KR20140147829A - Benzofluorene compound, material for light-emitting layer which is produced using said compound, and organic electroluminescent element - Google Patents

Abstract

[식 중, R 은 탄소수 1 ∼ 6 의 알킬 등, A 및 B 중 어느 일방은 9-카르바졸릴, 다른 일방은 디아릴아미노이고, 9-카르바졸릴 및 디아릴아미노의 아릴은, 각각 독립적으로 탄소수 1 ∼ 6 의 알킬 등으로 치환되어 있어도 되고, 식 (1) 로 나타내는 화합물에 있어서의 적어도 1 개의 수소가 중수소로 치환되어 있어도 된다.]By using a benzofluorene compound in which a benzene ring condensed with a five-membered ring represented by the following formula (1) is substituted with a diphenylamino group and a carbazolyl group, as a material for a light emitting layer of an organic electroluminescent device, Thereby providing an element having improved lifetime characteristics.

Wherein R is alkyl having 1 to 6 carbon atoms, etc., either one of A and B is 9-carbazolyl and the other is diarylamino, and the aryl of 9-carbazolyl and diarylamino are each independently May be substituted with alkyl having 1 to 6 carbon atoms or the like, and at least one hydrogen in the compound represented by formula (1) may be substituted with deuterium.

Description

FIELD OF THE INVENTION [0001] The present invention relates to a benzofluorene compound, a material for a light emitting layer using the compound, and an organic electroluminescent device. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a benzofluorene compound, a material for a light emitting layer using the compound, and an organic electroluminescent device.

The organic electroluminescent device is a self-luminous type light emitting device and is expected as a light emitting device for display or illumination. Conventionally, a display device using an electroluminescent light emitting element has been studied in terms of power saving and thinning, and an organic electroluminescent device made of an organic material has been actively studied for its ease of weight reduction and enlargement . Particularly, in the development of an organic material having a light emission characteristic including blue which is one of the three primary colors of light, and the development of an organic material having a charge transport ability (which has the potential to become a semiconductor or a superconductor) , And low-molecular compounds have been actively studied until now.

The organic electroluminescent device has a pair of electrodes composed of an anode and a cathode and a structure composed of one layer or a plurality of layers arranged between the pair of electrodes and containing an organic compound. A layer containing an organic compound has a charge transporting / injecting layer for transporting or injecting charges such as a light emitting layer, a hole and an electron, and various organic materials have been developed as such organic compounds (see, for example, Japanese Patent Application Laid-Open No. 2004/061047, International Publication No. 2004/061048 (Japanese Patent Publication No. 2006-512395), International Publication No. 2005/056633 (International Patent Publication No. 2005/056633), Patent Documents 1, 2 and 3).

However, in the examples of these patent documents, only the polymer compound of benzofluorene is not disclosed. Further, for example, a dibenzofluorene compound having aryl-substituted amino is disclosed in International Publication No. 2003/051092 (Japanese Patent Application Publication No. 2005-513713) (see Patent Document 4). However, only the structural formula thereof is disclosed in the literature, and its specific properties are not reported.

International Publication No. 2004/061047 pamphlet International Publication No. 2004/061048 pamphlet (Japanese Unexamined Patent Publication No. 2006-512395) International Publication No. 2005/056633 pamphlet International Publication No. 2003/051092 pamphlet (Japanese Unexamined Patent Publication No. 2005-513713)

However, an organic electroluminescent device having sufficient performance in terms of device lifetime and the like has not yet been obtained even by using the above-described organic material. In addition, a material having such a constitution that blue light emission with higher color purity can be obtained in order to improve the NTSC ratio is required. Under such circumstances, development of an organic electroluminescent device, that is, a compound capable of obtaining the device, with better performance in terms of device lifetime and color purity has been desired.

As a result of intensive studies to solve the above problems, the present inventors have found that a benzofluorene compound represented by the following general formula (1), and further a benzofluorene compound represented by the following general formula (1'-1) or the following general formula (1'-2) Benzofluorene compound, and succeeded in the production thereof. It has also been found that an organic electroluminescent device improved in device lifetime and the like can be obtained by disposing a layer containing the benzofluorene compound between a pair of electrodes to form an organic electroluminescent device, thereby completing the present invention. That is, the present invention provides the following benzofluorene compounds.

[1] A benzofluorene compound represented by the following general formula (1).

[Chemical formula 10]

Wherein each R is independently selected from the group consisting of alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 24 carbon atoms which may be substituted with alkyl having 1 to 4 carbon atoms, or alkyl having 1 to 4 carbon atoms A heteroaryl group having 5 to 24 carbon atoms which may be substituted,

Wherein either one of A and B is 9-carbazolyl and the other is diarylamino,

Aryl of 9-carbazolyl and diarylamino are each independently selected from the group consisting of alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 10 carbon atoms and silyl substituted with alkyl having 1 to 4 carbon atoms , And when two or more groups are substituted adjacent to each other, they may be bonded to each other to form an aliphatic ring or a benzene ring,

At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium.

[2] A benzofluorene compound according to [1], which is represented by the following formula (1-1).

(11)

Wherein each R is independently an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms which may be substituted with an alkyl having 1 to 4 carbon atoms,

R ¹ is each independently silyl substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 10 carbon atoms, or alkyl having 1 to 4 carbon atoms,

m is even, and each independently represent an integer of 0 to 4, when substituted by two or more adjacent R ¹ is according to one benzene ring, combine to form a cyclohexane ring or benzene ring,

n are each independently an integer from 0 to 5, substituted by two or more adjacent R ¹ is according to one benzene ring, all of which are coupled to may form a cyclohexane ring or a benzene ring.

[3] The benzofluorene compound according to [1], which is represented by the following formula (1-2).

[Chemical Formula 12]

Wherein each R is independently an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms which may be substituted with an alkyl having 1 to 4 carbon atoms,

R ¹ is each independently silyl substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 10 carbon atoms, or alkyl having 1 to 4 carbon atoms,

m is even, and each independently represent an integer of 0 to 4, when substituted by two or more adjacent R ¹ is according to one benzene ring, combine to form a cyclohexane ring or benzene ring,

n are each independently an integer from 0 to 5, substituted by two or more adjacent R ¹ is according to one benzene ring, all of which are coupled to may form a cyclohexane ring or a benzene ring.

[4] Each R is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t- butyl, cyclohexyl, phenyl or naphthyl,

R ¹ is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t- butyl, cyclohexyl, phenyl, naphthyl, trimethylsilyl, triethylsilyl or dimethylmono- And,

m is independently an integer of 0 to 2,

n are each independently an integer from 0-2, optionally substituted by at least two R ¹ are adjacent in one benzene ring, which may optionally combine to form a benzene ring,

A benzofluorene compound according to the above [2] or [3].

[5] Each R is independently methyl, ethyl, isopropyl, s-butyl, t-butyl,

R ¹ is each independently methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl or trimethylsilyl,

m and n are each independently an integer of 0 to 2,

A benzofluorene compound according to the above [2] or [3].

[6] The benzofluorene compound according to [1], which is represented by the following formula (1-1-24), formula (1-1-54), or formula (1-1-84).

[Chemical Formula 13]

[7] A compound of formula (1-1-1), formula (1-1-10), formula (1-1-70), formula (1-1-101) The benzofluorene compound according to the above [1], which is represented by the formula (1-2-24), the formula (1-2-84) or the formula (1-2-85)

[Chemical Formula 14]

[8] The benzofluorene compound according to [1], which is represented by the following formula (1-1-140), formula (1-2-121) or formula (1-2-174).

[Chemical Formula 15]

[9] A compound represented by the following formula (1-1-61), formula (1-1-76), formula (1-1-103), formula (1-1-123) The benzofluorene compound according to [1] above.

[Chemical Formula 16]

[10] A benzofluorene compound represented by the following formula (1'-1).

[Chemical Formula 17]

Wherein,

R ¹ is each independently silyl substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 10 carbon atoms, or alkyl having 1 to 4 carbon atoms,

m is even, and each independently represent an integer of 0 to 4, when substituted by two or more adjacent R ¹ is according to one benzene ring, combine to form a cyclohexane ring or benzene ring,

n are each independently an integer from 0 to 5, substituted by two or more adjacent R ¹ is according to one benzene ring, all of which are coupled to may form a cyclohexane ring or a benzene ring.

[11] A benzofluorene compound represented by the following formula (1'-2).

[Chemical Formula 18]

Wherein,

R ¹ is each independently silyl substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 10 carbon atoms, or alkyl having 1 to 4 carbon atoms,

m is even, and each independently represent an integer of 0 to 4, when substituted by two or more adjacent R ¹ is according to one benzene ring, combine to form a cyclohexane ring or benzene ring,

n are each independently an integer from 0 to 5, substituted by two or more adjacent R ¹ is according to one benzene ring, all of which are coupled to may form a cyclohexane ring or a benzene ring.

[12] R ¹ is each independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t- butyl, cyclohexyl, phenyl, naphthyl, trimethylsilyl, -Butylsilyl, and < RTI ID = 0.0 >

m is independently an integer of 0 to 2,

n are each independently an integer from 0-2, optionally substituted by at least two R ¹ are adjacent in one benzene ring, which may optionally combine to form a benzene ring,

The benzofluorene compound according to the above [10] or [11].

[13] R ¹ is each independently methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl or trimethylsilyl,

m and n are each independently an integer of 0 to 2,

The benzofluorene compound according to the above [10] or [11].

[14] A material for a light emitting layer containing a benzofluorene compound according to any one of [1] to [13], as a light emitting layer material for a light emitting device.

[15] An organic electroluminescent device comprising a pair of electrodes made of an anode and a cathode, and a light emitting layer disposed between the pair of electrodes and containing the material for a light emitting layer described in [14].

The electron transport layer and / or the electron injection layer may include an electron transporting layer and / or an electron injection layer disposed between the cathode and the light emitting layer. At least one of the electron transporting layer and the electron injection layer may be a quinolinol metal complex, a pyridine derivative, a phenanthroline derivative , A borane derivative, and a benzimidazole derivative. The organic electroluminescent device according to the above [15]

[17] The organic electroluminescent device according to any one of [1] to [5], wherein the electron transporting layer and / or the electron injecting layer further comprises an alkali metal, alkaline earth metal, rare earth metal, alkali metal oxide, alkali metal halide, alkaline earth metal oxide, The organic electroluminescent device according to the above item [16], wherein the organic electroluminescent device comprises at least one selected from the group consisting of an oxide, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal and an organic complex of a rare earth metal.

[18] A display device comprising the organic electroluminescent device according to any one of [15] to [17].

[19] An illumination device comprising the organic electroluminescent device according to any one of [15] to [17].

According to a preferred embodiment of the present invention, for example, a benzofluorene compound having excellent properties as a material for a light emitting layer can be provided. In addition, it is possible to provide an organic electroluminescent device exhibiting excellent color purity and improved characteristics such as device lifetime.

1 is a schematic cross-sectional view showing an organic electroluminescent device according to this embodiment.

1. A benzofluorene compound represented by the general formula (1)

The benzofluorene compound of the present invention will be described in detail. The benzofluorene compound related to the present invention is a benzofluorene compound represented by the above general formula (1). The benzofluorene compounds represented by the general formulas (1-1) and (1-2) are one embodiment of the benzofluorene compounds represented by the general formula (1) , And the substituent for the aryl of the 9-carbazolyl and the diarylamino in the formula (1) corresponds to R ¹ in the formulas (1-1) and (1-2).

The "alkyl of 1 to 6 carbon atoms" in R in the general formula (1) may be either a linear chain or branched chain (linear alkyl of 1 to 6 carbon atoms or branched chain alkyl of 3 to 6 carbon atoms). Preferably alkyl having 1 to 4 carbon atoms (branched chain alkyl having 3 to 4 carbon atoms).

Specific examples of the "alkyl" include methyl (Me), ethyl (Et), n-propyl, isopropyl (i-Pr), n- butyl, isobutyl, s- Pentyl, isopentyl, neopentyl, t-pentyl, n-hexyl, 1-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl and 2-ethylbutyl.

Examples of the "cycloalkyl having 3 to 6 carbon atoms" in R in the general formula (1) include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, cycloheptyl and the like.

The " aryl having 6 to 24 carbon atoms " in R in the general formula (1) is preferably aryl having 6 to 16 carbon atoms, more preferably aryl having 6 to 12 carbon atoms.

Specific examples of the "aryl" include monocyclic aryl such as phenyl, (o-, m-, p-) tolyl, (2,3-, 2,4-, 2,5-, (2-, 3-, 4-) biphenylyl, which is a bicyclic aryl, a condensed bicyclic aryl ( M-terphenyl-4'-yl, m-terphenyl-5'-yl, o- M-terphenyl-3-yl, m-terphenyl-2'-yl, Yl, o-terphenyl-2-yl, o-terphenyl-3-yl, o- (1-, 2-, 3-, 4- or 5-membered heterocyclic ring), acenaphthylene- (1-, 3-, (5'-phenyl), which is a quinolyl group, a quinolyl group, a quinolyl group, a quinolyl group, a quinolyl group, m-terphenyl-4-yl, m-quaterphenyl), condensed quaternary aryl Triphenylene- (1 (1-, 2-, 5- or 6-membered heterocyclic ring), which is a fused 5- to 7-membered heterocyclic aryl, -, 3-) yl, pentacene- (1-, 2-, 5-, 6-) yl and the like.

The "aryl" in R may be substituted with alkyl having 1 to 4 carbon atoms, and examples of the substituent in this case include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, -Butyl, and methyl is preferred. The number of substituents is, for example, a maximum possible substitution number, preferably 1 to 3, more preferably 1 to 2, and still more preferably 1, but it is preferable that there is no "substituent".

The "heteroaryl having 5 to 24 carbon atoms" in R in the general formula (1) is preferably a heteroaryl having 2 to 20 carbon atoms, more preferably a heteroaryl having 2 to 15 carbon atoms, And heteroaryl having 2 to 10 carbon atoms. Examples of the "heteroaryl" include a heterocyclic group containing 1 to 5 hetero atoms selected from oxygen, sulfur and nitrogen in addition to carbon as a ring constituting atom, and examples thereof include aromatic heterocyclic rings And the like.

The "heterocyclic group" includes, for example, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, Benzoimidazolyl, benzothiazolyl, 1H-benzotriazolyl, quinolyl, quinolyl, quinolyl, quinolyl, quinolyl, quinolyl, quinolyl, Phenanthrenyl, phenazinyl, indolyl, pyrazinyl, pyrazinyl, pyrazinyl, pyrazinyl, pyrazinyl, pyrazinyl, And imidazolyl, pyridyl, carbazolyl and the like are preferable.

Examples of the "aromatic heterocyclic group" include furyl, thienyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, imidazolyl, pyrazolyl, oxadiazolyl, Benzo [b] thienyl, indolyl, isoindolyl, 1H-benzo [b] thiazolyl, triazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, benzofuranyl, isobenzofuranyl, Benzothiazolyl, 1H-benzotriazolyl, quinolyl, isoquinolyl, cinnolyl, quinazolyl, quinoxalinyl, phthalazinyl, naphthyridinyl, furyl, isothiazolyl, benzothiazolyl, Pyridyl, thienyl, indolizinyl and the like, and examples of the substituent include thienyl, imidazolyl, pyridyl, pyridyl, pyridyl, , Carbazolyl and the like are preferable.

One of A and B in the general formula (1) is 9-carbazolyl, and the other is diarylamino. The aryl of the diarylamino includes the same aryl as the above-mentioned aryl. Aryl of 9-carbazolyl and diarylamino are each independently selected from the group consisting of alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 10 carbon atoms and silyl substituted with alkyl having 1 to 4 carbon atoms , And "alkyl", "cycloalkyl" and "aryl" may be the same as those described above. The substitution position of the 9-carbazolyl and diarylamino of these substituents with respect to the aryl is not particularly limited. For example, when the diarylamino is diphenylamino, the substitution position of the phenyl group at the para position (N bonding position , There is an advantage that the side reaction in the halogenation step in Schemes 2 and 3 described in the " Process for the Production of a Benzofluorene Compound "

As the "silyl substituted with alkyl having 1 to 4 carbons" which may be substituted with aryl of 9-carbazolyl and diarylamino, the three hydrogens in the silyl group are each independently methyl, ethyl, n-propyl, Isopropyl, n-butyl, s-butyl, t-butyl and the like.

Specific examples of the "substituted silyl" include trimethylsilyl (TMS), triethylsilyl, tripropylsilyl, triisopropylsilyl, tributylsilyl, tri-s-butylsilyl, tri-t-butylsilyl, ethyldimethylsilyl, Isopropyldimethylsilyl, butyldimethylsilyl, s-butyldimethylsilyl, t-butyldimethylsilyl, methyldiethylsilyl, propyldiethylsilyl, isopropyldiethylsilyl, butyldiethylsilyl, s-butyldiethylsilyl, t Butyldipropylsilyl, t-butyldipropylsilyl, methyldiisopropylsilyl, ethyldiisopropylsilyl, butyldiisopropylsilyl, ethyldiisopropylsilyl, ethyldiisopropylsilyl, Propylsilyl, s-butyldiisopropylsilyl, t-butyldiisopropylsilyl, and the like.

