JP6238410B2 - Phosphorescent materials, compounds, phosphorescent paints, and organic light emitting devices - Google Patents

Description

  The present invention relates to a compound useful as a phosphorescent material, a phosphorescent paint using the compound, and an organic light emitting device.

When a phosphorescent material transitions from the ground singlet state to the excited singlet state by energy absorption, then an intersystem crossing occurs to transition to the excited triplet state, and then returns from this excited triplet state to the ground singlet state. It is a substance that emits phosphorescence. Here, since the transition from the excited triplet state to the ground singlet state is spin-forbidden, the speed is low, and phosphorescence is emitted compared to the fluorescence emitted during the transition from the excited singlet state to the ground state. Is persistent. Such phosphorescent materials are expected to be applied to phosphorescent paints and materials for light emitting layers of organic light emitting elements.
Here, in order to use the phosphorescent material for these applications, it is desirable that the phosphorescent material emits light at room temperature and a longer luminous life is obtained. However, triplet excitons generated in the phosphorescence process usually disappear due to thermal deactivation without transitioning to the ground singlet state at room temperature. For this reason, in order to observe phosphorescence, it is necessary to suppress the thermal motion of molecules at an extremely low temperature below the temperature of liquid nitrogen. For this reason, it is difficult to use phosphorescent materials for practical applications. It is.
On the other hand, a heavy atom with a large spin-orbit interaction, such as an iridium complex, is introduced into the molecule to alleviate spin inhibition, and a light-emitting material (guest material) is dispersed in the host material constituting the matrix. A phosphorescent material capable of emitting phosphorescence at room temperature has been reported by using a host-guest mixed system and suppressing the thermal deactivation of triplet excitons by the medium effect of host molecules. Among these, as a method using a host-guest mixed system, studies on a system using a compound having a steroid skeleton as a host molecule and an aromatic compound having a tertiary amino group introduced as a guest compound can be found.

Patent Document 1 discloses an organic phosphorescent material containing a matrix containing a reversible agent and a dye having a phosphorescence lifetime of 0.1 seconds or longer in a 77K rigid medium, using cholesterol or estradiol as the reversible agent, It is an example in which a compound having a structure in which a diphenylamino group is substituted on a fluorene ring is used as a dye, and it is described that a luminous lifetime exceeding 1 second is observed at room temperature. Further, in Patent Document 1, as a function of a reversible agent, by using a compound (sterol compound or the like) composed of massive molecules in which a plurality of cyclo rings are connected as a reversible agent, the matrix becomes rigid and locally. It is described that the molecular motion is reduced and this prevents the excitation energy loss of the dye.
Also in Non-Patent Document 1, in a mixed system using estradiol as a host compound and a compound having a structure in which an aromatic ring such as a fluorene ring is substituted with a tertiary amino group such as a diphenylamino group, at room temperature for 1 second. It is described that a phosphorescent lifetime exceeding 15 mm was observed.

International Publication No. 2009/069790

Adv. Funct. Mater. 2013, 23, 3386-3397

However, the phosphorescent materials described in Patent Document 1 and Non-Patent Document 1 are both host-guest mixed systems using two components of a host material and a guest material. There is no description of phosphorescent materials.
When the present inventors evaluated the usefulness as a phosphorescent material about the host-guest mixed system which uses two components, when the density | concentration of a guest material is made high in a host-guest mixed system, aggregation and a density | concentration of a guest molecule are carried out. It has been found that there is a problem that it is difficult to emit phosphorescence by quenching, and it is difficult to increase luminous efficiency. In addition, in the host-guest mixed system, the phosphorescent material must be prepared by mixing the two components synthesized separately, then melting the host material to disperse the guest molecules, and then solidifying. It has also become clear that the process until obtaining the phosphorescent material is complicated.
Under these circumstances, the present inventors have repeated research aiming to find a compound that emits phosphorescence at room temperature, has a long phosphorescent lifetime, and has excellent luminescent properties even when used as a single component. It was. Then, a general formula of a compound useful as a phosphorescent material was derived, and further intensive studies were conducted for the purpose of obtaining phosphorescent paints and organic light-emitting devices that emit phosphorescence continuously at room temperature and have excellent visibility. It was.

  As a result of intensive studies, the present inventors emitted phosphorescence at room temperature even when used as a single component in a group of compounds in which an aryl group having a tertiary amino group was introduced into the steroid skeleton. The inventors have found that some phosphorescent materials have excellent properties. In addition, it has been clarified that by using the compound, phosphorescent light can be continuously emitted at room temperature, and a phosphorescent paint and an organic light emitting device excellent in visibility can be provided. Based on these findings, the present inventors have provided the following present invention as means for solving the above problems.

［一般式（１）において、Ｒ¹〜Ｒ⁴、Ｒ⁶〜Ｒ⁸、Ｒ^10a〜Ｒ^15a、Ｒ^10b〜Ｒ^15bは各々独立に水素原子または置換基を表す。Ｒ⁵は３級アミノ基を有するアリール基を表す。Ｒ^9aは水素原子または水酸基（−ＯＨ）を表し、Ｒ^9bは水素原子を表すか、あるいはＲ^9aとＲ^9bは一緒になってオキソ基（＝Ｏ）を表す。］
［２］ 一般式（１）のＲ⁵が、３級アミノ基を有するフェニル基または３級アミノ基を有するフルオレニル基であることを特徴とする［１］に記載のリン光材料。
［３］ 一般式（１）のＲ⁵が表す基に含まれる３級アミノ基が、置換もしくは無置換のカルバゾリル基、置換もしくは無置換のジアリールアミノ基、または置換もしくは無置換のジアルキルアミノ基であることを特徴とする［１］または［２］に記載のリン光材料。
［４］ 一般式（１）のＲ⁵が、下記一般式（２）〜（８）のいずれかで表される基であることを特徴とする［１］に記載のリン光材料。

［一般式（２）〜（８）において、Ｌ¹²〜Ｌ¹⁸は置換もしくは無置換のアリーレン基を表し、＊は一般式（１）におけるステロイド骨格への結合部位を表す。Ｒ¹¹〜Ｒ²⁰、Ｒ²¹〜Ｒ²⁸、Ｒ³¹〜Ｒ³⁸、Ｒ^3a、Ｒ^3b、Ｒ⁴¹〜Ｒ⁴⁸、Ｒ^4a、Ｒ⁵¹〜Ｒ⁵⁸、Ｒ⁶¹〜Ｒ⁶⁸、Ｒ⁷¹〜Ｒ⁷⁸は、各々独立に水素原子または置換基を表す。Ｒ¹¹とＲ¹²、Ｒ¹²とＲ¹³、Ｒ¹³とＲ¹⁴、Ｒ¹⁴とＲ¹⁵、Ｒ¹⁶とＲ¹⁷、Ｒ¹⁷とＲ¹⁸、Ｒ¹⁸とＲ¹⁹、Ｒ¹⁹とＲ²⁰、Ｒ²¹とＲ²²、Ｒ²²とＲ²³、Ｒ²³とＲ²⁴、Ｒ²⁴とＲ²⁵、Ｒ²⁵とＲ²⁶、Ｒ²⁶とＲ²⁷、Ｒ²⁷とＲ²⁸、Ｒ³¹とＲ³²、Ｒ³²とＲ³³、Ｒ³³とＲ³⁴、Ｒ³⁵とＲ³⁶、Ｒ³⁶とＲ³⁷、Ｒ³⁷とＲ³⁸、Ｒ^3aとＲ^3b、Ｒ⁴¹とＲ⁴²、Ｒ⁴²とＲ⁴³、Ｒ⁴³とＲ⁴⁴、Ｒ⁴⁵とＲ⁴⁶、Ｒ⁴⁶とＲ⁴⁷、Ｒ⁴⁷とＲ⁴⁸、Ｒ⁵¹とＲ⁵²、Ｒ⁵²とＲ⁵³、Ｒ⁵³とＲ⁵⁴、Ｒ⁵⁵とＲ⁵⁶、Ｒ⁵⁶とＲ⁵⁷、Ｒ⁵⁷とＲ⁵⁸、Ｒ⁶¹とＲ⁶²、Ｒ⁶²とＲ⁶³、Ｒ⁶³とＲ⁶⁴、Ｒ⁶⁵とＲ⁶⁶、Ｒ⁶⁶とＲ⁶⁷、Ｒ⁶⁷とＲ⁶⁸、Ｒ⁷¹とＲ⁷²、Ｒ⁷²とＲ⁷³、Ｒ⁷³とＲ⁷⁴、Ｒ⁷⁵とＲ⁷⁶、Ｒ⁷⁶とＲ⁷⁷、Ｒ⁷⁷とＲ⁷⁸はそれぞれ互いに結合して環状構造を形成していてもよい。］
［５］ 一般式（２）〜（８）のＬ¹²〜Ｌ¹⁸が置換もしくは無置換のフェニレン基であることを特徴とする［４］に記載のリン光材料。
［６］ 一般式（１）のＲ⁵が一般式（３）で表される基であることが特徴とする［４］に記載のリン光材料。
［７］ 一般式（３）のＲ²¹〜Ｒ²⁸が水素原子であることを特徴とする［６］に記載のリン光材料。
［８］ 一般式（１）のＲ⁵が一般式（２）で表される基であることを特徴とする［４］に記載のリン光材料。
［９］ 一般式（１）のＲ⁵が、下記一般式（９）で表される基であることを特徴とする［１］に記載のリン光材料。

