WO2009154207A1 - Anthracene derivative and organic electroluminescent element using the same - Google Patents

Abstract

Disclosed is an anthracene derivative represented by formula (1) (excluding an anthracene derivative represented by formula (1')). (In the formulae, Ar11-Ar14 each represents a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group; and Ar21-Ar24 each represents a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted aromatic heterocyclic group.  Incidentally, when all of the Ar11-Ar14 are benzene rings, not all of the Ar21-Ar24 are hydrogen atoms; and when at least one of the Ar11-Ar14 is a 9,9'-dimethylfluorenyl group or a 9,9'-diphenylfluorenyl group, not all of the others are unsubstituted phenyl groups.)

Description

Anthracene derivative and organic electroluminescence device using the same

The present invention relates to a novel anthracene compound useful as a light-emitting material of an organic electroluminescence device and an organic electroluminescence device using the same.

An organic electroluminescence (EL) element is a self-luminous element utilizing the principle that a light-emitting material emits light by recombination energy of holes injected from an anode and electrons injected from a cathode when an electric field is applied.
Organic EL devices have made remarkable progress, and organic EL devices have features such as low-voltage driving, high brightness, diversity of emission wavelengths, high-speed response, and the ability to produce thin and light-emitting devices. Application to applications is expected.
Luminescent materials used in organic EL elements have been actively studied since they have a great influence on the color of light emitted from the elements and the emission lifetime.
As the light-emitting material, one that emits light by a single substance or one that emits light by adding a small amount of dopant to a host material is known. In addition to fluorescent materials, it has been studied to use phosphorescent compounds as light emitting materials and to use triplet state energy for light emission. With such various light emitting materials, light emission in a visible region from blue to red is obtained.

As a light emitting material, for example, Patent Documents 1 to 3 disclose anthracene compounds tetra-substituted with a phenyl group or a biphenyl group. Patent Document 4 discloses an anthracene compound tetrasubstituted with a substituent containing a fluorenyl group. Patent Documents 5 to 8 disclose anthracene compounds having substituents at the 2, 6, 9, and 10 positions of the anthracene skeleton.

An object of the present invention is to provide a novel luminescent material and an organic EL element using the luminescent material.

US Pat. No. 5,077,142 Japanese Patent No. 3807018 JP 2006-049570 A JP 2002-154993 A JP 2003-146951 A International Publication No. WO07 / 102683 International publication WO08 / 094399 International Publication WO07 / 110129

（式中、Ａｒ_１１～Ａｒ_１４はそれぞれ、置換もしくは無置換の芳香族炭化水素基、又は置換もしくは無置換の複素環基である。Ａｒ_２１～Ａｒ_２４はそれぞれ、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換の芳香族炭化水素基、又は置換もしくは無置換の複素環基である。
　但し、Ａｒ_１１～Ａｒ_１４が全てベンゼン環である場合、Ａｒ_２１～Ａｒ_２４が全て水素原子になることはない。また、Ａｒ_１１～Ａｒ_１４の少なくとも１つが９，９’－ジメチルフルオレニル基又は９，９’－ジフェニルフルオレニル基である場合、残りのＡｒ_１１～Ａｒ_１４が全て無置換のフェニル基になることはない。）
２．下記式（１’）で表されるアントラセン誘導体。

（式中、Ａｒ_１１～Ａｒ_１４、Ａｒ_２１～Ａｒ_２４は、請求項１と同様の基である。但し、式（１’）では、Ａｒ_１１～Ａｒ_１４がそれぞれベンゼン環又はナフタレン環である場合、Ａｒ_２１～Ａｒ_２４の全てが水素原子になることはない。）
３．下記式（２）～（６）で表される１に記載のアントラセン誘導体。

（式中、Ａｒ_１１～Ａｒ_１４、Ａｒ_２１～Ａｒ_２４は、請求項１と同様の基である。）
４．下記式（７）で表されるアントラセン誘導体。

（式中、Ａｒ_３１、Ａｒ_３２、Ａｒ_３４、Ａｒ_３５及びＡｒ_３６は、それぞれ置換もしくは無置換の環形成炭素数が６～３０の芳香族炭化水素基、または置換もしくは無置換の環形成原子数が５～３０の複素環基を示す。Ａｒ_３３は、水素原子または置換もしくは無置換の環形成炭素数が６～３０の芳香族炭化水素基、または置換もしくは無置換の環形成原子数が５～３０の複素環基を示す。但し、Ａｒ_３１～Ａｒ_３４の少なくとも２つは、置換もしくは無置換の環形成炭素数が１０～３０の縮合芳香族環基、または、置換もしくは無置換の環形成原子数が９～３０の複素環基を示す。）
５．前記Ａｒ_３３が水素原子で、Ａｒ_３１が無置換の炭素数１０～３０の縮合芳香族環基である４記載のアントラセン誘導体。
６．前記Ａｒ_３１がメタフェニレン基である５記載のアントラセン誘導体。
７．Ａｒ_３１及びＡｒ_３２が、それぞれ置換もしくは無置換のフェニレン基、Ａｒ_３３～Ａｒ_３６が置換もしくは無置換の環形成炭素数が６～３０の芳香族炭化水素基、または置換もしくは無置換の環形成原子数が５～３０の複素環基である４記載のアントラセン誘導体。
８．下記式（８）で表されるアントラセン誘導体。

（式中、Ａｒ_３５～Ａｒ_３８は、それぞれ置換もしくは無置換の環形成炭素数が６～３０の芳香族炭化水素基、又は置換もしくは無置換の環形成原子数が５～３０の複素環基を示す。
　Ｒａ及びＲｂは、それぞれ水素原子又は置換基を表し、ｐ，ｑは１～４の整数を表す。）
９．前記Ａｒ_３７及びＡｒ_３８が、それぞれ置換もしくは無置換の環形成炭素数が１０～３０の縮合環基である８記載のアントラセン誘導体。
１０．下記式（９）で表されるアントラセン誘導体。

（式中、Ａｒ_４１～Ａｒ_４６は、それぞれ置換もしくは無置換の環形成炭素数が６～３０の芳香族炭化水素基、又は置換もしくは無置換の環形成原子数が５～３０の複素環基を示す。ただし、Ａｒ_４３～Ａｒ_４６の少なくとも２つは置換もしくは無置換の環形成炭素数が１０～３０の縮合芳香族環基、又は、置換もしくは無置換の環形成原子数が１０～３０の複素環基を示す。）
１１．上記１～１０のいずれかに記載のアントラセン誘導体からなる発光材料。
１２．前記アントラセン誘導体がホスト材料である１１に記載の発光材料。
１３．陽極と陰極間に一層以上の有機薄膜層が挟持されている有機エレクトロルミネッセンス素子であって、前記有機薄膜層の少なくとも一層が、１～１０のいずれかに記載のアントラセン誘導体を含有する有機エレクトロルミネッセンス素子。
１４．前記アントラセン誘導体を含有する層が、さらに、りん光性ドーパント及び蛍光性ドーパントの少なくとも１つを含有する１３に記載の有機エレクトロルミネッセンス素子。
１５．前記蛍光性ドーパントが、アリールアミン化合物、スチリルアミン化合物及びフルオランテン化合物の少なくとも１つである１４に記載の有機エレクトロルミネッセンス素子。
１６．前記りん光性ドーパントが、金属錯体である１４又は１５に記載の有機エレクトロルミネッセンス素子。
１７．上記１１又は１２に記載の発光材料を含む有機エレクトロルミネッセンス材料含有溶液。
１８．上記１７に記載の有機エレクトロルミネッセンス材料含有溶液を用いて作製した有機エレクトロルミネッセンス素子。 According to the present invention, the following anthracene derivatives, organic EL devices and the like are provided.
1. An anthracene derivative represented by the following formula (1) (except for an anthracene derivative represented by the following formula (1 ′)).

(In the formula, Ar ₁₁ to Ar ₁₄ are each a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. Ar ₂₁ to Ar ₂₄ are each a hydrogen atom, substituted or unsubstituted, An alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group.
However, when Ar ₁₁ to Ar ₁₄ are all benzene rings, Ar ₂₁ to Ar ₂₄ are not all hydrogen atoms. When at least one of Ar ₁₁ to Ar ₁₄ is a 9,9′-dimethylfluorenyl group or a 9,9′-diphenylfluorenyl group, the remaining Ar ₁₁ to Ar ₁₄ are all unsubstituted phenyl groups. Never become. )
2. An anthracene derivative represented by the following formula (1 ′).

(In the formula, Ar ₁₁ to Ar ₁₄ and Ar ₂₁ to Ar ₂₄ are the same groups as in claim 1. However, in the formula (1 ′), Ar ₁₁ to Ar ₁₄ are each a benzene ring or a naphthalene ring. In this case, not all of Ar ₂₁ to Ar ₂₄ become hydrogen atoms.)
3. 2. The anthracene derivative according to 1, represented by the following formulas (2) to (6):

(In the formula, Ar ₁₁ to Ar ₁₄ and Ar ₂₁ to Ar ₂₄ are the same groups as in claim 1).
4). An anthracene derivative represented by the following formula (7).

(Wherein Ar ₃₁ , Ar ₃₂ , Ar ₃₄ , Ar ₃₅ and Ar ₃₆ are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring-forming atom. Represents a heterocyclic group having a number of 5 to 30. Ar ₃₃ represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring forming atom number. Represents a heterocyclic group of 5 to 30, provided that at least two of Ar ₃₁ to Ar ₃₄ are a substituted or unsubstituted condensed aromatic ring group having 10 to 30 ring carbon atoms, or a substituted or unsubstituted ring group; (It represents a heterocyclic group having 9 to 30 ring atoms.)
5). 5. The anthracene derivative according to 4, wherein Ar ₃₃ is a hydrogen atom, and Ar ₃₁ is an unsubstituted condensed aromatic ring group having 10 to 30 carbon atoms.
6). 6. The anthracene derivative according to 5, wherein Ar ₃₁ is a metaphenylene group.
7). Ar ₃₁ and Ar ₃₂ are each a substituted or unsubstituted phenylene group, Ar ₃₃ to Ar ₃₆ are substituted or unsubstituted aromatic hydrocarbon groups having 6 to 30 ring carbon atoms, or substituted or unsubstituted ring formation 5. The anthracene derivative according to 4, which is a heterocyclic group having 5 to 30 atoms.
8). An anthracene derivative represented by the following formula (8).

(Wherein Ar ₃₅ to Ar ₃₈ are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. Indicates.
Ra and Rb each represents a hydrogen atom or a substituent, and p and q each represents an integer of 1 to 4. )
9. 9. The anthracene derivative according to 8, wherein Ar ₃₇ and Ar ₃₈ are each a substituted or unsubstituted condensed ring group having 10 to 30 ring carbon atoms.
10. An anthracene derivative represented by the following formula (9).

(In the formula, each of Ar ₄₁ to Ar ₄₆ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. Provided that at least two of Ar ₄₃ to Ar ₄₆ are substituted or unsubstituted condensed aromatic ring groups having 10 to 30 ring carbon atoms, or substituted or unsubstituted ring forming atoms having 10 to 30 ring atoms. A heterocyclic group of
11. A light emitting material comprising the anthracene derivative according to any one of 1 to 10 above.
12 12. The light emitting material according to 11, wherein the anthracene derivative is a host material.
13. An organic electroluminescence device in which one or more organic thin film layers are sandwiched between an anode and a cathode, wherein at least one of the organic thin film layers contains the anthracene derivative according to any one of 1 to 10 element.
14 14. The organic electroluminescence device according to 13, wherein the layer containing the anthracene derivative further contains at least one of a phosphorescent dopant and a fluorescent dopant.
15. 15. The organic electroluminescence device according to 14, wherein the fluorescent dopant is at least one of an arylamine compound, a styrylamine compound, and a fluoranthene compound.
16. 16. The organic electroluminescence device according to 14 or 15, wherein the phosphorescent dopant is a metal complex.
17. 13. An organic electroluminescent material-containing solution containing the light-emitting material according to 11 or 12 above.
18. 18. An organic electroluminescent device produced using the organic electroluminescent material-containing solution described in 17 above.

