be improved particularly the durability and lifetime of the organic EL element.

L ₁₂ is preferably a linking group containing a substituted or unsubstituted linear or branched alkylene group having 3 to 12 carbon atoms.
When L ₁₂ contains a linear or branched alkylene group having 3 to 12 carbon atoms, the solubility of the monomer in the coating solvent can be improved.

The group (vi) is preferably a group having a substituted or unsubstituted epoxy group or oxetane group.
When the group containing a polymerizable functional group is the group (vi), the polymerization reaction can be performed at a low temperature, and adverse effects due to heat on the hole injection / transport unit can be reduced.

In the present invention, when at least one of R ¹ and R ² in the above formula (1) has a polymerizable functional group, charge injection hopping transport between molecules is advantageous due to the proximity of the hole injection transport units. This is preferable because hole transport is promoted.
In addition, when at least one of R ³ and R ⁴ has a polymerizable functional group, the polymerizable functional group can be separated from the hole injecting and transporting unit, and the radical and / or cation that is a reactive species of the polymerization The adverse effect on the hole injecting and transporting unit can be reduced. Moreover, since the freedom degree of a polymeric functional group increases, since a polymerization reaction rate is high, an unreacted monomer reduces, and durability and lifetime of an organic device, especially an organic EL element can be improved, it is preferable.
In addition, when at least one of Ar ¹ and Ar ² has a polymerizable functional group, the hole injection and transport units come close to each other, which makes charge hopping transport between molecules advantageous and facilitates hole transport. Therefore, it is preferable.

At least one of R ¹ and R ^{2 in} the formula (1) has a polymerizable functional group, and at least one of R ³ , R ⁴ , R ¹¹ , R ¹² , Ar ¹ and Ar ² is a polymerizable functional group. It preferably has a group.
Also, at least one of R ³ , R ⁴ , R ¹¹ , and R ¹² has a polymerizable functional group, and at least one of R ¹ , R ² , Ar ^1, and Ar ² has a polymerizable functional group Is preferred.
Furthermore, it is preferable that at least one of Ar ¹ and Ar ² has a polymerizable functional group, and at least one of R ¹ to R ⁴ , R ¹¹ , and R ¹² has a polymerizable functional group.
In the above case, the polymerizable functional group crosslinks the molecules on the network, and as a result of improving the film formability, the organic device, particularly the organic EL element can be driven at a low voltage, and the durability and life are improved. Can do.

Specific examples of the groups related to the formulas (1) to (4) and the groups (i) to (iv) containing a polymerizable functional group and each substituent are shown below.
In the present specification, the aryl group includes a monocyclic aromatic hydrocarbon ring group and a condensed aromatic hydrocarbon ring group in which a plurality of hydrocarbon rings are condensed, and the heteroaryl group is a monocyclic heteroaromatic group. And a hetero-fused aromatic ring group in which a plurality of heteroaromatic rings are condensed, and a hetero-fused aromatic ring group in which an aromatic hydrocarbon ring and a heteroaromatic ring are condensed.
Ring-forming carbon (nuclear carbon) means a carbon atom constituting an aromatic ring, and ring-forming atom (nuclear atom) constitutes a heterocyclic ring (including a saturated ring, an unsaturated ring and an aromatic heterocyclic ring). Means carbon and heteroatoms.
The “carbon number ab” in the expression “substituted or unsubstituted X group having carbon number ab” represents the number of carbons when the X group is unsubstituted, and the X group is substituted. The carbon number of the substituent in the case where it is present is not included.
In the present invention, the hydrogen atom includes isotopes having different numbers of neutrons, that is, light hydrogen (protium), deuterium (triuterium), and tritium.

Examples of aryl groups:
Specific examples of the aryl group include, for example, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3- Phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, biphenyl-2-yl group, Biphenyl-3-yl group, biphenyl-4-yl group, p-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, m-terphenyl-4 -Yl group, m-terphenyl-3-yl group, m-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, pt-butylphenyl Group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4′-methylbiphenyl-4-yl group Examples include a 4 ″ -t-butyl-p-terphenyl-4-yl group, a fluoren-1-yl group, a fluoren-2-yl group, a fluoren-3-yl group, and a fluoren-4-yl group.
Among them, phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, biphenyl-2-yl group, biphenyl-3-yl group, biphenyl-4-yl group P-terphenyl-4-yl group, p-terphenyl-3-yl group, p-terphenyl-2-yl group, o-tolyl group, m-tolyl group, p-tolyl group, fluorene-2- Yl group and fluoren-3-yl group are preferable, and phenyl group, 1-naphthyl group, 2-naphthyl group, m-tolyl group, p-tolyl group, fluoren-2-yl group and fluoren-3-yl group are more preferable. preferable.

Examples of arylene groups:
Each of the aryl groups is selected from divalent groups obtained by removing one aromatic hydrogen.
Among them, 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthylene group, 1,10-anthrylene group, 4,4′-biphenylylene group, 3,4′-biphenylylene group, 4,3 ′ -Biphenylylene group, 4,4 "-p-terphenylylene group, 3,4" -p-terphenylylene group, 4,3 "-p-terphenylylene group, 1,4-tolylene group, 4,4" -fluorenylene group, 3 , 3 "-fluorenylene group is preferred, 1,4-phenylene group, 1,4-naphthylene group, 1,10-anthrylene group, 4,4'-biphenylylene group, 3,4'-biphenylylene group, 4,4" -P-terphenylylene group, 2,7-fluorenylene group and 3,6-fluorenylene group are more preferable.

Examples of substituents when the above aryl group and arylene group are substituted, and examples of other groups are shown below. In addition, what overlaps with the above is abbreviate | omitted.

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, n-hexyl group, n- Heptyl, n-octyl, hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 2-hydroxyisobutyl, 1,2-dihydroxyethyl, 1,3-dihydroxyisopropyl, 2,3- And dihydroxy-t-butyl group, 1,2,3-trihydroxypropyl group, and the like, preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, A tert-butyl group.
Of these, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group and t-butyl group are preferable.

Specific examples of the cycloalkyl group include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, a cyclohexylethyl group, a 4-fluorocyclohexyl group, a 1-adamantyl group, and a 2-adamantyl group. Group, 1-norbornyl group, 2-norbornyl group and the like, and a cyclopentyl group and a cyclohexyl group are preferable.

An alkoxy group, a cycloalkoxy group, and an aryloxy group are groups in which an O atom is interposed at the substitution site of the alkyl group, cycloalkyl group, or aryl group.

Aralkyl group is a group in which the aryl group is substituted for the alkyl group.

Specific examples of the trialkylsilyl group include, for example, a trimethylsilyl group, a vinyldimethylsilyl group, a triethylsilyl group, a tripropylsilyl group, a propyldimethylsilyl group, a tributylsilyl group, a t-butyldimethylsilyl group, a tripentylsilyl group, Examples thereof include a triheptylsilyl group and a trihexylsilyl group, and a trimethylsilyl group and a triethylsilyl group are preferable. The alkyl group substituted by the silyl group may be the same or different.

Specific examples of the triarylsilyl group include, for example, a triphenylsilyl group and a trinaphthylsilyl group. Preferably,
Triphenylsilyl group. The aryl groups substituted on the silyl group may be the same or different.

Specific examples of the dialkylarylsilyl group include, for example, dimethylphenylsilyl group, diethylphenylsilyl group, dipropylphenylsilyl group, dibutylphenylsilyl group, dipentylphenylsilyl group, diheptylphenylsilyl group, dihexylphenylsilyl group, dimethyl Naphthylsilyl group, dipropylnaphthylsilyl group, dibutylnaphthylsilyl group, dipentylnaphthylsilyl group, diheptylnaphthylsilyl group, dihexylnaphthylsilyl group, dimethylanthrylsilyl group, diethylanthrylsilyl group, dipropylanthrylsilyl group, Examples include dibutylanthrylsilyl group, dipentylanthrylsilyl group, diheptylanthrylsilyl group, dihexylanthrylsilyl group, and diphenylmethyl group. Nirushiriru group, diethyl phenyl silyl group.

Specific examples of the alkyldiarylsilyl group include, for example, methyldiphenylsilyl group, ethyldiphenylsilyl group, propyldiphenylsilyl group, butyldiphenylsilyl group, pentyldiphenylsilyl group, heptyldiphenylsilyl group, and the like. A methyldiphenylsilyl group and an ethyldiphenylsilyl group.