［一般式（９）において、＊は一般式（１）におけるステロイド骨格への結合部位を表す。Ｒ⁸¹〜Ｒ⁸⁸は各々独立に水素原子または置換基を表し、Ｒ⁸¹〜Ｒ⁸⁸の少なくとも１つは３級アミノ基を表す。Ｒ⁸¹とＲ⁸²、Ｒ⁸²とＲ⁸³、Ｒ⁸³とＲ⁸⁴、Ｒ⁸⁴とＲ⁸⁵、Ｒ⁸⁵とＲ⁸⁶、Ｒ⁸⁶とＲ⁸⁷、Ｒ⁸⁷とＲ⁸⁸は互いに結合して環状構造を形成していてもよい。］
［１０］ 一般式（１）が重水素原子を含むことを特徴とする［１］〜［９］のいずれか１項に記載のリン光材料。
［１１］ 一般式（１）のＲ^9aとＲ^9bが一緒になってオキソ基（＝Ｏ）を形成していることを特徴とする［１］〜［１０］のいずれか１項に記載のリン光材料。
［１２］ 一般式（１）のＲ¹がアルキル基であり、Ｒ²〜Ｒ⁴、Ｒ⁶〜Ｒ⁸、Ｒ^10a〜Ｒ^15a、Ｒ^10b〜Ｒ^15bが水素原子であることを特徴とする［１］〜［１１］のいずれか１項に記載のリン光材料。
［１３］ ［１］〜［１２］のいずれか１項に記載のリン光材料を含むことを特徴とする蓄光塗料。
［１４］ ［１］〜［１２］のいずれか１項に記載のリン光材料を含むことを特徴とする有機発光素子。
［１５］ 有機エレクトロルミネッセンス素子であることを特徴とする［１４］に記載の有機発光素子。 [1] A phosphorescent material comprising a compound represented by the following general formula (1).

[In the general formula (1) represents ^{R 1 ~R 4, R 6 ~R} 8, R 10a ~R 15a, R 10b ~R 15b each independently represent a hydrogen atom or a substituent. R ⁵ represents an aryl group having a tertiary amino group. R ^9a represents a hydrogen atom or a hydroxyl group (—OH), R ^9b represents a hydrogen atom, or R ^9a and R ^9b together represent an oxo group (═O). ]
[2] The phosphorescent material according to [1], wherein R ^{5 in the} general formula (1) is a phenyl group having a tertiary amino group or a fluorenyl group having a tertiary amino group.
[3] The tertiary amino group contained in the group represented by R ^{5 in the} general formula (1) is a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted diarylamino group, or a substituted or unsubstituted dialkylamino group. The phosphorescent material according to [1] or [2], which is characterized in that it exists.
[4] The phosphorescent material according to [1], wherein R ^{5 in the} general formula (1) is a group represented by any one of the following general formulas (2) to (8).

[In General Formulas (2) to (8), L ^{12 to} L ¹⁸ represent a substituted or unsubstituted arylene group, and * represents a binding site to the steroid skeleton in General Formula (1). ^{R 11 ~R 20, R 21 ~R} 28, R 31 ~R 38, R 3a, R 3b, R 41 ~R 48, R 4a, R 51 ~R 58, R 61 ~R 68, R 71 ~R 78 Each independently represents a hydrogen atom or a substituent. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , R ²¹ And R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ , R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ³¹ and R ³² , R ³² and R ^33, R ³³ and R ^34, R ³⁵ and R ^36, R ³⁶ and R ^37, R ³⁷ and R ^38, R ^3a and R ^3b, R ⁴¹ and R ^42, R ⁴² and R ^43, R ⁴³ and R ^{44, R45} and ^R46 , ^R46 and ^R47 , ^R47 and ^R48 , ^R51 and ^R52 , ^R52 and ^R53 , ^R53 and ^R54 , ^R55 and ^R56 , ^R56 and ^R57 , ^R57 And R ⁵⁸ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁵ and R ⁶⁶ , R ⁶⁶ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁷¹ and R ⁷² , R ⁷² and R ⁷³ , ^R73 and ^R74 , ^R75 and ^R76 , ^R76 and ^R77 , and ^R77 and ^R78 may be bonded to each other to form a cyclic structure. ]
[5] The phosphorescent material according to [4], wherein L ^{12 to} L ^{18 in the} general formulas (2) to (8) are substituted or unsubstituted phenylene groups.
[6] The phosphorescent material according to [4], wherein R ^{5 in the} general formula (1) is a group represented by the general formula (3).
[7] The phosphorescent material according to [6], wherein R ^{21 to} R ^{28 in} the general formula (3) are hydrogen atoms.
[8] The phosphorescent material according to [4], wherein R ^{5 in the} general formula (1) is a group represented by the general formula (2).
[9] The phosphorescent material according to [1], wherein R ^{5 in the} general formula (1) is a group represented by the following general formula (9).

[In General Formula (9), * represents a binding site to the steroid skeleton in General Formula (1). R ^{81 to} R ⁸⁸ each independently represents a hydrogen atom or a substituent, and at least one of R ^{81 to} R ⁸⁸ represents a tertiary amino group. ^R81 and ^R82 , ^R82 and ^R83 , ^R83 and ^R84 , ^R84 and ^R85 , ^R85 and ^R86 , ^R86 and ^R87 , ^R87 and ^R88 are bonded to each other to form a cyclic structure. You may do it. ]
[10] The phosphorescent material according to any one of [1] to [9], wherein the general formula (1) contains a deuterium atom.
[11] The method according to any one of [1] to [10], wherein R ^9a and R ^{9b in} the general formula (1) are combined to form an oxo group (═O). Phosphorescent material.
[12] R ^{1 in the} general formula (1) is an alkyl group, and R ^{2 to} R ⁴ , R ^{6 to} R ⁸ , R ^{10a to} R ^15a , and R ^{10b to} R ^15b are hydrogen atoms. The phosphorescent material according to any one of [1] to [11].
[13] A phosphorescent paint comprising the phosphorescent material according to any one of [1] to [12].
[14] An organic light-emitting device comprising the phosphorescent material according to any one of [1] to [12].
[15] The organic light-emitting device according to [14], which is an organic electroluminescence device.