ADVANTAGE OF THE INVENTION According to this invention, the organic EL element obtained using a novel anthracene derivative, a luminescent material which consists of this, an organic EL material containing solution containing a luminescent material, and an organic EL material containing solution can be provided.
The organic EL device using the anthracene derivative of the present invention has an excellent lifetime.

It is a schematic sectional drawing of one Embodiment of the organic EL element of this invention.

The anthracene derivative of the present invention is a compound represented by the following formula (1) (except when it is an anthracene derivative represented by the following formula (1 ′)).

　但し、式（１’）では、Ａｒ_１１～Ａｒ_１４がそれぞれベンゼン環又はナフタレン環である場合、Ａｒ_２１～Ａｒ_２４の全てが水素原子になることはない。 Moreover, the anthracene derivative of the present invention is a compound represented by the following formula (1 ′).

However, in Formula (1 ′), when Ar ₁₁ to Ar ₁₄ are each a benzene ring or a naphthalene ring, all of Ar ₂₁ to Ar ₂₄ do not become hydrogen atoms.

In the formulas (1) and (1 ′), Ar ₁₁ to Ar ₁₄ are each a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group.
Ar ₂₁ to Ar ₂₄ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group.
When only hydrogen atoms are bonded to each group of Ar ₁₁ to Ar ₁₄ , Ar ₂₁ to Ar ₂₄ are assumed to be hydrogen atoms, and each group of Ar ₁₁ to Ar ₁₄ includes other than hydrogen atoms and hydrogen atoms. When these groups are bonded, groups other than the hydrogen atom are referred to as Ar ₂₁ to Ar ₂₄ .

As the aromatic hydrocarbon group for Ar ₁₁ to Ar ₁₄ , when Ar ₂₁ to Ar ₂₄ are hydrogen atoms, a substituted or unsubstituted phenyl group, indenyl group, fluorenyl group, naphthyl group, anthryl group, phenanthryl group, naphthacenyl group Group, acenaphthylenyl group, biphenyl group, chrysenyl group, pyrenyl group, triphenyl group, fluoranthenyl group, perylenyl group, fluorenyl group, and terphenyl group. Specifically, phenyl group, 6-indenyl group, 7-indenyl group, 1-fluorenyl group, 2-fluorenyl 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, 5-naphthacenyl group, 3-acenaphthylenyl group, 4- Acenaphthylenyl group, 2-biphenyl group, 3-biphenyl group, 4-biphenyl group, 1-chrysenyl group, 2-chrysenyl group, 3-chrysenyl group, 6-chrenyl group, 1-pyrenyl group, 2-pyrenyl group, 4- Pyrenyl group, 1-triphenyl group, 2-triphenyl group, 1-fluoranthenyl group, 2-fluoranthenyl group, - fluoranthenyl group, 7-fluoranthenyl group, 8-fluoranthenyl group, 1-perylenyl group, 2-perylenyl group, and a 3-perylenyl group.
Preferred are a substituted or unsubstituted phenyl group, 1-naphthyl group, 2-naphthyl group, 9-phenanthryl group, 2-phenanthryl group, and 2-fluorenyl group.

The aromatic hydrocarbon group of Ar ₁₁ to Ar ₁₄ preferably has 6 to 60 ring-forming carbon atoms, and more preferably 6 to 30 carbon atoms.
When Ar ₂₁ to Ar ₂₄ are not hydrogen atoms, examples of Ar ₁₁ to Ar ₁₄ include divalent groups obtained by removing one hydrogen atom from the above groups.

Examples of the heterocyclic group of Ar ₁₁ to Ar ₁₄ include, when Ar ₂₁ to Ar ₂₄ are hydrogen atoms, a substituted or unsubstituted pyrrolyl group, pyridinyl group, pyrazinyl group, indolyl group, furyl group, dibenzofuranyl group , Dibenzothienyl group, quinolyl group, carbazolyl group and the like. Specifically, 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl 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, 5-isoindolyl group, 6- Isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 1-benzofuranyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7- Benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3-dibenzofuranyl group, 4-dibenzofuranyl group Group, 1-benzothiophenyl group, 2-benzothiophenyl group, 3-benzothiophenyl group, 4-benzothiophenyl group, 5-benzothiophenyl group, 6-benzothiophenyl group, 7-benzothiophenyl group 1-dibenzothiophenyl group, 2-dibenzothiophenyl group, 3-dibenzothiophenyl group, 4-dibenzothiophenyl 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-iso Noryl 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-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1,7-phenanthrolin-2-yl group, 1,7-phenanthrolin-3-yl group, 1,7-phenanthrolin-4-yl group, 1,7-phenanthroline-5-yl group, 1,7-phenanthrolin-6-yl group, 1,7-phenanthrolin-8-yl group, 1,7-phenanthrolin-9-yl Group, 1,7-phenanthroline-10-yl group, 1,8-phenanthrolin-2-yl group, 1,8-phenanthrolin-3-yl group, 1,8-phenanthrolin-4 -Yl group, 1,8-phenanthroline-5-yl group, 1,8-phenanthrolin-6-yl group, 1,8-phenanthrolin-7-yl group, 1,8-phenanthroline -9-yl group, 1,8-phenanthrolin-10-yl group, 1,9-phenanthrolin-2-yl group, 1,9-phenanthrolin-3-yl group, 1,9-phen group Nanthrolin-4-yl group, 1,9-phenanthrolin-5-yl group, 1,9-phenane Lorin-6-yl group, 1,9-phenanthrolin-7-yl group, 1,9-phenanthrolin-8-yl group, 1,9-phenanthrolin-10-yl group, 1,10- Phenanthrolin-2-yl group, 1,10-phenanthrolin-3-yl group, 1,10-phenanthrolin-4-yl group, 1,10-phenanthrolin-5-yl group, 2, 9-phenanthrolin-1-yl group, 2,9-phenanthrolin-3-yl group, 2,9-phenanthrolin-4-yl group, 2,9-phenanthrolin-5-yl group, 2,9-phenanthrolin-6-yl group, 2,9-phenanthrolin-7-yl group, 2,9-phenanthrolin-8-yl group, 2,9-phenanthrolin-10-yl Group, 2,8-phenanthrolin-1-yl group, 2,8-phenanthroline 3-yl group, 2,8-phenanthrolin-4-yl group, 2,8-phenanthrolin-5-yl group, 2,8-phenanthrolin-6-yl group, 2,8-phenanth Lorin-7-yl group, 2,8-phenanthrolin-9-yl group, 2,8-phenanthrolin-10-yl group, 2,7-phenanthrolin-1-yl group, 2,7- Phenanthrolin-3-yl group, 2,7-phenanthrolin-4-yl group, 2,7-phenanthrolin-5-yl group, 2,7-phenanthrolin-6-yl group, 2, 7-phenanthrolin-8-yl group, 2,7-phenanthrolin-9-yl group, 2,7-phenanthrolin-10-yl group, 1-phenazinyl group, 2-phenazinyl group, 1-pheno Thiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenyl Enothiazinyl 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 and the like.
Preferably, 1-dibenzofuranyl group, 2-dibenzofuranyl group, 3-dibenzofuranyl group, 4-dibenzofuranyl group, 1-carbazolyl group, 2-carbazolyl group, 3-carbazolyl group, 4-carbazolyl group , 9-carbazolyl group, 1-dibenzothiophenyl group, 2-dibenzothiophenyl group, 3-dibenzothiophenyl group, 4-dibenzothiophenyl group and the like.

The heterocyclic group of Ar ₁₁ to Ar ₁₄ preferably has 5 to 18 ring carbon atoms.
An example of Ar ₁₁ to Ar ₁₄ when Ar ₂₁ to Ar ₂₄ is not a hydrogen atom is a divalent group obtained by removing one hydrogen atom from the above group.

The aromatic hydrocarbon group and heterocyclic group of Ar ₁₁ to Ar ₁₄ may be substituted. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 6 to 60 carbon atoms, Examples thereof include a heterocyclic group having 2 to 60 carbon atoms.
Specific examples of the substituent include an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methyl, ethyl, isopropyl, t-butyl, and n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.), alkenyl groups (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably carbon numbers). 2 to 8, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.), alkynyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably carbon number) 2 to 8, for example, propargyl, 3-pentynyl, etc.), an aryl group (preferably having 6 to 60 carbon atoms, more preferably 6 to 30 carbon atoms, particularly preferably 6 to 20 carbon atoms, such as phenyl, fluorenyl, naphthyl, anthryl, phenanthryl, chrysenyl, pyrenyl, triphenylenyl, fluoranthenyl, etc.), substituted or unsubstituted amino Group (preferably having 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, particularly preferably 0 to 6 carbon atoms, and examples thereof include amino, methylamino, dimethylamino, diethylamino, diphenylamino, dibenzylamino and the like. An alkoxy group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methoxy, ethoxy, butoxy, etc.), an aryloxy group ( Preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferred Has 6 to 12 carbon atoms, for example, phenyloxy, 2-naphthyloxy, etc.), an acyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 carbon atom). For example, acetyl, benzoyl, formyl, pivaloyl, etc.), an alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms). For example, methoxycarbonyl, ethoxycarbonyl, etc.), aryloxycarbonyl groups (preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenyl Oxycarbonyl, etc.), acyloxy groups (preferably having 2 to 20 carbon atoms, more preferably having carbon atoms) It has 2 to 16, particularly preferably 2 to 10 carbon atoms, and examples thereof include acetoxy and benzoyloxy. ), An acylamino group (preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, such as acetylamino, benzoylamino, etc.), an alkoxycarbonylamino group (Preferably having 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms such as methoxycarbonylamino), aryloxycarbonylamino group (preferably having carbon number) 7 to 20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino), substituted or unsubstituted sulfonylamino groups (preferably having 1 carbon atom) To 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms. And substituted or unsubstituted sulfamoyl groups (preferably having 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, and particularly preferably 0 to 12 carbon atoms. For example, sulfamoyl , Methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl etc.), substituted or unsubstituted carbamoyl groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms such as carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl, etc.), an alkylthio group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably carbon atoms). 1 to 12, for example, methylthio, ethylthio, etc. An arylthio group (preferably having 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio), substituted or unsubstituted sulfonyl A group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl, tosyl, etc.), a substituted or unsubstituted sulfinyl group (preferably Has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methanesulfinyl, benzenesulfinyl, etc.), a substituted or unsubstituted ureido group (preferably It has 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms. For example, ureido, methylureido, phenyl Luureid etc. are mentioned. ), Substituted or unsubstituted phosphate amide groups (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as diethyl phosphate amide, phenyl phosphate amide) Hydroxy group, mercapto group, halogen atom (eg fluorine atom, chlorine atom, bromine atom, iodine atom), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino Group, imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and examples of the hetero atom include a nitrogen atom, an oxygen atom, and a sulfur atom. Is, for example, imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzoimidazolyl Benzothiazolyl, carbazolyl, etc.), silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, such as trimethylsilyl, triphenylsilyl, etc. And the like. These substituents may be further substituted. Moreover, when there are two or more substituents, they may be the same or different. If possible, they may be linked to each other to form a ring.

Examples of suitable substituents include methyl, ethyl, propyl, isopropyl, butyl, sec-butyl, tert-butyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, trimethylsilyl, triphenylsilyl.
Preferred examples of Ar ₁₁ to Ar ₁₄ are shown below.

