JP2003026616A - Compound for organic el(electroluminescent) device and organic el device using it - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a compound for an organic EL device which is highly durable to keep luminescence for a long period, has high color purity and a good luminescent performance, and to provide such organic EL devices. SOLUTION: This compound for the organic EL devices has a fundamental skeleton shown by formula (1): Xn-Y [X represents a compound of formula (2); Y is a single bond or a linkage group consisting of a (substituted) aryl or a heterocyclic group; n is an integer of 2 or 3; wherein when Y is bound with the positional combination of R7 and R7 , R8 and R8 or R7 and R8 , Y includes neither single bond nor compound of formula (11) or (12); and R1 to R8 and (a) to d are each H, an alkyl, or (substituted) aryl, allyl, heterocyclic, amino or arylamino group].

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic EL (electroluminescence) device, and more particularly to a compound used in a device for emitting light by applying an electric field to a thin film made of an organic compound.

[0002]

2. Description of the Related Art An organic EL device has a structure in which a thin film containing a fluorescent organic compound is sandwiched between an electron injecting electrode and a hole injecting electrode, and electrons and holes are injected into the thin film to recombine. Generate excitons,
Emission of light when this exciton is deactivated (fluorescence / phosphorescence)
Is an element that emits light by utilizing.

The characteristic of the organic EL device is that it is capable of surface emission with a very high brightness of several hundreds to several tens of thousand cd / m ² at a voltage of about 10 V, and it can be selected from blue to red by selecting the type of fluorescent substance. It is capable of emitting light.

There is a doping method as a method for obtaining an arbitrary luminescent color of an organic EL device, and it has been reported that the luminescent color is changed from blue to green by doping a trace amount of tetracene in an anthracene crystal (Jpn. J. Appl. Phys., 10,527 (1
971)) In an organic thin film EL device having a laminated structure, a small amount of a fluorescent dye, which emits light emission different from that of the host substance in response to the light emission, is mixed as a dopant into a host substance having a light-emitting function to form a light-emitting layer. To change the emission color from orange to red (Japanese Patent Laid-Open No. Sho 63-63)
-264692).

Regarding long-wavelength emission from yellow to red, as a light emitting material or a dopant material, a laser dye that emits red light (EPO281381), a compound exhibiting exciplex light emission (JP-A-2-255788), and a perylene compound ( JP-A-3-791), coumarin compound (JP-A-3-792), dicyanomethylene compound (JP-A-3-162482), thioxanthene compound (JP-A-3-177486), conjugated system A mixture of a polymer and an electron transporting compound (JP-A-6-73374), a squarylium compound (JP-A-6-93257), an oxadiazole compound (JP-A-6-136359), an oxynate derivative (special Kaihei 6-145146), pyrene-based compounds (JP-A-6-24024) JP) there is.

Further, the fact that the benzofluoranlane derivative has a very high fluorescence quantum yield is reported in J. Am. Che
m. Soc 1996, 118, 2374-2379, and in JP-A-10-330295 and JP-A-11-233261, dibenzo [f, f '] derived from benzofluoranthene in various host materials. Diindeno [1,2,3-cd: 1 ',
Disclosed is an organic EL device in which a light emitting layer is formed by doping a 2 ', 3'-lm] perylene derivative.

As another light emitting material, a condensed polycyclic aromatic compound (JP-A-5-32966 and JP-A-5-21433).
No. 4) is also disclosed. Further, as a dopant material, various condensed polycyclic aromatic compounds (Japanese Patent Laid-Open No. 5-2588)
No. 59) is proposed.

However, in these conventional fluorescent materials, there are very few examples in which a luminescent color close to pure blue is obtained, and a highly efficient pure blue fluorescent material has been desired in order to realize a high-quality full-color display. .

[0009]

It is an object of the present invention to obtain light emission with sufficient brightness, particularly light emission at long wavelengths, and to obtain excellent color purity, particularly color purity sufficient for use in a full color display, It is also intended to provide a compound for an organic EL device, which has excellent durability in which good light emitting performance is maintained for a long time, and an organic EL device.

[0010]

[Means for Solving the Problems] The above-mentioned objects are constituted as follows.
Achieved by (1) Organic having a basic skeleton represented by the following formula (1)
Compound for EL device. Xn-Y (1) [In the formula (1), X represents a compound represented by the following formula (2).
However, they may be the same or different. Y is also a single bond
Or a substituted or unsubstituted aryl group or heterocyclic group
And represents an integer of 2 or 3.
However, Y is R ₇ And R₇ , R₈ And R₈ Or R₇ And R₈ 
When combining with the combination of positions, a single bond and
The compounds represented by the formulas (11) and (12) are not included. ]

[0011]

[Chemical 19]

[In the formula (2), R _{1 to} R ₈ and a to d are hydrogen, an alkyl group, an aryl group which may have a substituent, an allyl group which may have a substituent, and a substituent. It represents either a heterocyclic group which may have a group, an amino group, or an arylamino group which may have a substituent. (2) The compound for organic EL device of the above (1), wherein Y is one kind selected from the following compounds.

[0013]

[Chemical 20]

(3) The compound for organic EL device according to the above (1) or (2), wherein n is 2. (4) The above (1) to be used as a dopant
The compound for organic EL device according to any one of (3). (5) The compound for organic EL device according to any one of (1) to (4), which is an electron transport material. (6) From (1) to (1), which is a hole injection or transport material
The compound for organic EL device according to any one of (4). (7) The compound for organic EL device according to any one of (1) to (6), which has a basic skeleton represented by the following formula (3a).

[0015]

[Chemical 21]

[In the formula (3a), R₁ ~ R₈ And a₁ ~
d₁ , R₁₁ ~ R₁₈ And a₂ ~ D ₂ Is hydrogen, alk
Group, an aryl group which may have a substituent, and a substituent
Allyl group which may have or may have substituent group
Heterocyclic group, amino group, optionally substituted aryl
Represents any of the luamino groups. Y is a substituted or unsubstituted
Phenylene, biphenylene, naphthacene, perylene, pi
Ren, phenanthrene, thiophene, pyridine, pyrazi
Amine, triazine, amine, triarylamine, pillow
Derivative, thiazole, thiadiazole, phenanthro
Made from either phosphorus, quinoline, or quinoxaline
Represents a linking group. ] (8) Having a basic skeleton represented by the following formula (3b)
The compound for organic EL devices according to any one of (1) to (6).