［一般式（１）において、Ｒ¹’〜Ｒ⁴’、Ｒ⁶’〜Ｒ⁸’、Ｒ^10a’〜Ｒ^15a’、Ｒ^10b’〜Ｒ^15b’は各々独立に水素原子または置換基を表す。Ｒ⁵’は３級アミノ基を有するアリール基を表す。Ｒ^9a’は水素原子または水酸基（−ＯＨ）を表し、Ｒ^9b’は水素原子を表すか、あるいはＲ^9a’とＲ^9b’は一緒になってオキソ基（＝Ｏ）を表す。］ [16] A compound represented by the following general formula (1 ′).

[In General Formula (1), R ¹ ′ to R ⁴ ′, R ⁶ ′ to R ⁸ ′, R ^10a ′ to R ^15a ′, R ^10b ′ to R ^15b ′ each independently represent a hydrogen atom or a substituent. . R ⁵ ′ represents an aryl group having a tertiary amino group. R ^9a ′ represents a hydrogen atom or a hydroxyl group (—OH), R ^9b ′ represents a hydrogen atom, or R ^9a ′ and R ^9b ′ together represent an oxo group (═O). ]

  Even when the compound of the present invention is used as a single component, it emits phosphorescence at room temperature, has a long phosphorescent lifetime, and exhibits excellent emission characteristics. For this reason, the compound of the present invention is useful as a phosphorescent material. In addition, the coating film formed by the phosphorescent paint of the present invention and the organic light-emitting device using the compound of the present invention can emit phosphorescence continuously at room temperature, and its shape, information to be displayed, and object The behavior of the object can be clearly seen.

It is a schematic sectional drawing which shows the layer structural example of an organic electroluminescent element. 2 is an emission spectrum of Compound 1 of Example 1. 2 is a transient decay curve of Compound 1 of Example 1. 2 is an emission spectrum of Comparative Compound A of Comparative Example 1.

  Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to such embodiments and specific examples. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. “Normal temperature” means 25 ° C.

<Compound represented by the general formula (1)>
The phosphorescent material of the present invention is characterized by comprising a compound represented by the following general formula (1).

In General formula (1), R < ¹ > -R < ⁴ >, R < ⁶ > -R < ⁸ >, R ^<10a > -R <^15a> , R ^<10b > -R <^15b> respectively independently represents a hydrogen atom or a substituent. The number of substituents is not particularly limited, and R ^{1 to} R ⁴ , R ^{6 to} R ⁸ , R ^{10a to} R ^15a , and R ^{10b to} R ^15b may all be unsubstituted (that is, a hydrogen atom) R ¹ is preferably an alkyl group, and more preferably a methyl group. When two or more of R ^{1 to} R ⁴ , R ^{6 to} R ⁸ , R ^{10a to} R ^15a , and R ^{10b to} R ^15b are substituents, the plurality of substituents may be the same or different from each other. Also good.
R ^9a represents a hydrogen atom or a hydroxyl group (—OH), R ^9b represents a hydrogen atom, or R ^9a and R ^9b together represent an oxo group (═O). R ^9a and R ^9b preferably together represent an oxo group (═O).
R ⁵ represents an aryl group having a tertiary amino group. The aryl group is preferably an aryl group having 6 to 18 carbon atoms. Examples of the aryl group having 6 to 18 carbon atoms include a phenyl group, a biphenyl group, a fluorenyl group, and a triphenylenyl group, and a more preferable aryl group is a phenyl group. The aryl group is substituted at least at one site with a tertiary amino group. Sites other than the site substituted with the tertiary amino group of the aryl group may be substituted with other substituents or may not be substituted. For descriptions and preferred ranges of other substituents that can be substituted on the aryl group, reference can be made to descriptions and preferred ranges of substituents that can be taken by the following R ^{1 to} R ^{4 and the} like.
The tertiary amino group that the aryl group has is an amino group that is substituted with an aryl group and has two substituents. In the compound represented by the general formula (1), when a tertiary amino group is substituted on the aryl group, the intersystem crossing speed when absorbing energy is increased, and phosphorescence can be efficiently emitted. it can. The number of tertiary amino groups substituted on the aryl group may be one or two or more, but is preferably one or two, more preferably one. preferable. When two or more tertiary amino groups are substituted on the aryl group, the plurality of tertiary amino groups may be the same or different from each other. The two substituents of the amino group may be the same or different from each other, but are preferably the same. For the explanation and preferred ranges of the substituents that the tertiary amino group has, the explanation and preferred ranges of the substituents that can be taken by the following R ^{1 to} R ^{4 and the} like can be referred to. In addition, substituents substituted with a tertiary amino group may be bonded to each other to form a cyclic structure. For the explanation and preferred examples of the cyclic structure formed by bonding substituents substituted with a tertiary amino group to each other, see the following explanation and preferred examples of the cyclic structure formed by bonding R ¹¹ and R ¹² etc. to each other. can do. Of these, the tertiary amino group is preferably a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted diarylamino group, or a substituted or unsubstituted dialkylamino group.

In addition, R ⁵ in the general formula (1) is also preferably a group represented by the following general formulas (2) to (8).

In the general formulas (2) to (8), L ^{12 to} L ¹⁸ represent a substituted or unsubstituted arylene group, and * represents a binding site to the steroid skeleton in the general formula (1). The arylene group represented by L ^{12 to} L ¹⁸ is preferably an arylene group having 6 to 18 carbon atoms. Examples of the arylene group having 6 to 18 carbon atoms include a phenylene group, a biphenylene group, a fluorenylene group, a triphenylenylene group, and the like. More preferable linking groups include a 1,2-phenylene group, a 1,3-phenylene group, It is a 1,4-phenylene group, and a more preferred linking group is a 1,4-phenylene group. Regarding the explanation and preferred range of the substituent when the arylene group has a substituent, the explanation and preferred range of the substituent that can be taken by the following R ^{1 to} R ^{4 and the} like can be referred to.
^{R 11 ~R 20, R 21 ~R} 28, R 31 ~R 38, R 3a, R 3b, R 41 ~R 48, R 4a, R 51 ~R 58, R 61 ~R 68, R 71 ~R 78 Each independently represents a hydrogen atom or a substituent. The number of substituents is not particularly limited, and R ^{11 to} R ²⁰ , R ^{21 to} R ²⁸ , R ^{31 to} R ³⁸ , R ^3a , R ^3b , R ^{41 to} R ⁴⁸ , R ^4a , R ^{51 to} R ⁵⁸ , R ^{All of 61 to} R ⁶⁸ and R ^{71 to} R ⁷⁸ may be unsubstituted (that is, a hydrogen atom). In each of the general formulas (2) ~ (8), R 11 ~R 20, R 21 ~R 28, R 31 ~R 38, R 3a, R 3b, R 41 ~R 48, R 4a, R 51 ~R ^When two or more of ⁵⁸ , R ^{61 to} R ⁶⁸ and R ^{71 to} R ⁷⁸ are substituents, the plurality of substituents may be the same or different from each other.

When a substituent exists in the general formulas (2) to (8), the substituent is preferably any one of R ^{12 to} R ¹⁹ if the substituent is the general formula (2). it is preferably either be of the R ²² to R ²⁷ long, if the general formula ^{(4) R 32 ~R 37,} R 3a, is preferably one of R ^3b, the general formula (5) is preferably one of R ⁴² to R ⁴⁷ as long, if the formula (6) is preferably one of R ⁵² to R ^57, if the general formula (7) R ⁶² ~ Any one of R ⁶⁷ is preferable, and any one of R ^{72 to} R ⁷⁷ is preferable in the case of the general formula (8).

In addition, R ⁵ in the general formula (1) is also preferably a group represented by the following general formula (9).