In the formula (1), Ar ₂₁ to Ar ₂₄ are each a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group.

The alkyl group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 8 carbon atoms. For example, methyl, ethyl, isopropyl, t-butyl, n-octyl, n -Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like.

Of Ar ₂₁ ~ _{Ar 24,} examples of the aromatic hydrocarbon group or heterocyclic group, similar to _Ar 11 ~ _{Ar 14} described above groups _(example when Ar 21 ~ _{Ar 24} is a hydrogen atom) and the like.

The alkyl group, aromatic hydrocarbon group and heterocyclic group of Ar ₂₁ to Ar ₂₄ may be substituted, and examples of the substituent include the same groups as Ar ₁₁ to Ar ₁₄ described above.
Preferred examples of Ar ₂₁ to Ar ₂₄ are shown below.

In the formula (1), when Ar ₁₁ to Ar ₁₄ are all benzene rings, Ar ₂₁ to Ar ₂₄ are not all hydrogen atoms. That is, the following compounds are not anthracene derivatives of the present invention.

When at least one of Ar ₁₁ to Ar ₁₄ is a 9,9′-dimethylfluorenyl group or a 9,9′-diphenylfluorenyl group, the remaining Ar ₁₁ to Ar ₁₄ are all unsubstituted phenyl groups. Never become.

　Ａｒ_１１～Ａｒ_１４及びＡｒ_２１～Ａｒ_２４は、上記式（１）と同様の基であり、具体例も同様である。 In the present invention, anthracene derivatives represented by the following formulas (2) to (6) are preferred.

Ar ₁₁ to Ar ₁₄ and Ar ₂₁ to Ar ₂₄ are the same groups as in the above formula (1), and specific examples thereof are also the same.

In the present invention, an anthracene derivative represented by the following formula (7) is also preferable.

In the formula, each of Ar ₃₁ , Ar ₃₂ , Ar ₃₄ , Ar _35, and Ar ₃₆ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring forming atom number. Represents a heterocyclic group of 5 to 30. Ar ₃₃ represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. Provided that at least two of Ar ₃₁ to Ar ₃₄ are a substituted or unsubstituted condensed aromatic ring group having 10 to 30 ring carbon atoms, or a heterocyclic group having 9 to 30 substituted or unsubstituted ring atoms. A ring group is shown.

In Formula (7), Ar ₃₃ is preferably a hydrogen atom, and Ar ₃₁ is preferably an unsubstituted condensed aromatic ring group having 10 to 30 carbon atoms.
Ar ₃₁ is preferably a metaphenylene group.
Further, Ar ₃₁ and Ar ₃₂ are each a substituted or unsubstituted phenylene group, Ar ₃₃ to Ar ₃₆ are substituted or unsubstituted aromatic hydrocarbon groups having 6 to 30 ring carbon atoms, or substituted or unsubstituted A heterocyclic group having 5 to 30 ring-forming atoms is preferable.

An anthracene derivative represented by the following formula (8) is also preferable.

In the formula, Ar ₃₅ to Ar ₃₈ each represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. Show.
Ra and Rb each represents a hydrogen atom or a substituent, and p and q each represents an integer of 1 to 4.

In the formula (8), Ar ₃₇ and Ar ₃₈ are each preferably a substituted or unsubstituted condensed ring group having 10 to 30 ring carbon atoms.

An anthracene derivative represented by the following formula (9) is also preferable.

In the formula, each of Ar ₄₁ to Ar ₄₆ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. Show. Provided that at least two of Ar ₄₃ to Ar ₄₆ are a substituted or unsubstituted condensed aromatic ring group having 10 to 30 ring carbon atoms, or a heterocyclic ring having 10 to 30 substituted or unsubstituted ring atoms. Indicates a group.

In addition, each group of formulas (7) to (9) represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring atom number of 5 to 30. Specific examples of the heterocyclic group are the same as the examples of Ar _{11 and the} like in formula (1) described above.
Examples of the substituent represented by Ra and Rb in the formula (8) are the same as the substituents that the groups Ar ₁₁ to Ar ₁₄ in the formula (1) can have.

Specific examples of the anthracene derivative of the present invention are shown below.

The anthracene derivative of the present invention can be synthesized by an ordinary method, for example, a method of synthesizing from a dihalogenated anthraquinone or a Suzuki coupling method. Examples of synthesis are given in the examples.

The anthracene derivative of the present invention can be used as a light emitting material for an organic EL device. Preferably it is used as a host material.
As the anthracene derivative of the present invention, a polymerized one can also be used. When the polymer is made, it is synthesized by a method usually used in polymer synthesis (polycondensation reaction, coupling reaction, radical reaction, living polymerization, etc.). Although there is no restriction | limiting in particular in a structure, It is preferable that it is molecular weight more than the polymerization degree which has a glass transition point.

In the organic EL device of the present invention, one or more organic thin film layers are sandwiched between the anode and the cathode, and at least one of the organic thin film layers contains the above-described anthracene derivative of the present invention.

The layer containing the anthracene derivative of the present invention can further contain at least one of a phosphorescent dopant and a fluorescent dopant. By including such a dopant, it can function as a phosphorescent light emitting layer, a fluorescent light emitting layer, and a hybrid light emitting layer having both phosphorescence and fluorescence.
As the fluorescent dopant, at least one of an arylamine compound, a styrylamine compound, and a fluoranthene compound is preferable. As the phosphorescent dopant, a metal complex is preferable. For these specific examples, the description of the light emitting layer described later may be referred to.

As a typical 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 transport layer / light emitting layer / insulating layer / Cathode (13) Anode / insulating layer / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode But, but it is not limited to these. Of these, the configuration of (8) is preferably used.

In the organic EL device of the present invention, the anthracene derivative of the present invention may be used in any of the organic layers described above, but is preferably contained in the light emitting band, and particularly preferably contained in the light emitting layer. The content is preferably 30 to 100 wt%.

Fig. 1 shows the configuration (8). The organic EL element includes a cathode 10 and an anode 20 and a hole injection layer 30, a hole transport layer 32, a light emitting layer 34, and an electron injection layer 36 sandwiched therebetween. The hole injection layer 30, the hole transport layer 32, the light emitting layer 34, and the electron injection layer 36 correspond to organic thin film layers, respectively. At least one of the layers 30, 32, 34, and 36 contains the anthracene derivative.

Hereinafter, each member of the organic EL element will be described.
The organic EL element is usually produced on a substrate, and the substrate supports the organic EL element. It is preferable to use a smooth substrate. When light is extracted through this substrate, it is desirable that the substrate is translucent and that the transmittance of light in the visible region with a wavelength of 400 to 700 nm is 50% or more.
As such a translucent board | substrate, a glass plate, a synthetic resin board, etc. are used suitably, for example. 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 synthetic resin plate include plates made of polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, polysulfone resin, and the like.

It is effective for the anode to inject holes into the hole injection layer, the hole transport layer, or the light emitting layer and to have a work function of 4.5 eV or more. Specific examples of the anode material include indium tin oxide (ITO), a mixture of indium oxide and zinc oxide, a mixture of ITO and cerium oxide (ITCO), a mixture of indium oxide and zinc oxide and cerium oxide (IZCO), an oxidation Examples thereof include a mixture of indium and cerium oxide (ICO), a mixture of zinc oxide and aluminum oxide (AZO), tin oxide (NESA), gold, silver, platinum, and copper.
The anode can be formed from these electrode materials by vapor deposition or sputtering.
When light emitted from the light emitting layer is extracted from the anode, it is preferable that the transmittance of the anode for light emission is greater than 10%. The sheet resistance of the anode is preferably several hundred Ω / □ or less. Although the film thickness of the anode depends on the material, it is usually 10 nm to 1 μm, preferably 10 to 200 nm.

The light emitting layer has the following functions.
(I) injection function; function capable of injecting holes from the anode or hole injection layer when an electric field is applied, and electron injection from the cathode or electron injection layer (ii) transport function; injected charge (electrons (Iii) light emission function; function to recombine electrons and holes and connect them to light emission

As a method for forming the light emitting layer, for example, a known method such as an evaporation method, a spin coating method, or an LB method can be applied. The light emitting layer is particularly preferably a molecular deposited film. The molecular deposited film is a film formed by depositing a material compound in a gas phase state or a film formed by solidifying a material compound in a solution state or a liquid phase state. Usually, this molecular deposited film is an LB. The thin film (molecular accumulation film) formed by the method can be classified by the difference in aggregated structure and higher order structure, and the functional difference resulting therefrom.
The light emitting layer can also be formed by dissolving a binder such as a resin and a material compound in a solvent to form a solution, and then thinning the solution by a spin coating method or the like.

Examples of the light emitting material (host material or dopant material) that can be used for the light emitting layer include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, Tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran Thiopyran, polymethine, merocyanine, imidazole chelating oxinoid compounds, quinacridone, rubrene and Etc. These derivatives and fluorescent dyes and the like, but not limited thereto.

In addition to the anthracene derivatives of the present invention, specific examples of host materials that can be used for the light emitting layer include compounds represented by the following (i) to (ix).
Asymmetric anthracene represented by the following formula (i).

(In the formula, Ar ⁰⁰¹ is a substituted or unsubstituted condensed aromatic hydrocarbon group having 10 to 50 ring carbon atoms. Ar ⁰⁰² is a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms. X ⁰⁰¹ to X ⁰⁰³ are each independently a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, and a substituted group. Or an unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, a substituted or unsubstituted number of ring atoms An aryloxy group having 5 to 50 atoms, a substituted or unsubstituted arylthio group having 5 to 50 ring atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, a carboxyl group, A gen atom, a cyano group, a nitro group, and a hydroxy group, a, b and c are each an integer of 0 to 4. n is an integer of 1 to 3. When n is 2 or more, [] May be the same or different.)

An asymmetric monoanthracene derivative represented by the following formula (ii).

(In the formula, Ar ⁰⁰³ and Ar ⁰⁰⁴ are each independently a substituted or unsubstituted aromatic ring group having 6 to 50 ring carbon atoms, and m and n are each an integer of 1 to 4, provided that , When m = n = 1 and the binding position of Ar ⁰⁰³ and Ar ^{004 to} the benzene ring is symmetrical, Ar ⁰⁰³ and Ar ⁰⁰⁴ are not the same, and m or n is an integer of 2 to 4 M and n are different integers.
R ⁰⁰¹ to R ⁰¹⁰ are each independently a hydrogen atom, a substituted or unsubstituted aromatic ring group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted group Or an unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 50 ring atoms, a substituted or unsubstituted arylthio group having 5 to 50 ring atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, substituted or An unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, and a hydroxy group. )

An asymmetric pyrene derivative represented by the following formula (iii).