In the case where two or more groups are substituted adjacent to each other with respect to a substituent substituted with an aryl group of 9-carbazolyl and diarylamino, they may be bonded to form an aliphatic ring or a benzene ring, Specifically, cyclobutane, cyclopentane, cyclohexane, and the like. For example, when a substituent group substituted with a phenyl group of a diphenylamino group forms a benzene ring, a benzene ring (i.e., a naphthyl group) condensed with the phenyl group is formed. The benzene ring may be in the form of a 1-naphthyl group, Or a naphthyl group.

In the formulas (1-1) and (1-2), n is independently an integer of 0 to 5, preferably n is an integer of 0 to 3, more preferably n is an integer of 0 to 2, Is zero. M is independently an integer of 0 to 4, preferably m is an integer of 0 to 2, more preferably m is an integer of 0 to 1, and more preferably m is 0.

The hydrogen atom in the benzofluorene ring constituting the compound represented by the general formula (1), the R group to be substituted with the benzofluorene ring, the 9-carbazolyl group, the diarylamino group, All or some of the hydrogen atoms in the hydrogen atoms may be deuterium atoms.

Further, in the benzofluorene compounds represented by the formula (1), the formulas (1-1) and (1-2), two R's may combine to form a fluorene ring. The case where two R's in the formula (1-1) or the formula (1-2) are combined to form a fluorene ring is preferably a compound represented by the general formula (1'-1) or the general formula (1'-2) ≪ / RTI > R ¹ , n and m in the compound represented by the formula (1'-1) or (1'-2) Explanations can be cited.

Specific examples of the compound represented by the general formula (1) include the following compounds represented by the following formulas (1-1-1) to (1-1-120), the following formulas (1-1-121) to Compounds represented by the following formulas (1-2-1) to (1-2-120) and the following formulas (1-2-121) to (1-2-180) . Specific examples of the compound represented by the general formula (1'-1) include compounds represented by the following formulas (1'-1-1) to (1'-1-15) Specific examples of the compound represented by the general formula (1'-2) include compounds represented by the following formulas (1'-2-1) to (1'-2-15).

[Chemical Formula 19]

[Chemical Formula 20]

[Chemical Formula 21]

[Chemical Formula 22]

(23)

≪ EMI ID =

(25)

(26)

(27)

(28)

[Chemical Formula 29]

(30)

(31)

(32)

(33)

(34)

(35)

(36)

(37)

(38)

[Chemical Formula 39]

(40)

(41)

(42)

(43)

(44)

[Chemical Formula 45]

(46)

(47)

(48)

(49)

(50)

(51)

(52)

(53)

(54)

(55)

(56)

(57)

(58)

Of the compounds represented by the formulas (1-1-1) to (1-1-120) and the formulas (1-2-1) to (1-2-120) ) To (1-1-3), (1-1-7) to (1-1-11), (1-1-16) to (1-1-33), (1 (1-1-41), (1-1-46) ~ (1-1-63), (1-1-67) ~ (1-1-71) , (1-1-76) to (1-1-90), (1-1-91), (1-1-93), (1-1-95) (1-1), (1-1), (1-1), (1-1) (1-1-19), (1-1-111), (1-1-113), (1-1-115), (1-1-117), (1-2 -1-21) to (1-2-3), (1-2-7) to (1-2-11), (1-2-16) to (1-2-33) (1-2-37) to (1-2-41), (1-2-46) to (1-2-63), (1-2-67) 71), Expressions (1-2-76) to Expressions (1-2-90), Expressions (1-2-91), Expressions (1-2-93), Expressions (1-2-95) 1-2-97), Equation 1-2-99, Equation 1-2-101, Equation 1-2-103, Equation 1-2-105, Equation 1-2-107, ), Expression (1-2-109), Expression (1-2-111), Expression (1-2-113), Expression (1-2-115), Expression (1-2-116), Expression -2-117) and Equation (1-2-119 ).

The above formulas (1-1-121) to (1-1-175), (1'-1-1) to (1'-1-15) Among the compounds represented by the formulas (1-1-121) to (1-2-180) and the formulas (1'-2-1) to (1'-2-15) (1-1-142), (1-1-142), (1-1-142), (1-1-146), (1-1-160), (1-2-121) (1-2-124), Expressions (1-2-127) to Expressions (1-2-131), Expressions (1-2-136) to Expressions (1-2-150), Expressions (1-2) (1-215) to (1-2153), (1-2-157) to (1-2-161), and (1-2-166) to (1-2-180) Do.

2. Preparation of benzofluorene compound

The benzofluorene compound represented by the general formula (1) can be prepared by using a conventional reaction such as Buchwald-Hartwig reaction, Ullmann reaction or aromatic nucleophilic substitution reaction. However, the compound represented by the general formula (1) is a compound in which one substituted or unsubstituted carbazolyl group is substituted, and it is an asymmetric compound. For this reason, in the production, it is preferable to utilize the selective reaction using the difference in the activity of the reactive substituent, or to use the purification separation technique or the like.

The Buchwald-Hartwig reaction is a method of coupling an aromatic halide with a primary aromatic amine, a secondary aromatic amine or carbazole using a palladium catalyst in the presence of a base. Specific examples of the reaction route for obtaining the compound represented by the general formula (1) by this method are as follows (schemes 1 to 5). As an example, a carbazolyl group and a diphenylamino group are bonded, but a diarylamino group containing a diphenylamino group can also be synthesized by the same method.

The reaction shown in the first step of Scheme 1 is a Suzuki coupling, and the X ¹ and X ² groups are taken as different reaction activity groups so that the Y group and X ¹ group in the two compounds to be reacted selectively. In consideration of easiness of obtaining the raw material, for example, a compound in which X ¹ group is triflate and X ² group is chlorine is preferable. It is also possible to react the X ¹ group and the Y group in the two compounds to be reacted with each other. In this case, the reaction activity of the Y group and X ² group substituted with benzoate is such that Y group> X ² group. In this first stage reaction, a Negishi coupling may be used instead of a Suzuki coupling. In this case, a zinc chloride complex is used instead of boronic acid or boronic acid ester as a compound having a Y group. Also, in the case of Negishi coupling, the reaction can be performed even when the X ¹ group and the Y group are interchanged (that is, a zinc chloride complex of benzoate is used), as described above. Further, in Scheme 1, raw materials in which a -COOR is substituted in advance of carbon to be coupled with a benzene ring are used to form a five-membered ring after the coupling reaction. However, May be replaced by -COOR. As a method of synthesizing an aromatic halide described in Scheme 1, for example, International Publication WO 2005/056633 pamphlet is referred to.

The monohalogen compound of benzofluorene is obtained by the reaction up to the third stage of Scheme 1 and can be used in Schemes 2 and 3 to be described later. In addition, the halogenation of the fourth step is carried out to obtain a dihalogenated form of benzofluorene, which can be used in Schemes 4 and 5 described later. Further, since the As described X ² group (e.g. chlorine) the reaction activity is low in, X ³ groups are the reason for introducing a group of the high reaction activity than this, the halogenating agent used in the fourth row Yes A brominating agent or an iodinating agent is preferred and an iodinating agent is more preferable.

Scheme 2 is a method in which, in the compound represented by the general formula (1), the positions corresponding to the two phenyl groups in total on the diphenylamino group side are bonded one by one, and then the carbazolyl group is bonded. Scheme 3 is a method in which a diphenylamino group is synthesized in advance, bound to a benzofluorene skeleton, and then a carbazolyl group is bonded. In Scheme 2 and Scheme 3, a method of first bonding a diphenylamino group is shown, but a carbazolyl group may be bonded first and then a diphenylamino group may be bonded.

Schemes 4 and 5 are synthesis methods using a dihalogenated compound as a starting point for Schemes 2 and 3 (synthesis method using a monohalogen compound of benzofluorene as a starting point), respectively. In these cases, a method of bonding a diphenylamino group is shown first, but a carbazolyl group may be bonded first and then a diphenylamino group may be bonded.

R, R ¹ , m and n in each scheme correspond to those used in the general formula (1), the formula (1-1) and the formula (1-2), respectively.

[Chemical Formula 59]

(60)

(61)

(62)

(63)

Specific examples of the palladium catalyst used in the above reaction are [1,1-bis (diphenylphosphino) ferrocene] palladium (II) dichloride: Pd (dppf) Cl ₂ , tetrakis (triphenylphosphine) palladium _{0): Pd (PPh 3)} 4, bis (triphenylphosphine) palladium (II) _{dichloride: PdCl 2 (PPh 3) 2} , palladium acetate (II): Pd (OAc) _2, tris (dibenzylideneacetone ) 2 Palladium (0): Pd ₂ (dba) ₃ , tris (dibenzylideneacetone) 2 palladium (0) chloroform complex: Pd ₂ (dba) ₃ .CHCl ₃ , bis (dibenzylideneacetone) palladium _{: Pd (dba) 2, PdCl} 2 {P (t-Bu) 2 - (p-NMe 2 -Ph)} 2, bis (tri -o- tolyl phosphine) -palladium (II) dichloride (PdCl ₂ ( o-tolyl ₃ ) ₂ ).

In order to accelerate the reaction, a phosphine compound may be added to these palladium compounds, as the case may be. Specific examples of the phosphine compound include tri (t-butyl) phosphine, tricyclohexylphosphine, 1- (N, N-dimethylaminomethyl) -2- (ditbutylphosphino) (N, N-dibutylaminomethyl) -2- (ditertiary butylphosphino) ferrocene, 1- (methoxymethyl) -2- (dit- butylphosphino) ferrocene, (Dit-butylphosphino) - 1,1'-binaphthyl, 2-methoxy-2 '- (dit- butylphosphino) (Diphenylphosphino) ferrocene, bis (diphenylphosphino) binaphthyl, 4-dimethylaminophenyldt-butylphosphine, phenyldi- Butylphosphine and the like.

Specific examples of the base used in this reaction include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, barium hydroxide, sodium ethoxide, sodium t-butoxide, sodium acetate, Potassium fluoride and the like.

Specific examples of the solvent used in this reaction include benzene, 1,2,4-trimethylbenzene, toluene, xylene, N, N-dimethylformamide, tetrahydrofuran, diethyl ether, , 1,4-dioxane, methanol, ethanol, isopropyl alcohol, and the like. These solvents can be appropriately selected depending on the structure of the aromatic halide, triflate, aromatic boronic acid ester and aromatic boronic acid to be reacted. The solvent may be used alone or as a mixed solvent.

The Ullmann reaction is a method of coupling an aromatic halide with a primary aromatic amine or a secondary aromatic amine using a copper catalyst in the presence of a base. Specific examples of the copper catalyst used in the Ullmann reaction include copper powder, copper chloride, copper bromide, or copper iodide. Specific examples of the base used in this reaction can be selected from the same Buchwald-Hartwig reaction. Specific examples of the solvent used in the Ullmann reaction include nitrobenzene, dichlorobenzene, N, N-dimethylformamide, and the like.

The compound represented by the general formula (1) can also be prepared by using the following reactions (Schemes 6 and 7). As an example, a carbazolyl group and a diphenylamino group are bonded, but a diarylamino group containing a diphenylamino group can also be synthesized by the same method. The reaction shown in the first step of Scheme 6 and Scheme 7 is Suzuki coupling, and the reaction can be carried out by exchanging X group and Y group in two compounds to be reacted. In this first stage reaction, a Negishi coupling may be used instead of a Suzuki coupling. In this case, a zinc chloride complex is used instead of boronic acid or boronic acid ester as a compound having a Y group. Also, in the case of Negishi coupling, the reaction can be carried out by replacing the X group and the Y group with each other as described above. R, R ¹ , m and n in each scheme correspond to those used in the general formula (1), the formula (1-1) and the formula (1-2), respectively.

≪ EMI ID =

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The compound of the present invention also contains at least a part of hydrogen atoms substituted with deuterium. Such a compound can be synthesized in the same manner as above by using a deuterated raw material at a desired point.

In the benzofluorene compound represented by the formula (1), the formula (1-1) and (1-2), a compound in which two R's are bonded to form a fluorene ring (for example, 1) or the compound represented by the formula (1'-2)) can be synthesized with reference to a synthesis method of a benzofluorene compound having a spiro structure as described in, for example, JP-A-2009-184933. In the paragraphs of this publication, a synthetic method (Scheme 1c) cited below is described, and a reactive substituent X substituted at two points is selected with different reactivity, and using Scheme 4 or 5 described above Can be synthesized.

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3. Organic electroluminescent device

The benzofluorene compound related to the present invention can be used, for example, as a material for an organic electroluminescent device.

An organic electroluminescent device according to this embodiment will be described in detail with reference to the drawings. 1 is a schematic cross-sectional view showing an organic electroluminescent device according to this embodiment.

≪ Structure of Organic Electroluminescent Device >

1 includes a substrate 101, an anode 102 formed on the substrate 101, a hole injection layer 103 formed on the anode 102, a hole injection layer 103 formed on the anode 102, A hole transporting layer 104 formed on the electron transporting layer 103, a light emitting layer 105 formed on the hole transporting layer 104, an electron transporting layer 106 formed on the light emitting layer 105, An injection layer 107, and a cathode 108 formed on the electron injection layer 107.

The organic electroluminescent device 100 includes a substrate 101, a cathode 108 formed on the substrate 101, and an electron injection layer 102 formed on the cathode 108, for example, An electron transport layer 106 formed on the electron injection layer 107, a light emission layer 105 formed on the electron transport layer 106, a hole transport layer 104 formed on the light emission layer 105, A hole injection layer 103 formed on the transport layer 104 and an anode 102 formed on the hole injection layer 103 may be used.

The minimum constitutional unit is composed of the anode 102, the light emitting layer 105 and the cathode 108, and the hole injecting layer 103, the hole transporting layer 104, the electron transporting layer 104, The electron injecting layer 106 and the electron injecting layer 107 are arbitrarily formed layers. Each of the layers may be a single layer or a plurality of layers.

The layer constituting the organic electroluminescence device may be in the form of a substrate, an anode, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer and a cathode in addition to the above- Anode / hole injection layer / light emitting layer / electron transport layer / electron injection layer / cathode "," substrate / anode / hole injection layer / hole transport layer / light emitting layer / electron "," transport layer / light emitting layer / electron transport layer / electron injection layer / cathode " Anode / hole transporting layer / light emitting layer / electron transporting layer / cathode "," substrate / anode / light emitting layer / electron transporting layer / electron injecting layer / cathode "," substrate / anode / hole transporting layer " Anode / hole injection layer / light emitting layer / electron injection layer / cathode "," substrate / anode / hole transport layer / light emitting layer / electron transport layer / cathode " Injection layer / light emitting layer / electron transporting layer / cathode "," substrate / anode / hole injecting layer / hole transporting layer / light emitting layer / cathode Anode / light emitting layer / electron transporting layer / cathode "," substrate / anode / light emitting layer / electron injection "," substrate / Layer / cathode "," substrate / anode / light emitting layer / cathode ".

≪ Substrate in Organic Electroluminescent Device >

The substrate 101 serves as a support for the organic electroluminescent device 100, and typically quartz, glass, metal, plastic, or the like is used. The substrate 101 is formed into a plate shape, a film shape, or a sheet shape, depending on the purpose. For example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, or the like is used. Among these, a glass plate and a plate made of a synthetic resin transparent to polyester, polymethacrylate, polycarbonate, polysulfone or the like are preferable. When the glass substrate is used, soda lime glass, alkali-free glass, or the like is used. The thickness of the glass substrate may be sufficient to maintain the mechanical strength. For example, it may be 0.2 mm or more. The upper limit of the thickness is, for example, 2 mm or less, preferably 1 mm or less. With respect to the material of the glass, it is preferable to use fewer eluted ions from the glass, so it is preferable to use an alkali-free glass, but a soda lime glass to which a barrier coat such as SiO _{2 is applied is} also commercially available. A gas barrier film such as a dense silicon oxide film may be formed on at least one surface of the substrate 101 in order to enhance the gas barrier property. In particular, a plate, film or sheet made of a synthetic resin having a low gas barrier property may be formed on the substrate 101 ), It is preferable to form a gas barrier film.

≪ Positive electrode in organic electroluminescent device >

The anode 102 serves to inject holes into the light emitting layer 105. When the hole injecting layer 103 and / or the hole transporting layer 104 are formed between the anode 102 and the light emitting layer 105, holes are injected into the light emitting layer 105 through the hole injecting layer 103 and / or the hole transporting layer 104.