[0017]

[Chemical formula 22]

[In the formula (3b), R₁ ~ R₈ And a₁ ~
d₁ , R₁₁ ~ R₁₈ And a₂ ~ D ₂ Is hydrogen, alk
Group, an aryl group which may have a substituent, and a substituent
Allyl group which may have or may have substituent group
Heterocyclic group, amino group, optionally substituted aryl
Represents any of the luamino groups. Y is a single bond, a substitution or
Linking group consisting of unsubstituted aryl group or heterocyclic group
Represents ] (9) Having a basic skeleton represented by the following formula (3c)
The compound for organic EL devices according to any one of (1) to (6).

[0019]

[Chemical formula 23]

[In the formula (3c), R₁ ~ R₈ And a₁ ~
d₁ , R₁₁ ~ R₁₈ And a₂ ~ D ₂ Is hydrogen, alk
Group, an aryl group which may have a substituent, and a substituent
Allyl group which may have or may have substituent group
Heterocyclic group, amino group, optionally substituted aryl
Represents any of the luamino groups. Y is a single bond, a substitution or
Linking group consisting of unsubstituted aryl group or heterocyclic group
Represents ] (10) Having a basic skeleton represented by the following formula (A)
The compound for organic EL devices according to any one of (1) to (6).

[0021]

[Chemical formula 24]

[In the formula (A), R _{1 to} R ₇ and R ₁₁ to
R ₁₇ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. ] (11) The compound for organic EL devices according to any one of the above (1) to (6), which has a basic skeleton represented by the following formula (B).

[0023]

[Chemical 25]

[In the formula (B), R _{1 to} R ₇ and R ₁₁ to
R ₁₇ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. (12) The compound for an organic EL device according to any one of the above (1) to (6), which has a basic skeleton represented by the following formula (E).

[0025]

[Chemical formula 26]

[In the formula (E), R _{1 to} R ₈ and R ₁₁ to
R ₁₈ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. ] (13) The compound for organic EL devices according to any one of the above (1) to (6), which has a basic skeleton represented by the following formula (H).

[0027]

[Chemical 27]

[In the formula (H), R _{1 to} R ₈ and R ₁₁ to
R ₁₈ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. (14) The compound for an organic EL device according to any one of (1) to (6), which has a basic skeleton represented by the following formula (X).

[0029]

[Chemical 28]

[In the formula (X), R _{1 to} R ₈ and R ₁₁ to
R ₁₈ represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. (15) The compound for an organic EL device according to any one of the above (1) to (6), which has a basic skeleton represented by the following formula (Z).

[0031]

[Chemical 29]

[In the formula (Z), R _{1 to} R ₇ and R ₁₁ to
R ₁₇ R represents hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. (16) The compound for an organic EL device according to any one of the above (1) to (6), which has a basic skeleton represented by the following formula (AAA ′).

[0033]

[Chemical 30]

[In the formula (AAA '), R _{1 to} R ₈ and R _{11 to} R ₁₈ are hydrogen, an alkyl group, an aryl group which may have a substituent or a substituent which may have a substituent. It represents any of a good allyl group, a heterocyclic group which may have a substituent, an amino group and an arylamino group which may have a substituent. (17) The compound for organic EL devices according to any one of the above (1) to (6), which has a basic skeleton represented by the following formula (BBB ′).

[0035]

[Chemical 31]

[In the formula (BBB '), R _{1 to} R ₈ and R _{11 to} R ₁₈ are each a hydrogen atom, an alkyl group, an aryl group which may have a substituent, or a substituent which may have a substituent. It represents any of a good allyl group, a heterocyclic group which may have a substituent, an amino group and an arylamino group which may have a substituent. (18) The compound for organic EL devices according to any one of the above (1) to (6), which has a basic skeleton represented by the following formula (CCC ′).

[0037]

[Chemical 32]

[In the formula (CCC '), R _{1 to} R ₈ and R _{11 to} R ₁₈ are each a hydrogen atom, an alkyl group, an aryl group which may have a substituent or a substituent which may have a substituent. It represents any of a good allyl group, a heterocyclic group which may have a substituent, an amino group and an arylamino group which may have a substituent. (19) The compound for organic EL devices according to any one of the above (1) to (6), which has a basic skeleton represented by the following formula (DDD ′).

[0039]

[Chemical 33]

[In the formula (DDD '), R _{1 to} R ₈ and R _{11 to} R _{18 each} have hydrogen, an alkyl group, an aryl group which may have a substituent, or a substituent which may have a substituent. It represents any of a good allyl group, a heterocyclic group which may have a substituent, an amino group and an arylamino group which may have a substituent. (20) The compound for organic EL devices according to any one of the above (1) to (6), which has a basic skeleton represented by the following formula (EEE ′).

[0041]

[Chemical 34]

[In the formula (EEE '), R _{1 to} R ₈ and R _{11 to} R _{18 each} have hydrogen, an alkyl group, an aryl group which may have a substituent or a substituent which may have a substituent. It represents any of a good allyl group, a heterocyclic group which may have a substituent, an amino group and an arylamino group which may have a substituent. (21) The compound for an organic EL device according to any one of (1) to (6), which has a basic skeleton represented by the following formula (RRR ′).

[0043]

[Chemical 35]

[In the formula (RRR '), R _{1 to} R ₈ and R _{11 to} R ₁₈ are hydrogen, an alkyl group, an aryl group which may have a substituent or a substituent which may have a substituent. It represents any of a good allyl group, a heterocyclic group which may have a substituent, an amino group and an arylamino group which may have a substituent. (22) The compound for an organic EL device according to any one of the above (1) to (6), which has a basic skeleton represented by the following formula (SSS ′).

[0045]

[Chemical 36]

[In the formula (SSS '), R _{1 to} R ₈ and R _{11 to} R _{18 each} have hydrogen, an alkyl group, an aryl group which may have a substituent or a substituent which may have a substituent. It represents any of a good allyl group, a heterocyclic group which may have a substituent, an amino group and an arylamino group which may have a substituent. (23) At least one organic layer involved in at least a light emitting function is provided between a pair of electrodes, and at least one of the organic layers is an organic layer according to any one of (1) to (22) above. Organic E containing one or more compounds for EL device
L element. (24) The organic EL device according to (23), which further contains one or more anthracene compounds in addition to the compound for organic EL device. (25) The organic EL device according to (24), which contains the anthracene derivative as a host material for a light emitting layer. (26) Organic E according to any one of (23) to (25), which contains the compound for organic EL device as a dopant.
L element. (27) The organic EL device according to any one of (23) to (26), wherein the light emitting layer contains the compound for organic EL. (28) The organic EL device according to any one of (23) to (25), wherein the electron transport layer contains the compound for organic EL. (29) The organic EL device according to any one of (23) to (28), wherein the hole injecting and transporting layer contains the compound for organic EL device. (30) The organic EL device according to any one of (23) to (29), which has two or more types of emission maximum wavelengths of two or more types of light emitting materials.