Specific examples of the heteroaryl group (heterocyclic group) include 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group. Group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group Group, 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group Group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isoben Furanyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, 9-carbazolyl group, 1-phenanthridinyl group, 2-phenanthridinyl group 3-phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8- Enanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1,7-phenanthroline 2-yl group, 1,7-phenanthroline-3-yl group, 1,7-phenanthroline-4-yl group, 1,7-phenanthroline-5-yl group, 1,7-phenanthroline-6-yl group, 1 , 7-phenanthroline-8-yl group, 1,7-phenanthroline-9-yl group, 1,7-phenanthroline-10-yl group, 1,8-phenanthroline-2-yl group, 1,8-phenanthroline-3 -Yl group, 1,8-phenanthroline-4-yl group, 1,8-phenanthroline-5-yl group, 1,8-phenanthroline-6-yl group 1,8-phenanthroline-7-yl group, 1,8-phenanthroline-9-yl group, 1,8-phenanthroline-10-yl group, 1,9-phenanthroline-2-yl group, 1,9- Phenanthroline-3-yl group, 1,9-phenanthroline-4-yl group, 1,9-phenanthroline-5-yl group, 1,9-phenanthroline-6-yl group, 1,9-phenanthroline-7-yl group 1,9-phenanthroline-8-yl group, 1,9-phenanthroline-10-yl group, 1,10-phenanthroline-2-yl group, 1,10-phenanthroline-3-yl group, 1,10-phenanthroline -4-yl group, 1,10-phenanthroline-5-yl group, 2,9-phenanthroline-1-yl group, 2,9-phenanthroline-3-yl group, 2, -Phenanthroline-4-yl group, 2,9-phenanthroline-5-yl group, 2,9-phenanthroline-6-yl group, 2,9-phenanthroline-7-yl group, 2,9-phenanthroline-8-yl group Group, 2,9-phenanthroline-10-yl group, 2,8-phenanthroline-1-yl group, 2,8-phenanthroline-3-yl group, 2,8-phenanthroline-4-yl group, 2,8- Phenanthroline-5-yl group, 2,8-phenanthroline-6-yl group, 2,8-phenanthroline-7-yl group, 2,8-phenanthroline-9-yl group, 2,8-phenanthroline-10-yl group 2,7-phenanthroline-1-yl group, 2,7-phenanthroline-3-yl group, 2,7-phenanthroline-4-yl group, 2,7-phenanthro N-5-yl group, 2,7-phenanthroline-6-yl group, 2,7-phenanthroline-8-yl group, 2,7-phenanthroline-9-yl group, 2,7-phenanthroline-10-yl group 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group, 4-phenothiazinyl group, 10-phenothiazinyl group, 1-phenoxazinyl group, 2-phenoxazinyl group 3-phenoxazinyl group, 4-phenoxazinyl group, 10-phenoxazinyl group, 2-oxazolyl group, 4-oxazolyl group, 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group , 3-thienyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrole-3 -Yl group, 2-methylpyrrol-4-yl group, 2-methylpyrrol-5-yl group, 3-methylpyrrol-1-yl group, 3-methylpyrrol-2-yl group, 3-methylpyrrole-4 -Yl group, 3-methylpyrrol-5-yl group, 2-t-butylpyrrol-4-yl group, 3- (2-phenylpropyl) pyrrol-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1-indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2-t-butyl 1-indolyl group, 4-t-butyl 1-indolyl group, 2-t -Butyl 3-indolyl group, 4-t-butyl 3-indolyl group and the like can be mentioned.
Preferred are 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group, and 9-carbazolyl group.

The mono- or dialkylamino group is a group in which the alkyl group is substituted on the amino group.

A mono or diarylamino group is a group obtained by substituting the aryl group for an amino group.

An alkylarylamino group is a group obtained by substituting the alkyl group and aryl group for an amino group.

Specific examples of the halogen atom are fluorine, chlorine and bromine.
Of these, fluorine is preferred. The reason is that since the surface tension of the obtained polymer is lowered, a more uniform coating film can be formed.

The alkyl group, cycloalkyl group, aryl group, alkoxy group, cycloalkoxy group, 6-30 aryloxy group, aralkyl group, heterocyclic group, mono- or dialkylamino group, mono- or diarylamino group, alkylarylamino group In the trialkylsilyl group, triarylsilyl group, dialkylarylsilyl group or alkyldiarylsilyl group, a hydrogen atom may be substituted with a halogen atom. Of the halogen atoms, a fluorine atom is preferred. The reason is that since the surface tension of the obtained polymer is lowered, a more uniform coating film can be formed.

Specific examples of the polymerizable monomer of the present invention are shown below.

The polymerizable monomer of the present invention can be synthesized by referring to, for example, International Publication No. 2010/103765.

The polymer of this invention is a polymer containing the structural unit derived from the polymerizable monomer of this invention mentioned above, and consists of either of the following.
(A) a homopolymer having a repeating unit derived from one type selected from the polymerizable monomers of the present invention described above (b) two or more types selected from the polymerizable monomers of the present invention described above Copolymer having repeating unit derived from monomer (c) Repeating unit derived from one or more monomers selected from the polymerizable monomers of the present invention described above and other monomer Copolymer containing repeating unit derived from body

In the copolymer (c), the unit derived from the polymerizable monomer of the present invention preferably contains 10 mol% or more, more preferably 30 mol% or more, and more preferably 50 mol%. More preferably, it is contained. By containing 70 mol% or more of units derived from the polymerizable monomer of the present invention, the effects obtained using the polymerizable monomer of the present invention are sufficiently exhibited, which is particularly preferable.

With respect to the copolymers (b) and (c), there is no particular limitation on the bonding mode, and random copolymers, alternating copolymers, block copolymers, graft copolymers, random block copolymers, comb shapes Any of a copolymer, a star copolymer and the like may be used.
In the case of the copolymer (c), a random copolymer (-ABBABBBAAABA) containing a repeating unit A (for example, polymerizable monomers (I) to (III)) and a repeating unit B (another monomer). -), Alternating copolymer (-ABABABABABAB-), block copolymer (-AAAAAAABBBBBB-), graft copolymer (either repeating unit A or repeating unit B may be the main chain, which is the side chain) Any of them).

The other monomer of the copolymer (c) is preferably a polymerization in which a monoamine aromatic compound, a diamine aromatic compound, and a triamine aromatic compound shown below are substituted with a group containing a polymerizable functional group. Monomer.

(Wherein, Ar ^a to Ar ^e are each independently a substituted or unsubstituted aryl group having 6 to 40 ring carbon atoms,
L ^a and L ^b are each independently a substituted or unsubstituted arylene group having 6 to 40 ring carbon atoms.
Examples of Ar ^a to Ar ^e and the aryl and arylene groups of L ^a and L ^b are the same as those described above.
^The substitution group of the Ar a ~ Ar ^e and ^{L a} and ^{L b} are each independently an alkyl group having 1 to 20 carbon atoms, having 3 to 10 carbon atoms a cycloalkyl group, ring-forming carbon number of 6 to 30 An aryl group, an alkoxy group having 1 to 20 carbon atoms, a cycloalkoxy group having 3 to 10 carbon atoms, an aryloxy group having 6 to 30 ring carbon atoms, an aralkyl group having 7 to 31 carbon atoms (the number of carbon atoms forming the ring of the aryl moiety) 6 to 30), a heterocyclic group having 3 to 30 ring atoms, a mono or dialkylamino group having an alkyl group having 1 to 20 carbon atoms, and a mono or diarylamino having an aryl group having 6 to 30 ring carbon atoms A trialkylsilyl group having 3 to 20 carbon atoms, a triarylsilyl group having 18 to 30 ring carbon atoms, a dialkylarylsilyl group having 8 to 30 carbon atoms, or an alkyldiary group. Rusilyl group (the aryl portion has 6 to 20 ring carbon atoms), 8 to 30 alkyl arylamino group (the aryl portion has 6 to 20 ring carbon atoms), halogen atom, nitro group, cyano group and hydroxyl group One or more groups selected from the group consisting of groups. )

The group containing a polymerizable functional group is preferably substituted with the terminal aromatic group of Ar ^a to Ar ^e of the above-described amine-based aromatic compound.
The group containing a polymerizable functional group on the terminal aromatic group is more preferably a para-position to the moiety other than the terminal aromatic group in the above formula (for example, 1 if the terminal aromatic group is a phenylene group). , 4 position).
This is because the interaction between the side chains is reduced and the occurrence of excimers and exciplexes can be reduced, so that the device performance such as the hole transport ability of the polymer is improved, the polymerization reaction rate is high, and the unreacted single unit. This is because the mass is reduced and the durability and life of the organic device, particularly the organic EL element, are improved.

By using such a copolymer (c), the solubility of the resulting polymer in a coating solvent can be improved, and hole injection characteristics and transport characteristics can be improved.