[ ^Wherein , Ar ⁰⁰⁵ and Ar ⁰⁰⁶ are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms. L ⁰⁰¹ and L ⁰⁰² are a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalenylene group, a substituted or unsubstituted fluorenylene group, or a substituted or unsubstituted dibenzosilolylene group, respectively.
m is an integer from 0 to 2, n is an integer from 1 to 4, s is an integer from 0 to 2, and t is an integer from 0 to 4.
L ⁰⁰¹ or Ar ⁰⁰⁵ binds to any of the 1-5 positions of pyrene, and L ⁰⁰² or Ar ⁰⁰⁶ binds to any of the 6-10 positions of pyrene. However, when n + t is an even number, Ar ⁰⁰⁵ , Ar ⁰⁰⁶ , L ⁰⁰¹ , and L ⁰⁰² satisfy the following (1) or (2).
(1) Ar ⁰⁰⁵ ≠ Ar ⁰⁰⁶ and / or L ⁰⁰¹ ≠ L ⁰⁰² (where ≠ indicates a group having a different structure)
(2) When Ar ⁰⁰⁵ = Ar ⁰⁰⁶ and L ⁰⁰¹ = L ⁰⁰² (2-1) m ≠ s and / or n ≠ t, or (2-2) When m = s and n = t,
(2-2-1) L ⁰⁰¹ and L ⁰⁰² or pyrene are bonded to different bonding positions on Ar ⁰⁰⁵ and Ar ⁰⁰⁶ , respectively (2-2-2) L ⁰⁰¹ and L ⁰⁰² , or pyrene is , Ar ⁰⁰⁵ and Ar ⁰⁰⁶ are bonded at the same bonding position, and L ⁰⁰¹ and L ⁰⁰² or Ar ⁰⁰⁵ and Ar ⁰⁰⁶ are substituted at positions 1 and 6 or 2 and 7 in pyrene There is no. ]

An asymmetric anthracene derivative represented by the following formula (iv):

^Wherein A ⁰⁰¹ and A ⁰⁰² are each independently a substituted or unsubstituted condensed aromatic ring group having 10 to 20 ring carbon atoms.
Ar ⁰⁰⁷ and Ar ⁰⁰⁸ are each independently a hydrogen atom or a substituted or unsubstituted aromatic ring group having 6 to 50 ring carbon atoms.
R ⁰¹¹ to R ⁰²⁰ are each independently a hydrogen atom, a substituted or unsubstituted aromatic ring group having 6 to 50 ring carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms, a substituted group Or an unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 6 to 50 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 50 ring atoms, a substituted or unsubstituted arylthio group having 5 to 50 ring atoms, a substituted or unsubstituted alkoxycarbonyl group having 1 to 50 carbon atoms, substituted or An unsubstituted silyl group, a carboxyl group, a halogen atom, a cyano group, a nitro group, or a hydroxy group.
Ar ⁰⁰⁷ , Ar ⁰⁰⁸ , R ⁰¹⁹ and R ⁰²⁰ may each be plural, and adjacent ones may form a saturated or unsaturated cyclic structure.
However, in the formula (iv), a group that is symmetrical with respect to the XY axis shown on the anthracene is not bonded to the 9th and 10th positions of the central anthracene. )

An anthracene derivative represented by the following formula (v).

(Wherein R ⁰²¹ to R ⁰³⁰ are each independently a hydrogen atom, alkyl group, cycloalkyl group, optionally substituted aryl group, alkoxyl group, aryloxy group, alkylamino group, alkenyl group, arylamino group, or substituted. A and b each represent an integer of 1 to 5, and when they are 2 or more, R ^021s or R ^022s may be the same or different from each other In addition, R ⁰²¹ or R ⁰²² may be bonded to each other to form a ring, or R ⁰²³ and R ⁰²⁴ , R ⁰²⁵ and R ⁰²⁶ , R ⁰²⁷ and R ⁰²⁸ , R ⁰²⁹ and R ⁰³⁰ are L ⁰⁰³ may be a single bond, —O—, —S—, —N (R) — (R is an alkyl group or an optionally substituted aryl group). Represents an alkylene group or an arylene group.)

An anthracene derivative represented by the following formula (vi).

(Wherein R ⁰³¹ to R ⁰⁴⁰ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an aryl group, an alkoxyl group, an aryloxy group, an alkylamino group, an arylamino group, or an optionally substituted multicyclic group) C, d, e and f each represent an integer of 1 to 5, and when they are 2 or more, R ^031s , R ^032s , R ^036s or R ^037s may be the same. R ⁰³¹ may be different from each other, R ⁰³² may be bonded to each other, R ⁰³³ may be bonded to each other, or R ⁰³⁷ may be bonded to each other to form a ring, and R ⁰³³ and R ⁰³⁴ , R ⁰³⁹ and R ⁰⁴⁰ are based on each other. bonded to ring the optionally formed .L ⁰⁰⁴ is a single bond, -O -, - S -, - N (R) - (R is an aryl group which may be alkyl or substituted), Al Shows the alkylene group or an arylene group.)

Spirofluorene derivatives represented by the following formula (vii).

( ^Wherein A ⁰⁰⁵ to A ⁰⁰⁸ are each independently a substituted or unsubstituted biphenylyl group or a substituted or unsubstituted naphthyl group.)

A condensed ring-containing compound represented by the following formula (viii):

( ^Wherein A ⁰¹¹ to A ⁰¹³ are each independently a substituted or unsubstituted arylene group having 6 to 50 ring carbon atoms. A ⁰¹⁴ to A ⁰¹⁶ are each independently a hydrogen atom, An unsubstituted aryl group having 6 to 50 ring carbon atoms, each of R ⁰⁴¹ to R ⁰⁴³ independently represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, a carbon atom; An alkoxyl group having 1 to 6 carbon atoms, an aryloxy group having 5 to 18 carbon atoms, an aralkyloxy group having 7 to 18 carbon atoms, an arylamino group having 5 to 16 carbon atoms, a nitro group, a cyano group, and 1 to 6 carbon atoms. Represents an ester group or a halogen atom, and at least one of A ⁰¹¹ to A ⁰¹⁶ is a group having three or more condensed aromatic rings.

A fluorene compound represented by the following formula (ix).

Wherein R ⁰⁵¹ and R ⁰⁵² are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, or a substituted amino group. Represents a cyano group or a halogen atom, and R ⁰⁵¹ and R ⁰⁵² bonded to different fluorene groups may be the same or different, and R ⁰⁵¹ and R ⁰⁵² bonded to the same fluorene group are the same. R ⁰⁵³ and R ⁰⁵⁴ may be a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic ring. R ⁰⁵³ and R ⁰⁵⁴ which represent a group and are bonded to different fluorene groups may be the same or different, R ⁰⁵³ and R ⁰⁵⁴ bonded to the same fluorene group may be the same or different, and Ar ⁰¹¹ and Ar ⁰¹² are substituted or unsubstituted condensed polycyclic aromatics having a total of three or more benzene rings. A hydrocarbon group or a condensed polycyclic heterocyclic group in which the total of a benzene ring and a heterocyclic ring is bonded to a fluorene group by 3 or more substituted or unsubstituted carbons, Ar ⁰¹¹ and Ar ⁰¹² are the same or different N represents an integer of 1 to 10.)

In the organic EL device of the present invention, the light emitting layer may contain a phosphorescent dopant and / or a fluorescent dopant in addition to the light emitting material of the present invention, if desired. In addition, a light emitting layer containing these dopants may be stacked on the light emitting layer containing the anthracene derivative of the present invention.

A phosphorescent dopant is a compound that can emit light from triplet excitons. Although it is not particularly limited as long as it emits light from triplet excitons, it is preferably a metal complex containing at least one metal selected from the group consisting of Ir, Ru, Pd, Pt, Os and Re, and is preferably a porphyrin metal complex or ortho Metalated metal complexes are preferred. The phosphorescent compounds may be used alone or in combination of two or more.

The porphyrin metal complex is preferably a porphyrin platinum complex.
There are various ligands that form orthometalated metal complexes. Preferred ligands include compounds having a phenylpyridine skeleton, bipyridyl skeleton or phenanthroline skeleton, or 2-phenylpyridine derivatives, 7,8. -Benzoquinoline derivatives, 2- (2-thienyl) pyridine derivatives, 2- (1-naphthyl) pyridine derivatives, 2-phenylquinoline derivatives and the like. These ligands may have a substituent as needed. In particular, a fluorinated compound or a compound having a trifluoromethyl group introduced is preferable as a blue dopant. Furthermore, you may have ligands other than the said ligands, such as an acetylacetonate and picric acid, as an auxiliary ligand.

Specific examples of such metal complexes include tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, tris (2- Phenylpyridine) osmium, tris (2-phenylpyridine) rhenium, octaethylplatinum porphyrin, octaphenylplatinum porphyrin, octaethylpalladium porphyrin, octaphenylpalladium porphyrin, etc. An appropriate complex is selected depending on the device performance and the host compound to be used.

There is no restriction | limiting in particular as content in the light emitting layer of a phosphorescent dopant, Although it can select suitably according to the objective, For example, it is 0.1-70 mass%, and 1-30 mass% is preferable. If the content of the phosphorescent compound is less than 0.1% by mass, the light emission is weak and the effect of the content may not be sufficiently exhibited. If the content exceeds 70% by mass, a phenomenon called concentration quenching becomes prominent. The device performance may be degraded.

Fluorescent dopants are required from amine compounds, aromatic compounds, chelate complexes such as tris (8-quinolinolato) aluminum complex, coumarin derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives, oxadiazole derivatives, etc. It is preferable to select a compound according to the emission color, and a styrylamine compound, a styryldiamine compound, an arylamine compound, and an aryldiamine compound are more preferable. Moreover, the condensed polycyclic aromatic compound which is not an amine compound is also preferable. These fluorescent dopants may be used alone or in combination.

As the styrylamine compound and styryldiamine compound, those represented by the following formula (A) are preferable.

(In the formula, Ar ¹⁰¹ is a p-valent group, and a corresponding p-valent group of a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, a stilbenyl group, or a distyrylaryl group, and Ar ¹⁰² and Ar ¹⁰³ are Each of them is an aromatic hydrocarbon group having 6 to 20 carbon atoms, and Ar ¹⁰¹ , Ar ¹⁰² and Ar ¹⁰³ may be substituted, and any one of Ar ¹⁰¹ to Ar ¹⁰³ is substituted with a styryl group. More preferably, at least one of Ar ¹⁰² or Ar ¹⁰³ is substituted with a styryl group, and p is an integer of 1 to 4, and preferably an integer of 1 to 2.
Here, examples of the aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a naphthyl group, an anthranyl group, a phenanthryl group, and a terphenyl group.

As the arylamine compound and the aryldiamine compound, those represented by the following formula (B) are preferable.

(In the formula, Ar ¹¹¹ is a q-valent substituted or unsubstituted aromatic hydrocarbon group having 5 to 40 ring carbon atoms, and Ar ¹¹² and Ar ¹¹³ are substituted or unsubstituted ring forming carbon atoms having 5 to 40 carbon atoms, respectively. Q is an integer of 1 to 4, preferably an integer of 1 to 2.)
Here, as the aryl group having 5 to 40 ring carbon atoms, for example, phenyl group, naphthyl group, anthranyl group, phenanthryl group, pyrenyl group, coronyl group, biphenyl group, terphenyl group, pyrrolyl group, furyl group, Thienyl group, benzothienyl group, oxadiazolyl group, diphenylanthranyl group, indolyl group, carbazolyl group, pyridyl group, benzoquinolyl group, fluoranthenyl group, acenaphthofluoranthenyl group, stilbene group, perylenyl group, chrysenyl group, picenyl group, A triphenylenyl group, a rubicenyl group, a benzoanthracenyl group, a phenylanthranyl group, a bisanthracenyl group and the like can be mentioned, and a naphthyl group, an anthranyl group, a chrysenyl group and a pyrenyl group are preferable.

Preferred substituents for substitution on the aryl group are alkyl groups having 1 to 6 carbon atoms (ethyl group, methyl group, i-propyl group, n-propyl group, s-butyl group, t-butyl group, pentyl group). Group, hexyl group, cyclopentyl group, cyclohexyl group, etc.), alkoxy group having 1 to 6 carbon atoms (ethoxy group, methoxy group, i-propoxy group, n-propoxy group, s-butoxy group, t-butoxy group, pentoxy group) Hexyloxy group, cyclopentoxy group, cyclohexyloxy group, etc.), an aryl group having 5 to 40 ring carbon atoms, an amino group substituted with an aryl group having 5 to 40 ring carbon atoms, and 5 to 5 carbon atoms forming a ring Examples include an ester group having a 40 aryl group, an ester group having an alkyl group having 1 to 6 carbon atoms, a cyano group, a nitro group, and a halogen atom.