[0047]

BEST MODE FOR CARRYING OUT THE INVENTION The compound for organic EL device of the present invention
Has a basic skeleton represented by the following formula (1)
It X_n -Y ... (1) [In the formula (1), X represents a compound represented by the following formula (2).
However, they may be the same or different. Y is also a single bond
Or a substituted or unsubstituted aryl group or heterocyclic group
And represents an integer of 2 or 3.
However, Y is R ₇ And R₇ , R₈ And R₈ Or R₇ And R₈ 
When combining with the combination of positions, a single bond and
Compounds represented by formulas (11) and (12) are not included.
Yes. ]

[0048]

[Chemical 37]

[In the formula (2), R _{1 to} R ₈ and a to d
Is hydrogen, an alkyl group, an aryl group which may have a substituent, an allyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, or a substituent Represents any of the arylamino groups which may have. ]

The compound represented by the above formula (1) will be described in more detail. In formula (1), X represents a compound represented by the above formula (2), and each X may be the same or different. That is, X may be the same compound or different compounds as long as they are compounds represented by the above formula (2), but it is preferable that they are the same. n = 3
In this case, the three kinds of X may be different from each other.

In the formula (2), R _{1 to} R ₈ and a to
d is hydrogen, an alkyl group, an aryl group which may have a substituent, an allyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, a substituent Represents any of the arylamino groups which may have. Further, preferably, any one of a methyl group, an ethyl group, a propyl group, a phenyl group, a tolyl group, a biphenyl group, a naphthyl group, a thiophenyl group, a pyridyl group, a pyrrole group, a styryl group, a triphenylamino group and a phenylamino group. Of these, a methyl group, a phenyl group, a tolyl group, a biphenyl group, a naphthyl group, a triphenylamino group and a phenylamino group are particularly preferable.

R _{1 to} R ₈ and a to d may be the same or different. In addition, a condensed ring may be formed between adjacent R _{1 to} R ₈ and a to d.

In particular, the R ₇ and R ₈ sites are structurally highly reactive and therefore preferably have a substituent. R
By masking the ₇ and R ₈ sites with a substituent, the compound can be chemically stabilized and deterioration of the material during EL emission can be prevented. It is preferable that at least one of R ₇ and R ₈ has a substituent, and it is particularly preferable that both have a substituent.

Examples of the substituents of R ₇ and R ₈ include those exemplified above, but an alkyl group, an aryl group, an allyl group and a heterocyclic group are particularly preferable.

Further, the emission wavelength is sensitively influenced by the kind of the substituent introduced into R ₇ and R ₈ . Therefore, R
_The emission wavelength can also be controlled by selecting the substituents to be introduced into ₇ and R ₈ .

N representing the number of X is an integer of 2 or 3, and preferably n = 2. When n = 3, the sublimation property deteriorates, thermal decomposition during sublimation occurs, and the stability of the compound slightly decreases. On the other hand, when n = 1, crystallization tends to occur, blue-ultraviolet emission tends to occur, and EL emission becomes difficult.

In the formula (1), Y represents a single bond or a substituted or unsubstituted aryl group, or a linking group composed of a heterocyclic group. However, Y is R ₇ and R ₇ , R ₈ and R ₈ or R
When bonding at the combination of ₇ and R ₈ positions, a single bond and naphthalene and anthracene compounds at the bonding positions represented by the following formulas (11) and (12) are not included.

[0058]

[Chemical 38]

The connecting position between X's is not particularly limited, and any position of X may be connected at any carbon of the connecting group. That is, the above formula (2)
In the basic skeleton represented by, it may be any position of R _{1 to} R ₈ and a to d, but preferably R ₁ to R ₈
Any site selected from R ₈ , especially R ₁ ,
Any of R ₆ , R ₇ , and R ₈ .

However, when Y is bonded at the R ₇ and R ₈ positions, it is a single bond, that is, when Xs are directly bonded, and the naphthalene and anthracene bonding groups at the bonding sites are not included. When X's are directly linked at the positions of R ₇ and R ₈ , thermal stability during sublimation purification and E
The electrochemical stability during L emission becomes unstable, and R ₇ , R
_{It connects} at 2 places (target position) of ₈ .

Y is a substituted or unsubstituted phenylene, biphenylene, naphthacene, perylene, pyrene, phenanthrene, thiophene, pyridine, pyrazine, triazine, amine, triarylamine, pyrrole derivative, thiazole, thiadiazole, phenanthroline,
A linking group composed of either quinoline or quinoxaline is preferable, and a substituted or unsubstituted benzene, tetracene, perylene, pyrene, or heterocyclic group is particularly preferable. Further, one kind of linking group selected from the following compounds is preferable.

[0062]

[Chemical Formula 39]

X is preferably the following formulas (3a) and (3
The compounds represented by b) and (3c).

[0064]

[Chemical 40]

[0065]

[Chemical 41]

[0066]

[Chemical 42]

In formulas (3a) to (3c), R _{1 to} R
₈ and a _{1 to} d ₁ , R _{11 to} R ₁₈ and a _{2 to} d ₂
Is synonymous with R _{1 to} R ₈ and a to d in the formula (2). Among formulas (3a) to (3c), the one represented by formula (3a) is the most preferable, and the one represented by formula (3b) is preferable.

The absolute value of the ionization potential of the compound of the present invention is preferably smaller than 5.9 eV, particularly preferably 5.8 eV or less, more preferably 5.7 eV or less. When the absolute value of the ionization potential is smaller than 5.9 eV, good light emission can be obtained in combination with a compound having an absolute value of the ionization potential of about 5.9 eV, particularly in combination with the anthracene dimer. The lower limit is not particularly limited, but is usually 5.2 eV
It is a degree.