Examples of the material for forming the anode 102 include an inorganic compound and an organic compound. Examples of the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium and the like), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO) Copper, etc.), sulfide, carbon black, ITO glass, Nessa glass, and the like. Examples of the organic compound include polythiophene such as poly (3-methylthiophene), conductive polymer such as polypyrrole, polyaniline, and the like. In addition, it can be appropriately selected from the materials used as the anode of the organic electroluminescent device and used.

The resistance of the transparent electrode is not particularly limited as long as it can supply a sufficient current for light emission of the light emitting element, but it is preferable that the resistance is low in view of power consumption of the light emitting element. For example, an ITO substrate of 300 OMEGA / & squ & or less functions as an element electrode, but it can be supplied with a substrate of about 10 OMEGA / It is particularly preferable to use a low resistance product of 50 to 5? / ?. Thickness of ITO can be arbitrarily selected in accordance with the resistance value, but it is often used in the range of 100 to 300 nm.

≪ Hole injection layer and hole transport layer in organic electroluminescent device >

The hole injection layer 103 serves to efficiently inject holes moving from the anode 102 into the light emitting layer 105 or into the hole transport layer 104. The hole transport layer 104 serves to efficiently transport the holes injected from the anode 102 or the holes injected from the anode 102 through the hole injection layer 103 to the light emitting layer 105. The hole injection layer 103 and the hole transport layer 104 are each formed by laminating or mixing one or more kinds of hole injecting and transporting materials or a mixture of a hole injecting and transporting material and a polymer binder. An inorganic salt such as iron (III) chloride may be added to the hole injecting and transporting material to form a layer.

As a hole injecting and transporting material, it is necessary to efficiently inject and transport holes from the positive electrode between the electrodes to which an electric field is applied, so that it is preferable that the hole injecting efficiency is high and the injected holes are efficiently transported. For this purpose, it is preferable that the material has a low ionization potential, a high hole mobility, an excellent stability and an impurity which is a trap, which does not easily occur during production and use.

As the material for forming the hole injecting layer 103 and the hole transporting layer 104, a hole injecting layer of a p-type semiconductor, a hole injecting layer of an organic electroluminescent device, a compound which is conventionally used as a hole transporting material in a photoconductive material, And a known hole transporting layer may be selected and used. Specific examples thereof include biscarbazole derivatives such as carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole and the like), bis (N-arylcarbazole) and bis (N-alkylcarbazole), triarylamine derivatives (A polymer having an aromatic tertiary amino group in its main chain or side chain, 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane, N, N'- N'-dinaphthyl-4,4'-diaminobiphenyl (hereinafter abbreviated as NPD), N, N'- N'-di (3-methylphenyl) -4,4'-diphenyl-1,1'-diamine, N, N'-dinaphthyl-N, N'-di Triphenylamine derivatives such as phenyl-4,4'-diphenyl-1,1'-diamine and 4,4 ', 4 "-tris (3-methylphenyl (phenyl) amino) triphenylamine; starburst amine derivatives , Stilbene derivatives, phthalocyanine derivatives (nonmetal, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone compounds, benzofuran derivatives, thiophene derivatives , Oxadiazole derivatives, porphyrin derivatives and the like, polysilane, etc. In the polymer system, polycarbonate or styrene derivatives having the above-mentioned monomer in the side chain, polyvinylcarbazole and polysilane are preferred, Is not particularly limited as far as it is a compound capable of forming a thin film necessary for production and injecting holes from the anode and transporting holes.

It is also known that the conductivity of an organic semiconductor is strongly influenced by its doping. Such an organic semiconductor matrix material is composed of a compound having a good electron acceptor or a compound having a good electron accepting property. For doping the electron donor, a strong electron acceptor such as tetracyanoquinodimethane (TCNQ) or 2,3,5,6-tetrafluorotetracano-1,4-benzoquinone dimethane (F4TCNQ) 73 (22), 3202-3204 (1998), and in J. Blochwitz, J. < RTI ID = 0.0 > , M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73 (6), 729-731 (1998)]. They produce so-called holes by an electron transfer process in an electron donor type base material (hole transport material). Due to the number of holes and mobility, the conductivity of the base material varies considerably. As the matrix material having hole transporting properties, for example, a benzidine derivative (TPD), a starburst amine derivative (TDATA or the like) or a specific metal phthalocyanine (in particular, zinc phthalocyanine ZnPc or the like) -167175).

≪ Light Emitting Layer in Organic Electroluminescent Device >

The light emitting layer 105 emits light by recombining holes injected from the anode 102 and electrons injected from the cathode 108 between electrodes to which an electric field is applied. As a material for forming the light-emitting layer 105, a compound (luminescent compound) that excites by the recombination of holes and electrons to emit light (luminescent compound) can be used and a stable thin film shape can be formed. Phosphorescence efficiency).

The light emitting layer may be a single layer or a plurality of layers or may be formed of a light emitting material (host material, dopant material), which may be a mixture of a host material and a dopant material, or a host material alone. That is, in each layer of the light-emitting layer, only the host material or the dopant material may emit light, or both the host material and the dopant material may emit light. Each of the host material and the dopant material may be one type, or a combination of two or more. The dopant material may be contained in the entire host material, partially contained, or may be either. The amount of the dopant to be used differs depending on the dopant and may be determined in accordance with the characteristics of the dopant. The amount of the dopant to be used is preferably 0.001 to 50% by weight, more preferably 0.1 to 10% by weight, and still more preferably 1 to 5% by weight based on the total weight of the light emitting material. As a doping method, it is possible to form it by a co-deposition method with a host material, but it may be deposited at the same time after mixing with a host material in advance.

Examples of the host material include, but are not limited to, condensed ring derivatives such as anthracene and pyrene previously known as phosphors, metal chelated oxinoid compounds including tris (8-quinolinolato) aluminum, bisstyryl anthracene derivatives A thiadiazole derivative, a thiadiazole derivative, a thiadiazole derivative, a thiadiazole derivative, a thiadiazole derivative, a thiadiazole derivative, a thiadiazole derivative, a pyridazine derivative, A polyphenylene vinylene derivative, a polyparaphenylene derivative, and a polythiophene derivative are preferably used.

In addition, as the host material, it is possible to appropriately select and use from among the compounds described in Chemical Industry 2004, June 2004, page 13 and the references cited therein.

The amount of the host material to be used is preferably from 50 to 99.999% by weight, more preferably from 80 to 99.95% by weight, and still more preferably from 90 to 99.9% by weight of the entire light emitting material.

As the dopant material, the benzofluorene compound of the above-mentioned general formula (1) can be used. In particular, the compound represented by the above formula (1-1) or the above-mentioned formula (1-2) (1-1-120), the formulas (1-1-121) to (1-1-175), the formulas (1-2-1) to (1-2-120) ) And compounds represented by the above formulas (1-2-121) to (1-2-180) are preferably used. The benzofluorene compound represented by the general formula (1'-1) or the general formula (1'-2) may also be used. The amount of these benzofluorene compounds used as a dopant material is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, and still more preferably 0.1 to 10% by weight based on the total weight of the light emitting material. As a doping method, it is possible to form it by a co-deposition method with a host material, but it may be deposited at the same time after mixing with a host material in advance.

Other dopant materials can be used at the same time. The other dopant materials are not particularly limited, and known compounds can be used, and various materials can be selected according to a desired luminescent color. Specific examples thereof include condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene and rubrene, benzoxazole derivatives, benzothiazole derivatives, A thiazole derivative, an imidazole derivative, a thiadiazole derivative, a triazole derivative, a pyrazoline derivative, a stilbene derivative, a thiophene derivative, a tetraphenylbutadiene derivative, an imidazole derivative, an oxazole derivative, an oxadiazole derivative, (Japanese Unexamined Patent Publication (Kokai) No. 1-245087), bisstyrylarylene derivatives (Japanese Unexamined Patent Application, First Publication No. Hei 2-247278, etc.), cyclopentadiene derivatives, bisstyryl anthracene derivatives and distyrylbenzene derivatives (2-methylphenyl) isobenzofuran, di (2-trifluoromethylphenyl) isobenzofuran, di (2-methylphenyl) isobenzofuran, di Methylphenyl) isobenzofuran, and phenyl isobenzofuran, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxy coumarin derivatives, 7-methoxy coumarin Derivatives such as coumarin derivatives such as 7-acetoxycoumarin derivatives, 3-benzothiazolyl coumarin derivatives, 3-benzimidazolyl coumarin derivatives and 3-benzoxazolyl coumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives , Polymethine derivatives, cyanine derivatives, oxobenzoanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluororesin derivatives, pyrylium derivatives, carbostyryl derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, Quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2,5-thiadiazolopyrrene derivatives, pyromethene derivatives, Pyranone derivatives, pyrrolopyrrole derivatives, squarylium derivatives, biorantrone derivatives, phenazine derivatives, acridone derivatives, and deazaplain derivatives.

Examples of the blue to blue green dopant materials include aromatic hydrocarbon compounds or derivatives thereof such as naphthalene, anthracene, phenanthrene, pyrene, triphenylene, perylene, fluorene and indene, furan, pyrrole, thiophene, And examples thereof include silane, silane, silane, 9-silafluorene, 9,9'-spirobisilafluorene, benzothiophene, benzofuran, indole, dibenzothiophene, dibenzofuran, imidazopyridine, phenanthroline, pyrazine, Aromatic heterocyclic compounds or derivatives thereof such as quinoxaline, pyrrolopyridine and thioxanthone, distyrylbenzene derivatives, tetraphenylbutadiene derivatives, stilbene derivatives, aldazine derivatives, coumarin derivatives, imidazole, thiazole, thiadiazole N, N'-di (3-methylphenyl) -4,4'-diphenyl-N, N'-di (3-methylphenyl) And aromatic amine derivatives represented by 1,1'-diamine.

Examples of the rust-yellow dopant material include coumarin derivatives, phthalimide derivatives, naphthalimide derivatives, perinone derivatives, pyrrolopyrrole derivatives, cyclopentadiene derivatives, acridone derivatives, quinacridone derivatives, Naphthacene derivatives such as naphthacene derivatives such as naphthalene and naphthacene derivatives, and compounds in which substituents capable of long wavelengths such as aryl, heteroaryl, arylvinyl, amino and cyano are introduced into the compounds exemplified as the blue to blue green dopant materials are also preferable For example.

Examples of the back-to-red dopant materials include naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic acid imide, perynone derivatives, and derivatives of acetylacetone, benzoyl acetone and phenanthroline, which are ligands Eu complex, a rare earth complex such as 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran or a derivative thereof, magnesium phthalocyanine, aluminum chlorophthalocyanine A quinacridone derivative, a phenoxazine derivative, an oxazine derivative, a quinazoline derivative, a pyrrolopyridine derivative, a squarylium derivative, a biorantrone derivative, a quinacridone derivative, Phenanthrene derivatives, phenoxazone derivatives, and thiadiazolopyrrene derivatives. In the compounds exemplified as the blue-blue-green and green-yellow dopant materials, aryl, he Preferred examples include compounds in which a substituent capable of long wavelength conversion is introduced, such as teroaryl, arylvinyl, amino, cyano, and the like. Preferable examples are phosphorescent metal complexes mainly composed of iridium or platinum represented by tris (2-phenylpyridine) iridium (III).

As the dopant material suitable for the light emitting layer material of the present invention, among the dopant materials described above, the benzofluorene compound represented by the above general formula (1) is the most preferable, and as the dopant material which can be used simultaneously, Borane derivatives, amine-containing styryl derivatives, aromatic amine derivatives, coumarin derivatives, pyran derivatives, iridium complexes or platinum complexes are preferable.

Examples of the perylene derivatives include 3,10-bis (2,6-dimethylphenyl) perylene, 3,10-bis (2,4,6-trimethylphenyl) perylene, Perylene, 3,4-diphenylperylene, 2,5,8,11-tetra-t-butylperylene, 3,4,9,10-tetraphenylperylene, 3- (1'-pyrenyl) Di (t-butyl) perylene, 3- (9'-anthryl) -8,11- t-butyl) perylenyl), and the like.

Japanese Laid-Open Patent Publication No. 11-97178, Japanese Laid-Open Patent Publication No. 2000-133457, Japanese Laid-Open Patent Publication No. 2000-26324, Japanese Laid-Open Patent Publication No. 2001-267079, Japanese Laid-Open Patent Publication No. 2001-267078, Perylene derivatives described in Patent Publications 2001-267076, 2000-34234, 2001-267075, and 2001-217077 may be used.

Examples of the borane derivative include 1,8-diphenyl-10- (dimethyisilbyl) anthracene, 9-phenyl-10- (dimethyisilbyl) anthracene, 4- (9'- Mesitylborylnaphthalene, 4- (10'-phenyl-9'-anthryl) dimethyisiloborylnaphthalene, 9- (dimethyisilbyl) anthracene, 9- Mesitylbutyl) anthracene, and 9- (4 '- (N-carbazolyl) phenyl) -10- (dimethyisilbyl) anthracene.

Also, a borane derivative described in International Publication WO 2000/40586 pamphlet may be used.

Examples of the amine-containing styryl derivatives include N, N, N ', N'-tetra (4-biphenylyl) -4,4'- diaminostilbene, N, N ', N'-tetra (2-naphthyl) -4,4'-diaminostilbene, N, N' Di (2-naphthyl) -N, N'-diphenyl-4,4'-diaminostilbene, N, N'-di (9-phenanthryl) Bis [4'-bis (diphenylamino) styryl] -biphenyl, 4'-diaminostilbene and 4,4'-bis [ -Benzene, 2,7-bis [4'-bis (diphenylamino) styryl] -9,9-dimethylfluorene, 4,4'- Phenyl, and 4,4'-bis (9-phenyl-3-carbazovinylene) -biphenyl. In addition, Japanese Unexamined Patent Application Publication No. 2003-347056 and Japanese Unexamined Patent Application Publication No. 2001-307884 Containing styryl derivatives may be used.

Examples of aromatic amine derivatives include N, N, N, N, N-tetraphenyl anthracene-9,10-diamine, 9,10-bis (4-diphenylamino- phenyl) anthracene, 9,10-bis (4-di (2-naphthylamino) phenyl) anthracene, 10-di-p- tolylamino-9- 1-naphthyl) anthracene, 10-diphenylamino-9- (6-diphenylamino-2-p-tolylamino- -Naphthalen-1-yl] -diphenylamine, [4- (4-diphenylamino-phenyl) 4,4'-bis [4-diphenylaminaphthalen-1-yl] biphenyl, 4,4'- Bis [4-diphenylaminophthalen-1-yl] -p-terphenyl, 4,4 "-bis [6- Diphenylaminonaphthalen-2-yl] -p-terphenyl and the like.

An aromatic amine derivative described in JP-A-2006-156888 may also be used.

Examples of coumarin derivatives include coumarin-6 and coumarin-334.

Also, coumarin derivatives described in JP-A-2004-43646, JP-A-2001-76876 and JP-A-6-298758 may be used.

Examples of the pyran derivative include DCM and DCJTB described below.

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Japanese Laid-Open Patent Publication Nos. 2005-126399, 2005-097283, 2002-234892, 2001-220577, 2001-081090, and Japanese Laid- A pyran derivative described in Patent Publication No. 2001-052869 may be used.

Examples of iridium complexes include Ir (ppy) ₃ shown below.

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It is also possible to use iridium ions described in Japanese Laid-Open Patent Publication Nos. 2006-089398, 2006-080419, 2005-298483, 2005-097263, and 2004-111379, Complex may be used.

Examples of the platinum complexes include PtOEP described below.

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In addition, platinum described in JP-A-2006-190718, JP-A 2006-128634, JP-A 2006-093542, JP-A 2004-335122, and JP-A 2004-331508 Complex may be used.

In addition, the dopant may be appropriately selected from the compounds described in Chemical Industry 2004, June 2004, page 13, the references cited therein, and the like.

≪ Electron injection layer and electron transport layer in organic electroluminescent device >

The electron injection layer 107 efficiently injects electrons moving from the cathode 108 into the light emitting layer 105 or into the electron transporting layer 106. The electron transporting layer 106 efficiently transports electrons injected from the cathode 108 or electrons injected from the cathode 108 via the electron injection layer 107 to the light emitting layer 105. The electron transporting layer 106 and the electron injecting layer 107 are each formed by laminating or mixing one or more kinds of electron transporting / injecting materials or a mixture of an electron transporting / injecting material and a polymer binder.

The electron injection / transport layer is a layer which is responsible for injecting electrons from the cathode and transporting electrons. It is preferable that the electron injection efficiency is high and the injected electrons are efficiently transported. In order to do so, it is preferable that the electron donating substance is large, the electron mobility is high, the stability is excellent, and the impurities which are trapped do not occur at the time of production and use. However, in the case of considering the transport balance of holes and electrons, in the case of mainly playing a role of effectively preventing the holes from the anode from flowing to the cathode side without recombining, it is necessary to improve the luminous efficiency The effect of improving is equivalent to that of a material having a high electron transporting ability. Therefore, the electron injecting and transporting layer in the present embodiment may also include the function of a layer capable of effectively blocking the movement of holes.