The light emitting layer may contain a hole transport material, an electron transport material, and a polymer binder as necessary.
The thickness of the light emitting layer is preferably 5 to 50 nm, more preferably 7 to 50 nm, and most preferably 10 to 50 nm. If the thickness is less than 5 nm, it is difficult to form a light emitting layer and the adjustment of chromaticity may be difficult, and if it exceeds 50 nm, the driving voltage may increase.

The hole injection layer and the hole transport layer help to inject holes into the light emitting layer and transport to the light emitting region, and have a high hole mobility and a small ionization energy of usually 5.5 eV or less. As a material for such a hole injection layer and a hole transport layer, a material that transports holes to the light emitting layer with lower electric field strength is preferable, and the hole mobility is, for example, 10 ⁴ to 10 ⁶ V / cm. When applying the electric field of 10 ⁻⁴ cm ² / V · sec or more, it is preferable.
The material for the hole injection layer and the hole transport layer is not particularly limited, and is conventionally used as a charge transport material for holes in optical transmission materials, and the hole injection layer and holes for organic EL devices. An arbitrary thing can be selected and used from the well-known things used for the transport layer.

　Ａｒ^２１１～Ａｒ^２１３、Ａｒ^２２１～Ａｒ^２２３及びＡｒ^２０３～Ａｒ^２０８はそれぞれ置換もしくは無置換の環形成炭素数６～５０の芳香族炭化水素基、又は置換もしくは無置換の環形成原子数５～５０の複素環基である。ａ～ｃ及びｐ～ｒはそれぞれ０～３の整数である。Ａｒ^２０３とＡｒ^２０４、Ａｒ^２０５とＡｒ^２０６、Ａｒ^２０７とＡｒ^２０８はそれぞれ互いに連結して飽和もしくは不飽和の環を形成してもよい。 For the hole injection layer and the hole transport layer, for example, an aromatic amine derivative represented by the following formula can be used.

Ar ²¹¹ to Ar ²¹³ , Ar ²²¹ to Ar ²²³ and Ar ²⁰³ to Ar ²⁰⁸ are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted ring atom number of 5 to 5 50 heterocyclic groups. a to c and p to r are integers of 0 to 3, respectively. Ar ²⁰³ and Ar ²⁰⁴ , Ar ²⁰⁵ and Ar ²⁰⁶ , Ar ²⁰⁷ and Ar ²⁰⁸ may be connected to each other to form a saturated or unsaturated ring.

　Ａｒ^２３１～Ａｒ^２３４はそれぞれ置換もしくは無置換の環形成炭素数６～５０の芳香族炭化水素基、又は置換もしくは無置換の環形成原子数５～５０の複素環基である。Ｌは連結基であり、単結合、もしくは置換もしくは無置換の環形成炭素数６～５０の芳香族炭化水素基、又は置換もしくは無置換の環形成原子数５～５０の複素環基である。ｘは０～５の整数である。Ａｒ^２３２とＡｒ^２３３は互いに連結して飽和もしくは不飽和の環を形成してもよい。ここで置換もしくは無置換の環形成炭素数６～５０の芳香族炭化水素基、及び置換もしくは無置換の環形成原子数５～５０の複素環基の具体例としては、前記と同様のものがあげられる。 Furthermore, a compound represented by the following formula can be used for the hole injection layer and the hole transport layer.

Ar ²³¹ to Ar ²³⁴ are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms. L is a linking group, which is a single bond, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms. x is an integer of 0 to 5. Ar ²³² and Ar ²³³ may ^combine with each other to form a saturated or unsaturated ring. Specific examples of the substituted or unsubstituted aromatic hydrocarbon group having 6 to 50 ring carbon atoms and the substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms are the same as those described above. can give.

Furthermore, specific examples of the material for the hole injection layer and the hole transport layer include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives. And amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers (particularly thiophene oligomers).

The above materials can be used for the hole injection layer and the hole transport layer, but porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds, particularly aromatic tertiary amine compounds should be used. Is preferred.

Further, compounds having two condensed aromatic rings in the molecule, such as 4,4′-bis (N- (1-naphthyl) -N-phenylamino) biphenyl (hereinafter abbreviated as NPD), triphenylamine unit It is preferable to use 4,4 ′, 4 ″ -tris (N- (3-methylphenyl) -N-phenylamino) triphenylamine (hereinafter abbreviated as MTDATA) or the like in which three are connected in a starburst type. .

　式中、Ｒ^２０１～Ｒ^２０６はそれぞれ置換もしくは無置換のアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換のアラルキル基、置換もしくは無置換の複素環基のいずれかを示す。Ｒ^２０１とＲ^２０２、Ｒ^２０３とＲ^２０４、Ｒ^２０５とＲ^２０６、Ｒ^２０１とＲ^２０６、Ｒ^２０２とＲ^２０３、又はＲ^２０４とＲ^２０５は縮合環を形成してもよい。 In addition, a nitrogen-containing heterocyclic derivative represented by the following formula can also be used.

In the formula, R ²⁰¹ to R ²⁰⁶ each represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aralkyl group, or a substituted or unsubstituted heterocyclic group. R ²⁰¹ and R ²⁰² , R ²⁰³ and R ²⁰⁴ , R ²⁰⁵ and R ²⁰⁶ , R ²⁰¹ and R ²⁰⁶ , R ²⁰² and R ²⁰³ , or R ²⁰⁴ and R ²⁰⁵ may form a condensed ring.

　Ｒ^２１１～Ｒ^２１６は置換基であり、好ましくはそれぞれシアノ基、ニトロ基、スルホニル基、カルボニル基、トリフルオロメチル基、ハロゲン等の電子吸引基である。 Furthermore, the compound of a following formula can also be used.

R ²¹¹ to R ²¹⁶ are substituents, each preferably an electron-withdrawing group such as a cyano group, a nitro group, a sulfonyl group, a carbonyl group, a trifluoromethyl group, or a halogen.

In addition, inorganic compounds such as p-type Si and p-type SiC can also be used as materials for the hole injection layer and the hole transport layer.
The hole injection layer and the hole transport layer can be formed by thinning the above-described compound by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. The thickness of the hole injection layer and the hole transport layer is not particularly limited, but is usually 5 nm to 5 μm. The hole injection layer and the hole transport layer may be composed of one or more layers made of the above-mentioned materials, or a plurality of hole injection layers and hole transport layers made of different compounds are laminated. There may be.

The organic semiconductor layer is a layer that assists hole injection or electron injection into the light emitting layer, and preferably has a conductivity of 10 ⁻¹⁰ S / cm or more. As a material for such an organic semiconductor layer, a conductive oligomer such as a thiophene-containing oligomer or an arylamine oligomer, a conductive dendrimer such as an arylamine dendrimer, or the like can be used.

The electron injection layer and the electron transport layer are layers that assist injection of electrons into the light emitting layer and transport them to the light emitting region, and have a high electron mobility. The adhesion improving layer is a kind of an electron injecting layer made of a material that particularly adheres well to the cathode.
The electron transport layer is appropriately selected with a film thickness of 5 nm to 5 μm. In particular, when the film thickness is large, the electron mobility is 10 ⁻⁵ cm when an electric field of 10 ⁴ to 10 ⁶ V / cm is applied in order to avoid an increase in voltage. It is preferable that it is ² / Vs or more.

As a material used for the electron injection layer and the electron transport layer, 8-hydroxyquinoline or a metal complex of its derivative or an oxadiazole derivative is preferable. Specific examples of metal complexes of 8-hydroxyquinoline or its derivatives include metal chelate oxinoid compounds containing a chelate of oxine (generally 8-quinolinol or 8-hydroxyquinoline), such as tris (8-quinolinolato) aluminum. it can.

（式中、Ａｒ^３０１、Ａｒ^３０２、Ａｒ^３０３、Ａｒ^３０５、Ａｒ^３０６、及びＡｒ^３０９はそれぞれ置換又は無置換のアリール基を示す。またＡｒ^３０４、Ａｒ^３０７、Ａｒ^３０８はそれぞれ置換又は無置換のアリーレン基を示す。） Examples of the oxadiazole derivative include an electron transfer compound represented by the following formula.

(In the formula, Ar ³⁰¹ , Ar ³⁰² , Ar ³⁰³ , Ar ³⁰⁵ , Ar ³⁰⁶ , and Ar ³⁰⁹ each represent a substituted or unsubstituted aryl group. Ar ³⁰⁴ , Ar ³⁰⁷ , and Ar ³⁰⁸ are each substituted or unsubstituted. Represents an arylene group.)

The electron transfer compound is preferably a thin film-forming compound.

（Ｍｅはメチル基、ｔＢｕはｔブチル基を示す。） Specific examples of the electron transfer compound include the following.

(Me represents a methyl group, and tBu represents a tbutyl group.)

Furthermore, materials represented by the following formulas (E) to (J) can also be used as materials used for the electron injection layer and the electron transport layer.

(In the formulas (E) and (F), A ³¹¹ to A ³¹³ each represent a nitrogen atom or a carbon atom.
Ar ³¹¹ is a substituted or unsubstituted aryl group having 6 to 60 ring carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 60 ring atoms, and Ar ^{311 ′} is a substituted or unsubstituted aryl group having 3 to 60 ring atoms. An arylene group having 6 to 60 ring carbon atoms or a substituted or unsubstituted heteroarylene group having 3 to 60 ring atoms; Ar ³¹² is a hydrogen atom, a substituted or unsubstituted ring carbon atom having 6 to 60 carbon atoms; An aryl group, a substituted or unsubstituted heteroaryl group having 3 to 60 ring atoms, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms . However, any one of Ar ³¹¹ and Ar ³¹² is a substituted or unsubstituted condensed ring group having 10 to 60 ring carbon atoms, or a substituted or unsubstituted monoheterofused ring group having 3 to 60 ring atoms. .
L ³¹¹ , L ³¹² and L ³¹³ each represent a single bond, a substituted or unsubstituted arylene group having 6 to 60 ring carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 60 ring atoms, or a substituted group. Or it is an unsubstituted fluorenylene group.
R and R ³¹¹ are each a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 60 ring carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 60 ring atoms, and a substituted or unsubstituted carbon number. An alkyl group having 1 to 20 carbon atoms, or a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, n is an integer of 0 to 5, and when n is 2 or more, a plurality of R may be the same or different. Alternatively, adjacent R groups may be bonded to each other to form a carbocyclic aliphatic ring or a carbocyclic aromatic ring. The nitrogen-containing heterocyclic derivative represented by this.

HAr-L ³¹⁴ -Ar ³²¹ -Ar ³²² (G)
(In the formula, HAr is a nitrogen-containing heterocyclic ring having 3 to 40 carbon atoms which may have a substituent, and L ³¹⁴ has a carbon number of 6 to 60 optionally having a single bond or a substituent. An arylene group, a heteroarylene group having 3 to 60 atoms which may have a substituent, or a fluorenylene group which may have a substituent, and Ar ³²¹ may have a substituent A divalent aromatic hydrocarbon group having 6 to 60 carbon atoms, and Ar ³²² is an aryl group having 6 to 60 carbon atoms which may have a substituent or an atomic number which may have a substituent A nitrogen-containing heterocyclic derivative represented by 3 to 60 heteroaryl groups).