The compound of the present invention is
The half-wave oxidation potential of the platinum electrode is preferably 1.5 V or less, particularly 1.4 V or less, and further 1.3 V or less. When the oxidation potential is the above value or less, the stability is increased and the life of the device is extended. Further, the same effect as the above-mentioned ionization potential can be obtained. The lower limit is not particularly limited, but is usually about 0.4V.

Preferred examples of the compound of the present invention are shown below.

[0071]

[Chemical 43]

[0072]

[Chemical 44]

[0073]

[Chemical formula 45]

[0074]

[Chemical formula 46]

[0075]

[Chemical 47]

[0076]

[Chemical 48]

[0077]

[Chemical 49]

[0078]

[Chemical 50]

[0079]

[Chemical 51]

[0080]

[Chemical 52]

[0081]

[Chemical 53]

Among these, the following formula (A),
(B), (E), (H), (X), (Z), and (A
AA '), (BBB'), (CCC '), (DD
The compounds represented by D '), (EEE'), (RRR ') and (SSS') are preferred.

[0083]

[Chemical 54]

[0084]

[Chemical 55]

[0085]

[Chemical 56]

[0086]

[Chemical 57]

[0087]

[Chemical 58]

[0088]

[Chemical 59]

[0089]

[Chemical 60]

[0090]

[Chemical formula 61]

[0091]

[Chemical formula 62]

[0092]

[Chemical formula 63]

[0093]

[Chemical 64]

[0094]

[Chemical 65]

[0095]

[Chemical formula 66]

More specific examples of the compounds of the present invention are shown below.

[0097]

[Table 1]

[0098]

[Table 2]

[0099]

[Table 3]

[0100]

[Table 4]

[0101]

[Table 5]

[0102]

[Table 6]

[0103]

[Table 7]

[0104]

[Table 8]

[0105]

[Table 9]

[0106]

[Table 10]

[0107]

[Table 11]

[0108]

[Table 12]

[0109]

[Table 13]

[0110]

[Table 14]

[0111]

[Table 15]

[0112]

[Table 16]

[0113]

[Table 17]

[0114]

[Table 18]

[0115]

[Table 19]

[0116]

[Table 20]

[0117]

[Table 21]

[0118]

[Table 22]

[0119]

[Table 23]

[0120]

[Table 24]

[0121]

[Table 25]

[0122]

[Table 26]

[0123]

[Table 27]

[0124]

[Table 28]

[0125]

[Table 29]

[0126]

[Table 30]

[0127]

[Table 31]

[0128]

[Table 32]

[0129]

[Table 33]

[0130]

[Table 34]

[0131]

[Table 35]

[0132]

[Table 36]

[0133]

[Table 37]

[0134]

[Table 38]

[0135]

[Table 39]

[0136]

[Table 40]

[0137]

[Table 41]

[0138]

[Table 42]

[0139]

[Table 43]

[0140]

[Table 44]

[0141]

[Table 45]

[0142]

[Table 46]

[0143]

[Table 47]

[0144]

[Table 48]

[0145]

[Table 49]

[0146]

[Table 50]

[0147]

[Table 51]

[0148]

[Table 52]

[0149]

[Table 53]

[0150]

[Table 54]

[0151]

[Table 55]

[0152]

[Table 56]

[0153]

[Table 57]

[0154]

[Table 58]

[0155]

[Table 59]

[0156]

[Table 60]

[0157]

[Table 61]

[0158]

[Table 62]

[0159]

[Table 63]

[0160]

[Table 64]

[0161]

[Table 65]

[0162]

[Table 66]

[0163]

[Table 67]

[0164]

[Table 68]

[0165]

[Table 69]

[0166]

[Table 70]

[0167]

[Table 71]

[0168]

[Table 72]

[0169]

[Table 73]

[0170]

[Table 74]

[0171]

[Table 75]

[0172]

[Table 76]

[0173]

[Table 77]

[0174]

[Table 78]

[0175]

[Table 79]

[0176]

[Table 80]

[0177]

[Table 81]

[0178]

[Table 82]

[0179]

[Table 83]

[0180]

[Table 84]

[0181]

[Table 85]

[0182]

[Table 86]

[0183]

[Table 87]

[0184]

[Table 88]

[0185]

[Table 89]

[0186]

[Table 90]

[0187]

[Table 91]

[0188]

[Table 92]

[0189]

[Table 93]

[0190]

[Table 94]

[0191]

[Table 95]

[0192]

[Table 96]

[0193]

[Table 97]

[0194]

[Table 98]

[0195]

[Table 99]

[0196]

[Table 100]

[0197]

[Table 101]

[0198]

[Table 102]

[0199]

[Table 103]

[0200]

[Table 104]

[0201]

[Table 105]

[0202]

[Table 106]

[0203]

[Table 107]

[0204]

[Table 108]

[0205]

[Table 109]

[0206]

[Table 110]

[0207]

[Table 111]

[0208]

[Table 112]

[0209]

[Table 113]

[0210]

[Table 114]

[0211]

[Table 115]

[0212]

[Table 116]

[0213]

[Table 117]

[0214]

[Table 118]

[0215]

[Table 119]

[0216]

[Table 120]

[0217]

[Table 121]

[0218]

[Table 122]

[0219]

[Table 123]

[0220]

[Table 124]

[0221]

[Table 125]

[0222]

[Table 126]

[0223]

[Table 127]

[0224]

[Table 128]

[0225]

[Table 129]

[0226]

[Table 130]

[0227]

[Table 131]

[0228]

[Table 132]

[0229]

[Table 133]

[0230]

[Table 134]

[0231]

[Table 135]

[0232]

[Table 136]

[0233]

[Table 137]

[0234]

[Table 138]

[0235]

[Table 139]

[0236]

[Table 140]

[0237]

[Table 141]

[0238]

[Table 142]

[0239]

[Table 143]

[0240]

[Table 144]

[0241]

[Table 145]

[0242]

[Table 146]

[0243]

[Table 147]

[0244]

[Table 148]

[0245]

[Table 149]

[0246]

[Table 150]

[0247]

[Table 151]

[0248]

[Table 152]

[0249]

[Table 153]

[0250]

[Table 154]

[0251]

[Table 155]

[0252]

[Table 156]

[0253]

[Table 157]

[0254]

[Table 158]

[0255]

[Table 159]

[0256]

[Table 160]

[0257]

[Table 161]

[0258]

[Table 162]

[0259]

[Table 163]

[0260]

[Table 164]