In the general formula (9), * represents a binding site to the steroid skeleton in the general formula (1).
R ^{81 to} R ⁸⁸ each independently represents a hydrogen atom or a substituent, and at least one of R ^{81 to} R ⁸⁸ represents a tertiary amino group. The tertiary amino group is an amino group substituted on the fluorene ring and having two substituents. The number of the tertiary amino group is not particularly limited, and may be only one or may be two or more, but preferably one or two, and preferably one. More preferred. When the tertiary amino group is only one of R ^{81 to} R ⁸⁸ , R ⁸² or R ⁸³ is preferably a tertiary amino group, and R ⁸² is more preferably a tertiary amino group.
On the other hand, when two or more of R ^{81 to} R ⁸⁸ are tertiary amino groups, the tertiary amino group should be at least one of R ^{81 to} R ⁸⁴ and at least one of R ^{85 to} R ^88. Is preferred. At this time, the tertiary amino group is preferably 1 to 3 of R ^{81 to} R ⁸⁴ and 1 to 3 of R ^{85 to} R ⁸⁸ , and one of R ^{81 to} R ⁸⁴ or two, more preferably one or two of R ⁸⁵ to R ^88. The number of tertiary amino groups in R ^{81 to} R ⁸⁴ and the number of tertiary amino groups in R ^{85 to} R ⁸⁸ may be the same or different, but are preferably the same. Of R ^{81 to} R ⁸⁴ , R ⁸² or R ⁸³ is preferably a tertiary amino group, and at least R ⁸² is more preferably a tertiary amino group. Of R ^{85 to} R ⁸⁸ , R ⁸⁶ or R ⁸⁷ is preferably a tertiary amino group, and at least R ⁸⁷ is more preferably a tertiary amino group. When the group represented by the general formula (9) has two or more tertiary amino groups, the plurality of tertiary amino groups may be the same or different.
The two substituents of the tertiary amino group may be the same or different, but are preferably the same. For the explanation and preferred ranges of the substituents that the tertiary amino group has, the explanation and preferred ranges of the substituents that can be taken by the following R ^{1 to} R ^{4 and the} like can be referred to. Further, the substituents of the tertiary amino group may be bonded to each other to form a cyclic structure. For preferred examples of the explanation of the cyclic structure formed by bonding of substituents of the tertiary amino group to each other, refer to the explanation and preferred examples of the cyclic structure formed by bonding of R ¹¹ and R ^{12 and the} like below. be able to. Of these, the tertiary amino group is preferably a substituted or unsubstituted dialkylamino group.

R ^{81 to} R ⁸⁸ other than the tertiary amino group substitution site are a hydrogen atom or a substituent other than the tertiary amino group. The number of substituents other than the tertiary amino group is not particularly limited, and all of R ^{81 to} R ⁸⁸ other than the substitution site of the tertiary amino group may be unsubstituted (that is, a hydrogen atom). When there are two or more substituents other than the tertiary amino group, the plurality of substituents may be the same as or different from each other.

R ^{1 to} R ⁴ , R ^{6 to} R ⁸ , R ^{10a to} R ^15a , R ^{10b to} R ^15b , R ^{11 to} R ²⁰ , R ^{21 to} R ²⁸ , R ^{31 to} R ³⁸ , R ^3a , R ^3b , R ⁴¹ to R ^48, R ^4a, the substituent ^{R 51 ~R 58, R 61 ~R} 68, R 71 ~R 78, R 81 ~R 88 can take, such as hydroxy group, a halogen atom, a cyano group, a carbon number 1 -20 alkyl group, C1-C20 alkoxy group, C1-C20 alkylthio group, C1-C20 alkyl-substituted amino group, C2-C20 acyl group, C6-C40 Aryl group, C3-C40 heteroaryl group, C2-C10 alkenyl group, C2-C10 alkynyl group, C2-C10 alkoxycarbonyl group, C1-C10 alkylsulfonyl group , C 1-10 haloalkyl group, amide group, C 2-10 alkyl An amide group, a trialkylsilyl group having 3 to 20 carbon atoms, a trialkylsilylalkyl group having 4 to 20 carbon atoms, a trialkylsilylalkenyl group having 5 to 20 carbon atoms, a trialkylsilylalkynyl group having 5 to 20 carbon atoms, and A nitro group etc. are mentioned. Among these specific examples, those that can be substituted with a substituent may be further substituted. More preferred substituents are a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, carbon A substituted or unsubstituted heteroaryl group having 3 to 40 carbon atoms and a dialkyl-substituted amino group having 1 to 20 carbon atoms. More preferable substituents are a fluorine atom, a chlorine atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted group having 6 to 15 carbon atoms. Or it is an unsubstituted aryl group, a C3-C12 substituted or unsubstituted heteroaryl group.

R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , R ²¹ And R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ , R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ³¹ and R ³² , R ³² and R ^33, R ³³ and R ^34, R ³⁵ and R ^36, R ³⁶ and R ^37, R ³⁷ and R ^38, R ^3a and R ^3b, R ⁴¹ and R ^42, R ⁴² and R ^43, R ⁴³ and R ^{44, R45} and ^R46 , ^R46 and ^R47 , ^R47 and ^R48 , ^R51 and ^R52 , ^R52 and ^R53 , ^R53 and ^R54 , ^R55 and ^R56 , ^R56 and ^R57 , ^R57 And R ⁵⁸ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁵ and R ⁶⁶ , R ⁶⁶ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁷¹ and R ⁷² , R ⁷² and R ⁷³ , R ⁷³ and R ⁷⁴ , R ⁷⁵ and R ⁷⁶ , R ⁷⁶ and R ⁷⁷ , R ⁷⁷ and R ⁷⁸ , R ⁸¹ and R ⁸² , R ⁸² and R ⁸³ , R ⁸³ and R ⁸⁴ , R ⁸⁴ and R ⁸⁵ , ^R85 and ^R86 , ^R86 and ^R87 , ^R87 and R ⁸⁸ may be bonded to each other to form a cyclic structure. The cyclic structure may be an aromatic ring or an alicyclic ring, may contain a hetero atom, and the cyclic structure may be a condensed ring of two or more rings. The hetero atom here is preferably selected from the group consisting of a nitrogen atom, an oxygen atom and a sulfur atom. Examples of cyclic structures formed include benzene ring, naphthalene ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyrrole ring, imidazole ring, pyrazole ring, triazole ring, imidazoline ring, oxazole ring, isoxazole ring, thiazole And a ring, an isothiazole ring, a cyclohexadiene ring, a cyclohexene ring, a cyclopentaene ring, a cycloheptatriene ring, a cycloheptadiene ring, and a cycloheptaene ring. These cyclic structures may be substituted with a substituent. For the explanation and preferred range of the substituent when the cyclic structure is substituted with a substituent, the explanation and preferred range of the substituent that can be taken by the above R ^{1 to} R ^{4 and the} like can be referred to.

^{R 11 ~R 20, R 21 ~R} 28, R 31 ~R 38, R 3a, R 3b, R 41 ~R 48, R 4a, R 51 ~R 58, R 61 ~R 68, R 71 ~R 78 , R ^{81 to} R ⁸⁸ each independently represents a tricyclic residue (L ^{12 to} L ^{18 in} which a group represented by any one of the above general formulas (2) to (8) is replaced by a single bond) ) Is also preferable. ^{Also, R 11 ~R 20, R 21} ~R 28, R 31 ~R 38, R 3a, R 3b, R 41 ~R 48, R 4a, R 51 ~R 58, R 61 ~R 68, R 71 ~ It is also preferred that all of R ⁷⁸ and R ^{81 to} R ⁸⁸ other than the tertiary amino group substitution site are unsubstituted (ie, hydrogen atoms).

R ^{5 in the} general formula (1) is preferably a group represented by any one of the general formulas (2), (3), and (9), and is a group represented by the general formula (3). More preferably.
In the following, specific examples of R ^5. * Represents the binding site to the steroid skeleton in the general formula (1).

More specific examples of R ⁵ are illustrated. * Represents the binding site to the steroid skeleton in the general formula (1).

Among these, R ⁵ is preferably a group in which an unsubstituted carbazolyl group is substituted at the 4-position of the phenylene group.