^Wherein X ³⁰¹ and Y ³⁰¹ are each a saturated or unsaturated hydrocarbon group having 1 to 6 carbon atoms, an alkoxy group, an alkenyloxy group, an alkynyloxy group, a hydroxy group, a substituted or unsubstituted aryl group, a substituted group Or an unsubstituted heterocycle or a structure in which X and Y are combined to form a saturated or unsaturated ring, and R ³⁰¹ to R ³⁰⁴ are each a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryloxy group Perfluoroalkyl group, perfluoroalkoxy group, amino group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, azo group, alkylcarbonyloxy group, arylcarbonyloxy group, alkoxycarbonyloxy group, aryl Oxycarbonyloxy group, sulfi Group, sulfonyl group, sulfanyl group, silyl group, carbamoyl group, aryl group, heterocyclic group, alkenyl group, alkynyl group, nitro group, formyl group, nitroso group, formyloxy group, isocyano group, cyanate group, isocyanate group, A thiocyanate group, an isothiocyanate group, or a cyano group, which may be substituted, or adjacent groups may form a substituted or unsubstituted condensed ring. Pentadiene derivative.

(Wherein R ³²¹ to R ³²⁸ and Z ³²² are each a hydrogen atom, a saturated or unsaturated hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic group, a substituted amino group, a substituted boryl group, an alkoxy group or an aryl group. X ³⁰² , Y ³⁰² and Z ³²¹ each represents a saturated or unsaturated hydrocarbon group, aromatic hydrocarbon group, heterocyclic group, substituted amino group, alkoxy group or aryloxy group; ³²¹ and Z ³²² may be bonded to each other to form a condensed ring. N represents an integer of 1 to 3, and when n or (3-n) is 2 or more, R ³²¹ to R ³²⁸ , X ³⁰² , Y ³⁰² , Z ³²² and Z ³²¹ may be the same or different, provided that n is 1, X ³⁰² , Y ³⁰² and R ³²² are methyl groups and R ³²⁸ is a hydrogen atom or a substituted boryl group. And a compound in which n is 3 and Z ³²¹ is a methyl group).

［式中、Ｑ^３０１及びＱ^３０２は、それぞれ、下記式（Ｋ）で示される配位子を表し、Ｌ^３１５は、ハロゲン原子、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換の複素環基、－ＯＲ（Ｒは、水素原子、置換もしくは無置換のアルキル基、置換もしくは無置換のシクロアルキル基、置換もしくは無置換のアリール基、置換もしくは無置換の複素環基である。）又は－Ｏ－Ｇａ－Ｑ^３０３（Ｑ^３０４）（Ｑ^３０３及びＱ^３０４は、Ｑ^３０１及びＱ^３０２と同じ）で示される配位子を表す。］で表されるガリウム錯体。

[ ^Wherein Q ³⁰¹ and Q ³⁰² each represent a ligand represented by the following formula (K), and L ³¹⁵ represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group , Substituted or unsubstituted aryl group, substituted or unsubstituted heterocyclic group, —OR (where R is a hydrogen atom, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted aryl Group, a substituted or unsubstituted heterocyclic group) or a ligand represented by —O—Ga—Q ³⁰³ (Q ³⁰⁴ ) (Q ³⁰³ and Q ³⁰⁴ are the same as Q ³⁰¹ and Q ³⁰² ). . ] The gallium complex represented by this.

［式中、環Ａ^３０１及びＡ^３０２は、それぞれ置換基を有してよい互いに縮合した６員アリール環構造である。］

[Wherein, ring A ³⁰¹ and A ³⁰² are each a 6-membered aryl ring structure condensed with each other, which may have a substituent. ]

This metal complex has strong properties as an n-type semiconductor and has a large electron injection capability. Furthermore, since the generation energy at the time of complex formation is also low, the bondability between the metal and the ligand of the formed metal complex is strengthened, and the fluorescence quantum efficiency as a light emitting material is large.

In a preferred form of the organic EL element, a reducing dopant is contained in a region for transporting electrons or an interface region between the cathode and the organic layer. Here, the reducing dopant is defined as a substance capable of reducing the electron transporting compound. Accordingly, various materials can be used as long as they have a certain reducibility, such as alkali metals, alkaline earth metals, rare earth metals, alkali metal oxides, alkali metal halides, alkaline earth metals. Oxides, alkaline earth metal halides, rare earth metal oxides or rare earth metal halides, alkali metal carbonates, alkaline earth metal carbonates, rare earth metal carbonates, alkali metal organic complexes, alkalis At least one substance selected from the group consisting of organic complexes of earth metals and organic complexes of rare earth metals can be preferably used.

Specifically, preferable reducing dopants include Na (work function: 2.36 eV), K (work function: 2.28 eV), Rb (work function: 2.16 eV) and Cs (work function: 1. 95 eV), at least one alkali metal selected from the group consisting of Ca (work function: 2.9 eV), Sr (work function: 2.0 to 2.5 eV), and Ba (work function: 2.52 eV) At least one alkaline earth metal selected from the group consisting of: A work function of 2.9 eV or less is particularly preferable. Among these, a more preferable reducing dopant is at least one alkali metal selected from the group consisting of K, Rb and Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have particularly high reducing ability, and the addition of a relatively small amount to the electron injection region can improve the light emission luminance and extend the life of the organic EL element. Further, as a reducing dopant having a work function of 2.9 eV or less, a combination of these two or more alkali metals is also preferable. Particularly, a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, A combination of Cs, Na and K is preferred. By including Cs in combination, the reducing ability can be efficiently exhibited, and by adding to the electron injection region, the emission luminance and the life of the organic EL element can be improved.

An electron injection layer composed of an insulator or a semiconductor may be further provided between the cathode and the organic layer. With such a layer, current leakage can be effectively prevented, and the electron injection property can be improved. If the electron injection layer is an insulating thin film, a more uniform thin film is formed, so that pixel defects such as dark spots can be reduced.

As the insulator, it is preferable to use at least one metal compound selected from the group consisting of alkali metal chalcogenides, alkaline earth metal chalcogenides, alkali metal halides and alkaline earth metal halides. It is preferable that the electron injection layer is composed of these alkali metal chalcogenides and the like, since the electron injection property can be further improved. Specifically, preferable alkali metal chalcogenides include, for example, Li ₂ O, K ₂ O, Na ₂ S, Na ₂ Se, and Na ₂ O, and preferable alkaline earth metal chalcogenides include, for example, CaO, BaO. , SrO, BeO, BaS, and CaSe. Further, preferable alkali metal halides include, for example, LiF, NaF, KF, CsF, LiCl, KCl, and NaCl. Examples of preferable alkaline earth metal halides include fluorides such as CaF ₂ , BaF ₂ , SrF ₂ , MgF ₂ and BeF ₂ , and halides other than fluorides.

In addition, as a semiconductor constituting the electron injection layer, an oxide containing at least one element of Ba, Ca, Sr, Yb, Al, Ga, In, Li, Na, Cd, Mg, Si, Ta, Sb, and Zn. , Nitrides or oxynitrides, or a combination of two or more. The inorganic compound constituting the electron injection layer is preferably a microcrystalline or amorphous insulating thin film.

As the cathode, a material having a work function (for example, 4 eV or less) metal, an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, cesium, magnesium / silver alloy, aluminum / aluminum oxide, Al / Li ₂ O, Al / LiO, Al / LiF, aluminum Examples include lithium alloys, indium, and rare earth metals.

The cathode can be produced from these electrode materials by vapor deposition or sputtering.
When light emitted from the light emitting layer is taken out from the cathode, the transmittance of the cathode for light emission is preferably greater 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.

In general, since an organic EL element applies an electric field to an ultrathin film, pixel defects are likely to occur due to leakage or short circuit. In order to prevent this, an insulating thin film layer may be inserted between the pair of electrodes.
Examples of the material 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, Examples include germanium oxide, silicon nitride, boron nitride, molybdenum oxide, ruthenium oxide, and vanadium oxide. A mixture or laminate of these may be used.

Regarding the method for producing the organic EL element, for example, the above-described materials and methods may be used to sequentially form the necessary layers from the anode and finally form the cathode. Moreover, an organic EL element can also be produced in the reverse order from the cathode to the anode.

Hereinafter, an example of manufacturing an organic EL element having a structure in which an anode / a hole injection layer / a light emitting layer / an electron injection layer / a cathode are sequentially provided on a translucent substrate will be described.
First, a thin film made of an anode material is formed on a translucent substrate by vapor deposition or sputtering to form an anode. Next, a hole injection layer is provided on the anode. The hole injection layer can be formed by a method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. However, it is easy to obtain a uniform film and pinholes are not easily generated. It is preferable to form by a vacuum evaporation method. When a hole injection layer is formed by vacuum deposition, the deposition conditions vary depending on the compound used (material of the hole injection layer), the structure of the target hole injection layer, etc., but generally the deposition source temperature is 50 to 450. It is preferable to appropriately select at a temperature of 10 ° C., a degree of vacuum of 10 ⁻⁷ to 10 ⁻³ Torr, a deposition rate of 0.01 to 50 nm / second, and a substrate temperature of −50 to 300 ° C.

Next, a light emitting layer is provided on the hole injection layer. The light emitting layer can also be formed by thinning the light emitting material by a method such as vacuum deposition, sputtering, spin coating, or casting, but it is easy to obtain a uniform film and pinholes are not easily generated. From the point of view, it is preferable to form by vacuum deposition. When the light emitting layer is formed by vacuum vapor deposition, the vapor deposition conditions vary depending on the compound used, but can generally be selected from the same condition range as the formation of the hole injection layer.

Next, an electron injection layer is provided on the light emitting layer. Also in this case, like the hole injection layer and the light emitting layer, it is preferable to form by a vacuum evaporation method because it is necessary to obtain a homogeneous film. Deposition conditions can be selected from the same condition range as the hole injection layer and the light emitting layer.
And finally, a cathode can be laminated | stacked and an organic EL element can be obtained. The cathode can be formed by vapor deposition or sputtering. In order to protect the underlying organic material layer from damage during film formation, vacuum deposition is preferred.
The above organic EL device is preferably produced from the anode to the cathode consistently by a single vacuum.

The method for forming each layer of the organic EL element is not particularly limited. The organic thin film layer containing the anthracene derivative of the present invention can be prepared by vacuum deposition, molecular beam deposition (MBE method), dipping method of a solution obtained by dissolving the anthracene derivative of the present invention in a solvent, spin coating method, casting method, bar coating. It can be formed by a known method using a coating method such as a method or a roll coating method.

In the case of a method generally referred to as a coating method, that is, a method of forming each layer of an organic EL element using a solution containing an organic EL material, the solvent used is a good solvent for the organic EL material according to its purpose. It is possible to prepare and use a uniform solution, or to use a poor solvent or to prepare a dispersion using a mixed solvent of a good solvent and a poor solvent.

The organic EL material-containing solution of the present invention contains the above-described anthracene derivative of the present invention.
The solvent to be used is not particularly limited as long as it is generally available, and may be selected depending on the viscosity and solubility in accordance with process compatibility.
For example, those that are often good solvents include aromatic solvents, halogen solvents, ether solvents, and those that are often poor solvents include alcohol solvents, ketone solvents, paraffin solvents. Examples thereof include a solvent or an alkylbenzene derivative having 4 or more carbon atoms.

Specific examples are given below. Examples of solvents that are often good solvents include aromatic solvents such as toluene, xylene, mesitylene, halogen solvents such as chlorobenzene, and ether solvents such as diphenyl ether. Alcohol-based linear or branched alcohols having 1 to 20 carbon atoms such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, etc., benzyl alcohol derivatives, hydroxyalkylbenzene derivatives, alkylbenzenes Examples of the derivatives include linear or branched butylbenzene, dodecylbenzene, tetralin, cyclohexylbenzene and the like.

The amount of the solvent used can be appropriately adjusted in consideration of the amount and type of the anthracene derivative, the thickness of the organic thin film layer, and the like.
The organic EL element of the present invention may be prepared by producing at least one organic thin film layer using the above-described organic EL material-containing solution of the present invention.