The material used for the electron transporting layer and the electron injecting layer may be selected arbitrarily from a compound conventionally used as an electron transporting compound in a photoconductive material, a known compound used in an electron injecting layer and an electron transporting layer of an organic electroluminescent device Can be used.

Specific examples thereof include a pyridine derivative, a naphthalene derivative, an anthracene derivative, a phenanthroline derivative, a perinone derivative, a coumarin derivative, a naphthalimide derivative, an anthraquinone derivative, a diphenoquinone derivative, a diphenylquinone derivative, A benzazole compound, a pyrazole derivative, a perfluorinated phenylene derivative, a triazine derivative, a pyrazine derivative, an imidazopyridine derivative, a borane derivative, a benzoin derivative, a thiadiazole derivative, a quinoxaline derivative, a quinoxaline derivative polymer, Oxazole derivatives, benzothiazole derivatives, quinoline derivatives, aldazine derivatives, carbazole derivatives, indole derivatives, phosphorus oxide derivatives, and bisstyryl derivatives. Also, oxadiazole derivatives such as 1,3-bis [(4-t-butylphenyl) 1,3,4-oxadiazolyl] phenylene and the like), triazole derivatives (N-naphthyl- Phenyl-1,3,4-triazole and the like), benzoquinoline derivatives (2,2'-bis (benzo [h] quinolin-2-yl) -9,9'-spirobifluorene, Derivatives such as tris (N-phenylbenzoimidazol-2-yl) benzene, bipyridine derivatives, terpyridine derivatives (1,3-bis (4 '- (2,2': 6'2 "-terpyridinyl ))) Benzene and the like), naphthyridine derivatives (bis (1-naphthyl) -4- (1,8-naphthyridin-2-yl) phenylphosphine oxide, etc.) However, they may be used in combination with different materials.

Further, a metal complex having an electron-accepting nitrogen may be used. For example, a hydroxyazole complex such as a quinolinol-based metal complex or a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, a flavonol metal complex And benzoquinoline metal complexes. These materials may be used alone, but they may be mixed with different materials.

Among the above-mentioned materials, quinolinol-based metal complexes, pyridine derivatives, phenanthroline derivatives, borane derivatives or benzoimidazole derivatives are preferable.

The quinolinol-based metal complex is a compound represented by the following formula (E-1).

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In the formulas, R ¹ to R ⁶ are hydrogen or a substituent, M is Li, Al, Ga, Be or Zn, and n is an integer of 1 to 3.

Specific examples of the quinolinol-based metal complexes include 8-quinolinolithium, tris (8-quinolinolato) aluminum, tris (4-methyl-8- quinolinolato) Quinolinolato) aluminum, tris (3,4-dimethyl-8-quinolinolato) aluminum, tris (4,5- (2-methyl-8-quinolinolate) aluminum (bis (2-methyl-8-quinolinolate) aluminum Aluminum, bis (2-methyl-8-quinolinolate) (4-methylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (2-methyl-8-quinolinolate) (3-phenylphenolate) aluminum, bis (2-methyl- (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolate (2-methyl-8-quinolinolate) aluminum (2,2-dimethylphenolate) aluminum, bis (2-methyl- (3,5-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolate) (3-methyl-8-quinolinolate) Aluminum, bis (2-methyl-8-quinolinolate) (2,6-diphenylphenolate) aluminum, bis Aluminum (2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolate) Aluminum, bis (2-methyl-8-quinolinolate) (1-naphtholate) aluminum, bis (2-naphtholate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (2-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (4-phenylphenolate) aluminum, bis (2,4- (3,5-dimethylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) (3,5-di- (2-methyl-8-quinolinolate) aluminum, bis (2,4-dimethyl-8-quinolinolate) aluminum-.mu.- (2-methyl-4-ethyl-8-quinolinolate) aluminum-? -Oxo-bis (2-methyl- Ethyl-8-quinolinolate) aluminum, bis (2-methyl-4-methoxy-8- quinolinolate) aluminum- (2-methyl-5-cyano-8-quinolinolate) aluminum,? -Oxo-bis (2- Methyl-5-trifluoromethyl-8-quinolinolate) aluminum,? -Oxo-bis (2-methyl- Benzo [h] quinoline) beryllium and the like.

The pyridine derivative is a compound represented by the following formula (E-2).

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In the formulas, G represents a simple bonding hand or an n-valent connecting group, and n is an integer of 2 to 8. The carbon atom which is not used in the coupling of pyridine-pyridine or pyridine-G may be substituted.

Examples of G in the general formula (E-2) include the following structural formulas. In the following structural formulas, R is independently hydrogen, methyl, ethyl, isopropyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, biphenyl or terphenyl.

(72)

Specific examples of pyridine derivatives include 2,5-bis (2,2'-bipyridin-6-yl) -1,1-dimethyl-3,4-diphenylsilole, 2,5- '- bipyridin-6-yl) -1,1-dimethyl-3,4-dim mesityl silole, 2,5-bis (2,2'-bipyridin- (2,2'-bipyridin-5-yl) -1,1-dimethyl-3,4-dimemethylsilylol, 9,10- (2,2'-bipyridin-5-yl) anthracene, 9,10-di (2,3'-bipyridin-6-yl) Anthracene, 9,10-di (2,3'-bipyridin-5-yl) anthracene, 9,10- Di (2,2'-bipyridin-6-yl) -2-phenylanthracene, 9,10-di (2,2'-bipyridin-5-yl) -2-phenylanthracene, 9,10- (3,4'-bipyridin-6-yl) -2-phenylanthracene, 9,10-di (3,4 ' -Bipyridin-5-yl) -2-phenylanthracene, 3,4-diphenyl-2,5-di (2,2'- Di (2-pyridyl) thiophene, 6'6'-di (2-pyridyl) , 2 ': 4', 4 ": 2", 2 "'- quaternary pyridine, and the like.

The phenanthroline derivative is a compound represented by the following formula (E-3-1) or (E-3-2).

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In the formulas, R ¹ to R ⁸ are each a hydrogen or a substituent, adjacent groups may be bonded to each other to form a condensed ring, G represents a simple bond or an n-valent connecting group, and n is an integer of 2 to 8. Examples of the G in the general formula (E-3-2) include the same ones described in the column of the bipyridine derivative.

Specific examples of phenanthroline derivatives include 4,7-diphenyl-1,10-phenanthroline, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, 9,10- Di (1,10-phenanthroline-2-yl) anthracene, 2,6-di (1,10-phenanthroline-5-yl) pyridine, 1,3,5- 5-yl) benzene, 9,9'-difluoro-bis (1,10-phenanthroline-5-yl), vicocloin or 1,3- -Henanthrene-9-yl) benzene, and the like.

Particularly, a case where a phenanthroline derivative is used for an electron transport layer and an electron injection layer will be described. In order to obtain stable luminescence over a long period of time, a material having excellent thermal stability and thin film formability is desired, and among the phenanthroline derivatives, the substituent itself has a three-dimensional stereostructure, or a phenanthroline skeleton, Dimensional steric structure or a plurality of phenanthroline skeletons are connected to each other by a three-dimensional repulsion. Further, when connecting a plurality of phenanthroline skeletons, a compound containing a conjugated bond, a substituted or unsubstituted aromatic hydrocarbon, and a substituted or unsubstituted aromatic heterocyclic ring is more preferable in the connecting unit.

The borane derivative is a compound represented by the following formula (E-4), and is disclosed in detail in JP-A-2007-27587.

≪ EMI ID =

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring or cyano, R ¹³ to R ¹⁶ are each independently , X is optionally substituted arylene, Y is optionally substituted aryl, substituted aryl, or optionally substituted carbazole, which may be optionally substituted, and X is optionally substituted arylene, n is independently an integer of 0 to 3;

Among the compounds represented by the above general formula (E-4), the compounds represented by the following general formula (E-4-1), the following general formulas (E-4-1-1) to (E- Are preferred. Specific examples include 9- [4- (4-dimetylthiophenylboranaphthalen-1-yl) phenyl] carbazole, 9- [4- Yl] carbazole and the like.

(75)

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring or cyano, R ¹³ to R ¹⁶ are each independently And R ²¹ and R ²² are each independently selected from the group consisting of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring, or optionally substituted cyano X ¹ is an optionally substituted arylene having 20 or less carbon atoms, n is independently an integer of 0 to 3, and m is independently an integer of 0 to 4.

[Formula 76]

In each formula, R ³¹ to R ³⁴ are each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl.

Among the compounds represented by the general formula (E-4), the compounds represented by the following formula (E-4-2) and the compounds represented by the following formula (E-4-2-1) are preferable.

[Formula 77]

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring or cyano, R ¹³ to R ¹⁶ are each independently , X ¹ is optionally substituted arylene having 20 or less carbon atoms, and n is independently an integer of 0 to 3.

(78)

Wherein R ³¹ to R ³⁴ are each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl.

Among the compounds represented by the general formula (E-4), the compounds represented by the following general formula (E-4-3), the compounds represented by the general formulas (E-4-3-1) Are preferred.

(79)

Wherein R ¹¹ and R ¹² are each independently at least one of hydrogen, alkyl, optionally substituted aryl, substituted silyl, optionally substituted nitrogen-containing heterocyclic ring or cyano, R ¹³ to R ¹⁶ are each independently , X ¹ is optionally substituted arylene having 10 or less carbon atoms, Y ¹ is optionally substituted aryl having 14 or less carbon atoms, and n is each independently a substituted or unsubstituted aryl group, It is an integer from 0 to 3.

(80)

In each formula, R ³¹ to R ³⁴ are each independently methyl, isopropyl or phenyl, and R ³⁵ and R ³⁶ are each independently hydrogen, methyl, isopropyl or phenyl.

The benzimidazole derivative is a compound represented by the following formula (E-5).

[Formula 81]

In the formulas, Ar ¹ to Ar ³ are each independently hydrogen or aryl having 6 to 30 carbon atoms which may be substituted. Particularly preferred is anthryl benzoimidazole derivatives in which Ar ¹ may be substituted.

Specific examples of aryl having 6 to 30 carbon atoms include phenyl, 1-naphthyl, 2-naphthyl, acenaphthylene-1-yl, acenaphthylene- Yl, phenalen-1-yl, phenalen-2-yl, fluoren-3-yl, fluoren- 2-yl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl, Yl, triphenylene-1-yl, triphenylene-2-yl, fluorenen-2-yl, fluorenen-2-yl, fluoranthene- Yl, chrysene-4-yl, chrysene-1-yl, chrysene-2-yl, Yl, naphthacen-2-yl, naphthacen-5-yl, perylen-1-yl, perylen- Pentacene-1-yl, pentacene-2-yl, pentacene-5-yl, pentacene-6-yl.

Specific examples of benzimidazole derivatives include 1-phenyl-2- (4- (10-phenylanthracen-9-yl) phenyl) -1H- benzo [d] imidazole, 2- (4- (10- Phenyl) -1H-benzo [d] imidazole and 2- (3- (10- (naphthalen-2-yl) anthracene- Benzo [d] imidazole, 1-phenyl-1H- benzo [d] imidazole, 5- (10- (naphthalen- Benzo [d] imidazole, 2- (4- (9,10-di (naphthalene-2-yl) Benzo [d] imidazole, 1- (4- (9,10-di (naphthalen-2-yl) anthracene- 2- yl) Benzo [d] imidazole, 5- (9,10-di (naphthalen-2-yl) anthracene- ] Imidazole.

The electron transporting layer or the electron injecting layer may further contain a substance capable of reducing the material forming the electron transporting layer or the electron injecting layer. The reducing material may be any of those having a certain reducing property, and examples thereof include alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, At least one selected from the group consisting of an oxide of a rare earth metal, a halide of a rare earth metal, an organic complex of an alkali metal, an organic complex of an alkaline earth metal and an organic complex of a rare earth metal is preferably used.

Preferable reducing materials include alkaline metals such as Na (work function 2.36 eV), K (copper 2.28 eV), Rb (copper 2.16 eV) or Cs (copper 1.95 eV) 2.0 to 2.5 eV) or Ba (copper eutectic 2.52 eV), and it is particularly preferable that the work function is 2.9 eV or less. Among them, the more preferable reducing material is an alkali metal of K, Rb or Cs, more preferably Rb or Cs, and most preferably Cs. These alkali metals have a high reducing ability, and the addition of a relatively small amount to a material forming the electron transporting layer or the electron injecting layer improves the luminescence brightness and the longevity of the organic EL device. In addition, a combination of two or more kinds of alkali metals is preferable as a reducing material having a work function of 2.9 eV or less. In particular, a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or Cs And a combination of Na and K are preferable. By containing Cs, the reducing ability can be efficiently exerted, and by the addition to the material for forming the electron transporting layer or the electron injecting layer, the luminescence brightness and the longevity of the organic EL element can be improved.

≪ Negative electrode in organic electroluminescent device >

The cathode 108 serves to inject electrons into the light emitting layer 105 via the electron injection layer 107 and the electron transport layer 106.

The material for forming the cathode 108 is not particularly limited as long as electrons can be efficiently injected into the organic layer, but the same material as the material for forming the anode 102 can be used. Among them, metals such as tin, magnesium, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or their alloys (magnesium- Magnesium-indium alloy, and aluminum-lithium alloy such as lithium fluoride / aluminum) and the like are preferable. In order to increase the electron injection efficiency and improve the device characteristics, alloys containing lithium, sodium, potassium, cesium, calcium, magnesium or their low-function metal are effective. However, these low-function metals are generally unstable in the atmosphere. In order to solve this problem, for example, a method of using an electrode with high stability by doping a small amount of lithium, cesium or magnesium into the organic layer is known. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide and cesium oxide may also be used. However, the present invention is not limited thereto.

In order to protect the electrodes, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium or alloys using these metals and inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, Based polymer compound or the like may be laminated. The manufacturing method of these electrodes is not particularly limited as long as it can take conduction such as resistance heating, electron beam beam, sputtering, ion plating and coating.

≪ Binder agent which may be used in each layer >

The above materials used for the hole injection layer, the hole transporting layer, the light emitting layer, the electron transporting layer, and the electron injecting layer can form each layer alone. However, as the polymer binder, polyvinyl chloride, polycarbonate, polystyrene, poly Polyvinyl pyrrolidone, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethylcellulose, vinyl acetate resin, ABS resin, Soluble resin such as a resin or a polyurethane resin or a curable resin such as a phenol resin, a xylene resin, a petroleum resin, a urea resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, an epoxy resin, have.

≪ Method of manufacturing organic electroluminescent device &

Each layer constituting the organic electroluminescence device can be formed by forming a material constituting each layer by a vapor deposition method, resistance heating deposition, electron beam deposition, sputtering, molecular lamination method, printing method, spin coating method, casting method, . The film thickness of each layer thus formed is not particularly limited and may be suitably set according to the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can be generally measured by a crystal oscillation type film thickness measuring apparatus or the like. In the case of thinning using a vapor deposition method, the deposition conditions differ depending on the kind of the material, the intended crystal structure of the film, the structure of the association, and the like. The deposition conditions are generally boat heating temperature +50 to +400 ° C, vacuum degree 10 ^-6 to 10 ^-3 Pa, deposition rate 0.01 to 50 nm / sec, substrate temperature -150 to +300 ° C, film thickness 2 nm to 5 Lt; RTI ID = 0.0 > m. ≪ / RTI >

Next, as an example of a method of manufacturing an organic electroluminescent device, a method of manufacturing an organic electroluminescent device comprising an anode / a hole injecting layer / a hole transporting layer / a light emitting layer / electron transporting layer / electron injecting layer / cathode made of a host material and a dopant material . A thin film of a cathode material is formed on a suitable substrate by vapor deposition or the like to produce a cathode, and then a thin film of a hole injection layer and a hole transport layer is formed on the anode. A host material and a dopant material are co-deposited thereon to form a thin film to form a light emitting layer, an electron transport layer and an electron injection layer are formed on the light emitting layer, and a thin film made of a material for a negative electrode is formed by evaporation or the like to form a cathode. An organic electroluminescent device is obtained. In the production of the above-described organic electroluminescent device, the cathode, the electron injecting layer, the electron transporting layer, the light emitting layer, the hole transporting layer, the hole injecting layer, and the anode may be fabricated in this order in reverse order.

When a direct current voltage is applied to the thus obtained organic electroluminescent device, the positive polarity may be applied to the positive electrode and the negative polarity may be applied to the negative polarity. When a voltage of approximately 2 to 40 V is applied, the transparent or semi- Cathode, and both) can be observed. The organic electroluminescent device emits light even when a pulse current or an alternating current is applied. The waveform of the applied alternating current may be arbitrary.

≪ Example of application of organic electroluminescent device &

The present invention can also be applied to a display device having an organic electroluminescent device or a lighting device having an organic electroluminescent device.