[0261]

[Table 165]

[0262]

[Table 166]

[0263]

[Table 167]

[0264]

[Table 168]

[0265]

[Table 169]

[0266]

[Table 170]

[0267]

[Table 171]

[0268]

[Table 172]

[0269]

[Table 173]

[0270]

[Table 174]

[0271]

[Table 175]

[0272]

[Table 176]

[0273]

[Table 177]

[0274]

[Table 178]

[0275]

[Table 179]

[0276]

[Table 180]

[0277]

[Table 181]

[0278]

[Table 182]

[0279]

[Table 183]

[0280]

[Table 184]

[0281]

[Table 185]

[0282]

[Table 186]

[0283]

[Table 187]

[0284]

[Table 188]

[0285]

[Table 189]

[0286]

[Table 190]

[0287]

[Table 191]

[0288]

[Table 192]

[0289]

[Table 193]

[0290]

[Table 194]

[0291]

[Table 195]

[0292]

[Table 196]

[0293]

[Table 197]

[0294]

[Table 198]

[0295]

[Table 199]

[0296]

[Table 200]

[0297]

[Table 201]

[0298]

[Table 202]

[0299]

[Table 203]

[0300]

[Table 204]

[0301]

[Table 205]

[0302]

[Table 206]

[0303]

[Table 207]

[0304]

[Table 208]

[0305]

[Table 209]

[0306]

[Table 210]

[0307]

[Table 211]

[0308]

[Table 212]

[0309]

[Table 213]

[0310]

[Table 214]

[0311]

[Table 215]

[0312]

[Table 216]

[0313]

[Table 217]

[0314]

[Table 218]

[0315]

[Table 219]

The fluoranthene derivative represented by the formula (I) can be produced, for example, according to the method described in J. Amer. Chem. Soc. 118, 2374 (1996). An example of the synthetic scheme is shown below.

[0317]

[Chemical formula 67]

[0318]

[Chemical 68]

The compound of the present invention has extremely excellent properties as a fluorescent material for organic EL devices. In particular, when used as a dopant, x = 0.05 to 0.
20, y = 0.02 to 0.30, especially x = 0.10
It is possible to obtain an emission color close to pure blue as shown by 0.20 and y = 0.05 to 0.20.

The compound of the present invention is extremely stable, exhibits stable properties even in the manufacturing process of organic EL devices such as vapor deposition and coating, and maintains stable properties for a long period after the manufacture.

When the compound of the present invention is used in an organic EL device, it can be used both as a host material and as a dopant, and particularly when used as a dopant, it is possible to obtain excellent emission color and emission efficiency as described above. You can Since the compound of the present invention has any of electron injecting and transporting property, hole injecting property, and transporting property, it can be used as an electron transporting material or as a hole injecting or transporting material.

In deciding the combination of the host material of the organic EL device and the dopant, it is important to consider the following points.

(1) Consider combinations based on structural formulas.
That is, the structure of the compound itself affects the light emission characteristics.

(2) The ionization potential of the dopant (light emitting material) is preferably equal to or smaller than the ionization potential of the host material. The dopant functions as a hole trap when light is emitted, and singlet excitons of the dopant are easily generated. Further, in such a case, energy exchange between the singlet excitons of the host and the ground state dopant is likely to occur, and the luminous efficiency is improved.

(3) The half-wave oxidation potential of the dopant (light-emitting material) is preferably equal to or smaller than the half-wave oxidation potential of the host material. The dopant functions as a hole trap when light is emitted, and singlet excitons of the dopant are easily generated. Further, in such a case, energy exchange between the singlet excitons of the host and the ground state dopant is likely to occur, and the luminous efficiency is improved.

When the compound of the present invention is used in the light emitting layer, it can be used both as a host material and as a dopant, and particularly preferably as a blue light emitting dopant. When the compound of the present invention is used as a dopant, it is preferable to use an anthracene-based material as the host material. It is also preferable to use in a mixed layer in which a mixed material of an electron transporting material and a hole transporting material is used as a host. The light emitting layer may contain a plurality of kinds of compounds other than the compound of the present invention, and a plurality of peaks can be obtained by laminating such a plurality of kinds of compounds or a plurality of kinds of light emitting layers. It is also possible to obtain a light emitting layer or device having a wavelength or a wide emission wavelength.

When the compound of the present invention is used as a host material, various fluorescent substances for organic EL can be used as the dopant. Among them, naphthene-based rubrene derivatives, diphenylnaphthacene derivatives, perylene-based red fluorescent materials, pentacene-based red fluorescent materials, and distyrylamine derivative-based materials used in the following examples are preferable.

When the compound of the present invention is used in the hole injecting and transporting layer, it can be used as both a hole transporting material and a light emitting material. When used as a hole transporting material, the above-mentioned dopants can be used.

When the compound of the present invention is used in the electron injecting and transporting layer, it can be used as both an electron transporting material and a light emitting material. When used as an electron transporting material, the above-mentioned ones can be used as the dopant. The electron injecting and transporting layer may be the above mixed layer.

When the compound of the present invention is used as a dopant, the doping amount is preferably 30% by mass or less, more preferably 0.1 to 20% by mass, further 0.1 to 10% by mass, and particularly 0.1. It is 1 to 5 mass%.

By using the compound of the present invention in an organic EL device, the following excellent effects can be obtained.

(1) It is extremely difficult to cause a monomer system (n = 1) to emit light with an anthracene type host material, but the compound of the present invention easily emits light and obtains extremely high emission brightness.

(2) The emission color can be controlled by the linking group Y. That is, for example, when Y is an amino group, greenish luminescence is obtained, and when triphenylamine is used, light blue luminescence is obtained. Therefore, the emission color can be easily adjusted.

(3) The dimer of X single-bonded at the Z position is
Although it is easy to undergo intramolecular polymerization or decomposition during sublimation purification or vapor deposition, the compound of the present invention is extremely stable and easy to use.

(4) Although it is a condensed polycyclic aromatic hydrocarbon compound, it is an extremely suitable material for an organic EL material that needs to transport both electrons and holes.

(5) It has excellent performance as a light emitting material,
It is possible to emit light with a high efficiency of 7.3 cd / A in a pure blue color close to the NTSC signal.

(6) It has excellent performance as a host material and can be used in combination with a wide range of compounds such as naphthacene derivatives, rubrene derivatives, perylene derivatives, coumarin derivatives and styrylamine derivatives.