There is no restriction | limiting in particular in the molecular weight of the polymer of this invention, From the oligomer more than a dimer to an ultra high molecular body is contained. The number average molecular weight (Mn) is preferably 10 ³ to 10 ⁸ , more preferably 10 ³ to 10 ⁶ . The weight average molecular weight (Mw) is preferably 10 ³ to 10 ⁸ , more preferably 10 ³ to 10 ⁶ . The molecular weight distribution represented by Mw / Mn is not particularly limited, but is preferably 10 or less, and more preferably 3 or less. If the molecular weight is too large, it becomes impossible to form a uniform film in forming the device due to gelation, and if the molecular weight is too small, it is difficult to control the solubility. Both molecular weights are obtained by calibration with standard polystyrene using size exclusion chromatography (SEC).
The reason for the blue light-emitting organic electroluminescence device is not clear, but for the polymer of the present invention, the number average molecular weight (Mn) is from 10 ³ to 5 × 10 ⁶ , or the weight average molecular weight (Mw) is from 10 ³ to In 5 × 10 ⁵ , higher emission efficiency, longer life, and higher heat resistance of a blue light-emitting organic electroluminescence element were confirmed.

The polymer of the present invention can be produced by addition, cyclization or ring-opening polymerization of a monomer. The polymerization method is not particularly limited, but can be carried out by heating, light irradiation, or addition of a reaction initiator.

The polymerization method of the polymer of the present invention is not limited, and examples thereof include a radical polymerization method, an ionic polymerization method, a living polymerization method, a radical living polymerization method, and coordination polymerization. In particular, radical polymerization or cationic polymerization is preferred. Examples of the radical polymerization initiator include azo compounds and peroxides, and azobisisobutyronitrile (AIBN), azobisisobutyric acid diester derivatives, and dibenzoyl peroxide (BPO) are preferable.
As the initiator for cationic polymerization, various strong acids (p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.) and Lewis acids are preferable.

The polymerization solvent is not particularly limited. For example, aromatic hydrocarbon solvents such as toluene and chlorobenzene, halogenated hydrocarbon solvents such as methylene chloride and dichloroethane and chloroform, ether solvents such as tetrahydrofuran and dioxane, dimethylformamide and the like. Amide solvents, alcohol solvents such as methanol, ester solvents such as ethyl acetate, ketone solvents such as acetone, and the like. Depending on the selection of the solvent, solution polymerization for polymerization in a homogeneous system and precipitation polymerization for precipitation of the produced polymer can also be carried out.
These organic solvents may be used alone or in combination of two or more. The amount of the organic solvent used is preferably such that the monomer concentration is 0.1 to 90% by weight, more preferably 1 to 50% by weight.

The polymerization temperature is not particularly limited as long as the reaction medium is kept in a liquid state. −100 to 200 ° C. is preferable, and 0 to 120 ° C. is more preferable. Although the reaction time varies depending on the reaction conditions such as reaction temperature, it is preferably 1 hour or longer, more preferably 2 to 500 hours.

The polymer product can be obtained by a known method, for example, by adding a reaction solution to a lower alcohol such as methanol and filtering and drying the resulting precipitate. When the purity of the polymer compound is low, it may be purified by a usual method such as recrystallization, Soxhlet continuous extraction, force ram chromatography or the like.
By purifying in this way, impurities such as unreacted monomers and polymerization catalyst are removed, so that the durability and life of the organic device, particularly the organic EL element, are improved.

The polymer of the present invention obtained as described above and the polymerizable monomer of the present invention are suitable for the following organic device materials, hole injection transport materials, and organic electroluminescence element materials. Organic devices, especially organic EL elements, that can be used in applications, have excellent element characteristics such as lifetime and light emission efficiency, and are suitable for practical use with little deterioration even after practical high-temperature driving for displays and lighting applications. An organic EL element can be provided.
In addition, since the hole injecting and transporting layer can be uniformly formed by a coating method, it is suitable for reducing the cost or increasing the screen size for displays and lighting applications.

Here, examples of organic devices include organic TFTs, photoelectric conversion elements such as organic TFTs and organic solar cells, image sensors, and the like.
Examples of organic EL elements are flat light emitters such as flat panel displays for wall-mounted televisions, general or special lighting, copying machines, printers, light sources such as backlights for liquid crystal displays or instruments, display boards, indicator lights, etc. it can.
The polymer of the present invention can also be used as a material for an electrophotographic photoreceptor.

In the organic EL device of the present invention, an organic thin film layer composed of one or more layers including at least a light emitting layer is sandwiched between a cathode and an anode, and at least one of the organic thin film layers contains the polymer of the present invention. To do.
In the organic EL device of the present invention, the organic thin film layer includes one or both of a hole transport layer and a hole injection layer, and the polymer of the present invention is either the hole transport layer or the hole injection layer. Or it is preferable to contain in both.
In the organic EL device of the present invention, the light emitting layer preferably contains one or both of a styrylamine compound and an arylamine compound.

The organic EL element of the present invention may be a fluorescent light emitting type or a phosphorescent light emitting type. Although there is no restriction | limiting in particular about the luminescent color of a light emitting layer, It is preferable that it is what emits blue light. An organic EL element that emits blue light generally has a short element life. However, when the polymer of the present invention is used for an organic thin film layer, the life is hardly lowered even when it is practically driven with high brightness and high temperature.

As a typical element configuration of the organic EL element of the present invention,
(1) Anode / light emitting layer / cathode (2) Anode / hole injection layer / light emitting layer / cathode (3) Anode / light emitting layer / electron injection layer / cathode (4) Anode / hole injection layer / light emitting layer / electron Injection layer / cathode (5) Anode / organic semiconductor layer / light emitting layer / cathode (6) Anode / organic semiconductor layer / electron barrier layer / light emitting layer / cathode (7) Anode / organic semiconductor layer / light emitting layer / adhesion improving layer / Cathode (8) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode (9) Anode / insulating layer / light emitting layer / insulating layer / cathode (10) Anode / inorganic semiconductor layer / insulating layer / Light emitting layer / insulating layer / cathode (11) Anode / organic semiconductor layer / insulating layer / light emitting layer / insulating layer / cathode (12) Anode / insulating layer / hole injection layer / hole transporting layer / light emitting layer / insulating layer / Cathode (13) Structure of anode / insulating layer / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode .
Of these, the configuration (8) is preferably used, but is not limited thereto.

<Translucent substrate>
The organic EL element of the present invention is produced by laminating a plurality of layers having the above various layer structures on a light-transmitting substrate. The translucent substrate referred to here is a substrate that supports the organic EL element, and is not limited as long as it has mechanical and thermal strength and transparency, but a visible region of 400 to 700 nm. A smooth substrate with a light transmittance of 50% or more is preferred.
Specifically, a glass plate, a polymer plate, a transparent resin film, etc. are mentioned. Examples of the glass plate include soda lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfone, and polysulfone.
Transparent resin films include polyethylene, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, polypropylene, polystyrene, polymethyl methacrylate, polyvinyl chloride, polyvinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone. , Polysulfone, polyethersulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoroethylene-ethylene copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, Examples include polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyimide, polyetherimide, polyimide, and polypropylene. It is.

<Anode>
As the conductive material used for the anode of the organic EL device of the present invention, a material having a work function larger than 4 eV is suitable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum Palladium, etc. and their alloys, metal oxides such as tin oxide and indium oxide used for ITO substrates and NESA substrates, and organic conductive resins such as polythiophene and polypyrrole are used.

<Cathode>
As the conductive material used for the cathode, those having a work function smaller than 4 eV are suitable, such as magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum, lithium fluoride, and the like. However, it is not limited to these. Examples of alloys include magnesium / silver, magnesium / indium, lithium / aluminum, and the like, but are not limited thereto. The ratio of the alloy is controlled by the temperature of the vapor deposition source, the atmosphere, the degree of vacuum, etc., and is selected to an appropriate ratio. If necessary, the anode and the cathode may be formed of two or more layers.
This cathode can be produced by forming a thin film of the above-described conductive material by a method such as vapor deposition or sputtering.
Here, when light emitted from the light emitting layer is taken out from the cathode, it is preferable that the transmittance with respect to the light emitted from the cathode is larger than 10%.
The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually 10 nm to 1 μm, preferably 50 to 200 nm.

<Insulating layer>
Since organic EL elements apply an electric field to an ultrathin film, pixel defects are likely to occur due to leaks or shorts. In order to prevent this, it is preferable to insert an insulating thin film layer between the pair of electrodes.
Examples of materials used for the insulating layer include aluminum oxide, lithium fluoride, lithium oxide, cesium fluoride, cesium oxide, magnesium oxide, magnesium fluoride, calcium oxide, calcium fluoride, aluminum nitride, titanium oxide, silicon oxide, and oxide. Germanium, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, vanadium oxide, and the like may be used, and a mixture or laminate of these may be used.

<Light emitting layer>
The organic EL device of the present invention may have a light emitting layer containing a fluorescent light emitting material, that is, a fluorescent light emitting layer. As the fluorescent light emitting layer, known fluorescent light emitting materials can be used. The fluorescent material is preferably at least one selected from anthracene derivatives, fluoranthene derivatives, styrylamine derivatives and arylamine derivatives, and more preferably anthracene derivatives and arylamine derivatives.
In particular, an anthracene derivative is preferable as the host material, and an arylamine derivative is preferable as the dopant. Specifically, suitable materials described in International Publication Nos. 2010/134350 and 2010/134352 are selected.