Hereinafter, examples will be described, but the present invention is not limited to these examples. The evaluation of the organic EL element is as follows.
(1) Initial performance: Emission luminance value and CIE1931 chromaticity coordinates at 10 mA / cm ² were measured and evaluated with a luminance meter (Spectral luminance radiometer CS-1000 manufactured by Minolta).
(2) life: 1000 cd / ^{m 2} or constant current driving at an initial luminance of 5000 cd / ^{m 2,} the half-life of luminance, and was evaluated by the change in chromaticity.

[Example 1]
(1) Synthesis of anthracene derivative Compound (H-1) was synthesized by the following reaction.

In a 100 ml three-necked flask, 6.72 g (20 mmol) of 1,5-dibromoanthracene, 10.4 g (42.0 mmol) of naphthylphenylboronic acid, and 0.693 g of tetrakis (triphenylphosphine) palladium (0) ( 0.6 mmol) and the inside of the reactor was purged with argon. Subsequently, 30 ml of toluene, 30 ml of dimethoxyethane, and 30 ml (3 eq) of 2M-sodium carbonate aqueous solution were added, and the mixture was heated to reflux in an oil bath at 90 ° C. for 8 hours. Ten hours later, the precipitate was collected by filtration, washed with ion-exchanged water, ethyl acetate, and methanol, and then vacuum-dried to obtain 8.51 g (14.6 mmol) of Intermediate 1. (Yield 73%, HPLC purity 99.3%)
Next, 8.51 g (14.6 mmol) of Intermediate 1 was put into a 500 ml three-necked flask, and the pressure reduction and decompression were repeated. After the atmosphere in the reactor was replaced with argon, 150 ml of dimethylformamide was added and stirred. Next, 6.24 g (35.1 mmol) of N-bromosuccinimide was dissolved in 100 ml of dimethylformamide and added dropwise over 20 minutes. After completion of dropping, the temperature was raised to 80 ° C. and reacted for 3 hours. After 10 hours, 200 ml of ion-exchanged water was added to the reaction solution to precipitate the target product, which was collected by filtration, washed with ion-exchanged water, acetone and methanol, and then vacuum dried to obtain 10.1 g (13 0.6 mmol). (Yield 93.2%, HPLC purity 99.4%)
Next, in a 100 ml three-necked flask, 10.1 g (13.6 mmol) of intermediate 2, 3.48 g (28.6 mmol) of phenylboronic acid, and 0.449 g of tetrakis (triphenylphosphine) palladium (0) (0.389 mmol) was added, and the inside of the reactor was purged with argon. Subsequently, 30 ml of toluene, 30 ml of dimethoxyethane, and 21 ml (3 eq) of 2M-sodium carbonate aqueous solution were added, and the mixture was heated to reflux in an oil bath at 90 ° C. for 8 hours. After 10 hours, the precipitate was collected by filtration, washed with ion-exchanged water, ethyl acetate, toluene and methanol, and then vacuum-dried to obtain 7.06 g (9.61 mmol) of H-1 (yield 71%) HPLC purity 99.9%).
Subsequently, the halogen content was reduced according to the method described in JP-A-2007-77078 (yield 6.85 g, HPLC purity 99.9%, FD-MS calcd for C ₄₆ H ₃₀ = 734, found m / Z = 734 (M ⁺ , 100)).

(2) Manufacture of organic EL element A glass substrate (manufactured by Geomatic Co., Ltd.) with an ITO transparent electrode (anode) having a thickness of 25 mm × 75 mm × 1.1 mm was subjected to ultrasonic cleaning in isopropyl alcohol for 5 minutes, and then UV ozone cleaning. For 30 minutes. A glass substrate with a transparent electrode line after cleaning is attached to a substrate holder of a vacuum deposition apparatus, and first, the transparent electrode is covered on the surface on which the transparent electrode line is formed, and a film thickness is formed as a hole injection layer. The following compound A-1 having a thickness of 60 nm was formed. Following the formation of the A-1 film, the following compound A-2 having a thickness of 20 nm was formed as a hole transport layer on the A-1 film.
Further, on this A-2 film, the compound H-1 of the present invention and the diamine derivative D-1 were formed in a film thickness ratio of 40: 2 at a film thickness ratio of 40: 2 to obtain a blue light emitting layer. H-1 functions as a host and D-1 functions as a dopant.
On this film, the following compound Alq was deposited as an electron transport layer with a thickness of 20 nm by vapor deposition. Thereafter, LiF was formed to a thickness of 1 nm. On the LiF film, metal Al was deposited to a thickness of 150 nm to form a metal cathode, thereby forming an organic EL device.

The initial performance (chromaticity, luminous efficiency) and lifetime of the obtained organic EL element were evaluated. The results are shown in Table 1. From the table, it can be seen that long-lived blue light emission was obtained.

[Examples 2 to 4]
A device was fabricated and evaluated in the same manner as in Example 1 except that D-1 was changed to the following dopant material shown in Table 1 in Example 1. The results are shown in Table 1.

[Example 5]
(1) Synthesis of anthracene derivative Compound (H-2) was synthesized by the following reaction.

In a 100 ml three-necked flask, 5.54 g (20.0 mmol) of 1,4 dichloroanthraquinone, 10.4 g (42.0 mmol) of naphthylphenylboronic acid, 0.693 g of tetrakis (triphenylphosphine) palladium (0) (0.6 mmol) was added, and the inside of the reactor was replaced with argon. Subsequently, 30 ml of toluene, 30 ml of dimethoxyethane, and 30 ml (3 eq) of 2M-sodium carbonate aqueous solution were added, and the mixture was heated to reflux in an oil bath at 90 ° C. for 8 hours. After 10 hours, the precipitate was collected by filtration, washed with ion-exchanged water, ethyl acetate, and methanol, and then vacuum-dried to obtain 7.72 g (12.6 mmol) of Intermediate 3 (yield 62%, HPLC (Purity 99.1%).
Next, 7.54 g (12.6 mmol) of the intermediate 3 obtained in a 1 L four-necked flask was added, and decompression and re-pressure with argon gas were repeated three times to replace the system with argon. Next, 150 ml of dry tetrahydrofuran was added and stirred, and then cooled to about −65 ° C. using a dry ice / acetone bath, and 15.4 ml (27.7 mmol) of a 1.8M di-n-butyl ether solution of phenyllithium was added for about 20 minutes. It was dripped over. After continuing the reaction at −65 ° C. for 2 hours, the temperature was raised to room temperature, the reaction was continued for another 2 hours, and stirring was stopped. After standing for about 18 hours, 100 ml of 1N hydrochloric acid was added, then the reaction solution was extracted with ethyl acetate / water, and the resulting organic layer was concentrated to give Intermediate 4 (9.46 g, yield 97.6). %).

Next, the 1L flask, the resulting intermediate 4 9.46 g (12.3 mmol), potassium iodide _{5.10g (30.8mmol), NaPH 2 O} 2 · H 2 O 1.63g (15.4mmol ) And the inside of the system was replaced with argon gas, and 150 ml of acetic acid was further added. Subsequently, it heated at 80 degreeC using the oil bath, and reacted for 8 hours. The heated and refluxed reaction solution was cooled to room temperature and allowed to stand for about 18 hours, and then the precipitate in the flask was filtered off, washed with acetic acid, methanol and water, and further dried in vacuo to give compound H-2 (8 .16 g, 90.3% yield).
Subsequently, the halogen content was reduced according to the method described in JP-A-2007-77078 (yield: 7.94 g, HPLC purity: 99.9%, FD-MS calcd for C ₄₆ H ₃₀ = 734, found m / Z = 734 (M ⁺ , 100)).

(2) Manufacture of organic EL element It implemented similarly to Example 1. FIG. The results are shown in Table 1.

[Examples 6 to 28]
A device was prepared and evaluated in the same manner as in Example 1 except that H-1 and / or D-1 was changed to the compounds shown in Table 1 in Example 1. The results are shown in Table 1 or 2.
The synthesis of the anthracene compound was sequentially carried out in the same manner as in Example 1 or 5 with reference to reaction formulas 1 to 3.

[Comparative Examples 1 and 2]
A device was fabricated and evaluated in the same manner as in Example 2 except that H-1 was changed to the following compound h-1 or h-2 in Example 1. The results are shown in Table 1 or 2.

[Examples 27 to 38, Comparative Examples 3 and 4]
A device was prepared and evaluated in the same manner as in Example 1 except that H-1 and / or D-1 was changed to the following compounds shown in Table 2 in Example 1. The results are shown in Table 3.

As can be seen from Tables 1 to 3, when the anthracene derivative of the present invention is used as a light emitting material, long-lived blue or green light emission can be obtained.

[Example 39]
Compound (H-12) was synthesized by the following reaction.

(1) Synthesis of 2,6-diphenylanthracene Under an argon atmosphere, 29.0 g of phenylboronic acid, 25.7 g of 2,6-dibromoanthracene, 4.62 g of tetrakis (triphenylphosphine) palladium (0), 800 mL of toluene, 2M A sodium carbonate aqueous solution (400 mL) was added, and the mixture was stirred at reflux for 8 hours. After cooling to room temperature, the precipitated crystals were collected by filtration. The obtained solid was recrystallized and washed repeatedly using toluene-hexane to obtain 25.0 g of 2-phenylanthracene (yield 75%).

(2) Synthesis of 9,10-dibromo-2,6-diphenylanthracene 25.0 g of 2,6-diphenylanthracene was dissolved by heating in 200 mL of N, N-dimethylformamide, and 29.4 g of N, N-bromosuccinimide was obtained. -A 20 mL solution of dimethylformamide was added, and the mixture was heated and stirred at 60 ° C for 6 hours. After cooling to room temperature, the reaction solution was poured into 1 L of water. The obtained solid was washed successively with methanol, water and methanol, recrystallized with toluene-hexane, and washed repeatedly to obtain 29.6 g of 9,10-dibromo-2-phenylanthracene (yield 80%).

(3) Synthesis of Compound H-12 Under an argon atmosphere, 2.44 g of 9,10-dibromo-2,6-diphenylanthracene, 2.98 g of 3- (1-naphthyl) phenylboronic acid synthesized by a known method, tetrakis (Triphenylphosphine) palladium (0) 0.231g, toluene 40mL, 2M sodium carbonate aqueous solution 20mL was prepared, and it stirred under reflux for 8 hours. After cooling to room temperature, the precipitated crystals were filtered off. The obtained crystals were washed with methanol, water and methanol and then recrystallized with toluene to obtain 5.12 g of pale yellow crystals. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 734.30, and m / e = 734.

[Example 40]
Compound (H-13) was synthesized by the following reaction.

Compound H-12 was synthesized in the same manner using 3- (2-naphthyl) phenylboronic acid synthesized by a known method instead of 3- (1-naphthyl) phenylboronic acid. As a result of mass spectrum analysis, the synthesized product was the target product, and the molecular weight was 734.30, and m / e = 734.

[Example 41]
Compound (H-14) was synthesized by the following reaction.

Compound H-12 was synthesized in the same manner using 1-naphthylboronic acid instead of phenylboronic acid. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 834.33, and m / e = 834.

[Example 42]
Compound (H-15) was synthesized by the following reaction.

In the synthesis of Compound H-12, 1-naphthylboronic acid was synthesized in place of phenylboronic acid, and 3- (2-naphthyl) phenylboronic acid synthesized by a known method instead of 3- (1-naphthyl) phenylboronic acid Was synthesized in the same manner using As a result of mass spectrum analysis, this was the target product, and the molecular weight was 834.33, and m / e = 834.

[Example 43]
Compound (H-16) was synthesized by the following reaction.

Compound H-12 was synthesized in the same manner using 2-naphthylboronic acid instead of phenylboronic acid. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 834.33, and m / e = 834.