(7) An element having a high glass transition temperature (Tg) and excellent in high temperature storage characteristics can be obtained.

The light emitting layer containing the host material and the dopant as described above has a function of injecting holes and holes, a function of transporting them and a function of generating excitons by recombination of holes and electrons. . By using a relatively electronically neutral compound in addition to the compound of the present invention, the light emitting layer can easily and well inject and transport electrons and holes.

The host material may be used alone or 2
You may mix and use 1 or more types. When two or more kinds are mixed and used, the mixing ratio is arbitrary. When the compound of the present invention is used as a host material, the light emitting layer preferably contains 80 to 99.9% by mass, particularly 90 to 99.9% by mass, and further 95.0 to 99.5% by mass. Is preferably provided.

The thickness of the light emitting layer is preferably less than the thickness of the organic compound layer from the thickness corresponding to one molecular layer, specifically, 1 to 85 nm,
Further, it is preferably 5 to 60 nm, and particularly preferably 5 to 50 nm.

As a method for forming the mixed layer, co-evaporation in which evaporation is performed from different evaporation sources is preferable. However, when vapor pressures (evaporation temperatures) are the same or very close, they are mixed in advance in the same evaporation board. It can also be vapor-deposited. Although it is preferable that the compounds are uniformly mixed in the mixed layer, the compounds may exist in an island shape in some cases. The light-emitting layer is generally formed by vapor-depositing an organic fluorescent material or by dispersing it in a resin binder and coating the light-emitting layer to a predetermined thickness.

<Anthracene compound> A phenylanthracene derivative which is one of the preferable host materials for the device of the present invention is represented by the formula (5).

In the device of the present invention, the anthracene derivative represented by the formula (5), preferably the formula (5-1), or the formula (5-2) is preferably used as the host material so that the interaction with the dopant material can be improved. It is possible to suppress and obtain strong light emission from the dopant. Moreover, this anthracene derivative is excellent in heat resistance and durability, and can provide a device having a long life.

In this EL device, the doping concentration for maintaining the color purity of the device and maximizing the efficiency is 1% by mass.
Although it is only about 2 to 3% by mass, it is possible to obtain an element that can sufficiently withstand practical use with only a decrease of about 10% or less.

[0346]

[Chemical 69]

In the formula (5), A ₁₀₁ represents a monophenylanthryl group or a diphenylanthryl group,
These may be the same or different. L represents hydrogen, a single bond or a divalent linking group. n is 1 or 2
Is an integer.

The above formula (5), preferably the following formula (5-
1) and a compound represented by the formula (5-2).

[0349]

[Chemical 70]

[0350]

[Chemical 71]

Since the vapor-deposited film of the above compound is in a stable amorphous state, the physical properties of the thin film are good and uniform light emission is possible without unevenness. In addition, it is stable for more than a year in the atmosphere and does not cause crystallization.

Explaining equation (5), A ₁₀₁ is
Each represents a monophenyl anthryl group or a diphenyl anthryl group, which may be the same or different. n is an integer of 1 or 2.

The monophenylanthryl group or diphenylanthryl group represented by A ₁₀₁ may be unsubstituted or may have a substituent, and in the case of having a substituent, the substituent may be an alkyl group or an aryl group. Group, an alkoxy group, an aryloxy group, an amino group, and the like, and these substituents may be further substituted. These substituents will be described later. The substitution position of such a substituent is not particularly limited, but it is preferably a phenyl group bonded to the anthracene ring, not the anthracene ring.

The bonding position of the phenyl group on the anthracene ring is preferably 9-position or 10-position on the anthracene ring.

In the formula (5-1), L represents hydrogen, a single bond or a divalent group, and the divalent group represented by L is preferably an arylene group in which an alkylene group or the like may be present. . Such an arylene group will be described later.

Among the phenylanthracene derivatives represented by the formula (5), those represented by the formulas (5-1) and (5-2) are preferable. Explaining formula (5-1), in formula (5), M ₁ and M ₂ are each an alkyl group, a cycloalkyl group, an aryl group, an alkoxy group,
It represents an aryloxy group, an amino group or a heterocyclic group.

The alkyl group represented by M ₁ and M ₂ may be linear or branched, and is a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms. Is preferred. In particular, an unsubstituted alkyl group having 1 to 4 carbon atoms is preferable, and specifically, a methyl group, an ethyl group,
(N-, i-) propyl group, (n-, i-, s-, t
-) Butyl group and the like can be mentioned.

Examples of the cycloalkyl group represented by M ₁ and M ₂ include a cyclohexyl group and a cyclopentyl group.

The aryl group represented by M ₁ and M ₂ preferably has 6 to 20 carbon atoms and may have a substituent such as a phenyl group and a tolyl group. Specific examples thereof include a phenyl group, (o-, m-, p-) tolyl group, pyrenyl group, naphthyl group, anthryl group, biphenyl group, phenylanthryl group, tolylanthryl group and the like.

The alkenyl group represented by M ₁ and M ₂ preferably has 6 to 50 carbon atoms in total, and may be unsubstituted or may have a substituent,
It is preferable to have a substituent. At this time, the substituent is preferably an aryl group such as a phenyl group. Specific examples include a triphenyl vinyl group, a tritolyl vinyl group, a tribiphenyl vinyl group and the like.

The alkoxy group represented by M ₁ and M ₂ preferably has an alkyl group moiety having 1 to 6 carbon atoms, and specific examples thereof include a methoxy group and an ethoxy group. The alkoxy group may be further substituted.

Examples of the aryloxy group represented by M ₁ and M ₂ include phenoxy group and the like.

The amino group represented by M ₁ and M ₂ may be unsubstituted or may have a substituent, but preferably has a substituent, and the substituent in this case is an alkyl group (methyl group). Groups, ethyl groups, etc.), aryl groups (phenyl groups, etc.) and the like. Specific examples thereof include a diethylamino group, a diphenylamino group and a di (m-tolyl) amino group.

The heterocyclic group represented by M ₁ and M ₂ is
Examples thereof include bipyridyl group, pyrimidyl group, quinolyl group, pyridyl group, thienyl group, furyl group and oxadiazoyl group. These may have a substituent such as a methyl group and a phenyl group.