The organic EL device of the present invention may have a light emitting layer containing a phosphorescent material, that is, a phosphorescent layer. As a material for the phosphorescent light emitting layer, a known phosphorescent light emitting material can be used. Specifically, International Publication No. 2005/079118 may be referred to. Among the phosphorescent materials, preferred examples of the dopant include iridium (Ir), osmium (Os), or platinum (Pt) metal orthometalated complexes, and iridium (Ir) orthometalated complexes are more preferred. Of the phosphorescent materials, the host material is preferably a compound containing a carbazolyl group, more preferably a compound containing a carbazolyl group and a triazine skeleton, and a compound having a carbazolyl group and a pyrimidine skeleton, and two carbazolyl groups and a triazine skeleton. And a compound having two carbazolyl groups and one pyrimidine skeleton are more preferable.

The light emitting layer of the organic EL element has the following functions (1) to (3).
(1) Injection function: a function capable of injecting holes from an anode or a hole injection layer when an electric field is applied, and a function capable of injecting electrons from a cathode or an electron injection layer (2) transport function: injected charge (electrons (3) Light-emitting function: A function to provide a recombination field between electrons and holes and connect it to light emission. However, the ease with which holes are injected and the injection of electrons There may be a difference in ease, and the transport ability represented by the mobility of holes and electrons may be large or small, but it is preferable to move one of the charges.

In the plurality of layers, the polymer of the present invention can be used as necessary. Furthermore, known light emitting materials, doping materials, hole injection materials and electron injection materials can be used, and the polymer of the present invention can also be used as a doping material. The organic EL element can prevent the brightness | luminance and lifetime fall by quenching by making the said organic thin film layer into a multilayer structure. If necessary, a light emitting material, a doping material, a hole injection material, and an electron injection material can be used in combination. Further, by using a doping material, it is possible to improve light emission luminance and light emission efficiency and to obtain red and blue light emission. Further, the hole injection layer, the light emitting layer, and the electron injection layer may each be formed of two or more layers. In that case, in the case of a hole injection layer, the layer that injects holes from the electrode is a hole injection layer, and the layer that receives holes from the hole injection layer and transports holes to the light emitting layer is a hole transport layer. Call. Similarly, in the case of an electron injection layer, a layer that injects electrons from an electrode is referred to as an electron injection layer, and a layer that receives electrons from the electron injection layer and transports electrons to a light emitting layer is referred to as an electron transport layer. Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to the organic layer or metal electrode.

Examples of host materials or doping materials that can be used in the light emitting layer together with the polymer of the present invention include naphthalene, phenanthrene, rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene. Condensed aromatic compounds such as fluorene, spirofluorene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis (9′-ethynylanthracenyl) benzene, and their derivatives , Organometallic complexes such as tris (8-quinolinolato) aluminum, bis- (2-methyl-8-quinolinolato) -4- (phenylphenolinato) aluminum, triarylamine derivatives, styrylamine derivatives , Stilbene derivatives, coumarin derivatives, pyran derivatives, oxazone derivatives, benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamic acid ester derivatives, diketopyrrolopyrrole derivatives, acridone derivatives, quinacridone derivatives, fluoranthene derivatives, etc. Although it is mentioned, it is not limited to these.

The hole injection / transport layer is a layer that assists hole injection into the light emitting layer and transports it to the light emitting region, and has a high hole mobility and a small ionization energy of usually 5.6 eV or less. As such a hole injecting / transporting layer, a material that transports holes to the light emitting layer with lower electric field strength is preferable. Further, the mobility of holes is, for example, when an electric field of 10 ⁴ to 10 ⁶ V / cm is applied. Preferably, at least 10 ⁻⁴ cm ² / V · sec.

As described above, the polymer of the present invention is particularly preferably used as a hole injection / transport layer.
When the polymer of the present invention is used in the hole transport zone, the hole transport material of the present invention alone may form a hole injection / transport layer, or may be used in combination with other materials.
Other materials for forming the hole injection / transport layer by mixing with the polymer of the present invention are not particularly limited as long as they have the above-mentioned preferable properties. Any material commonly used as a material and known materials used for a hole injection / transport layer of an organic EL element can be selected and used. In the present invention, a material that has a hole transporting ability and can be used in the hole transporting zone is referred to as a hole transporting material.

Specific examples of materials other than the polymer of the present invention for the hole injection / transport layer include phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazoles, oxadiazoles, triazoles, imidazoles, imidazolones, imidazolethiones, pyrazolines. , Pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acyl hydrazone, polyarylalkane, stilbene, butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, and their derivatives, And a group containing a polymerizable functional group in polyvinyl carbazole, polysilane, conductive polymer (polyaniline, polythiophene), the above-mentioned monoamine, diamine, or triamine type aromatic compound. Although the polymeric material of the polymer and the like of the conversion the polymerizable monomer include, but are not limited thereto.

Among the hole injection materials that can be used in the organic EL device of the present invention, more effective hole injection materials are aromatic tertiary amine derivatives and phthalocyanine derivatives.
Examples of the aromatic tertiary amine derivative include triphenylamine, tolylamine, tolyldiphenylamine, N, N′-diphenyl-N, N ′-(3-methylphenyl) -1,1′-biphenyl-4,4 '-Diamine, N, N, N', N '-(4-methylphenyl) -1,1'-phenyl-4,4'-diamine, N, N, N', N '-(4-methylphenyl) ) -1,1′-biphenyl-4,4′-diamine, N, N′-diphenyl-N, N′-dinaphthyl-1,1′-biphenyl-4,4′-diamine, N, N ′-( Methylphenyl) -N, N ′-(4-n-butylphenyl) -phenanthrene-9,10-diamine, N, N-bis (4-di-4-tolylaminophenyl) -4-phenyl-cyclohexane, etc. Or oligomers having these aromatic tertiary amine skeletons Or is a polymer, but is not limited thereto.

Examples of the phthalocyanine (Pc) derivative include H ₂ Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl ₂ SiPc, (HO) AlPc, (HO) GaPc, Examples include, but are not limited to, phthalocyanine derivatives and naphthalocyanine derivatives such as VOPc, TiOPc, MoOPc, and GaPc—O—GaPc. The organic EL device of the present invention includes a layer containing these aromatic tertiary amine derivatives and / or phthalocyanine derivatives, for example, the hole transport layer or the hole injection layer, between the light emitting layer and the anode. Preferably formed.

In the organic EL device of the present invention, as a material for forming the hole injection layer other than the polymer of the present invention, in addition to the above-mentioned compounds, for example, carbazole derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Starburst amines, styrylamine compounds, polysilane compounds, poly (N-vinylcarbazole) derivatives, organic silane derivatives, and polymers containing one or more selected from these, vanadium oxide, tantalum oxide, tungsten oxide, molybdenum oxide , Conductive metal oxides such as ruthenium oxide and aluminum oxide; conductive polymers and oligomers such as polyaniline, aniline copolymers, thiophene oligomers and polythiophenes; poly (3,4-ethylenedioxythiophene), polystyrenesulfonic acid , Polypyro Organic conductive materials such as ruthenium and polymers containing these organic conductive materials; acceptor organic compounds such as amorphous carbon, tetracyanoquinodimethane derivatives, 1,4-naphthoquinone derivatives, diphenoquinone derivatives, polynitro compounds; octadecyltri Examples include silane coupling agents such as methoxysilane.

The material may be a single component or a composition comprising a plurality of components. The hole injection layer may have a single layer structure composed of one or more of the above materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions.

Various known methods can be used as a method for forming the hole injection layer.
When the material for forming the hole injection layer is an inorganic compound material, examples of the method for forming the hole injection layer include a vacuum deposition method, a sputtering method, and an ion plating method.
When the material for forming the hole injection layer is a low molecular weight organic material, examples of the method for producing the hole injection layer include a vacuum deposition method, a transfer method, and a film formation method from a solution.
As a method for producing the hole injection layer when the material for the hole injection layer is a polymer organic material, a method by film formation from a solution is exemplified.

Next, the electron injection layer / transport layer will be described. The electron injection layer / transport layer is a layer that assists the injection of electrons into the light emitting layer and transports it to the light emitting region, and has a high electron mobility. It is a layer made of a material with good adhesion.
In addition, since light emitted from an organic EL element is reflected by an electrode (in this case, a cathode), it is known that light emitted directly from the anode interferes with light emitted via reflection by the electrode. . In order to efficiently use this interference effect, the electron transport layer is appropriately selected with a film thickness of several nm to several μm. However, particularly when the film thickness is thick, in order to avoid a voltage increase, 10 ⁴ to 10 ⁶ V / It is preferable that the electron mobility is at least 10 ⁻⁵ cm ² / Vs or more when an electric field of cm is applied.