The display device or the lighting device provided with the organic electroluminescent device can be manufactured by a known method such as connecting the organic electroluminescent device related to the present embodiment and a known driving device, And the like can be driven appropriately.

Examples of the display device include a panel display such as a color flat panel display and a flexible display such as a flexible color organic electroluminescence (EL) display (see, for example, Japanese Laid-Open Patent Publication No. 10-335066 , Japanese Unexamined Patent Application Publication No. 2003-321546, Japanese Unexamined Patent Publication No. 2004-281086, etc.). The display method of the display may be, for example, a matrix and / or a segment method. The matrix display and the segment display may coexist in the same panel.

The matrix means that pixels for display are arranged two-dimensionally, such as a lattice-like or a mosaic-like, and displays a character or an image as a set of pixels. The shape and size of the pixel are determined depending on the application. For example, in the case of a large-sized display such as a display panel, a square pixel having a side of 300 mu m or less is usually used for image and character display of a PC, a monitor, and a television. do. In the case of monochrome display, pixels of the same color can be arranged. In the case of color display, red, green and blue pixels are displayed in a list. In this case, there are typically a delta type and a stripe type. As the driving method of the matrix, either a line-sequential driving method or an active matrix may be used. The line-sequential driving is advantageous in that the structure is simple. However, when the operating characteristics are taken into consideration, the active matrix may be superior to the line-sequential driving.

In the segment method (type), a pattern is formed so as to display predetermined information, and a predetermined area is emitted. Examples of the display include a time and temperature display in a digital clock or a thermometer, an operation status display of an audio device or an electromagnetic cooker, and a panel display of an automobile.

Examples of the illumination device include an illumination device such as an indoor illumination, and a backlight of a liquid crystal display device (see, for example, JP-A-2003-257621, JP-A-2003-277741, Japanese Unexamined Patent Publication (Kokai) No. 2004-119211). The backlight is mainly used for the purpose of improving the visibility of a display device that does not emit light, and is used for a liquid crystal display device, a watch, an audio device, an automobile panel, a display panel, and a cover. Particularly, considering that it is difficult to reduce the thickness of a backlight of a liquid crystal display device, particularly a PC for which the thinning is a problem, because the conventional system is a fluorescent lamp or a light guide plate, the backlight using the light- It is thin and features light weight.

Example

<Synthesis Example of Benzofluorene Compound>

Hereinafter, the expression (1-1-24), the expression (1-1-54), the expression (1-1-84), the expression (1-2-84) (1-1-2), (1-2-174), (1-1-140), (1-1-101), and , (1-1-113), (1-1-1), (1-1-10), (1-1-123), (1-1-61) 1-76), the compound represented by the formula (1-1-103) and the compound represented by the formula (1-1-154) will be described.

[Synthesis Example 1] Synthesis of Compound (1-1-24)

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Synthesis of 4- (t-butyl) -N- (4- (t-butyl) phenyl) -N-

(20.0 g), 1-bromo-4- (t-butyl) benzene (100.0 g), palladium acetate (1.1 g), tri-t-butylphosphine (2.8 g) -Butoxide (52.0 g) and toluene (300 ml) was stirred at reflux temperature for 14 hours. After the reaction solution was cooled to room temperature, the celite was separated by filtration with a Kanrigiyama funnel, and water and ethyl acetate were added to the filtrate to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by a silica gel short column (eluent: toluene). After the solvent was distilled off under reduced pressure, the low boiling fraction was distilled off at a temperature of 0.01 ° C and 100 ° C to give 4- (t-butyl) -N- (4- (t-butyl) Phenylaniline (78.0 g) was obtained.

Synthesis of 4-bromo-N, N-bis (4- (t-butyl) phenyl)

A THF (300 mL) solution of 4- (t-butyl) -N- (4- (t-butyl) phenyl) -N-phenylaniline (78.0 g) dissolved in a nitrogen atmosphere was cooled in an ice bath, MoSuccinimide (38.0 g) was added portionwise. After completion of the addition, the mixture was stirred at room temperature for 1 hour, and then an aqueous sodium hydrogen sulfite solution was added to terminate the reaction. THF was distilled off under reduced pressure, water was added, and suction filtration was carried out. The residue was purified by silica gel short column (eluent: toluene) and recrystallized from heptane to obtain 4-bromo-N, N-bis (4- (t-butyl) phenyl) aniline (79.4 g).

Preparation of 4- (t-butyl) -N- (4- (t-butyl) phenyl) -N- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane- 2-yl) phenyl) aniline &gt;

(55.0 g), Pd (dppf) Cl ₂ (4.4 g), potassium acetate (53.0 g), and the like were dissolved in a mixed solvent of tetrahydrofuran g) and cyclopentyl methyl ether (500 ml) were stirred at reflux temperature for 6 hours under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the liquid, and the solvent was distilled off under reduced pressure After the solvent was distilled off under reduced pressure, the residue was washed with heptane to obtain 4- (t-butyl) -N- (4- (t-butyl) phenyl) (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) aniline (74.3 g).

Synthesis of methyl 1- (4- (bis (4- (t-butyl) phenyl) amino) phenyl) -2-naphthoate [

(61.0 g) of methyl 1 - (((trifluoromethyl) sulfonyl) oxy) -2-naphthoate synthesized by the known method, 4- (t- ) phenyl) -N- (4- (4,4,5,5- tetramethyl-1,3,2 dioxaborolan-2-yl) phenyl) aniline (74.3 g), Pd (PPh 3) 4 (1.8 g), potassium phosphate (65.0 g), toluene (500 mL), ethanol (150 mL) and water (50 mL) was stirred at reflux temperature for 2 hours under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure and the residue was purified by silica gel and then activated alumina short column (eluent: toluene / heptane = 1/1 (volume ratio)) to obtain methyl 1- (4- (bis (4- (t- Phenyl) amino) phenyl) -2-naphthoate (77.0 g).

Synthesis of 2- (1- (4- (bis (4- (t-butyl) phenyl) amino) phenyl) naphthalen-2-yl) propan-

To a flask containing methyl 1- (4- (bis (4- (t-butyl) phenyl) amino) phenyl) -2-naphthoate (77.0 g) and THF (200 ml), methylmagnesium Bromide THF solution (1.1 M, 300 mL) was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 15 hours, and water was added to stop the reaction. Ethyl acetate and an aqueous ammonium chloride solution were added to the reaction mixture to separate the layers, and the ethyl acetate layer was further washed with water. The solvent was distilled off under reduced pressure, and the residue was purified by activated alumina column chromatography (eluent: toluene / ethyl acetate mixed solvent). At this time, with reference to the method described in "Organic Chemistry Experiment Guide (1) -Material Handling Method and Separation and Refinement Method" published by Kagaku Tobin Co., Ltd., page 94, the ratio of ethyl acetate in the developing solution was gradually increased, Lt; / RTI &gt; The eluate was distilled off under reduced pressure to obtain 44.0 g of 2- (1- (4- (bis (4- (t-butyl) phenyl) amino) phenyl) naphthalen-2-yl) propan-2-ol.

Synthesis of N, N-bis (4- (t-butyl) phenyl) -7,7-dimethyl-7H-benzo [c] fluorene-

To a flask containing a solution of 2- (1- (4- (bis (4- (t-butyl) phenyl) amino) phenyl) naphthalen- Boron trifluoride diethyl ether complex (16 g) was added dropwise at room temperature under a nitrogen atmosphere. After completion of the dropwise addition, water was added to stop the reaction and neutralized with sodium hydrogencarbonate. After the separation, the solvent was distilled off under reduced pressure, and the residue was purified by activated alumina column chromatography (eluent: toluene / heptane = 1/9 (volume ratio)). The residue was washed with methanol to obtain N, N-bis (4- (t-butyl) phenyl) -7,7-dimethyl-7H-benzo [c] fluoren-9-amine (38.0 g).

Synthesis of 5-bromo-N, N-bis (4- (t-butyl) phenyl) -7,7-dimethyl-7H- benzo [c] fluorene-

To a flask containing N, N-bis (4- (t-butyl) phenyl) -7,7-dimethyl-7H-benzo [c] fluorene- N-Bromosuccinimide (13.6 g) was added portionwise while cooling in an ice bath. After completion of the addition, the mixture was stirred at room temperature for 15 hours, and then an aqueous sodium hydrogen sulfite solution was added to terminate the reaction. The precipitated solid was collected by suction filtration, and the solid was washed with water and then with methanol. Further, by dissolving in toluene and adding heptane to reprecipitate, 5-bromo-N, N-bis (4- (t-butyl) phenyl) -7,7-dimethyl- 9-amine (33.3 g) was obtained.

&Lt; Synthesis of Compound (1-1-24) >

7,7-dimethyl-7H-benzo [c] fluorene-9-amine (2.00 g) was added to a solution of 5-bromo- , A solution of Pd (dba) ₂ (0.17 g), a 1 M toluene solution of tri-t-butylphosphine (0.9 ml), sodium t-butoxide (0.50 g) and xylene (15 ml) And the mixture was stirred at reflux temperature for 20 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by activated alumina column chromatography (eluent: toluene / heptane mixed solution). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product. Subsequently, the product was purified by silica gel column chromatography (eluent: chlorobenzene / heptane = 1/5 (volume ratio)) and then recrystallized from toluene to obtain a compound represented by formula (1-1-24) 7,7-dimethyl-7H-benzo [c] fluorene-9-amine (0.78 g) was obtained.

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

Synthesis Example 2 Synthesis of Compound (1-1-54)

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&Lt; Synthesis of Compound (1-1-54) >

Butyl-9H-carbazole (1.10 g), 5-bromo-N, N-bis (4- (tert- butyl) phenyl) -7,7- c] fluoren-9-amine (2.00 g), Pd (dba ) 2 (0.06 g), tree -t- butylphosphine 1 M toluene solution (0.3 ㎖), sodium -t- butoxide (0.50 g) of the pin And 1,2,4-trimethylbenzene (15 ml) were stirred in a nitrogen atmosphere at a reflux temperature for 10 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane / ethyl acetate mixed solution). At this time, the amount of ethyl acetate in the developing solution was not changed, and the proportion of toluene in toluene / heptane was gradually increased to elute the target product. After the solvent was distilled off under reduced pressure, the residue was dissolved in ethyl acetate and re-precipitated by addition of methanol. The residue was further purified by activated carbon column chromatography (eluent: toluene / heptane = 1/4 (volume ratio) (3, 6-di-t-butyl-9H-carbazol-9-yl) -7, 7-dimethyl-7H-benzo [c] fluorene-9-amine (0.99 g) was obtained.

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 3] Synthesis of compound (1-1-84)

(84)

&Lt; Synthesis of Compound (1-1-84) >

Carbamate (1.30 g), 5-bromo-N, N-bis (4- (tert- butyl) phenyl) -7,7-dimethyl-7H- benzo [c] (0.3 ml), sodium-t-butoxide (0.50 g), and 1, _2- diisopropylethylamine were added to a solution of _2- amino-9-amine (2.00 g), Pd A flask containing 2,4-trimethylbenzene (15 ml) was stirred under a nitrogen atmosphere at a reflux temperature for 8 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane / ethyl acetate = 5/95/1 (volume ratio)). The solvent was distilled off under reduced pressure, and the residue was purified by activated carbon column chromatography (eluent: toluene / heptane = 7/3 (volume ratio)). The solvent was distilled off under reduced pressure and the residue was recrystallized from heptane to obtain a compound represented by the formula (1-1-84), N, N-bis (4- (t-butyl) phenyl) -5- (3,6- 9H-carbazol-9-yl) -7,7-dimethyl-7H-benzo [c] fluorene-9-amine (1.13 g).

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 4] Synthesis of compound (1-2-84)

(85)

<Synthesis of methyl 5-chloro-2- (naphthalen-1-yl) benzoate>

Under a nitrogen atmosphere, 1-naphthalene boronic acid (38.0 g), methyl 2-bromo-5-chlorobenzoate (50.0 g), Pd (PPh 3) 4 (2.3 g), potassium phosphate (85.0 g), toluene ( 500 ml), 2-propanol (150 ml) and water (50 ml) were stirred in a nitrogen atmosphere at reflux temperature for 2 hours. After the reaction solution was cooled to room temperature, water was added thereto to separate the layers, and the solvent was distilled off under reduced pressure. The resulting oily substance was purified by silica gel column chromatography (eluent: toluene / heptane mixed solvent) to obtain methyl 5-chloro-2- (naphthalen-1-yl) benzoate (58.3 g). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product.

Synthesis of 2- (5-chloro-2- (naphthalen-1-yl) phenylpropan-

(250 mL) solution of methyl 5-chloro-2- (naphthalen-1-yl) benzoate (58.0 g) in a nitrogen atmosphere was cooled in a water bath and to this solution was added methylmagnesium bromide THF solution (1.1 M, 300 ml) was added dropwise. After completion of the dropwise addition, the water bath was removed, and the mixture was stirred at 30 ° C for 3 hours. Thereafter, the reaction mixture was cooled in an ice bath, and an aqueous solution of ammonium chloride was added to terminate the reaction, and about half of the THF was distilled off under reduced pressure. Ethyl acetate was added to this solution and the solution was separated, and then the solvent was distilled off under reduced pressure. The resulting solid was purified by activated alumina column chromatography (eluent: toluene / heptane mixed solvent). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product. Subsequently, the eluate was distilled off under reduced pressure, and the obtained solid was washed with heptane to obtain 2- (5-chloro-2- (naphthalen-1-yl) phenylpropan-2-ol (43.0 g).

Synthesis of <9-chloro-7,7-dimethyl-7H-benzo [c] fluorene>

A flask containing a boron trifluoride diethyl ether complex (29.0 g) and chloroform (400 ml) in a nitrogen atmosphere was cooled in an ice bath and 2- (5-chloro-2- (naphthalen- -2-ol (43.0 g) in chloroform was added dropwise. After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 1 hour and then water was added to stop the reaction. The solvent was distilled off under reduced pressure to obtain 9-chloro-7,7-dimethyl-7H-benzo [c] fluorene (41.3 g).

Synthesis of <9-chloro-5-iodo-7,7-dimethyl-7H-benzo [c]

(41.3 g), iodine (3.9 g), ortho-iodic acid (2.6 g), acetic acid (200 ml) and sulfuric acid (4 ml) were added to a solution of 9-chloro-7,7-dimethyl- The flask was stirred under nitrogen atmosphere at 100 占 폚 for 4 hours. After the reaction solution was cooled to room temperature, an aqueous solution of sodium hydrogensulfite was added to terminate the reaction, and further ethyl acetate was added to separate the layers. The solvent was distilled off under reduced pressure, and the obtained oily substance was purified with a silica gel short column (eluent: toluene). The residue was purified by silica gel column chromatography (eluent: heptane) to obtain 9-chloro-5-iodo-7,7-dimethyl-7H-benzo [c] fluorene (8.1 g).

Synthesis of N, N-bis (4- (t-butyl) phenyl) -9-chloro-7,7-dimethyl-7H-benzo [c] fluoren-

Benzo [c] fluorene (4.0 g), bis (4- (t-butyl) phenyl) amine (2.8 g), bis tree -o- tolyl phosphine) -palladium (II) dichloride _{(PdCl 2 (o-tolyl 3} ) 2) (0.4 g), sodium -t- butoxide (1.4 g) and 1,2,4-trimethylbenzene (30 ml) was stirred at 130 占 폚 for 3 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solution: toluene / heptane / ethyl acetate = 5/95/1 (volume ratio)), followed by activation alumina column chromatography (eluent: toluene / Ethyl acetate = 5/95/1 (volume ratio)). The solvent was distilled off under reduced pressure, and the residue was dissolved in methanol and re-precipitated by adding water to obtain N, N-bis (4- (t-butyl) phenyl) -9-chloro-7,7-dimethyl- c] fluoren-5-amine (4.0 g).

&Lt; Synthesis of compound (1-2-84)

Benzo [c] fluoren-5-amine (2.0 g), 3,6-diphenyl- 9H- carbazole (1.4 g), Pd (dba ) 2 (0.06 g), 1 of the tree -t- butylphosphine M toluene solution (0.3 ㎖), sodium -t- butoxide (0.5 g) and 1,2 , And 4-trimethylbenzene (15 ml) were stirred in a nitrogen atmosphere at reflux temperature for 8 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure to obtain a solid, which was dissolved in chlorobenzene and re-precipitated by adding heptane to obtain a compound represented by the formula (1-2-84), N, N-bis (4- (t- -7- dimethyl-7H-benzo [c] fluoren-5-amine (2.3 g) was obtained.