Moreover, the preferable example of a compound represented by General formula (1) below is given. However, the compound represented by the general formula (1) in the present invention should not be construed as being limited by this specific example.

It is preferable that at least a part of the hydrogen atoms contained in the compound represented by the general formula (1) is substituted with a deuterium atom. Thereby, the luminous lifetime of the phosphorescence emitted from the compound represented by the general formula (1) can be further extended. When deuterium atoms are contained in the compound represented by the general formula (1), the larger the ratio of the number of deuterium atoms to the total number of hydrogen atoms (the total number of hydrogen atoms and the number of deuterium atoms), the light emission The phosphorescent life of phosphorescence is long. However, since phosphorescence is observed even when no deuterium atom is present, it is still useful as a phosphorescent material.
A compound containing a deuterium atom can be obtained by substituting a hydrogen atom of a compound not containing a deuterium atom with a deuterium atom. In addition, the compound represented by the general formula (1) containing a deuterium atom is obtained by substituting a deuterium atom for an intermediate hydrogen atom generated in the synthesis raw material or in the synthesis process, and deuterated synthetic raw material or intermediate. It can also be obtained by synthesis from Deuteration of the compound can be carried out using the method described in Chem. Soc. Rev. 1997, 26, 401 .; Chem. Soc. Rev. 2000, 29, 239, for example.

The molecular weight of the compound represented by the general formula (1) is, for example, 1500 or less when the organic layer containing the compound represented by the general formula (1) is intended to be formed by vapor deposition. Preferably, it is preferably 1200 or less, more preferably 1000 or less, and even more preferably 800 or less. The lower limit of the molecular weight is the molecular weight of the minimum compound represented by the general formula (1).
The compound represented by the general formula (1) may be formed by a coating method regardless of the molecular weight. If a coating method is used, a film can be formed even with a compound having a relatively large molecular weight.

By applying the present invention, it is also conceivable to use a compound containing a plurality of structures represented by the general formula (1) in the molecule as a light emitting material.
For example, it is conceivable to use a polymer obtained by previously polymerizing a polymerizable group in the structure represented by the general formula (1) and polymerizing the polymerizable group as a light emitting material. Specifically, a monomer containing a polymerizable functional group is prepared for R ^{1 to} R ⁸ , R ^{10a to} R ^15a , R ^{10b to} R ^15b in the general formula (1), and this is polymerized alone, It is conceivable to obtain a polymer having a repeating unit by copolymerizing with the above monomer and to use the polymer as a light emitting material. Alternatively, it is also possible to obtain a dimer or trimer by coupling compounds having a structure represented by the general formula (1) and use them as a light emitting material.

As an example of a polymer having a repeating unit including a structure represented by the general formula (1), a polymer including a structure represented by the following general formula (10) or (11) can be given.

In General Formula (10) or (11), Q represents a group including the structure represented by General Formula (1), and L ¹ and L ² represent a linking group. Carbon number of a coupling group becomes like this. Preferably it is 0-20, More preferably, it is 1-15, More preferably, it is 2-10. And preferably has a structure represented by - linking group -X ¹¹ -L ^11. Here, X ¹¹ represents an oxygen atom or a sulfur atom, and is preferably an oxygen atom. L ¹¹ represents a linking group, preferably a substituted or unsubstituted alkylene group, or a substituted or unsubstituted arylene group, and a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms, or a substituted or unsubstituted group A phenylene group is more preferable.
In the general formula (10) or (11), R ¹⁰¹ , R ¹⁰² , R ¹⁰³ and R ¹⁰⁴ each independently represent a substituent. Preferably, it is a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 6 carbon atoms, or a halogen atom, more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms. An unsubstituted alkoxy group having 1 to 3 carbon atoms, a fluorine atom, and a chlorine atom, and more preferably an unsubstituted alkyl group having 1 to 3 carbon atoms and an unsubstituted alkoxy group having 1 to 3 carbon atoms.
The linking group represented by L ¹ and L ² is a structure of R ^{1 to} R ⁸ , R ^{10a to} R ^15a , R ^{10b to} R ^15b , or a structure of the general formula (2) that constitutes Q. Any one of R ^{11 to} R ²⁰ , any one of R ^{21 to} R ^{28 in} the structure of the general formula (3), any of R ^{31 to} R ³⁸ , R ^3a and R ^{3b in} the structure of the general formula (4), Any of R ^{41 to} R ⁴⁸ and R ^4a in the structure of the general formula (5), R ^{51 to} R ^{58 in} the structure of the general formula (6), R ^{61 to} R ^{68 in} the structure of the general formula (7) Any one of R ^{71 to} R ^{78 having} the structure of the general formula (8), or any one of R ^{81 to} R ^{88 having} the structure of the general formula (9). Two or more linking groups may be linked to one Q to form a crosslinked structure or a network structure.

Specific examples of the structure of the repeating unit include structures represented by the following formulas (12) to (15).

The polymer having a repeating unit containing these formulas (12) to (15) introduces a hydroxy group into R ^{1 to} R ⁸ , R ^{10a to} R ^15a , and R ^{10b to} R ^15b of the structure of the general formula (1). In addition, it can be synthesized by reacting the following compound as a linker to introduce a polymerizable group and polymerizing the polymerizable group.

  The polymer containing the structure represented by the general formula (1) in the molecule may be a polymer composed only of repeating units having the structure represented by the general formula (1), or other structures may be used. It may be a polymer containing repeating units. The repeating unit having a structure represented by the general formula (1) contained in the polymer may be a single type or two or more types. Examples of the repeating unit not having the structure represented by the general formula (1) include those derived from monomers used in ordinary copolymerization. Examples thereof include a repeating unit derived from a monomer having an ethylenically unsaturated bond such as ethylene and styrene.

一般式（１’）において、Ｒ¹’〜Ｒ⁴’、Ｒ⁶’〜Ｒ⁸’、Ｒ^10a’〜Ｒ^15a’、Ｒ^10b’〜Ｒ^15b’は各々独立に水素原子または置換基を表す。Ｒ⁵’は３級アミノ基を有するアリール基を表す。Ｒ^9a’は水素原子または水酸基（−ＯＨ）を表し、Ｒ^9b’は水素原子を表すか、あるいはＲ^9a’とＲ^9b’は一緒になってオキソ基（＝Ｏ）を表す。一般式（１’）におけるＲ¹’〜Ｒ⁸’、Ｒ^9a’〜Ｒ^15a’、Ｒ^9b’〜Ｒ^15b’の説明と好ましい範囲については、一般式（１）で表される化合物の説明を参照することができる。 [Compound represented by the general formula (1 ′)]
The compound represented by the general formula (1 ′) is a novel compound.

In the general formula (1 ′), R ¹ ′ to R ⁴ ′, R ⁶ ′ to R ⁸ ′, R ^10a ′ to R ^15a ′, R ^10b ′ to R ^15b ′ each independently represent a hydrogen atom or a substituent. . R ⁵ ′ represents an aryl group having a tertiary amino group. R ^9a ′ represents a hydrogen atom or a hydroxyl group (—OH), R ^9b ′ represents a hydrogen atom, or R ^9a ′ and R ^9b ′ together represent an oxo group (═O). About description and preferable ranges of R ¹ ′ to R ⁸ ′, R ^9a ′ to R ^15a ′, R ^9b ′ to R ^15b ′ in General Formula (1 ′), description of the compound represented by General Formula (1) Can be referred to.

[Synthesis Method of Compound Represented by General Formula (1 ′)]
The compound represented by the general formula (1 ′) can be synthesized by combining known reactions. For example, a compound in which R ^{5 ′} in the general formula (1 ′) is a group represented by the general formula (3) and L ¹³ is a 1,4-phenylene group is obtained by reacting the following two compounds: It is possible to synthesize.