Specific examples of materials used for the electron injection layer include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthra. Examples thereof include, but are not limited to, quinodimethane, anthrone, and the like. Further, it can be sensitized by adding an electron accepting substance to the hole injecting material and an electron donating substance to the electron injecting material.

In the organic EL device of the present invention, more effective electron injection materials are metal complex compounds and nitrogen-containing five-membered ring derivatives.
Examples of the metal complex compound include 8-hydroxyquinolinate lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, and tris. (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (o-cresolate) gallium, bis (2-methyl-8- Quinolinate) (1-naphtholato) aluminum, bis (2-methyl) Le-8-quinolinate) (2-naphtholato) Gallium like, but it is not limited thereto.

As the nitrogen-containing five-membered derivative, for example, oxazole, thiazole, oxadiazole, thiadiazole, and triazole derivatives are preferable. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, dimethyl POPOP, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5- Bis (1-phenyl) -1,3,4-oxadiazole, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) 1,3,4-oxadiazole, 2,5 -Bis (1-naphthyl) -1,3,4-oxadiazole, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyloxa) Diazolyl) -4-tert-butylbenzene], 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) ) -1,3,4-thiadiazole, 1,4-bis 2- (5-phenylthiadiazolyl)] benzene, 2- (4′-tert-butylphenyl) -5- (4 ″ -biphenyl) -1,3,4-triazole, 2,5-bis (1- Naphthyl) -1,3,4-triazole, 1,4-bis [2- (5-phenyltriazolyl)] benzene and the like, but are not limited thereto.

In the organic EL device of the present invention, in the light emitting layer, in addition to the polymer of the present invention, at least one of a light emitting material, a doping material, a hole injection material and an electron injection material may be contained in the same layer. . In order to improve the stability of the organic EL device obtained by the present invention with respect to temperature, humidity, atmosphere, etc., a protective layer is provided on the surface of the device, or the entire device is protected by silicon oil, resin, etc. Is also possible.

In the organic EL device of the present invention, in order to emit light efficiently, it is desirable that at least one surface be sufficiently transparent in the light emission wavelength region of the device. The substrate is also preferably transparent. The transparent electrode is set using the above-described conductive material so as to ensure a predetermined translucency by a method such as vapor deposition or sputtering. The electrode on the light emitting surface preferably has a light transmittance of 10% or more.

For the formation of each layer of the organic EL device of the present invention, a known method such as a dry film forming method such as vacuum deposition, sputtering, plasma, or ion plating, or a wet film forming method such as spin coating, dipping, or flow coating is applied. be able to. The film thickness is not particularly limited, but must be set to an appropriate film thickness. If the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes and the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. The normal film thickness is suitably in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm.

Examples of a method for forming a layer containing the polymer of the present invention (particularly, a hole injection / transport layer) include a method of forming a polymer solution. Film formation methods include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, slit coating, wire bar coating, dip coating, spray coating, and screen printing. , Flexographic printing method, offset printing method, ink jet method, nozzle printing method, and the like. In the case of pattern formation, screen printing method, flexographic printing method, offset printing method, and ink jet printing method are preferable. Film formation by these methods can be performed under conditions well known to those skilled in the art, and details thereof are omitted.
After the film formation, the solvent may be removed by vacuum and heating (at most 200 ° C.) to remove the solvent, and a polymerization reaction by heating with light and high temperature (200 ° C. or more) is unnecessary. Therefore, performance degradation due to light and high temperature heating is suppressed.

The film-forming solution only needs to contain at least one polymer of the present invention. In addition to the above materials, other hole transport materials, electron transport materials, light-emitting materials, acceptor materials, solvents, stabilizers, and the like The additive may be included. The content of the polymer in the film forming solution is preferably 20 to 100% by weight, more preferably 40 to 100% by weight, based on the total weight of the composition excluding the solvent. The proportion of the solvent is preferably 1 to 99.9% by weight of the film-forming solution, and more preferably 80 to 99% by weight.

Film-forming solutions are additives for adjusting viscosity and / or surface tension, such as thickeners (high molecular weight compounds, poor solvents for polymers of the present invention, etc.), viscosity reducing agents (low molecular weight compounds, etc.) Further, it may contain a surfactant or the like. Moreover, in order to improve storage stability, you may contain antioxidants which do not influence the performance of organic EL elements, such as a phenolic antioxidant and phosphorus antioxidant.

High molecular weight compounds that can be used include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose, and copolymers thereof, poly-N-vinyl. Examples thereof include photoconductive resins such as carbazole and polysilane, and conductive resins such as polythiophene and polypyrrole.

Examples of the solvent for the film-forming solution include chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ethers such as tetrahydrofuran, dioxane, dioxolane and anisole. Solvents; aromatic hydrocarbon solvents such as toluene and xylene; cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, etc. Aliphatic hydrocarbon solvents; Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, benzophenone, and acetophenone; Ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate, and phenyl acetate; ethylene glycol , Ethylene glycol monobuty Polyhydric alcohols such as ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof; methanol, Examples include alcohol solvents such as ethanol, propanol, isopropanol, and cyclohexanol; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination. Of these, aromatic hydrocarbon solvents, ether solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents are preferred from the viewpoints of solubility, film formation uniformity, viscosity characteristics, etc., toluene, Xylene, ethylbenzene, diethylbenzene, trimethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, 5-butylbenzene, n-hexylbenzene, cyclohexylbenzene, 1-methylnaphthalene, tetralin, 1, 3-dioxane, 1,4-dioxane, 1,3-dioxolane, anisole, ethoxybenzene, cyclohexane, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, decalin, benzoic acid Methyl to cyclo Sanon, cyclohexanone to 2-propylcyclopentadienyl, heptanone to 2, heptanone to 3, heptanone to 4, 2-octanone, 2-nonanone, 2-decanone, Kishiruketon dicyclohexyl, acetophenone, benzophenone more preferable.

<Method for producing organic EL element>
An organic EL device is formed by forming an anode, a light emitting layer, a hole injecting / transporting layer if necessary, an electron injecting / transporting layer if necessary, and further forming a cathode by various materials and layer forming methods exemplified above. Can be produced. Moreover, an organic EL element can also be produced from the cathode to the anode in the reverse order.

[Synthesis of polymerizable monomer]
Synthesis Example 1
A polymerizable monomer H-1 was synthesized according to the following synthesis scheme.

(1) Synthesis of Intermediate 1-1 In a flask equipped with a condenser tube under a nitrogen atmosphere, 15.0 g (30.5 mmol) of 2,7-dibromo-9,9-dihexylfluorene, 5.85 g (35.0 mmol) of carbazole ), 34 mg (0.15 mmol) of palladium acetate, 60 mg (0.30 mmol) of tri-t-butylphosphine, 4.09 g (42.6 mmol) of t-butoxy sodium, and 150 mL of mixed xylene, and then at 120 ° C. for 13 hours. Reacted. After cooling, 100 ml of water was added and washed with water (implemented three times), and the xylene layer was concentrated. Thereafter, purification was performed by silica gel column chromatography using hexane as a developing solvent to obtain 5.0 g (yield 28%) of a white solid.
The powder was identified as Intermediate 1-1 by FD-MS analysis.

(2) Synthesis of Intermediate 1-2 In a nitrogen atmosphere, in a flask with a condenser tube, 5.01 g (8.7 mmol) of Intermediate 1-1, 2.73 g (8.5 mmol) of bis (biphenyl) amine, acetic acid After adding 10 mg (0.045 mmol) of palladium, 17 mg (0.084 mmol) of tri-t-butylphosphine, 1.14 g (11.9 mmol) of sodium t-butoxy, and 70 mL of mixed xylene, the mixture was reacted at 120 ° C. for 1 hour. . After cooling, 100 ml of water was added and washed with water (implemented three times), and the xylene layer was concentrated. Thereafter, purification was performed by column chromatography using toluene / hexane as a developing solvent to obtain 5.7 g (yield 80%) of a white solid.
The powder was identified as Intermediate 1-2 by FD-MS analysis.

(3) Synthesis of Intermediate 1-3 After adding 5.72 g (7.0 mmol) of Intermediate 1-2 and 100 ml of tetrahydrofuran to a flask with a condenser under a nitrogen atmosphere, N-bromosuccinimide (NBS) 2 50 mL of a tetrahydrofuran solution of .42 g (13.6 mmol) was added dropwise. After completion of dropping, the reaction was allowed to proceed at room temperature for 72 hours. Toluene 100 mL and water 100 mL were added and washed with water (implemented 3 times), and the toluene layer was concentrated. Thereafter, purification was carried out by column chromatography using toluene / hexane as a developing solvent to obtain 3.4 g (yield 50%) of a pale yellow solid.
The powder was identified as Intermediate 1-3 by FD-MS analysis.