In the formula (5-1), q1 and q2
Each represents 0 or an integer of 1 to 5, and 0 or 1 is particularly preferable. q1 and q2 are respectively
When it is an integer of 1 to 5, particularly 1 or 2, M ₁ and M ₂ are preferably an alkyl group, an aryl group, an alkenyl group, an alkoxy group, an aryloxy group and an amino group, respectively.

In the formula (5-1), M ₁ and M ₂ may be the same or different, and when a plurality of M ₁ and M ₂ are present, M ₁ and M ₂ are respectively They may be the same or different, and M _{1 s} or M _{2 s} may be bonded to each other to form a ring such as a benzene ring, and the case of forming a ring is also preferable.

In the formula (5-1), L ₁ represents hydrogen, a single bond or an arylene group. The arylene group represented by L ₁ is preferably an unsubstituted arylene group, and specifically, a normal arylene group such as a phenylene group, a biphenylene group and an anthrylene group, and two or more arylene groups directly Examples include those that are linked. As L ₁ , a single bond, a p-phenylene group, a 4,4′-biphenylene group and the like are preferable.

The arylene group represented by L ₁ is 2
One or more arylene groups are alkylene groups, -O
It may be linked by interposing-, -S- or -NR-. Here, R represents an alkyl group or an aryl group. Examples of the alkyl group include a methyl group and an ethyl group, and examples of the aryl group include a phenyl group. Of these, an aryl group is preferable, and in addition to the above phenyl group, A ₁₀₁ may be used, and further, a phenyl group substituted with A ₁₀₁ may be used.

As the alkylene group, a methylene group,
Ethylene groups and the like are preferred. Specific examples of such an arylene group are shown below.

[0370]

[Chemical 72]

Next, the equation (5-2) will be explained.
In the formula (5-2), M ₃ and M ₄ are represented by the formula (5-1).
M ₁ and M ₂ in the formula (1), q3 and q4 have the same meanings as q1 and q2 in the formula (5-1), and L ₂ has the same meaning as L ₁ in the formula (5-1), and the preferred ones are also the same. .

[0372] formula (5-2) may be one that is different even in the same and M ₃ and M _4, when M ₃ and M ₄ there are a plurality each, M ₃ each other, M ₄ each other, respectively They may be the same or different, and M _{3 s} or M _{4 s} may combine with each other to form a ring such as a benzene ring, and the case of forming a ring is also preferable.

The compounds represented by formula (5-1) and formula (5-2) are exemplified below, but the invention is not limited thereto. Note that chemical formula 41, chemical formula 43, chemical formula 45, chemical formula 4
7, chemical formula 49, chemical formula 51, chemical formula 53, chemical formula 56 show general formulas, and chemical formula 42, chemical formula 44, chemical formula 46, chemical formula 48, chemical formula 50, chemical formula 5
2, chemical formula 54, chemical formula 55, and chemical formula 57, corresponding specific examples are M _{11 to} M ₁₅ , M _{21 to} M ₂₅ or M _{31 to} M ₃₅ , M _{41 to} M.
_{Shown in 45} combinations.

[0374]

[Chemical formula 73]

[0375]

[Chemical 74]

[0376]

[Chemical 75]

[0377]

[Chemical 76]

[0378]

[Chemical 77]

[0379]

[Chemical 78]

[0380]

[Chemical 79]

[0380]

[Chemical 80]

[0382]

[Chemical 81]

[0383]

[Chemical formula 82]

[0384]

[Chemical 83]

[0385]

[Chemical 84]

[0386]

[Chemical 85]

[0387]

[Chemical 86]

[0388]

[Chemical 87]

[0389]

[Chemical 88]

[0390]

[Chemical 89]

[0391]

[Chemical 90]

[0390]

[Chemical Formula 91]

[0393]

[Chemical Formula 92]

[0394]

[Chemical formula 93]

The phenylanthracene derivative used in the present invention is (1) a halogenated diphenylanthracene compound is coupled with Ni (cod) ₂ [cod: 1,5-cyclooctadiene] or a dihalogenated aryl is Grignard-ized to form NiCl. ₂ (dppe) [dpp
e: diphenylphosphinoethane], NiCl ₂ (d
cross-coupling using a Ni complex such as ppp) [dpppp: diphenylphosphinopropane]; And a method of cross-coupling by reduction, and the like.

The compound thus obtained can be identified by elemental analysis, mass spectrometry, infrared absorption spectrum, ¹ H or ¹³ C nuclear magnetic resonance absorption (NMR) spectrum and the like.

The phenylanthracene derivative has a molecular weight of 400-
It has a molecular weight of about 2000, further about 400 to 1000, a high melting point of 200 to 500 ° C., and 80 to 25.
0 ° C, even 100-250 ° C, even more 130
It exhibits a glass transition temperature (Tg) of ~ 250 ° C, especially 150-250 ° C. Therefore, a smooth and good film in an amorphous state, which is transparent and stable even at room temperature or more, is formed by ordinary vacuum deposition, and the good film state is maintained for a long period of time.

Since the phenylanthracene derivative is a relatively neutral compound, it is possible to obtain preferable results by using it in the light emitting layer. Also, the light emitting layer to be combined,
The recombination and emission regions can be freely designed by controlling the film thickness while considering the carrier mobility and carrier density (determined by the ionization potential and electron affinity) of the electron injecting and transporting layer and the hole injecting and transporting layer. It is possible to control the emission color, control the emission brightness and emission spectrum by the interference effect of both electrodes, and control the spatial distribution of emission.

<Organic EL Device> As an example of the constitution of an organic EL light emitting device produced by using the compound of the present invention, for example,
A hole injecting electrode, a hole injecting / transporting layer, a light emitting / electron injecting / transporting layer, and an electron injecting electrode are sequentially provided on a substrate. If necessary, an auxiliary electrode or a sealing layer may be provided on the electron injection electrode.

The organic EL device of the present invention is not limited to the above-mentioned examples and may have various constitutions. For example, a light emitting layer is provided alone, and an electron injecting and transporting layer is provided between the light emitting layer and the electron injecting electrode. An intervening structure can also be used. If necessary, the hole injection / transport layer and the light emitting layer may be mixed.

The thickness of the light emitting layer, the thickness of the hole injecting and transporting layer, and the thickness of the electron injecting and transporting layer are not particularly limited, and are usually about 5 to 500 nm, particularly 1
The thickness is preferably 0 to 300 nm.