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 5] Synthesis of compound (1-1-70)

&Lt; EMI ID =

Synthesis of <5-bromo-7,7-dimethyl-7H-benzo [c] fluorene>

The flask containing 7,7-dimethyl-7H-benzo [c] fluorene (10.0 g), N-bromosuccinimide (7.3 g) and acetic acid (200 ml) was stirred at 70 ° C for 1 hour under a nitrogen atmosphere. Respectively. After the reaction solution was cooled to room temperature, an aqueous solution of sodium hydrogen sulfite and then ethyl acetate were added to separate the layers. The solvent of the organic layer was distilled off under reduced pressure, and the obtained solid was washed with methanol and then recrystallized from heptane and then an ethyl acetate / ethanol mixed solvent to obtain 5-bromo-7,7-dimethyl-7H-benzo [c] 11.0 g) was obtained.

Synthesis of <5-bromo-9-iodo-7,7-dimethyl-7H-benzo [c]

(11.0 g), iodine (3.4 g), iodic acid (3.0 g), acetic acid (200 ml), and sulfuric acid (4 ml) were added to a solution of 5-bromo-7,7- The flask was stirred in a nitrogen atmosphere at 120 占 폚 for 2 hours. After the reaction solution was cooled to room temperature, an aqueous solution of sodium hydrogensulfite was added to terminate the reaction, followed by the addition of sodium carbonate in an amount capable of neutralizing the used sulfuric acid. Further, toluene and water were added to separate the layers, and the solvent of the organic layer was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent: heptane). The solvent was distilled off under reduced pressure, and heptane was added to the obtained oily substance to reprecipitate to obtain 5-bromo-9-iodo-7,7-dimethyl-7H-benzo [c] fluorene (10.0 g).

Synthesis of 5-bromo-7,7-dimethyl-N- (naphthalen-1-yl) -N-phenyl-7H-benzo [c] fluorene-

(5.0 g), N-phenylnaphthalen-1 -amine (2.4 g), (PdCl ₂ (o), and the like were added to a solution of 5- -tolyl ₃ ) ₂ ) (0.3 g), sodium-t-butoxide (1.6 g) and 1,2,4-trimethylbenzene (50 ml) was stirred at 90 ° C for 12 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent of the organic layer was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane / ethyl acetate = 5/95/1 (volume ratio)). Reprecipitation was carried out by adding heptane to the obtained oily substance by distilling off the solvent under reduced pressure, and the resulting solid was dissolved in chlorobenzene and then re-precipitated by adding heptane to obtain 5-bromo-7,7-dimethyl- Phenyl-7H-benzo [c] fluorene-9-amine (3.6 g) was obtained.

&Lt; Synthesis of Compound (1-1-70) >

7H-benzo [c] fluorene-9-amine (2.0 g), 3,6-diphenyl-9H -Carbazole (1.3 g), Pd (dba) ₂ (0.06 g), a 1 M toluene solution of tri-t-butylphosphine (0.3 ml), sodium t-butoxide (0.50 g) A flask containing 4-trimethylbenzene (15 ml) was stirred under a nitrogen atmosphere at a reflux temperature for 8 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane / ethyl acetate = 10/90/1 (volume ratio)). The compound represented by the formula (1-1-70), 5- (3,6-dihydro-2H-1,5-benzodiazepin- Phenyl-7H-benzo [c] fluorene-9-amine (1.1 g) was added to a solution of .

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 6] Synthesis of compound (1-2-121)

[Chemical Formula 87]

&Lt; Synthesis of methyl 2-bromo-5-fluorobenzoate >

A flask containing 2-bromo-5-fluorobenzoic acid (50.0 g), sulfuric acid (7 ml) and methanol (500 ml) was stirred at reflux temperature for 8 hours under a nitrogen atmosphere. After the reaction solution was cooled to room temperature, the methanol was distilled off under reduced pressure, and ethyl acetate and an aqueous sodium hydrogencarbonate solution were added to separate the layers. The solvent of the organic layer was distilled off under reduced pressure to obtain methyl 2-bromo-5-fluorobenzoate (50.0 g).

<Synthesis of methyl 5-fluoro-2- (naphthalen-1-yl) benzoate>

Under a nitrogen atmosphere, 1-naphthalene boronic acid (38.7 g), methyl 2-bromo-5-chlorobenzoate (50.0 g), Pd (PPh 3) 4 (2.5 g), potassium phosphate (91.0 g), xylene (500 ml), 2-propanol (150 ml) and water (50 ml) was stirred at a reflux temperature for 2 hours and a half. After the reaction solution was cooled to room temperature, water was added thereto to separate the layers, and the solvent was distilled off under reduced pressure. The obtained oily substance was purified by silica gel column chromatography (eluent: toluene / heptane mixed solvent) to obtain methyl 5-fluoro-2- (naphthalen-1-yl) benzoate (58.0 g). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product.

Synthesis of 2- (5-fluoro-2- (naphthalen-1-yl) phenyl) propan-

(250 mL) solution of methyl 5-fluoro-2- (naphthalen-1-yl) benzoate (58.0 g) in a nitrogen atmosphere was cooled in a water bath and to this solution was added a solution of methylmagnesium bromide THF , 540 ml) was added dropwise. After completion of the dropwise addition, the water bath was removed, and the mixture was stirred at 30 ° C for 3 hours. Thereafter, the reaction mixture was cooled in an ice bath, and an aqueous solution of ammonium chloride was added to terminate the reaction, and about half of the THF was distilled off under reduced pressure. Ethyl acetate was added to this solution to separate out the liquid, and then the solvent was distilled off under reduced pressure. The resulting solid was purified by silica gel column chromatography (eluent: toluene / heptane mixed solvent). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product. Then, recrystallization from an ethyl acetate / heptane mixed solvent gave 46.0 g of 2- (5-fluoro-2- (naphthalen-1-yl) phenyl) propan-2-ol.

Synthesis of <9-fluoro-7,7-dimethyl-7H-benzo [c] fluorene>

The flask containing the boron trifluoride diethyl ether complex (33.0 g) and chloroform (100 ml) was cooled in an ice bath under a nitrogen atmosphere and 2- (5-fluoro-2- (naphthalen- 2-ol (46.0 g) was added dropwise. After completion of the dropwise addition, the ice bath was removed, stirred at room temperature for 10 minutes, and then water was added to stop the reaction. The obtained oily substance was purified by silica gel column chromatography (eluent: heptane) to obtain 9-fluoro-7,7-dimethyl-7H-benzo [c ] Fluorene (40.0 g) was obtained.

Synthesis of <5-bromo-9-fluoro-7,7-dimethyl-7H-benzo [c]

A flask containing 9-fluoro-7,7-dimethyl-7H-benzo [c] fluorene (40.0 g), N-bromosuccinimide (28.5 g) and acetic acid C &lt; / RTI &gt; for 2 hours. The reaction solution was cooled to room temperature, and an aqueous solution of sodium hydrogen sulfite and then toluene were added thereto to separate the layers. 9-fluoro-7,7-dimethyl-7H-benzo [c] thiophene was obtained by distilling off the solvent of the organic layer under reduced pressure and purifying the obtained oily substance with silica gel column chromatography (eluent: heptane) Fluorene (50.0 g) was obtained.

Synthesis of 9- (5-bromo-7,7-dimethyl-7H-benzo [c] fluorene-9-yl) -3,6-diphenyl-9H-

Benzo [c] fluorene (2.0 g), 3,6-diphenyl-9H-carbazole (2.2 g), and carbonic acid Cesium (2.9 g) and N-methylpyrrolidone (15 ml) was stirred at 180 占 폚 for 8 hours. After the reaction solution was cooled to room temperature, water and toluene were added thereto to separate the layers, and the solvent was distilled off under reduced pressure. Ethanol was added to the obtained oily substance to reprecipitate and then purified by silica gel column chromatography (eluent: heptane / toluene = 9/1 (volume ratio)). The solvent was distilled off under reduced pressure and the resulting solid was washed with heptane to obtain 9- (5-bromo-7,7-dimethyl-7H-benzo [c] fluoren- 9H-carbazole (3.3 g).

&Lt; Synthesis of Compound (1-2-121) >

Carbazole (1.6 g), N-phenyl-4- (4-fluorophenyl) (0.6 g), Pd (dba) ₂ (0.02 g), 4-dimethylaminophenyl di-t-butylphosphine (0.02 g), sodium t-butoxide (0.60 g) and xylene 15 ml) was stirred in a nitrogen atmosphere at 90 占 폚 for 3 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane / triethylamine = 10/90/1 (volume ratio)). The solvent was distilled off under reduced pressure, and the obtained solid was dissolved in toluene and re-precipitated by adding heptane to obtain a compound represented by the formula (1-2-121), 9- (3,6-diphenyl-9H-carbazole- 7,7-dimethyl-N-phenyl-N- (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluoren-5-amine (1.8 g).

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 7] Synthesis of compound (1-2-85)

[Formula 88]

&Lt; Synthesis of Compound (1-2-85)

9-yl) -3,6-diphenyl-9H-carbazole (1.6 g), 4- (t-butyl (0.7 g), Pd (dba) ₂ (0.02 g), 4-dimethylaminophenyl di-t-butylphosphine (0.02 g), sodium t-butoxide (0.6 g) and xylene (15 ml) were stirred in a nitrogen atmosphere at 90 占 폚 for 2 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. After the solvent was distilled off under reduced pressure, the residue was dissolved in chlorobenzene and re-precipitated by adding ethyl acetate to obtain a compound represented by the formula (1-2-85), N- (4- (t-butyl) phenyl) -9- 7,7-dimethyl-N- (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluoren- ).

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 8] Synthesis of compound (1-2-24)

(89)

&Lt; Synthesis of Compound (1-2-24)

Benzo [c] fluoren-5-amine (1.0 g), 9H-carbazole (0.4 g, ), Pd (dba) ₂ (0.03 g), a 1 M toluene solution of tri-t-butylphosphine (0.2 ml), sodium t-butoxide (0.3 g) and 1,2,4-trimethylbenzene Ml) was stirred in a nitrogen atmosphere at 150 占 폚 for 2 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure and the resulting solid was purified by silica gel column chromatography (eluent: toluene / heptane mixed solvent) to obtain the compound represented by the formula (1-2-24), N, N-bis (4- -Butyl) phenyl) -9- (9H-carbazol-9-yl) -7,7-dimethyl-7H-benzo [c] fluoren-5-amine (0.8 g). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product.

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 9] Synthesis of compound (1-2-174)

(90)

Synthesis of <5-methyl-2-nitro-1,1 ': 3', 1 "-terphenyl>

Under a nitrogen atmosphere, 2-chloro-4-methyl-1-nitrobenzene (7.3 g), 1,1'- biphenyl-3 Daily acid (8.8 g), Pd (PPh 3) 4 (0.5 g), sodium carbonate (11.8 g), xylene (80 ml), ethanol (20 ml) and water (20 ml) was stirred at reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, water was added to separate the layers, and the organic layer was purified by silica gel column chromatography (eluent: toluene / heptane mixed solvent). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product. The eluate was distilled off under reduced pressure to obtain 5-methyl-2-nitro-1,1 ': 3', 1 "-terphenyl (12.1 g).

Synthesis of 6-methyl-1-phenyl-9H-carbazole and 3-methyl-6-phenyl-9H-

(12.1 g), triphenylphosphine (27.0 g) and N-methylpyrrolidone (90 ml) were added to a solution of 5-methyl-2-nitro-1,1 ': 3' And the resulting flask was stirred for 16 hours at 160 DEG C. The reaction solution was cooled to room temperature and then purified by silica gel column chromatography (eluent: toluene / heptane mixed solvent) to obtain 6-methyl-1-phenyl-9H- (6.3 g) and 3-methyl-6-phenyl-9H-carbazole (3.0 g) were obtained by gradually increasing the proportion of toluene in the developing solution.

&Lt; Synthesis of Compound (1-2-174)

Phenyl) -9-chloro-7,7-dimethyl-7H-benzo [c] fluoren- -9H- carbazole (0.6 g), Pd (dba ) 2 (0.03 g), tree -t- butylphosphine 1 M toluene solution (0.2 ㎖), sodium -t- butoxide (0.3 g) and the pin 1, The flask containing 2,4-trimethylbenzene (10 ml) was stirred for 2 hours at 160 ° C in a nitrogen atmosphere. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was purified by silica gel column chromatography (eluent: toluene / heptane mixed solvent). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product. The compound represented by the formula (1-2-174), N, N-bis (4-methoxybenzyl) piperazine was obtained by purifying by an activated carbon column chromatography (eluent: toluene / heptane = 1/1 -7H-benzo [c] fluoren-5-amine (1.1 &lt; / RTI &gt; g).

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 10] Synthesis of Compound (1-1-140)

[Formula 91]

&Lt; Synthesis of Compound (1-1-140) >

Phenyl-7H-benzo [c] fluorene-9-amine (1.9 g), 3-methyl-6-phenyl- (1.0 g), Pd (dba) ₂ (0.06 g), a 1 M toluene solution of tri-t-butylphosphine (0.3 ml), sodium t-butoxide (0.5 g) , And 4-trimethylbenzene (15 ml) were stirred in a nitrogen atmosphere at reflux temperature for 8 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane = 3/7 (volume ratio)). The compound represented by the formula (1-1-140), 7,7-dimethyl-5- (3-methyl-pyridin- Phenyl-7H-benzo [c] fluorene-9-amine (1.3 g) was obtained in the form of a white solid.

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 11] Synthesis of Compound (1-1-101)

&Lt; EMI ID =

&Lt; Synthesis of Compound (1-1-101) >

Benzo [c] fluorene-9-amine (1.8 g), 3,5-dimethyl-9H-1,2,4- (0.7 g), Pd (dba) ₂ (0.06 g), a 1 M toluene solution of tri-t-butylphosphine (0.3 ml), sodium t-butoxide (0.5 g) -Trimethylbenzene (15 ml) was stirred in a nitrogen atmosphere at reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane = 2/8 (volume ratio)). The reaction mixture was further purified by an activated carbon column chromatography (eluent: toluene / heptane = 1/1 (volume ratio)) to obtain a compound represented by the formula (1-1-101), 5- (3,6-dimethyl- -7-dimethyl-N- (naphthalen-1-yl) -N-phenyl-7H-benzo [c] fluoren-9-amine (1.4 g).

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

Synthesis Example 12 Synthesis of Compound (1-1-113)

&Lt; EMI ID =

&Lt; Synthesis of Compound (1-1-113) >

Dimethyl-7H-benzo [c] fluorene (0.78 g), 5-bromo-N, 9-amine (2.00 g), Pd (dba ) 2 (0.06 g), 1 of the tree -t- butylphosphine M toluene solution (0.3 ㎖), sodium -t- butoxide (0.50 g) and 1,2 , And 4-trimethylbenzene (15 ml) were stirred in a nitrogen atmosphere at reflux temperature for 6 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the resulting solid was washed with methanol and then purified by silica gel column chromatography (eluent: toluene / heptane). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product. The solvent was distilled off under reduced pressure and the resulting solid was reprecipitated with a toluene / heptane mixed solvent to obtain a compound represented by the formula (1-1-113), N, N-bis (4- (t- Dimethyl-9H-carbazol-9-yl) -7,7-dimethyl-7H-benzo [c] fluorene-9-amine (1.7 g).

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 13] Synthesis of compound (1-1-1)

(94)

<Synthesis of methyl 5-chloro-2- (4-fluoronaphthalen-1-yl) benzoate>

Under nitrogen atmosphere, 4-fluoro-naphthalene-1-boronic acid (92.0 g), methyl 2-bromo-5-chlorobenzoate (120.0 g), Pd (PPh 3) 4 (15.0 g), potassium phosphate (204.0 g), toluene (800 ml), ethanol (200 ml) and water (200 ml) were stirred at reflux temperature for 4 hours. The reaction solution was cooled to room temperature and water was added thereto to separate the layers. The mixture was purified by silica gel column chromatography (eluent: toluene) to obtain methyl 5-chloro-2- (4-fluoronaphthalen- (150.0 g) was obtained.

Synthesis of 2- (5-chloro-2- (4-fluoronaphthalen-1-yl) phenyl) propan-

A cyclopentyl methyl ether (800 ml) solution in which methyl 5-chloro-2- (4-fluoronaphthalen-1-yl) benzoate (150.0 g) was dissolved in a nitrogen atmosphere was cooled in an ice bath, and methyl magnesium Chloride THF solution (3.0 M, 320 ml) was added dropwise. After completion of dropwise addition, the water bath was removed, and the mixture was stirred at room temperature for 2 hours and a half, and then stirred at 60 ° C for further 1 hour. Thereafter, the reaction mixture was cooled in an ice bath, and an aqueous solution of ammonium chloride was added to terminate the reaction, and about half of the THF was distilled off under reduced pressure. Ethyl acetate was added to this solution and the solution was separated and then purified by silica gel column chromatography (developing solution: toluene) to obtain 2- (5-chloro-2- (4- fluoronaphthalen- -2-ol (100.0 g).