(4) Synthesis of polymerizable monomer H-1 In a nitrogen atmosphere, in a flask equipped with a condenser tube, 3.33 g (3.4 mmol) of intermediate 1-3 and 1.10 g of 4-vinylphenylboronic acid (7. 4 mmol), 0.39 g (0.34 mmol) of tetrakis (triphenylphosphine) palladium (0) and 50 mL of tetrahydrofuran were added, and 37 mL (37 mmol) of 1M aqueous potassium carbonate solution was added, followed by reaction at 80 ° C. for 24 hours. I let you. After completion of the reaction, 50 mL of toluene and 50 mL of water were added and washed with water (implemented 3 times), and the toluene layer was concentrated. Thereafter, purification was performed by column chromatography using toluene / hexane as a developing solvent to obtain 1.1 g (yield 30%) of a white powder.
The product was identified as polymerizable monomer H-1 by FD-MS analysis.

Synthesis Example 2
A polymerizable monomer H-2 was synthesized according to the following synthesis scheme.

(1) Synthesis of Intermediate 2-1 4-formylphenylboronic acid 19.8 g (132.0 mmol), p-bromoiodobenzene 37.2 g (132.0 mmol), tetrakis (triphenylphosphine) palladium under argon atmosphere (0) To 3.0 g (2.58 mmol), 600 mL of toluene, 150 mL of dimethoxyethane, and 132 mL (264.0 mmol) of 2M Na ₂ CO ₃ aqueous solution were added, and the mixture was heated to reflux with stirring for 10 hours.
After completion of the reaction, 300 mL of water was added, followed by liquid separation, and the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 17.2 g (yield 50%) of a white solid.
The powder was identified as Intermediate 2-1 by FD-MS analysis.

(2) Synthesis of Intermediate 2-2 Under argon atmosphere, Intermediate 2-1 (17.1 g, 66.0 mmol) was charged with ethylene glycol 150 mL, p-toluenesulfonic acid monohydrate 7.5 g (39.4 mmol). Toluene 300 mL was added and stirred at 70 ° C. for 12 hours.
After completion of the reaction, 300 mL of water was added, followed by liquid separation, and the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 18.1 g (yield 90%) of a white solid.
The powder was identified as Intermediate 2-2 by FD-MS analysis.

(3) Synthesis of Intermediate 2-3 In an argon atmosphere, 200 g of xylene and 1.2 g (13.6 mmol) of N, N-dimethylethylenediamine were added to 0.9 g (4.7 mmol) of copper iodide (CuI) at room temperature. For 1 hour. Next, 26.6 g (46.0 mmol) of intermediate 1-1 synthesized in the same manner as in Synthesis Example 1, 4 g (68.0 mmol) of acetamide, and 13 g (130.0 mmol) of calcium carbonate were dispersed in 100 mL of xylene. , And stirred at 140 ° C. for 16 hours.
After completion of the reaction, 300 mL of water was added, followed by liquid separation, and the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 19.2 g (yield 75%) of a white solid.
The powder was identified as Intermediate 2-3 by FD-MS analysis.

(4) Synthesis of Intermediate 2-4 Under an argon atmosphere, 550 mL of toluene and 25 mL of 28% NaOMe / MeOH were added to 19.2 g (34.5 mmol) of Intermediate 2-3, and the mixture was stirred at 60 ° C. for 16 hours.
After completion of the reaction, 500 mL of water was added, followed by liquid separation, and the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 15.8 g (yield 89%) of a white solid.
The powder was identified as Intermediate 2-4 by FD-MS analysis.

(5) Synthesis of Intermediate 2-5 Under an argon atmosphere, 18.3 g (60.0 mmol) of Intermediate 2-2, 15.4 g (30.0 mmol) of Intermediate 2-4, 5.8 g of sodium t-butoxy ( 60.0 mmol) was added with 150 mL of dehydrated toluene and stirred. 135 mg (0.6 mmol) of palladium acetate and 120 mg (0.6 mmol) of tri-t-butylphosphine were added and reacted at 80 ° C. for 8 hours.
After cooling, the reaction mixture was filtered through celite / silica gel and the filtrate was concentrated under reduced pressure. The obtained residue was recrystallized from toluene, and it was collected by filtration and then dried to obtain 23.7 g (yield 82%) of a white solid.
The powder was identified as Intermediate 2-5 by FD-MS analysis.

(6) Polymerizable monomer H-2
150 g of water, 300 mL of toluene, and 6.0 g (31.5 mmol) of p-toluenesulfonic acid were added to 4.4 g (6.0 mmol) of Intermediate 2-5, and the mixture was stirred at 80 ° C. for 5 hours.
After completion of the reaction, the solution was separated and the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated.
Under an argon atmosphere, 150 mL of dehydrated THF and 9.0 g (25.2 mmol) of methyltriphenylphosphonium bromide were stirred into the resulting concentrate. 3.6 g (32.1 mmol) of t-butoxypotassium and 150 mL of dehydrated THF were further added and stirred, and the mixture was stirred at room temperature for 10 hours. Thereafter, 150 mL of water was added dropwise to terminate the reaction.
After completion of the reaction, 500 mL of toluene was added, followed by liquid separation, and the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 2.1 g (yield 40%) of a white solid.
The product was identified as polymerizable monomer H-2 by FD-MS analysis.

Synthesis Example 3
A polymerizable monomer H-3 was synthesized according to the following synthesis scheme.

(1) Synthesis of Intermediate 3-1 In the synthesis of Intermediate 2-5 (Synthesis Example 2 (5)), 17.4 g (30.0 mmol) of Intermediate 1-1 was used instead of Intermediate 2-2. Then, a reaction was carried out in the same manner except that 5.1 g (30.0 mmol) of diphenylamine was used instead of the intermediate 2-4, to obtain 14.2 g (yield 71%) of a white solid. The powder was identified as Intermediate 3-1 by FD-MS analysis.

(2) Synthesis of Intermediate 3-2 Under an argon atmosphere, 200 mL of toluene and 120 mL of ethyl acetate were added to 13.3 g (20.0 mmol) of Intermediate 3-1, and the mixture was stirred. 14.2 g (80 mmol) of N-bromosuccinimide was added and reacted at room temperature for 24 hours. Further, 0.8 g (4.4 mmol) of N-bromosuccinimide was added and reacted at room temperature for 3 hours.
After completion of the reaction, 300 mL of water was added and extracted with toluene. The organic layer was washed with saturated brine, dried over MgSO ₄ , filtered and concentrated. The obtained residue was recrystallized from toluene, collected by filtration and dried to obtain 17.1 g (yield 87%) of a white solid.
The powder was identified as Intermediate 3-2 by FD-MS analysis.

(3) Synthesis of polymerizable monomer H-3 Under argon atmosphere, intermediate 3-2 2.9 g (3.0 mmol), 4-vinylphenylboronic acid 2.2 g (15.0 mmol), tetrakis (triphenyl) To 0.17 g (0.15 mmol) of phosphine) palladium (0) were added 10 mL of toluene, 5 mL of dimethoxyethane, 5 mL (10.0 mmol) of 2M aqueous Na ₂ CO ₃ solution, and the mixture was heated to reflux for 10 hours.
After completion of the reaction, the sample was transferred to a separatory funnel and extracted with toluene. The organic layer was dried over MgSO ₄ , filtered and concentrated. The concentrated residue was purified by silica gel column chromatography. The obtained crude product was recrystallized with toluene, collected by filtration, and dried to obtain 1.7 g (yield 54%) of a white solid.
The product was identified as polymerizable monomer H-3 by FD-MS analysis.

Synthesis Example 4
A polymerizable monomer H-4 was synthesized according to the following synthesis scheme.

The same reaction as in Synthesis Example 1 except that 21.4 g (45.0 mmol) of 2,7-dibromo-9,9-diphenylfluorene was used instead of 2,7-dibromo-9,9-dihexylfluorene. As a result, 1.5 g of a white solid was obtained. It was identified as a polymerizable monomer (H-4) by FD-MS analysis.

Synthesis Example 5
A polymerizable monomer H-5 was synthesized according to the following synthesis scheme.

(1) Synthesis of Intermediate 5-1 Under an argon atmosphere, 19.5 g (60.0 mmol) of 3,6-dibromocarbazole, 19.8 g (132.0 mmol) of 4-formylphenylboronic acid, tetrakis (triphenylphosphine) To 3.5 g (3.0 mmol) of palladium (0), 200 mL of toluene, 100 mL of dimethoxyethane, 92 mL (184.0 mmol) of 2M Na ₂ CO ₃ aqueous solution were added, and the mixture was heated to reflux with stirring for 10 hours.
After completion of the reaction, the sample was transferred to a separatory funnel and extracted with toluene. The organic layer was dried over MgSO ₄ , filtered and concentrated. The concentrated residue was purified by silica gel column chromatography. The obtained crude product was recrystallized with toluene, collected by filtration and dried to obtain 15.8 g (yield 70%) of a white solid.
The powder was identified as Intermediate 5-1 by FD-MS analysis.