For the explanation of R ¹ ′ to R ⁴ ′, R ⁶ ′ to R ⁸ ′, R ^9a ′ to R ^15a ′, R ^9b ′ to R ^15b ′, R ^{21 to} R ^{28 in} the above reaction formula, the general formula ( Reference can be made to the corresponding description in 1). Tf represents a trifluoromethylsulfonyl group.
The above reaction is an application of a known coupling reaction, and known reaction conditions can be appropriately selected and used. The details of the above reaction can be referred to the synthesis examples described below. The compound represented by the general formula (1 ′) can also be synthesized by combining other known synthesis reactions.

<Application of phosphorescent materials>
Even when the compound represented by the general formula (1) of the present invention is used as a single component in which the host material does not coexist, phosphorescence is emitted at room temperature, and a long luminous life can be obtained. In particular, the compound represented by the general formula (1) in a solid state efficiently emits phosphorescence. This is presumably due to the following reasons.
In other words, the compound represented by the general formula (1) has a steroid skeleton and an aryl group having a tertiary amino group, and the aryl group having a tertiary amino group transitions to an excited triplet state and is phosphorylated. It is presumed to function as a light emitting site that emits light. However, as shown in the evaluation results of Comparative Example 1 described later, fluorescence is not emitted from a compound composed only of the light emitting site of the compound represented by the general formula (1), that is, an aromatic compound having a tertiary amino group. Although it is observed, no phosphorescence is observed. Therefore, in the compound represented by the general formula (1), any process of phosphorescence emission is promoted by the interaction between the aryl group having a tertiary amino group and the steroid skeleton, or the heat of excited triplet state. It is presumed that inactivation is suppressed and phosphorescence is emitted. Furthermore, since the compound represented by the general formula (1) has a steroid skeleton composed of a plurality of cyclo rings, in the solid state, molecules aggregate to form an integrated structure. In the compound represented by the general formula (1), it is presumed that such molecular aggregation works advantageously in the phosphorescence process and improves the phosphorescence efficiency.
Such a compound represented by the general formula (1) can be suitably used as a phosphorescent material used in various applications including phosphorescent paints and organic light-emitting devices.
Hereinafter, a phosphorescent paint (phosphorescent paint of the present invention) to which a phosphorescent material composed of a compound represented by the general formula (1) is applied and an organic light emitting element (organic light emitting element of the present invention) will be described.

[Phosphorescent paint]
The luminous paint of the present invention contains a compound represented by the general formula (1) and a solvent.
Regarding the description of the compound represented by the general formula (1) contained in the phosphorescent paint, the above description can be referred to.
The solvent is not particularly limited as long as it can dissolve the compound represented by the general formula (1) and does not react with the compound. For example, aromatic such as benzene, toluene, xylene, chlorobenzene and the like Ethers such as diethyl ether, dibutyl ether, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, diethylene glycol dimethyl ether, esters such as methyl acetate, ethyl acetate, butyl acetate, ethyl propionate, acetone, methyl ethyl ketone, methyl isobutyl ketone , Ketones such as cyclohexanone, hydrocarbons such as hexane, heptane, octane and nonane, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, organic acids such as formic acid, acetic acid and propionic acid, N, N-dimethyl Formamide, N, N- dimethylacetamide, include polar solvents and water, such as N- methylpyrrolidone, a mixed solvent thereof can be used.

The content of the compound represented by the general formula (1) in the phosphorescent paint is preferably 50% by mass or more, more preferably 90% by mass or more, and further preferably 95% by mass or more.
An additive may be added to the phosphorescent paint as necessary. Examples of the additive include polymer viscosity modifiers such as polyacrylic acid and polyvinyl alcohol.
The phosphorescent paint as described above is applied as a desired pattern and dried to form a solid coating film. When this coating film is irradiated with light energy at room temperature, the compound represented by the general formula (1) contained in the coating film is excited to the excited triplet state, and then returns to the ground state while emitting phosphorescence. . Thereby, the area | region where this phosphorescent coating material was apply | coated continuously light-emits, and the planar shape and the information to display can be visually recognized clearly.

[Organic light emitting device]
The phosphorescent material of the present invention can also be suitably used as a light emitting material for organic light emitting devices. By using the phosphorescent material of the present invention, an organic light emitting device with high luminous efficiency can be realized. The reason will be described below by taking an organic electroluminescence element as an example.

  In an organic electroluminescence element, carriers are injected into a light emitting material from both positive and negative electrodes to generate an excited light emitting material and emit light. In general, in the case of a carrier injection type organic electroluminescence element, 25% of the generated excitons are excited to the excited singlet state, and the remaining 75% are excited to the excited triplet state. Therefore, the use efficiency of energy is higher when phosphorescence, which is light emission from an excited triplet state, is used. However, phosphorescent materials made of conventional organic compounds have sufficient light emission at room temperature in the excited triplet state due to saturation of the excited state and interaction with the excited triplet state excitons. There was a problem that efficiency could not be obtained. On the other hand, the phosphorescent material of the present invention comprises a novel compound represented by the general formula (1), and this compound emits phosphorescence even at room temperature and is generated with a probability of 75%. The excited triplet state energy can be efficiently converted into phosphorescence. For this reason, by using the phosphorescent material of the present invention, the light emission efficiency of the organic electroluminescent element can be dramatically improved as compared with the case of using a phosphorescent material or a conventional phosphorescent material made of an organic compound.

Thus, by using the compound represented by the general formula (1) of the present invention as the light emitting material of the light emitting layer, excellent organic photoluminescence elements (organic PL elements), organic electroluminescence elements (organic EL elements), and the like. An organic light emitting device can be provided. The organic photoluminescence element has a structure in which at least a light emitting layer is formed on a substrate. The organic electroluminescence element has a structure in which an organic layer is formed at least between an anode, a cathode, and an anode and a cathode. The organic layer includes at least a light emitting layer, and may consist of only the light emitting layer, or may have one or more organic layers in addition to the light emitting layer. Examples of such other organic layers include a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron injection layer, an electron transport layer, and an exciton blocking layer. The hole transport layer may be a hole injection / transport layer having a hole injection function, and the electron transport layer may be an electron injection / transport layer having an electron injection function. A specific example of the structure of an organic electroluminescence element is shown in FIG. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is an electron transport layer, and 7 is a cathode.
Below, each member and each layer of an organic electroluminescent element are demonstrated. In addition, description of a board | substrate and a light emitting layer corresponds also to the board | substrate and light emitting layer of an organic photo-luminescence element.

(substrate)
The organic electroluminescence device of the present invention is preferably supported on a substrate. The substrate is not particularly limited and may be any substrate conventionally used for organic electroluminescence elements. For example, a substrate made of glass, transparent plastic, quartz, silicon, or the like can be used.

(anode)
As the anode in the organic electroluminescence element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. Alternatively, an amorphous material such as IDIXO (In ₂ O ₃ —ZnO) capable of forming a transparent conductive film may be used. For the anode, a thin film may be formed by vapor deposition or sputtering of these electrode materials, and a pattern of a desired shape may be formed by photolithography, or when pattern accuracy is not so high (about 100 μm or more) ), A pattern may be formed through a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material. Or when using the material which can be apply | coated like an organic electroconductivity compound, wet film-forming methods, such as a printing system and a coating system, can also be used. When light emission is extracted from the anode, it is desirable that the transmittance be greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 to 1000 nm, preferably 10 to 200 nm.

(cathode)
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting 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, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the point of durability against electron injection and oxidation, a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, Suitable are a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, a lithium / aluminum mixture, aluminum and the like. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 5 μm, preferably 50 to 200 nm. In order to transmit the emitted light, if either one of the anode or the cathode of the organic electroluminescence element is transparent or translucent, the emission luminance is advantageously improved.
In addition, by using the conductive transparent material mentioned in the description of the anode as a cathode, a transparent or semi-transparent cathode can be produced. By applying this, an element in which both the anode and the cathode are transparent is used. Can be produced.