Synthesis of <9-chloro-5-fluoro-7,7-dimethyl-7H-benzo [c]

The flask containing 2- (5-chloro-2- (4-fluoronaphthalen-1-yl) phenyl) propan-2-ol (100.0 g) and chloroform (2000 ml) was cooled in an ice bath under a nitrogen atmosphere, A boron trifluoride diethyl ether complex (54.0 g) was added dropwise thereto. After completion of the dropwise addition, the ice bath was removed, and the mixture was stirred at room temperature for 1.5 hours, and then methanol was added to stop the reaction. Subsequently, sodium bicarbonate was added to neutralize and separated, and the residue was purified by silica gel column chromatography (eluent: heptane) to obtain 9-chloro-5-fluoro-7,7-dimethyl- Fluorene (64.0 g) was obtained.

Synthesis of 9- (9-chloro-7,7-dimethyl-7H-benzo [c] fluoren-5-yl) -9H-

(40.0 g), carbazole (27.0 g), cesium carbonate (65.9 g), and dimethyl sulfoxide ( DMSO, 650 ml) was stirred at 120 ° C for 5 hours. After completion of the reaction was confirmed, DMSO was distilled off under reduced pressure. The residue was purified by silica gel column chromatography (eluent: heptane / toluene = 1 (volume ratio)) to obtain 9- (9-chloro-7,7-dimethyl- c] fluoren-5-yl) -9H-carbazole (55.1 g).

&Lt; Synthesis of Compound (1-1-1) >

(18.0 g), diphenylamine (7.6 g), Pd (dba) ₂ (prepared as described in Example ₁ , 0.2 g), 4-dimethylaminophenyl ditertylphosphine (0.2 g), sodium-t-butoxide (4.7 g) and xylene (160 ml) was stirred at reflux temperature for 1 hour Lt; / RTI &gt; After the reaction solution was cooled to room temperature, water and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane = 1/3 (volume ratio)). Subsequently, the product was purified by an activated carbon column chromatography (developing solution: toluene) and then recrystallized from toluene to obtain the compound represented by the formula (1-1-1), 5- (9H-carbazol-9-yl) Dimethyl-N, N-diphenyl-7H-benzo [c] fluorene-9-amine (17.0 g) was obtained.

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 14] Synthesis of compound (1-1-10)

&Lt; EMI ID =

&Lt; Synthesis of Compound (1-1-10) >

N-phenylnaphthalen-l-amine (9.8 g), Pd (9 g), and the like were added to a solution of 9- (9-chloro-7,7- _{(dba) 2 (0.2 g)} , 4- dimethylaminophenyl di t- butylphosphine (0.2 g), sodium -t- butoxide (4.7 g) and xylene (160 ㎖) is a nitrogen atmosphere into a flask and, And stirred at reflux temperature for 2 hours. After the reaction solution was cooled to room temperature, water and toluene were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane = 1/2 (volume ratio)). Subsequently, the product was purified by an activated carbon column chromatography (developing solution: toluene) and then recrystallized from toluene to obtain a compound represented by the formula (1-1-10), 5- (9H-carbazol-9-yl) Phenyl-7H-benzo [c] fluorene-9-amine (15.6 g) was obtained.

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 15] Synthesis of Compound (1-1-123)

&Lt; EMI ID =

Synthesis of 5-bromo-7,7-dimethyl-N-phenyl-N- (4- (trimethylsilyl) phenyl) -7H-benzo [c] fluorene-

Benzo [c] fluorene (5.0 g), N-phenyl-4- (trimethylsilyl) aniline (2.7 g), (PdCl ₂ (o-tolyl ₃ ) ₂ (0.3 g), sodium-t-butoxide (1.6 g) and 1,2,4-trimethylbenzene (50 ml) was stirred at 120 ° C for 2 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent of the organic layer was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (developing solution: toluene / heptane / triethylamine = 5/95/1 (volume ratio)) and then purified by activated carbon column chromatography (eluent: toluene / Heptane / triethylamine = 50/50/1) to give 5-bromo-7,7-dimethyl-N-phenyl-N- (4- (trimethylsilyl) 9-amine (2.8 g).

&Lt; Synthesis of Compound (1-1-123) >

Benzo [c] fluorene-9-amine (1.0 g), 3,6-diphenyl-2,6-dimethyl- -9H- carbazole (0.7 g), Pd (dba ) 2 (0.03 g), tree -t- butylphosphine 1 M toluene solution (0.2 ㎖), sodium -t- butoxide (0.26 g) and the pin 1, The flask containing 2,4-trimethylbenzene (10 ml) was stirred under a nitrogen atmosphere at a reflux temperature for 10 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane / triethylamine mixed solvent). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product. After purification by an activated carbon column chromatography (eluent: toluene / heptane / triethylamine = 50/50/1 (volume ratio)), the solvent was distilled off under reduced pressure, and methanol was added to re- Phenyl) -N- (4- (trimethylsilyl) phenyl) - &lt; / RTI &gt; 7H-benzo [c] fluorene-9-amine (0.7 g) was obtained.

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 16] Synthesis of the compound (1-1-61)

[Formula 97]

&Lt; Synthesis of Compound (1-1-61) >

Compound (1-1-123), 5- (3,6-diphenyl-9H-carbazol-9-yl) -7,7-dimethyl- 1-p-toluenesulfonic acid was added to a toluene (5 ml) solution of 4 - ((trimethylsilyl) phenyl) -7H-benzo [c] fluorene-9-amine (0.4 g) and the mixture was stirred at 60 ° C for 1 minute. The reaction solution was cooled to room temperature, neutralized with triethylamine, and water was added to separate the layers. After the solvent of the organic layer was distilled off under reduced pressure, heptane was added to re-precipitate to obtain a compound represented by the formula (1-1-61), 5- (3,6-diphenyl-9H-carbazol- , 7-dimethyl-N, N-diphenyl-7H-benzo [c] fluorene-9-amine (0.3 g).

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 17] Synthesis of the compound (1-1-76)

(98)

Synthesis of 5-bromo-7,7-dimethyl-N, N-di-p-tolyl-7H-benzo [c] fluorene-

Benzo [c] fluorene (5.0 g), di-p-tolylamine (2.2 g), (PdCl ₂ (o-tolyl ₃ ) ₂ ) (0.3 g), sodium-t-butoxide (1.6 g) and 1,2,4-trimethylbenzene (50 ml) was stirred at 100 ° C for 2 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent of the organic layer was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane = 1/9 (volume ratio)) and then purified by activated carbon column chromatography (eluent: toluene / heptane = &Lt; / RTI &gt; The solvent was distilled off under reduced pressure and the residue was washed with heptane to obtain 2.7 g of 5-bromo-7,7-dimethyl-N, N-di-p-tolyl-7H-benzo [c] fluoren- .

&Lt; Synthesis of Compound (1-1-76) >

Benzo [c] fluorene-9-amine (1.0 g), 3,6-diphenyl-9H-carbazole 0.7 g), Pd (dba) ₂ (0.03 g), a 1 M toluene solution of tri-t-butylphosphine (0.2 ml), sodium t-butoxide (0.28 g) and 1,2,4- (10 ml) were stirred in a nitrogen atmosphere at reflux temperature for 8 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane mixed solvent). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product. The product was purified again by an activated carbon column chromatography (eluent: toluene / heptane = 1/1 (volume ratio)), dissolved in ethyl acetate and re-precipitated by adding ethanol to obtain the compound represented by formula (1-1-76) 7-dimethyl-N, N-ditolyl-7H-benzo [c] fluorene-9-amine (0.8 g) &Lt; / RTI &gt;

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 18] Synthesis of Compound (1-1-103)

[Formula 99]

&Lt; Synthesis of Compound (1-1-103) >

Benzo [c] fluorene-9-amine (1.0 g), 3,6-dimethyl-9H-carbazole (0.5 g), Pd (dba) ₂ (0.03 g), a 1 M toluene solution of tri-t-butylphosphine (0.2 ml), sodium t-butoxide (0.28 g) and 1,2,4-trimethylbenzene 10 ml) was stirred in a nitrogen atmosphere at a reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane mixed solvent). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product. Subsequently, the solution was washed with ethanol and then re-precipitated with a toluene / heptane mixed solvent to obtain a compound represented by the formula (1-1-103), 5- (3,6-dimethyl-9H-carbazol- , 7-dimethyl-N, N-ditolyl-7H-benzo [c] fluorene-9-amine (0.9 g).

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

[Synthesis Example 19] Synthesis of Compound (1-1-154)

(100)

&Lt; Synthesis of Compound (1-1-154) >

Benzo [c] fluorene-9-amine (2.0 g), 3-methyl-6- (4- (1.0 g), Pd (dba) ₂ (0.06 g), a 1 M toluene solution of tri-t-butylphosphine (0.3 ml), sodium-t-butoxide , And 2,4-trimethylbenzene (15 ml) were stirred in a nitrogen atmosphere at reflux temperature for 4 hours. After the reaction solution was cooled to room temperature, water and ethyl acetate were added to separate the layers. The solvent was distilled off under reduced pressure, and the residue was purified by silica gel column chromatography (eluent: toluene / heptane). At this time, the proportion of toluene in the developing solution was gradually increased to elute the target product. The solvent was distilled off under reduced pressure and the obtained solid was washed with heptane to obtain a compound represented by the formula (1-1-154), N, N-bis (4- (t-butyl) phenyl) -7,7- (3-methyl-6-phenyl-9H-carbazol-9-yl) -7H-benzo [c] fluorene-9-amine (1.6 g).

The structure of the benzofluorene compound obtained by NMR measurement was confirmed.

Other benzofluorene compounds can be synthesized by the method according to the above Synthesis Example by appropriately selecting the starting material compound.

&Lt; Characteristics when used in electroluminescent device >

Hereinafter, to describe the present invention in more detail, examples of the organic EL device using the compound of the present invention are shown, but the present invention is not limited thereto.

The electroluminescent elements related to Examples 1 to 4 and Comparative Examples 1 and 2 were manufactured and checked for luminescence and chromaticity respectively and then the luminance was attenuated to 90% of the initial value when driven at a constant current of 30 mA / (Hr) was measured. Examples and Comparative Examples will be described in detail below.

Table 1 shows the material composition of each layer in the devices related to the manufactured Examples 1 to 4 and Comparative Examples 1 and 2. In addition, the cathodes were composed of 8-quinolinolithium (Liq) / magnesium and silver complexes of silver in all.

In Table 1, &quot; HI &quot; represents N ⁴ , N ^{4 '} -diphenyl-N ⁴ , N ^4' -bis (9-phenyl-9H-carbazol- ] -4,4'-diamine, &quot; NPD &quot; refers to N ⁴ , N ^{4 '} -di (naphthalene-1-yl) -N ⁴ , N ^4' -diphenyl- [ Diamine, the compound (A) is 9,10-di (naphthalen-1-yl) anthracene, the compound (B) is 4,4 ' -5,9- fluorene-diyl) bis ((phenyl) amino)), di-benzonitrile, compound (C) is 7,7-dimethyl -N ^5, N ^5, N ^{9, 9} N - tetraphenyl -7H- benzo [ c] fluorene-5,9-diamine, and compound (D) is 5,5 '- (2-phenylanthracene-9,10-diyl) di-2,2'-bipyridine. Liq &quot; used in the negative electrode shows the chemical structure below.

(101)

&Lt; Example 1 >

&Lt; Device using Compound (1-1-24) as a light emitting layer >

A glass substrate (manufactured by Optoscience Co., Ltd.) having a size of 26 mm x 28 mm x 0.7 mm in which ITO film having a thickness of 180 nm was polished to 150 nm by sputtering was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and molybdenum-containing boats containing HI, molybdenum-containing boats containing NPD, molybdenum containing compound (A) Molybdenum boats with compounds (1-1-24), molybdenum boats with compound (D), molybdenum boats with Liq, molybdenum boats with magnesium And silver tungsten boats were installed.

Each layer was sequentially formed on the ITO film of the transparent support substrate. The vacuum tank was evacuated to 5 x 10 &lt; ~ ⁴ &gt; Pa. First, an evacuation boat containing HI was heated to form a hole injecting layer with a film thickness of 40 nm. Subsequently, the evacuation boat containing NPD was heated And a film thickness of 25 nm was deposited thereon to form a hole transporting layer. Next, an evaporation boat containing the compound (A) and an evaporation boat containing the compound (1-1-24) were simultaneously heated to deposit a film having a film thickness of 25 nm to form a light emitting layer. The deposition rate was controlled so that the weight ratio of compound (A) to compound (1-1-24) was approximately 95: 5. Next, an evaporation donor boat containing the compound (D) was heated and evaporated to a film thickness of 20 nm to form an electron transport layer. The deposition rate was 0.01 to 1 nm / sec.

Thereafter, the deposition boats containing Liq were heated to deposit at a deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Subsequently, a boat containing magnesium and a boat containing silver were simultaneously heated to deposit a film having a thickness of 100 nm to form a negative electrode. At this time, the deposition rate was controlled so that the ratio of the atomic ratio of magnesium and silver was 10: 1, and the cathode was formed so that the deposition rate was 0.1 nm to 10 nm. Thus, an organic electroluminescent device was obtained.

Blue light emission with CIE chromaticity (x, y) = (0.145, 0.110) was obtained when a DC voltage was applied with the ITO electrode as a positive electrode and the electrode comprising Liq / magnesium and silver as a negative electrode. Further, as a result of the constant current drive test at 30 mA / cm 2, the time for maintaining the luminance of 90% or more of the initial value was 110 hours.

&Lt; Example 2 >

&Lt; Device using Compound (1-1-54) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-1-24) was changed to the compound (1-1-54). Blue light emission with CIE chromaticity (x, y) = (0.146, 0.105) was obtained when the direct current voltage was applied with the ITO electrode as a positive electrode and the electrode comprising Liq / magnesium and silver as a negative electrode. As a result of the constant current drive test at 30 mA / cm &lt; 2 &gt;, the time for maintaining the luminance of 90% or more of the initial value was 40 hours.

&Lt; Example 3 >

&Lt; Device using Compound (1-1-84) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-1-24) was changed to the compound (1-1-84). When a DC voltage was applied to the ITO electrode as a positive electrode and an electrode composed of Liq / Mg and silver as a negative electrode, CIE chromaticity (x, y) = (0.147, 0.112) blue luminescence was obtained. As a result of conducting a constant current drive test at 30 mA / cm 2, it was found that the time for maintaining the luminance of 90% or more of the initial value was 80 hours.

<Example 4>

&Lt; Device using Compound (1-2-121) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-1-24) was changed to the compound (1-2-121). Blue light emission with CIE chromaticity (x, y) = (0.143, 0.102) was obtained when the direct current voltage was applied with the ITO electrode as a positive electrode and the electrode consisting of Liq / magnesium and silver as a negative electrode. As a result of the constant current drive test at 30 mA / cm &lt; 2 &gt;, the time for maintaining the luminance of 90% or more of the initial value was 113 hours.

&Lt; Comparative Example 1 &

An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-1-24) was changed to the compound (B). Blue light emission of CIE chromaticity (x, y) = (0.145, 0.092) was obtained when a direct current voltage was applied with the ITO electrode as a positive electrode and the electrode comprising Liq / magnesium and silver as a negative electrode. As a result of conducting a constant current drive test at 30 mA / cm 2, it was 14 hours to maintain the luminance of 90% or more of the initial value.

&Lt; Comparative Example 2 &

An organic EL device was obtained in the same manner as in Example 1 except that the compound (1-1-24) was changed to the compound (C). Blue light emission with CIE chromaticity (x, y) = (0.149, 0.135) was obtained when the direct current voltage was applied with the ITO electrode as a positive electrode and the electrode comprising Liq / magnesium and silver as a negative electrode. As a result of conducting a constant current drive test at 30 mA / cm 2, the time for maintaining the luminance of 90% or more of the initial value was 55 hours.

Table 2 summarizes the above results.

Next, the electroluminescent elements related to Examples 5 to 13 and Comparative Examples 3 to 4 were manufactured and checked for luminescence and chromaticity, respectively. Next, when driven at a constant current of 30 mA / cm 2, (%) &Lt; / RTI &gt;

Table 3 shows the material composition of each layer in the devices related to the manufactured Examples 5 to 13 and Comparative Examples 3 to 4.

In Table 3, HT is a mixture of N - ([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9- Phenyl) -9H-fluorene-2-amine, Compound (E) is 9-phenyl-10- (4-phenylnaphthalen- Anthracene-9,10-diyl) bis (4,1-phenylene)) dipyridine. The chemical structure is shown below.

&Lt; EMI ID =

&Lt; Example 5 >

&Lt; Device using Compound (1-1-70) as a light emitting layer >

A glass substrate (manufactured by Optoscience Co., Ltd.) having a size of 26 mm x 28 mm x 0.7 mm in which ITO film having a thickness of 180 nm was polished to 150 nm by sputtering was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and molybdenum-containing boats containing HI, molybdenum-containing boats containing HT, molybdenum containing compound (E) Molybdenum boats with compounds (1-1-70), molybdenum boats with compound (F), molybdenum boats with Liq, molybdenum boats with magnesium and silver The tungsten boat was installed.