[Example 44]
Compound (H-17) was synthesized by the following reaction.

In the synthesis of compound H-12, 2-naphthylboronic acid was used instead of phenylboronic acid, and 3- (2-naphthyl) phenylboronic acid synthesized by a known method instead of 3- (1-naphthyl) phenylboronic acid Was synthesized in the same manner using As a result of mass spectrum analysis, this was the target product, and the molecular weight was 834.33, and m / e = 834.

[Example 45]
Compound (H-18) was synthesized by the following reaction.

Compound H-12 was synthesized in the same manner using 3-biphenylboronic acid instead of phenylboronic acid. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 886.36, and m / e = 886.

[Example 46]
Compound (H-19) was synthesized by the following reaction.

In the synthesis of Compound H-12, 3-biphenylboronic acid was substituted for phenylboronic acid, and 3- (2-naphthyl) phenylboronic acid was synthesized by a known method instead of 3- (1-naphthyl) phenylboronic acid Was synthesized in the same manner using As a result of mass spectrum analysis, this was the target product, and the molecular weight was 886.36, and m / e = 886.

[Example 47]
Compound (H-20) was synthesized by the following reaction.

Compound H-12 was synthesized in the same manner using 4-biphenylboronic acid instead of phenylboronic acid. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 886.36, and m / e = 886.

[Example 48]
Compound (H-21) was synthesized by the following reaction.

In the synthesis of Compound H-12, 4-biphenylboronic acid was used instead of phenylboronic acid, and 3- (2-naphthyl) phenylboronic acid synthesized by a known method instead of 3- (1-naphthyl) phenylboronic acid Was synthesized in the same manner using As a result of mass spectrum analysis, this was the target product, and the molecular weight was 886.36, and m / e = 886.

[Example 49]
Compound (H-22) was synthesized by the following reaction.

In the synthesis of compound H-12, the same method was used, using 3- (1-naphthyl) phenylboronic acid instead of phenylboronic acid and 2-naphthylboronic acid instead of 3- (1-naphthyl) phenylboronic acid. Was synthesized. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 834.33, and m / e = 834.

[Example 50]
Compound (H-23) was synthesized by the following reaction.

In the synthesis of compound H-12, the same method was used using 3- (1-naphthyl) phenylboronic acid instead of phenylboronic acid and 2-naphthylboronic acid instead of 3- (2-naphthyl) phenylboronic acid. Was synthesized. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 834.33, and m / e = 834.

[Example 51]
Compound (H-24) was synthesized by the following reaction.

Compound H-12 was synthesized in the same manner using 2-dibenzofuranylboronic acid instead of phenylboronic acid. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 914.32 and m / e = 914.

[Example 52]
Compound (H-25) was synthesized by the following reaction.

Compound H-12 was synthesized in the same manner using 3- (2-dibenzofuranyl) phenylboronic acid synthesized by a known method instead of 3- (1-naphthyl) phenylboronic acid. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 814.29, and m / e = 814.

[Example 53]
Compound (H-26) was synthesized by the following reaction.

(1) Synthesis of 9-bromo-2,6-diphenylanthracene 33.0 g of 2,6-diphenylanthracene was heated and dissolved in 300 mL of N, N-dimethylformamide, and 19.6 g of N, N-dimethyl was added to N-bromosuccinimide. A formamide 50 mL solution was added, and the mixture was heated and stirred at 60 ° C. for 6 hours. After cooling to room temperature, the reaction solution was poured into 1 L of water. The obtained solid was washed successively with methanol, water and methanol, then recrystallized with toluene-hexane and washed repeatedly to obtain 32.7 g of 9-bromo-2-phenylanthracene (yield 80%).

(2) Synthesis of 2,6-diphenyl-9- (2-naphthyl) anthracene In an argon atmosphere, 32.7 g of 9-bromo-2,6-diphenylanthracene, 16.5 g of 2-naphthylboronic acid, tetrakis (triphenyl) Phosphine) palladium (0) 1.85 g, toluene 300 mL, 2M aqueous sodium carbonate solution 150 mL were charged and stirred at reflux for 8 hours. After cooling to room temperature, the precipitated crystals were collected by filtration. The obtained solid was recrystallized and washed repeatedly using toluene-hexane to obtain 29.2 g (yield 80%) of 2,6-diphenyl-9- (2-naphthyl) anthracene.

(3) Synthesis of 9-bromo-2,6-diphenyl-10- (2-naphthyl) anthracene 29.2 g of 2,6-diphenylanthracene was dissolved in 300 mL of N, N-dimethylformamide with heating to give N-bromosuccinimide 12 0.5 g of N, N-dimethylformamide 20 mL solution was added, and the mixture was heated and stirred at 60 ° C. for 6 hours. After cooling to room temperature, the reaction solution was poured into 1 L of water. The obtained solid was washed successively with methanol, water and methanol, then recrystallized with toluene-hexane and washed repeatedly to give 29.1 g of 9-bromo-2,6-diphenyl-10- (2-naphthyl) anthracene (yield) 85%).

(4) Synthesis of Compound H-26 Under argon atmosphere, 9.35 g of 9-bromo-2,6-diphenyl-10- (2-naphthyl) anthracene, 3- (1-naphthyl) phenylboron synthesized by a known method 2.73 g of acid, 0.231 g of tetrakis (triphenylphosphine) palladium (0), 300 mL of toluene, and 150 mL of 2M aqueous sodium carbonate solution were charged and stirred at reflux for 8 hours. After cooling to room temperature, the precipitated crystals were collected by filtration. The obtained solid was recrystallized and washed repeatedly using toluene-hexane to obtain 5.4 g of yellow crystals. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 658.27, and m / e = 658.

[Example 54]
Compound (H-27) was synthesized by the following reaction.

In the synthesis of compound H-26, synthesis was performed in the same manner using 3- (2-naphthyl) phenylboronic acid synthesized by a known method instead of 3- (1-naphthyl) phenylboronic acid. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 658.27, and m / e = 658.

[Example 55]
Compound (H-28) was synthesized by the following reaction.

In the synthesis of Compound H-12, synthesis was performed in the same manner using 6-phenylnaphthalene-2-boronic acid synthesized by a known method instead of 3- (1-naphthyl) phenylboronic acid. As a result of mass spectrum analysis, this was the target product, and the molecular weight was 734.30, and m / e = 734.

[Examples 56-106]
An organic EL device was produced using the anthracene derivative synthesized in Examples 39-55. Specifically, in Example 1, instead of H-1, the anthracene derivative synthesized in Examples 39-55 was replaced with the compounds shown in Table 4-6 instead of D-1, and instead of A-2 The following A-3 was used for the hole transport layer. Further, the following ET-1 was used in place of Alq. The other elements were fabricated and evaluated in the same manner as in Example 1. The results are shown in Table 4.

[Comparative Example 5]
A device was prepared and evaluated in the same manner as in Example 56 except that H-12 was changed to the following compound h-4. The results are shown in Table 6.

The anthracene derivative of the present invention can be used as a light emitting material for an organic EL device. Further, the organic EL device of the present invention can be suitably used for light sources such as flat light emitters and display backlights, display units such as mobile phones, PDAs, car navigation systems, and vehicle instrument panels, and lighting.
The entire contents of the documents described in this specification are incorporated herein by reference.

Claims (18)

An anthracene derivative represented by the following formula (1) (except for an anthracene derivative represented by the following formula (1 ′)).

(In the formula, Ar ₁₁ to Ar ₁₄ are each a substituted or unsubstituted aromatic hydrocarbon group or a substituted or unsubstituted heterocyclic group. Ar ₂₁ to Ar ₂₄ are each a hydrogen atom, substituted or unsubstituted, An alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group.
However, when Ar ₁₁ to Ar ₁₄ are all benzene rings, Ar ₂₁ to Ar ₂₄ are not all hydrogen atoms. When at least one of Ar ₁₁ to Ar ₁₄ is a 9,9′-dimethylfluorenyl group or a 9,9′-diphenylfluorenyl group, the remaining Ar ₁₁ to Ar ₁₄ are all unsubstituted phenyl groups. Never become. ) An anthracene derivative represented by the following formula (1 ′).

(In the formula, Ar ₁₁ to Ar ₁₄ and Ar ₂₁ to Ar ₂₄ are the same groups as in claim 1. However, in the formula (1 ′), Ar ₁₁ to Ar ₁₄ are each a benzene ring or a naphthalene ring. In this case, not all of Ar ₂₁ to Ar ₂₄ become hydrogen atoms.) The anthracene derivative according to claim 1, which is represented by the following formulas (2) to (6):

(In the formula, Ar ₁₁ to Ar ₁₄ and Ar ₂₁ to Ar ₂₄ are the same groups as in claim 1). An anthracene derivative represented by the following formula (7).

(Wherein Ar ₃₁ , Ar ₃₂ , Ar ₃₄ , Ar ₃₅ and Ar ₃₆ are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring-forming atom. Represents a heterocyclic group having a number of 5 to 30. Ar ₃₃ represents a hydrogen atom, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted ring forming atom number. Represents a heterocyclic group of 5 to 30, provided that at least two of Ar ₃₁ to Ar ₃₄ are a substituted or unsubstituted condensed aromatic ring group having 10 to 30 ring carbon atoms, or a substituted or unsubstituted ring group; (It represents a heterocyclic group having 9 to 30 ring atoms.) The anthracene derivative according to claim 4, wherein Ar ₃₃ is a hydrogen atom and Ar ₃₁ is an unsubstituted condensed aromatic ring group having 10 to 30 carbon atoms. The anthracene derivative according to claim 5, wherein Ar ₃₁ is a metaphenylene group. Ar ₃₁ and Ar ₃₂ are each a substituted or unsubstituted phenylene group, Ar ₃₃ to Ar ₃₆ are substituted or unsubstituted aromatic hydrocarbon groups having 6 to 30 ring carbon atoms, or substituted or unsubstituted ring formation The anthracene derivative according to claim 4, which is a heterocyclic group having 5 to 30 atoms. An anthracene derivative represented by the following formula (8).

(Wherein Ar ₃₅ to Ar ₃₈ are each a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. Indicates.
Ra and Rb each represents a hydrogen atom or a substituent, and p and q each represents an integer of 1 to 4. ) The anthracene derivative according to claim 8, wherein Ar ₃₇ and Ar ₃₈ are each a substituted or unsubstituted condensed ring group having 10 to 30 ring carbon atoms. An anthracene derivative represented by the following formula (9).

(In the formula, each of Ar ₄₁ to Ar ₄₆ represents a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. Provided that at least two of Ar ₄₃ to Ar ₄₆ are substituted or unsubstituted condensed aromatic ring groups having 10 to 30 ring carbon atoms, or substituted or unsubstituted ring forming atoms having 10 to 30 ring atoms. A heterocyclic group of A luminescent material comprising the anthracene derivative according to any one of claims 1 to 10. The luminescent material according to claim 11, wherein the anthracene derivative is a host material. An organic electroluminescence device in which one or more organic thin film layers are sandwiched between an anode and a cathode, wherein at least one of the organic thin film layers contains an anthracene derivative according to any one of claims 1 to 10. Electroluminescence element. The organic electroluminescence device according to claim 13, wherein the layer containing the anthracene derivative further contains at least one of a phosphorescent dopant and a fluorescent dopant. The organic electroluminescent device according to claim 14, wherein the fluorescent dopant is at least one of an arylamine compound, a styrylamine compound, and a fluoranthene compound. The organic electroluminescence device according to claim 14 or 15, wherein the phosphorescent dopant is a metal complex. An organic electroluminescent material-containing solution containing the luminescent material according to claim 11 or 12. An organic electroluminescent device produced using the organic electroluminescent material-containing solution according to claim 17.

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