(Light emitting layer)
The light emitting layer is a layer that emits light after excitons are generated by recombination of holes and electrons injected from each of the anode and the cathode, and at least the compound represented by the general formula (1) of the present invention Containing. The compound represented by the general formula (1) of the present invention emits phosphorescence at room temperature even when used as a single component. For this reason, although the light emitting layer may contain the host material, it may be comprised only with the compound represented by General formula (1). Even when the light emitting layer is composed of the compound represented by the general formula (1) alone, high luminous efficiency can be obtained. As a luminescent material, the 1 type (s) or 2 or more types chosen from the compound group of this invention represented by General formula (1) can be used.
When the light emitting layer includes a host material, an organic compound having at least one of excited singlet energy and excited triplet energy higher than that of the light emitting material of the present invention can be used as the host material. As a result, singlet excitons and triplet excitons generated in the light emitting material of the present invention can be confined in the molecules of the light emitting material of the present invention, and the light emission efficiency can be sufficiently extracted. However, even if singlet excitons and triplet excitons cannot be sufficiently confined, there are cases where high luminous efficiency can be obtained, so that host materials that can achieve high luminous efficiency are particularly limited. And can be used in the present invention. In the organic light emitting device or organic electroluminescent device of the present invention, light emission is generated from the light emitting material of the present invention contained in the light emitting layer. This luminescence includes both phosphorescence and fluorescence. However, light emission from the host material may be partly or partly emitted.
When the host material is used, the amount of the compound of the present invention, which is a light emitting material, is preferably 0.1% by weight or more, more preferably 1% by weight or more, and 50% or more. It is preferably no greater than wt%, more preferably no greater than 20 wt%, and even more preferably no greater than 10 wt%.
The host material in the light-emitting layer is preferably an organic compound that has a hole transporting ability and an electron transporting ability, prevents the emission of longer wavelengths, and has a high glass transition temperature.

(Injection layer)
The injection layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminance of light emission, and includes a hole injection layer and an electron injection layer, Further, it may be present between the cathode and the light emitting layer or the electron transport layer. The injection layer can be provided as necessary.

(Blocking layer)
The blocking layer is a layer that can prevent diffusion of charges (electrons or holes) and / or excitons existing in the light emitting layer to the outside of the light emitting layer. The electron blocking layer can be disposed between the light emitting layer and the hole transport layer and blocks electrons from passing through the light emitting layer toward the hole transport layer. Similarly, a hole blocking layer can be disposed between the light emitting layer and the electron transporting layer to prevent holes from passing through the light emitting layer toward the electron transporting layer. The blocking layer can also be used to block excitons from diffusing outside the light emitting layer. That is, each of the electron blocking layer and the hole blocking layer can also function as an exciton blocking layer. The term “electron blocking layer” or “exciton blocking layer” as used herein is used in the sense of including a layer having the functions of an electron blocking layer and an exciton blocking layer in one layer.

(Hole blocking layer)
The hole blocking layer has a function of an electron transport layer in a broad sense. The hole blocking layer has a role of blocking holes from reaching the electron transport layer while transporting electrons, thereby improving the recombination probability of electrons and holes in the light emitting layer. As the material for the hole blocking layer, the material for the electron transport layer described later can be used as necessary.

(Electron blocking layer)
The electron blocking layer has a function of transporting holes in a broad sense. The electron blocking layer has a role to block electrons from reaching the hole transport layer while transporting holes, thereby improving the probability of recombination of electrons and holes in the light emitting layer. .

(Exciton blocking layer)
The exciton blocking layer is a layer for preventing excitons generated by recombination of holes and electrons in the light emitting layer from diffusing into the charge transport layer. It becomes possible to efficiently confine in the light emitting layer, and the light emission efficiency of the device can be improved. The exciton blocking layer can be inserted on either the anode side or the cathode side adjacent to the light emitting layer, or both can be inserted simultaneously. That is, when the exciton blocking layer is provided on the anode side, the layer can be inserted adjacent to the light emitting layer between the hole transport layer and the light emitting layer, and when inserted on the cathode side, the light emitting layer and the cathode Between the luminescent layer and the light-emitting layer. Further, a hole injection layer, an electron blocking layer, or the like can be provided between the anode and the exciton blocking layer adjacent to the anode side of the light emitting layer, and the excitation adjacent to the cathode and the cathode side of the light emitting layer can be provided. Between the child blocking layer, an electron injection layer, an electron transport layer, a hole blocking layer, and the like can be provided. When the blocking layer is disposed, at least one of the excited singlet energy and the excited triplet energy of the material used as the blocking layer is preferably higher than the excited singlet energy and the excited triplet energy of the light emitting material.

(Hole transport layer)
The hole transport layer is made of a hole transport material having a function of transporting holes, and the hole transport layer can be provided as a single layer or a plurality of layers.
The hole transport material has any one of hole injection or transport and electron barrier properties, and may be either organic or inorganic. Known hole transport materials that can be used include, for example, triazole derivatives, oxadiazole derivatives, imidazole derivatives, carbazole derivatives, indolocarbazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, Examples include 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. An aromatic tertiary amine compound and an styrylamine compound are preferably used, and an aromatic tertiary amine compound is more preferably used.

(Electron transport layer)
The electron transport layer is made of a material having a function of transporting electrons, and the electron transport layer can be provided as a single layer or a plurality of layers.
The electron transport material (which may also serve as a hole blocking material) may have a function of transmitting electrons injected from the cathode to the light emitting layer. Examples of the electron transport layer that can be used include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide oxide derivatives, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, and the like. Furthermore, in the above oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron transport material. Furthermore, a polymer material in which these materials are introduced into a polymer chain or these materials are used as a polymer main chain can also be used.

  When producing an organic electroluminescent element, you may use not only the compound represented by General formula (1) for a light emitting layer but layers other than a light emitting layer. In that case, the compound represented by General formula (1) used for a light emitting layer and the compound represented by General formula (1) used for layers other than a light emitting layer may be same or different. For example, the compound represented by the general formula (1) may be used for the injection layer, blocking layer, hole blocking layer, electron blocking layer, exciton blocking layer, hole transporting layer, electron transporting layer, and the like. . The method for forming these layers is not particularly limited, and the layer may be formed by either a dry process or a wet process.

In the organic electroluminescence element configured as described above, by applying an electric field between the anode and the cathode of the obtained element, the wavelength corresponding to the energy level is confirmed as phosphorescence.
The organic electroluminescence element of the present invention can be applied to any of a single element, an element having a structure arranged in an array, and a structure in which an anode and a cathode are arranged in an XY matrix. According to the present invention, an organic light emitting device with greatly improved light emission efficiency can be obtained by containing the compound represented by the general formula (1) in the light emitting layer. The organic light emitting device such as the organic electroluminescence device of the present invention can be further applied to various uses. For example, it is possible to produce an organic electroluminescence display device using the organic electroluminescence element of the present invention. For details, see “Organic EL Display” (Ohm Co., Ltd.) written by Shizushi Tokito, Chiba Adachi and Hideyuki Murata. ) Can be referred to. In particular, the organic electroluminescence device of the present invention can be applied to organic electroluminescence illumination and backlights that are in great demand.

  The features of the present invention will be described more specifically with reference to synthesis examples and examples. The following materials, processing details, processing procedures, and the like can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below. Note that the evaluation of the light emission characteristics is as follows: source meter (manufactured by Keithley: 2400 series), semiconductor parameter analyzer (manufactured by Agilent Technologies: E5273A), optical power meter measuring device (manufactured by Newport: 1930C), optical spectrometer (Ocean Optics Co., Ltd .: USB2000), spectroradiometer (Topcon Co., Ltd .: SR-3), and streak camera (Hamamatsu Photonics Co., Ltd. model C4334) were used.