Each layer was sequentially formed on the ITO film of the transparent support substrate. The vacuum tank was evacuated to 5 x 10 &lt; ^-4 &gt; Pa. First, an evacuation boat containing HI was heated to deposit a film having a film thickness of 40 nm to form a hole injection layer. And a film thickness of 30 nm was deposited thereon to form a hole transport layer. Next, the evaporation boats containing the compound (E) and the evaporation boats containing the compound (1-1-70) were simultaneously heated to form a light emitting layer with a film thickness of 35 nm. The deposition rate was controlled so that the weight ratio of the compound (E) and the compound (1-1-70) was approximately 95: 5. Next, an evaporation boat containing the compound (F) was heated and evaporated to a film thickness of 20 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / sec.

Thereafter, the deposition boats containing Liq were heated to deposit at a deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Subsequently, a boat containing magnesium and a boat containing silver were simultaneously heated to deposit a film having a thickness of 100 nm to form a negative electrode. At this time, the deposition rate was controlled so that the atomic ratio between magnesium and silver was 10 to 1, and a cathode was formed so as to have a deposition rate of 0.1 to 10 nm / sec to obtain an organic electroluminescent device.

Blue light emission with CIE chromaticity (x, y) = (0.148, 0.067) was obtained when a DC voltage was applied with the ITO electrode as a positive electrode and the electrode consisting of Liq / magnesium and silver as a negative electrode. As a result of conducting a constant current drive test at 30 mA / cm 2, the time for maintaining the luminance of 90% or more of the initial value was 53 hours.

&Lt; Example 6 >

&Lt; Device using Compound (1-1-84) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was changed to the compound (1-1-84). As a result of the same test, blue light emission of CIE chromaticity (x, y) = (0.144, 0.090) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 63 hours.

&Lt; Example 7 >

&Lt; Device using Compound (1-1-113) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was changed to the compound (1-1-113). As a result of the same test, blue light emission of CIE chromaticity (x, y) = (0.147, 0.079) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 50 hours.

&Lt; Example 8 >

&Lt; Device using Compound (1-2-85) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was changed to the compound (1-2-85). As a result of the same test, blue light emission of CIE chromaticity (x, y) = (0.147, 0.119) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 69 hours.

&Lt; Example 9 >

&Lt; Device using Compound (1-1-101) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was changed to the compound (1-1-101). As a result of the same test, blue light emission of CIE chromaticity (x, y) = (0.151, 0.061) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 19 hours.

&Lt; Example 10 >

&Lt; Device using Compound (1-1-1) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was changed to the compound (1-1-1). As a result of the same test, blue light emission of CIE chromaticity (x, y) = (0.151, 0.060) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 18 hours.

&Lt; Example 11 >

&Lt; Device using Compound (1-1-140) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was changed to the compound (1-1-140). As a result of the same test, blue light emission of CIE chromaticity (x, y) = (0.150, 0.065) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 16 hours.

&Lt; Example 12 >

&Lt; Device using Compound (1-1-10) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was changed to the compound (1-1-10). As a result of the same test, blue light emission of CIE chromaticity (x, y) = (0.150, 0.060) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 17 hours.

&Lt; Example 13 >

&Lt; Device using Compound (1-2-174) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was changed to the compound (1-2-174). As a result of the same test, blue light emission of CIE chromaticity (x, y) = (0.141, 0.115) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 60 hours.

&Lt; Comparative Example 3 &

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was changed to the compound (B). As a result of the same test, blue light emission of CIE chromaticity (x, y) = (0.146, 0.084) was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 9 hours.

&Lt; Comparative Example 4 &

An organic EL device was obtained in the same manner as in Example 5 except that the compound (1-1-70) was changed to the compound (C). As a result of the same test, CIE chromaticity (x, y) = (0.144, 0.126) blue luminescence was obtained, and the time for maintaining the luminance of 90% or more of the initial value was 40 hours.

Table 4 summarizes the above results.

Next, the electroluminescent elements related to Examples 14 to 18 and Comparative Example 5 were manufactured, and the luminescence and the chromaticity thereof were confirmed. Next, when the luminance was driven to a constant current of 30 mA / cm 2, the luminance reached 90% of the initial value The time to decay (hr) was measured.

Table 5 shows the material composition of each layer in the devices related to Examples 14 to 18 and Comparative Example 5 manufactured.

In Table 5, the compound (G) is 9- (4- (naphthalen-1-yl) phenyl) -10-phenylanthracene. The chemical structure is shown below.

&Lt; EMI ID =

&Lt; Example 14 >

&Lt; Device using Compound (1-1-123) as a light emitting layer >

A glass substrate (manufactured by Optoscience Co., Ltd.) having a size of 26 mm x 28 mm x 0.7 mm in which ITO film having a thickness of 180 nm was polished to 150 nm by sputtering was used as a transparent support substrate. The transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Showa Vacuum Co., Ltd.), and molybdenum-containing boats containing HI, molybdenum-containing boats containing HT, molybdenum containing compound (G) Molybdenum boats with compounds (1-1-123), molybdenum boats with compound (F), molybdenum boats with Liq, molybdenum boats with magnesium, and silver The tungsten boat was installed.

Each layer was sequentially formed on the ITO film of the transparent support substrate. The vacuum tank was evacuated to 5 x 10 &lt; ^-4 &gt; Pa. First, an evacuation boat containing HI was heated to deposit a film having a film thickness of 40 nm to form a hole injection layer. And a film thickness of 30 nm was deposited thereon to form a hole transport layer. Next, the evaporation boats containing the compound (G) and the evaporation boats containing the compounds (1-1-123) were simultaneously heated to deposit a film having a film thickness of 35 nm to form a light emitting layer. The deposition rate was controlled so that the weight ratio of compound (G) and compound (1-1-123) was approximately 95: 5. Next, an evaporation boat containing the compound (F) was heated and evaporated to a film thickness of 20 nm to form an electron transport layer. The deposition rate of each layer was 0.01 to 1 nm / sec.

Thereafter, the deposition boats containing Liq were heated to deposit at a deposition rate of 0.01 to 0.1 nm / sec so as to have a film thickness of 1 nm. Subsequently, a boat containing magnesium and a boat containing silver were simultaneously heated to deposit a film having a thickness of 100 nm to form a negative electrode. At this time, the deposition rate was controlled so that the atomic ratio between magnesium and silver was 10 to 1, and a cathode was formed so as to have a deposition rate of 0.1 to 10 nm / sec to obtain an organic electroluminescent device.

Blue light emission with CIE chromaticity (x, y) = (0.147, 0.076) was obtained when a direct current voltage was applied with the ITO electrode as a positive electrode and the electrode consisting of Liq / magnesium and silver as a negative electrode. As a result of conducting a constant current drive test at 30 mA / cm &lt; 2 &gt;, the time for maintaining the luminance of 90% or more of the initial value was 66 hours.

&Lt; Example 15 >

&Lt; Device using Compound (1-1-61) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 14 except that the compound (1-1-123) was changed to the compound (1-1-61). Blue light emission with CIE chromaticity (x, y) = (0.146, 0.076) was obtained when a direct current voltage was applied with the ITO electrode as a positive electrode and the electrode comprising Liq / magnesium and silver as a negative electrode. As a result of conducting a constant current drive test at 30 mA / cm 2, the time for maintaining the luminance of 90% or more of the initial value was 53 hours.

&Lt; Example 16 >

&Lt; Device using Compound (1-1-76) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 14 except that the compound (1-1-123) was changed to the compound (1-1-76). Blue light emission of CIE chromaticity (x, y) = (0.144, 0.100) was obtained when a direct current voltage was applied with the ITO electrode as a positive electrode and the electrode comprising Liq / magnesium and silver as a negative electrode. As a result of the constant current drive test at 30 mA / cm &lt; 2 &gt;, the time for maintaining the luminance of 90% or more of the initial value was 60 hours.

&Lt; Example 17 >

&Lt; Device using Compound (1-1-103) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 14 except that the compound (1-1-123) was changed to the compound (1-1-103). Blue light emission with CIE chromaticity (x, y) = (0.144, 0.095) was obtained when a DC voltage was applied with the ITO electrode as a positive electrode and the electrode comprising Liq / magnesium and silver as a negative electrode. As a result of the constant current drive test at 30 mA / cm &lt; 2 &gt;, the time for maintaining the luminance of 90% or more of the initial value was 67 hours.

&Lt; Example 18 >

&Lt; Device using Compound (1-1-154) as a light emitting layer >

An organic EL device was obtained in the same manner as in Example 14 except that the compound (1-1-123) was changed to the compound (1-1-154). Blue light emission of CIE chromaticity (x, y) = (0.144, 0.094) was obtained when a DC voltage was applied with the ITO electrode as a positive electrode and the electrode comprising Liq / magnesium and silver as a negative electrode. As a result of conducting a constant current drive test at 30 mA / cm &lt; 2 &gt;, the time for maintaining the luminance of 90% or more of the initial value was 93 hours.

&Lt; Comparative Example 5 &

An organic EL device was obtained in the same manner as in Example 14 except that the compound (1-1-123) was changed to the compound (C). Blue light emission of CIE chromaticity (x, y) = (0.148, 0.132) was obtained when a DC voltage was applied with the ITO electrode as a positive electrode and the electrode comprising Liq / magnesium and silver as a negative electrode. As a result of conducting a constant current drive test at 30 mA / cm &lt; 2 &gt;, the time for maintaining the luminance of 90% or more of the initial value was 31 hours.

Table 6 summarizes the above results.

As can be seen from the performance evaluation of the electroluminescent element related to the above-described embodiment and comparative example, the electroluminescent element related to the embodiment exhibited excellent color purity at the same level as or higher than that of the electroluminescent element related to the comparative example , Lifetime characteristics are improved.

Industrial availability

According to a preferred embodiment of the present invention, it is possible to provide an organic electroluminescent device which exhibits excellent color purity and excellent device lifetime, a display device having the organic electroluminescent device, and a lighting device including the same.

100 organic electroluminescent device
101 substrate
102 anode
103 Hole injection layer
104 hole transport layer
105 luminescent layer
106 electron transport layer
107 electron injection layer
108 cathode

Claims (19)

A benzofluorene compound represented by the following formula (1).
[Chemical Formula 1]

Wherein each R is independently selected from the group consisting of alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 24 carbon atoms which may be substituted with alkyl having 1 to 4 carbon atoms, or alkyl having 1 to 4 carbon atoms A heteroaryl group having 5 to 24 carbon atoms which may be substituted,
Wherein either one of A and B is 9-carbazolyl and the other is diarylamino,
Aryl of 9-carbazolyl and diarylamino are each independently selected from the group consisting of alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 10 carbon atoms and silyl substituted with alkyl having 1 to 4 carbon atoms , And when two or more groups are substituted adjacent to each other, they may be bonded to each other to form an aliphatic ring or a benzene ring,
At least one hydrogen in the compound represented by the formula (1) may be substituted with deuterium. The method according to claim 1,
A benzofluorene compound represented by the following formula (1-1).
(2)

Wherein each R is independently an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms which may be substituted with an alkyl having 1 to 4 carbon atoms,
R ¹ is each independently silyl substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 10 carbon atoms, or alkyl having 1 to 4 carbon atoms,
m is even, and each independently represent an integer of 0 to 4, when substituted by two or more adjacent R ¹ is according to one benzene ring, combine to form a cyclohexane ring or benzene ring,
n are each independently an integer from 0 to 5, substituted by two or more adjacent R ¹ is according to one benzene ring, all of which are coupled to may form a cyclohexane ring or a benzene ring. The method according to claim 1,
A benzofluorene compound represented by the following formula (1-2).
(3)

Wherein each R is independently an alkyl having 1 to 6 carbon atoms, a cycloalkyl having 3 to 6 carbon atoms, or an aryl having 6 to 12 carbon atoms which may be substituted with an alkyl having 1 to 4 carbon atoms,
R ¹ is each independently silyl substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 10 carbon atoms, or alkyl having 1 to 4 carbon atoms,
m is even, and each independently represent an integer of 0 to 4, when substituted by two or more adjacent R ¹ is according to one benzene ring, combine to form a cyclohexane ring or benzene ring,
n are each independently an integer from 0 to 5, substituted by two or more adjacent R ¹ is according to one benzene ring, all of which are coupled to may form a cyclohexane ring or a benzene ring. The method according to claim 2 or 3,
Each R is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t-butyl, cyclohexyl, phenyl or naphthyl,
R ¹ is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t- butyl, cyclohexyl, phenyl, naphthyl, trimethylsilyl, triethylsilyl or dimethylmono- And,
m is independently an integer of 0 to 2,
n are each independently an integer of 0 to 2, when substituted by two or more adjacent R ¹ is in the one benzene ring, all of which are coupled to benzo fluorene compound which may form a benzene ring. The method according to claim 2 or 3,
Each R is independently methyl, ethyl, isopropyl, s-butyl, t-butyl, or phenyl,
R ¹ is each independently methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl or trimethylsilyl,
m and n are each independently an integer of 0 to 2; The method according to claim 1,
A benzofluorene compound represented by the following formula (1-1-24), formula (1-1-54), or formula (1-1-84).
[Chemical Formula 4]

The method according to claim 1,
(1-1-1), (1-1-1), (1-1-1), (1-1-1), 2-24), a compound represented by the formula (1-2-84) or a compound represented by the formula (1-2-85).
[Chemical Formula 5]

The method according to claim 1,
A benzofluorene compound represented by the following formula (1-1-140), formula (1-2-121), or formula (1-2-174).
[Chemical Formula 6]

The method according to claim 1,
Benzofluorene represented by the following formulas (1-1-61), (1-1-76), (1-1-103), (1-1-123) compound.
(7)

A benzofluorene compound represented by the following formula (1'-1).
[Chemical Formula 8]

Wherein,
R ¹ is each independently silyl substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 10 carbon atoms, or alkyl having 1 to 4 carbon atoms,
m is even, and each independently represent an integer of 0 to 4, when substituted by two or more adjacent R ¹ is according to one benzene ring, combine to form a cyclohexane ring or benzene ring,
n are each independently an integer from 0 to 5, substituted by two or more adjacent R ¹ is according to one benzene ring, all of which are coupled to may form a cyclohexane ring or a benzene ring. A benzofluorene compound represented by the following formula (1'-2).
[Chemical Formula 9]

Wherein,
R ¹ is each independently silyl substituted with alkyl having 1 to 6 carbon atoms, cycloalkyl having 3 to 6 carbon atoms, aryl having 6 to 10 carbon atoms, or alkyl having 1 to 4 carbon atoms,
m is even, and each independently represent an integer of 0 to 4, when substituted by two or more adjacent R ¹ is according to one benzene ring, combine to form a cyclohexane ring or benzene ring,
n are each independently an integer from 0 to 5, substituted by two or more adjacent R ¹ is according to one benzene ring, all of which are coupled to may form a cyclohexane ring or a benzene ring. The method according to claim 10 or 11,
R ¹ is independently selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, s-butyl, t- butyl, cyclohexyl, phenyl, naphthyl, trimethylsilyl, triethylsilyl or dimethylmono- And,
m is independently an integer of 0 to 2,
n are each independently an integer of 0 to 2, when substituted by two or more adjacent R ¹ is in the one benzene ring, all of which are coupled to benzo fluorene compound which may form a benzene ring. The method according to claim 10 or 11,
R ¹ is each independently methyl, ethyl, isopropyl, t-butyl, cyclohexyl, phenyl or trimethylsilyl,
m and n are each independently an integer of 0 to 2; A material for a light emitting layer of a light emitting device, which comprises the benzofluorene compound according to any one of claims 1 to 13. A pair of electrodes made of an anode and a cathode, and an organic electroluminescent element disposed between the pair of electrodes and having a light emitting layer containing a material for a light emitting layer according to claim 14. 16. The method of claim 15,
Further, it is preferable that at least one of the electron transporting layer and the electron injecting layer disposed between the cathode and the light emitting layer has an electron transporting layer and / or an electron injecting layer, and at least one of the electron transporting layer and the electron injecting layer is a quinolinol metal complex, a pyridine derivative, a phenanthroline derivative, And at least one selected from the group consisting of benzoimidazole derivatives. 17. The method of claim 16,
Wherein the electron transporting layer and / or the electron injecting layer further comprises an alkali metal, an alkaline earth metal, a rare earth metal, an oxide of an alkali metal, a halide of an alkali metal, an oxide of an alkaline earth metal, a halide of an alkaline earth metal, An organic complex of an alkaline earth metal, and an organic complex of a rare earth metal. 2. The organic electroluminescent device according to claim 1, wherein the organic metal complex is at least one selected from the group consisting of a halide of a metal, an organic complex of an alkali metal, 18. A display device comprising the organic electroluminescent device according to any one of claims 15 to 17. An illumination device comprising the organic electroluminescent device according to any one of claims 15 to 17.

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