(2) Synthesis of Intermediate 5-2 Under an argon atmosphere, at room temperature, 15.8 g (42 mmol) of Intermediate 5-1, 150 mL of ethylene glycol, 7.5 g of p-toluenesulfonic acid monohydrate (39. 4 mmol) and 300 mL of toluene were added and stirred at 70 ° C. for 12 hours.
After completion of the reaction, 500 mL of water was added, followed by liquid separation, and the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 17.5 g (yield 90%) of a white solid.
The powder was identified as Intermediate 5-2 by FD-MS analysis.

(3) Synthesis of Intermediate 5-3 Under an argon atmosphere, Intermediate 5-2 9.3 g (20.0 mmol), 2,7-dibromo-9,9-dihexylfluorene 9.8 g (20.0 mmol), t -To 3.8 g (40.0 mmol) of butoxy sodium, 100 mL of dehydrated toluene was added and stirred. Palladium acetate 90 mg (0.4 mmol) and tri-t-butylphosphine 80 mg (0.4 mmol) were added and reacted at 80 ° C. for 8 hours.
After cooling, the reaction mixture was filtered through celite / silica gel and the filtrate was concentrated under reduced pressure. The obtained residue was recrystallized with toluene, filtered, and dried to obtain 9.6 g (yield 80%) of a white solid. The powder was identified as Intermediate 5-3 by FD-MS analysis.

(4) Synthesis of Intermediate 5-4 44.0-bromoacetanilide 24.0 g (112.0 mmol), dibenzofuran-4-boronic acid 28.6 g (135.0 mmol), tetrakis (triphenylphosphine) palladium under argon atmosphere To 2.6 g (2.24 mmol) of (0), 450 mL of toluene, 100 mL of dimethoxyethane, 110 mL (220.0 mmol) of 2M Na ₂ CO ₃ aqueous solution were added, and the mixture was heated to reflux with stirring for 10 hours.
After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated crystals were filtered. The obtained crystals were dissolved in tetrahydrofuran, filtered through celite / silica gel, and the filtrate was concentrated under reduced pressure. The obtained residue was washed with methanol / hexane and dried to obtain 18.0 g of white solid (yield 53%).
The powder was identified as Intermediate 5-4 by FD-MS analysis.

(5) Synthesis of Intermediate 5-5 To 18.0 g (59.7 mmol) of Intermediate 5-4, 120 mL of xylene, 1200 mL of water and 60 mL of ethanol were added and stirred. 20.0 g (360.0 mmol) of potassium hydroxide was added, and the mixture was heated to reflux with stirring for 10 hours.
After completion of the reaction, the mixture was cooled to room temperature, and the sample was transferred to a separatory funnel and extracted with ditoluene. The organic layer was dried over MgSO ₄ , filtered and concentrated. The obtained residue was recrystallized from xylene, collected by filtration and dried to obtain 14.7 g (yield 95%) of a white solid.
The powder was identified as Intermediate 5-5 by FD-MS analysis.

(6) Synthesis of Intermediate 5-6 Under an argon atmosphere, 11.7 g (50.0 mmol) of 4-bromobiphenyl, 13.0 g (50.0 mmol) of Intermediate 5-5, 9.6 g of sodium t-butoxy (100 0.0 mmol) was added 250 mL of dehydrated toluene and stirred. Palladium acetate (225 mg, 1.0 mmol) and tri-t-butylphosphine (202 mg, 1.0 mmol) were added, and the mixture was reacted at 80 ° C. for 8 hours.
After cooling, the reaction mixture was filtered through celite / silica gel and the filtrate was concentrated under reduced pressure. The obtained residue was recrystallized from toluene, collected by filtration and dried to obtain 16.5 g (yield 80%) of a white solid. The powder was identified as Intermediate 5-6 by FD-MS analysis.

(7) Synthesis of Intermediate 5-7 Under an argon atmosphere, 8.7 g (10.0 mmol) of Intermediate 5-3, 4.1 g (10.0 mmol) of Intermediate 5-6, 9.6 g of sodium t-butoxy ( 20.0 mmol) was added with 50 mL of dehydrated toluene and stirred. 45 mg (0.2 mmol) of palladium acetate and 40 mg (0.2 mmol) of tri-t-butylphosphine were added and reacted at 80 ° C. for 8 hours.
After cooling, the reaction mixture was filtered through celite / silica gel and the filtrate was concentrated under reduced pressure. The obtained residue was recrystallized with toluene, filtered, and dried to obtain 9.6 g (yield 80%) of a white solid. The powder was identified as Intermediate 5-7 by FD-MS analysis.

(8) Synthesis of polymerizable monomer H-5 To 7.2 g (6.0 mmol) of intermediate 5-7, 150 mL of water, 300 mL of toluene, and 6.0 g (31.5 mmol) of p-toluenesulfonic acid were added, Stir at 80 ° C. for 5 hours.
After completion of the reaction, the solution was separated and the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated.
Under an argon atmosphere, at room temperature, 150 mL of dehydrated THF and 9.0 g (25.2 mmol) of methyltriphenylphosphonium bromide were added to the resulting concentrate and stirred. 3.6 g (32.1 mmol) of t-butoxypotassium and 150 mL of dehydrated THF were further added and stirred, and the mixture was stirred at room temperature for 10 hours. Thereafter, 150 mL of water was added dropwise to terminate the reaction. After completion of the reaction, 500 mL of toluene was added, followed by liquid separation, and the aqueous layer was removed. The organic layer was dried over sodium sulfate and concentrated. The residue was purified by silica gel column chromatography to obtain 1.7 g (yield 25%) of a white solid.
The product was identified as polymerizable monomer H-5 by FD-MS analysis.

[Production of organic EL element]
Example 1 (Production and evaluation of organic EL element)
A glass substrate with an ITO transparent electrode having a thickness of 25 mm × 75 mm × 1.1 mm (manufactured by Geomatic Co., Ltd.) was ultrasonically cleaned in isopropyl alcohol for 5 minutes, and then UV ozone cleaning was performed for 30 minutes. On the glass substrate with a transparent electrode after cleaning, a film of polyethylene dioxythiophene / polystyrene sulfonic acid (PEDOT: PSS) used for the hole injection layer by spin coating is formed to a thickness of 10 nm, and the hole injection layer is formed. (PSS is an acceptor). Next, as a polymerizable monomer, a xylene solution (1.0 wt%) of the following monomer H-1 obtained in Synthesis Example 1 was formed into a film having a thickness of 40 nm by a spin coat method. The hole transport layer was formed by drying and heat curing at 30 ° C. for 30 minutes.
Next, a xylene solution (1.0 wt%) in which the following compound EM1 (host) and the following amine compound D1 (dopant) having a styryl group are mixed at a solid content weight ratio of 95: 5 is spin-coated to 40 nm. A light emitting layer was formed by drying at 150 ° C. for 30 minutes. The following Alq was deposited on this film to a thickness of 10 nm by vapor deposition. This layer functions as an electron injection layer. Thereafter, Li (Li source: manufactured by Saesgetter Co.), which is a reducing dopant, and Alq were vapor-deposited, and an Alq: Li film (film thickness: 10 nm) was formed as an electron injection layer (cathode). Metal Al was vapor-deposited on the Alq: Li film to form a metal cathode, which was sealed with glass in nitrogen to produce an organic EL device.

When the current was passed through the produced organic EL device and the performance was evaluated, it emitted blue light, the luminous efficiency was 7.0 cd / A, and the luminance half-life at room temperature (LT50, @ 1,000 cd / m ² ) was 3,000. It was time. The results are shown in Table 1.

Examples 2-5
Example 1 was carried out except that the following monomers H-2 to H-5 synthesized in Synthesis Examples 2 to 5 shown in Table 1 were used instead of the monomer H-1 as the hole transport material in Example 1. An organic EL device was produced and evaluated in the same manner as in Example 1. The results are shown in Table 1.

Comparative Examples 1 and 2
In Example 1, an organic EL device was prepared and evaluated in the same manner as in Example 1 except that the following comparative compounds 1 and 2 were used instead of the monomer H-1. The results are shown in Table 1.

From the results of Table 1, it can be seen that the organic EL device of the example provided with the hole transport layer made of the polymer derived from the monomer of the present invention is excellent in luminous efficiency and lifetime. On the other hand, it turns out that the element of a comparative example is inferior in luminous efficiency and lifetime compared with the element of an Example.