Synthesis Example 1 Synthesis of Compound 1 (3- [4- (N-carbazolylphenyl)]-estradi 1,3,5 (10) -trien-17-one)

1,3,5 (10) -estraditrien-17-one-3-trifluoromethanesulfonate (1.0 g, 2.57 mmol), 4- (9-carbazolyl) phenylboronic acid (0.9 g, 3. 13 mmol), tetrakis (triphenylphosphine) palladium (0.2 g, 0.17 mmol), cesium carbonate (3.0 g, 9.21 mmol), toluene (50 mL), water (10 mL) at 100 ° C. under a nitrogen atmosphere. Heated for 24 hours. The reaction solution was cooled, extracted with toluene, and the resulting organic layer was dried under reduced pressure. The dried organic layer was purified by silica gel column chromatography using a mixed solvent of dichloromethane: hexane = 9: 1 as a developing solvent. Thereafter, the obtained fraction was purified by sublimation to obtain a white product (Compound 1) in a yield of 0.71 g (1.47 mmol) and a yield of 57%.
¹ H-NMR: (500 MHz, CDCl ₃ , 25 ° C.): δ (ppm) = 8.16 {d, 2H} 7.80 {d, 2H} 7.62 {d, 2H} 7.50-7. 41 {m, 7H} 7.30 {t, 2H} 3.05 {m, 2H} 2.56-2.45 {m, 2H} 2.39 {td, 2H} 2.21-2.09 { m, 3H} 2.02 {m, 1H} 1.73-1.52 {m, 8H} 0.95 {s, H}
MS (FD): m / z 495.7 [M] ⁺
_{Elemental Analysis: calcd.for C 36 H 33} NO: C, 87.24; H, 6.71; N, 2.83; found: C, 87.28; H, 6.69; N, 2.85.

(Example 1) Evaluation of Compound 1 With respect to the sample of Compound 1 in a solid state, an emission spectrum and a transient decay curve with 330 nm excitation light were measured at 25 ° C. The emission spectrum is shown in FIG. 2, and the transient decay curve is shown in FIG.
From FIG. 2, it was confirmed that Compound 1 emits phosphorescence together with fluorescence emission under 25 ° C. conditions. Further, from FIG. 3, it was found that the phosphorescent lifetime of Compound 1 is 0.93 seconds, which is a long lifetime.

(Comparative Example 1) Evaluation of Comparative Example Compound A An emission spectrum of a sample of Comparative Compound A in a solid state was measured under the same conditions as in Example 1. The measurement results are shown in FIG.
As shown in FIG. 4, Comparative Compound A showed fluorescence emission at the same position as Compound 1 at 25 ° C., but did not show any phosphorescence emission.

  The compounds of the present invention are useful as phosphorescent materials. For this reason, the compound of this invention is effectively used as a phosphorescent material of a phosphorescent paint or an organic light emitting element. For this reason, this invention has high industrial applicability.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Electron transport layer 7 Cathode

Claims (9)

A phosphorescent material comprising a compound represented by the following general formula (1).

[In the general formula (1) represents ^{R 1 ~R 4, R 6 ~R} 8, R 10a ~R 15a, R 10b ~R 15b each independently represent a hydrogen atom or a substituent. R ⁵ represents a group represented by any one of the following general formulas (2) to (8) . R ^9a represents a hydrogen atom or a hydroxyl group (—OH), R ^9b represents a hydrogen atom, or R ^9a and R ^9b together represent an oxo group (═O). ]

[In General Formulas (2) to (8), L ^{12 to} L ¹⁸ represent a substituted or unsubstituted arylene group, and * represents a binding site to the steroid skeleton in General Formula (1). ^{R 11 ~R 20, R 21 ~R} 28, R 31 ~R 38, R 3a, R 3b, R 41 ~R 48, R 4a, R 51 ~R 58, R 61 ~R 68, R 71 ~R 78 Each independently represents a hydrogen atom or a substituent. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , R ²¹ And R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ , R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ³¹ and R ³² , R ³² and R ^33, R ³³ and R ^34, R ³⁵ and R ^36, R ³⁶ and R ^37, R ³⁷ and R ^38, R ^3a and R ^3b, R ⁴¹ and R ^42, R ⁴² and R ^43, R ⁴³ and R ^44, R ⁴⁵ and R ^46, R ⁴⁶ and R ^47, R ⁴⁷ and R ^48, R ⁵¹ and R ^52, R ⁵² and R ^53, R ⁵³ and R ^54, R ⁵⁵ and R ^56, R ⁵⁶ and R ^57, R ⁵⁷ And R ⁵⁸ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁵ and R ⁶⁶ , R ⁶⁶ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁷¹ and R ⁷² , R ⁷² and R ⁷³ , ^R73 and ^R74 , ^R75 and ^R76 , ^R76 and ^R77 , and ^R77 and ^R78 may be bonded to each other to form a cyclic structure. ] 2. The phosphorescent material according to claim 1 , wherein L ^{12 to} L ^{18 in the} general formulas (2) to (8) are substituted or unsubstituted phenylene groups. The phosphorescent material according to claim 1 , wherein R ^{5 in the} general formula (1) is a group represented by the general formula (3). Phosphorescent material according to claim 3, R ²¹ to R ²⁸ in the general formula (3) is characterized in that it is a hydrogen atom. The phosphorescent material according to claim 1 , wherein R ^{5 in the} general formula (1) is a group represented by the general formula (2). A phosphorescent paint comprising the phosphorescent material according to any one of claims 1 to 5 . The organic light emitting device which comprises a phosphorescent material according to any one of claims 1-5. The organic light-emitting device according to claim 7 , wherein the organic light-emitting device is an organic electroluminescence device. The compound represented by the following general formula ( 1 ).

[In the general formula (1) represents ^{R 1 ~R 4, R 6 ~R} 8, R 10a ~R 15a, R 10b ~R 15b each independently represent a hydrogen atom or a substituent. R ⁵ represents a group represented by any one of the following general formulas (2) to (8). R ^9a represents a hydrogen atom or a hydroxyl group (—OH), R ^9b represents a hydrogen atom, or R ^9a and R ^9b together represent an oxo group (═O). ]

[In General Formulas (2) to (8), L ^{12 to} L ¹⁸ represent a substituted or unsubstituted arylene group, and * represents a binding site to the steroid skeleton in General Formula (1). ^{R 11 ~R 20, R 21 ~R} 28, R 31 ~R 38, R 3a, R 3b, R 41 ~R 48, R 4a, R 51 ~R 58, R 61 ~R 68, R 71 ~R 78 Each independently represents a hydrogen atom or a substituent. R ¹¹ and R ¹² , R ¹² and R ¹³ , R ¹³ and R ¹⁴ , R ¹⁴ and R ¹⁵ , R ¹⁶ and R ¹⁷ , R ¹⁷ and R ¹⁸ , R ¹⁸ and R ¹⁹ , R ¹⁹ and R ²⁰ , R ²¹ And R ²² , R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ , R ²⁵ and R ²⁶ , R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ³¹ and R ³² , R ³² and R ^33, R ³³ and R ^34, R ³⁵ and R ^36, R ³⁶ and R ^37, R ³⁷ and R ^38, R ^3a and R ^3b, R ⁴¹ and R ^42, R ⁴² and R ^43, R ⁴³ and R ^44, R ⁴⁵ and R ^46, R ⁴⁶ and R ^47, R ⁴⁷ and R ^48, R ⁵¹ and R ^52, R ⁵² and R ^53, R ⁵³ and R ^54, R ⁵⁵ and R ^56, R ⁵⁶ and R ^57, R ⁵⁷ And R ⁵⁸ , R ⁶¹ and R ⁶² , R ⁶² and R ⁶³ , R ⁶³ and R ⁶⁴ , R ⁶⁵ and R ⁶⁶ , R ⁶⁶ and R ⁶⁷ , R ⁶⁷ and R ⁶⁸ , R ⁷¹ and R ⁷² , R ⁷² and R ⁷³ , ^R73 and ^R74 , ^R75 and ^R76 , ^R76 and ^R77 , and ^R77 and ^R78 may be bonded to each other to form a cyclic structure. ]

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