Although several embodiments and / or examples of the present invention have been described in detail above, those skilled in the art will appreciate that these exemplary embodiments and / or embodiments are substantially without departing from the novel teachings and advantages of the present invention. It is easy to make many changes to the embodiment. Accordingly, many of these modifications are within the scope of the present invention.
All the contents of the Japanese application specification that is the basis of the priority of Paris in this application are incorporated herein.

Claims

A polymerizable monomer represented by the following formula (1).

(In the formula, Ar 1 and Ar 2 each independently represent a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms. The substituents that Ar 1 and Ar 2 may have are substituted with a linear or branched alkyl group having 1 to 30 carbon atoms and a polymerizable functional group which may be substituted with a polymerizable functional group. An optionally substituted cycloalkyl group having 3 to 10 ring carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms which may be substituted with a polymerizable functional group, and a triarylsilyl group having 18 to 30 ring carbon atoms An alkylarylsilyl group having 8 to 15 carbon atoms that may be substituted with a polymerizable functional group (the ring of an aryl group that has 1 to 5 carbon atoms and may be substituted with a polymerizable functional group) The number of carbons formed is 6-14 An aryl group having 6 to 50 ring carbon atoms which may be substituted with a polymerizable functional group, a heteroaryl group having 5 to 50 ring atoms which may be substituted with a polymerizable functional group, halogen An atom or a cyano group.
R 1 and R 2 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, substituted Or an unsubstituted trialkylsilyl group having 3 to 10 carbon atoms, a substituted or unsubstituted triarylsilyl group having 18 to 30 ring carbon atoms, a substituted or unsubstituted alkylarylsilyl group having 8 to 15 carbon atoms, substituted Alternatively, it represents an unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, a polymerizable functional group, a halogen atom, or a cyano group.
R 11 and R 12 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, substituted Or an unsubstituted trialkylsilyl group having 3 to 10 carbon atoms, a substituted or unsubstituted triarylsilyl group having 18 to 30 ring carbon atoms, a substituted or unsubstituted alkylarylsilyl group having 8 to 15 carbon atoms, substituted Alternatively, it represents an unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, a polymerizable functional group, a halogen atom, or a cyano group.
R 3 and R 4 are each independently a substituted or unsubstituted linear or branched alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 10 ring carbon atoms, substituted Alternatively, it represents an unsubstituted aryl group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 50 ring atoms, or a polymerizable functional group. R 3 and R 4 may combine with each other to form a saturated or unsaturated divalent group that forms a ring.
n 1 and n 2 each independently represents an integer of 0 to 4.
m 1 and m 2 each independently represents an integer of 0 to 3.
When n 1 is 2 to 4, a plurality of R 1 may be the same or different from each other, and a plurality of adjacent R 1 are bonded to each other to form a saturated or unsaturated divalent group that forms a ring. It may be formed.
When n 2 is 2 to 4, a plurality of R 2 may be the same or different from each other, and a plurality of adjacent R 2 are bonded to each other to form a saturated or unsaturated divalent group that forms a ring. It may be formed.
When m 1 is 2 or 3, a plurality of R 11 may be the same or different from each other, and a plurality of adjacent R 11 are bonded to each other to form a saturated or unsaturated divalent group that forms a ring. It may be formed.
When m 2 is 2 or 3, a plurality of R 12 may be the same or different from each other, and a plurality of adjacent R 12 are bonded to each other to form a saturated or unsaturated divalent group forming a ring. It may be formed.
Two or more of R 1 to R 4 , R 11 , R 12 , Ar 1 and Ar 2 contain a polymerizable functional group. )
The polymerizable monomer according to claim 1 represented by the following formula (2).

(In the formula, R 1 to R 4 , R 11 , R 12 , Ar 1 , Ar 2 , n 1 , n 2 , m 1 and m 2 have the same meanings as those in the formula (1)).
The polymerizable monomer according to claim 1, wherein at least one of R 1 and R 2 has a polymerizable functional group.
The polymerizable monomer according to claim 1, wherein at least one of R 3 and R 4 has a polymerizable functional group.
The polymerizable monomer according to claim 1, wherein at least one of Ar 1 and Ar 2 has a polymerizable functional group.
6. The polymerizable monomer according to claim 1, wherein the number of polymerizable functional groups is 2 to 4.
At least one of the R 1 and R 2 has a polymerizable functional group, and at least one of the R 3 , R 4 , R 11 , R 12 , Ar 1 and Ar 2 has a polymerizable functional group, The polymerizable monomer according to any one of claims 1 to 6.
At least one of the R 3 , R 4 , R 11 , and R 12 has a polymerizable functional group, and at least one of the R 1 , R 2 , Ar 1, and Ar 2 has a polymerizable functional group, The polymerizable monomer according to any one of claims 1 to 6.
7. At least one of Ar 1 and Ar 2 has a polymerizable functional group, and at least one of R 1 to R 4 , R 11 , and R 12 has a polymerizable functional group. The polymerizable monomer according to any one of the above.
2. The R 3 and R 4 are each a substituted or unsubstituted linear alkyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms. The polymerizable monomer according to any one of 1 to 9.
The polymerizable monomer according to claim 1, wherein at least one of Ar 1 and Ar 2 is a group represented by the following formula (3) or (4).

[Wherein, L 1 represents a single bond or a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
L 2 is a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms.
The substituent that L 1 and L 2 may have is substituted with a linear or branched alkyl group having 1 to 30 carbon atoms and a polymerizable functional group which may be substituted with a polymerizable functional group. An optionally substituted cycloalkyl group having 3 to 10 ring carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms which may be substituted with a polymerizable functional group, and a triarylsilyl group having 18 to 30 ring carbon atoms An alkylarylsilyl group having 8 to 15 carbon atoms that may be substituted with a polymerizable functional group (the ring of an aryl group that has 1 to 5 carbon atoms and may be substituted with a polymerizable functional group) The number of carbon atoms formed is 6 to 14.), an aryl group having 6 to 50 ring carbon atoms that may be substituted with a polymerizable functional group, and a ring atom number 5 that may be substituted with a polymerizable functional group Up to 50 heteroaryl groups, halogen atoms or An anode group.
X is a substituted or unsubstituted heteroatom.
When X is substituted, the substituent is an alkyl group having 1 to 20 carbon atoms which may be substituted with a polymerizable functional group, or a carbon group having 3 to 10 carbon atoms which may be substituted with a polymerizable functional group. A cycloalkyl group, an aryl group having 6 to 30 ring carbon atoms which may be substituted with a polymerizable functional group, an aralkyl group having 7 to 31 carbon atoms which may be substituted with a polymerizable functional group (ring of the aryl moiety) And one or more groups selected from the group consisting of heterocyclic groups having 6 to 30 carbon atoms and 3 to 30 ring-forming atoms optionally substituted with a polymerizable functional group.
R 13 to R 16 are each independently substituted with a polymerizable functional group, a linear or branched alkyl group having 1 to 30 carbon atoms which may be substituted with a polymerizable functional group, or a polymerizable functional group. An optionally substituted cycloalkyl group having 3 to 10 ring carbon atoms, a trialkylsilyl group having 3 to 10 carbon atoms which may be substituted with a polymerizable functional group, and a triarylsilyl group having 18 to 30 ring carbon atoms An alkylarylsilyl group having 8 to 15 carbon atoms that may be substituted with a polymerizable functional group (the ring of an aryl group that has 1 to 5 carbon atoms and may be substituted with a polymerizable functional group) The number of carbon atoms formed is 6 to 14.), an aryl group having 6 to 50 ring carbon atoms that may be substituted with a polymerizable functional group, and a ring atom number 5 that may be substituted with a polymerizable functional group ~ 50 heteroaryl groups, halogen Komata is a cyano group.
a is an integer of 0 to 3.
b to d are each independently an integer of 0 to 4. ]
An organic device material containing the polymerizable monomer according to any one of claims 1 to 11.
An organic electroluminescent element material containing the polymerizable monomer according to any one of claims 1 to 11.
A polymer having a repeating unit derived from one or more selected from the group consisting of the polymerizable monomers according to any one of claims 1 to 11.
An organic device material containing the polymer according to claim 14.
An organic electroluminescent element material containing the polymer according to claim 14.
The organic electroluminescent element in which the organic thin film layer which consists of the organic thin film layer which consists of at least one light emitting layer between a cathode and an anode is sandwiched, and at least 1 layer of the said organic thin film layer contains the polymer of Claim 14. Organic electroluminescence device.
The organic thin film layer has one or both of a hole transport layer and a hole injection layer, and the polymer according to claim 14 is provided in one or both of the hole transport layer and the hole injection layer. The organic electroluminescent element according to claim 17, which is contained.
The organic electroluminescence device according to claim 17 or 18, wherein the light emitting layer contains one or both of a styrylamine compound and an arylamine compound.
The organic electroluminescence device according to any one of claims 17 to 19, which emits blue light.