The thickness of the hole injecting and transporting layer and the thickness of the electron injecting and transporting layer may be about the same as the thickness of the light emitting layer or about 1/10 to 10 times, depending on the design of the recombination / light emitting region. When the injection layer and the transport layer for holes or electrons are separated, it is preferable that the injection layer has a thickness of 1 nm or more and the transport layer has a thickness of 1 nm or more. At this time, the upper limit of the thickness of the injection layer and the transport layer is usually about 500 nm for the injection layer and 50 for the transport layer.
It is about 0 nm. Such a film thickness is the same when two injecting and transporting layers are provided.

The hole injecting and transporting layer has a function of facilitating the injection of holes from the hole injecting electrode, a function of stably transporting the holes and a function of hindering electrons, and the electron injecting and transporting layer is formed from the electron injecting electrode. It has the function of facilitating electron injection, the function of stably transporting electrons, and the function of hindering holes. These layers increase and confine holes and electrons injected into the light-emitting layer, and recombine regions. To improve the luminous efficiency.

Further, in the hole injecting and transporting layer, for example, in addition to the compound of the present invention, JP-A-63-295695,
JP-A-2-191694, JP-A-3-792, JP-A-5-234681, and JP-A-5-239.
455, JP-A-5-299174, JP-A-7-126225, JP-A-7-126226, JP-A-8-100172, EP065095.
Various organic compounds described in 5A1 and the like can be used. For example, a tetraarylbenzidine compound (triaryldiamine or triphenyldiamine:
TPD), aromatic tertiary amine, hydrazone derivative, carbazole derivative, triazole derivative, imidazole derivative, oxadiazole derivative having amino group, polythiophene and the like. Two or more of these compounds may be used in combination, and when they are used in combination, they may be laminated in different layers or mixed.

When the hole injecting and transporting layer is separately formed into the hole injecting layer and the hole transporting layer, preferable combinations can be selected and used from the compounds for the hole injecting and transporting layer. At this time, it is preferable to stack layers of a compound having a small ionization potential in this order from the hole injection electrode (ITO or the like) side. Further, it is preferable to use a compound having a good thin film property on the surface of the hole injecting electrode. This stacking order is the same when two or more hole injecting and transporting layers are provided. By adopting such a stacking order, the driving voltage is lowered, and it is possible to prevent the occurrence of current leakage and the generation / growth of dark spots. In addition, when it is made into a device, since a thin film of about 1 to 10 nm can be made uniform and pinhole-free because vapor deposition is used, the ionization potential of the hole injection layer is small, and absorption in the visible region seems to occur. Even if such a compound is used, it is possible to prevent a decrease in efficiency due to a change in the color tone of the emission color or reabsorption.
The hole injecting and transporting layer can be formed by vapor-depositing the above compound as in the light emitting layer and the like.

In addition to the compound of the present invention, tris (8-quinolinolato) aluminum (A
nitrogen-containing heterocycles such as quinoline derivatives such as organometallic complexes having 8-quinolinol or its derivatives such as lq3) as ligands, oxadiazole derivatives, perylene derivatives, pyridine derivatives, pyrimidine derivatives, quinoxaline derivatives, phenanthroline derivatives, etc. Aromatic, diphenylquinone derivatives, nitro-substituted fluorene derivatives and the like can be used. The electron injecting and transporting layer may also serve as the light emitting layer, and in such a case, it is preferable to use the light emitting layer of the present invention. The electron injecting and transporting layer may be formed by vapor deposition or the like as in the light emitting layer.

When the electron injecting and transporting layer is separately laminated on the electron injecting layer and the electron transporting layer, preferable combinations can be selected and used from the compounds for the electron injecting and transporting layer. At this time, it is preferable to stack from the electron injection electrode side in order of a compound having a large electron affinity value. The stacking order is the same when two or more electron injecting and transporting layers are provided.

For forming the hole injecting and transporting layer, the light emitting layer and the electron injecting and transporting layer, it is preferable to use the vacuum deposition method because a uniform thin film can be formed. When the vacuum deposition method is used, an amorphous state or a homogeneous thin film having a crystal grain size of 0.1 μm or less can be obtained. When the crystal grain size exceeds 0.1 μm, non-uniform light emission occurs, the driving voltage of the device must be increased, and the hole injection efficiency is significantly reduced.

The conditions of vacuum vapor deposition are not particularly limited, but 1
The degree of vacuum is 0 ^-4 Pa or less, and the deposition rate is 0.01 to 1 nm.
/ Sec is preferable. Moreover, it is preferable to form each layer continuously in a vacuum. If they are continuously formed in a vacuum, it is possible to prevent impurities from adsorbing to the interface of each layer, so that high characteristics can be obtained. Further, it is possible to lower the driving voltage of the element and suppress the growth / occurrence of dark spots.

When a vacuum vapor deposition method is used to form each of these layers, when a plurality of compounds are contained in one layer, it is preferable to co-evaporate the boats containing the compounds by individually controlling the temperature.

The electron injection electrode preferably has a work function of 4
Consists of a metal, alloy or intermetallic compound with eV or less. When the work function exceeds 4 eV, the electron injection efficiency decreases, and the light emission efficiency also decreases. Examples of constituent metals of the electron injection electrode film having a work function of 4 eV or less include Li,
Alkali metals such as Na and K, alkaline earth metals such as Mg, Ca, Sr, and Ba, rare earth metals such as La and Ce, and A
1, In, Ag, Sn, Zn, Zr and the like. As a constituent alloy of a film having a work function of 4 eV or less, for example, Ag
-Mg (Ag: 0.1-50 at%), Al-Li (L
i: 0.01-12 at%), In.Mg (Mg: 50-)
80at%), Al-Ca (Ca: 0.01-20at%)
Etc. These may be present alone or as a combination of two or more kinds, and in the case of combining two or more kinds, the mixing ratio is arbitrary. Alternatively, a thin film of an oxide or a halide of an alkali metal, an alkaline earth metal, or a rare earth metal may be formed and a supporting electrode (auxiliary electrode, wiring electrode) made of aluminum or the like may be used.

This electron injection electrode can be formed by a vapor deposition method, a sputtering method or the like.

The thickness of such an electron injecting electrode may be a certain thickness or more for sufficiently injecting electrons, and is 0.1 nm.
The above is sufficient. The upper limit value is not particularly limited, but the film thickness is usually about 0.1 to 500 nm.

For the hole injecting electrode, it is preferable to determine the material and thickness such that the transmittance of emitted light is 80% or more. Specifically, an oxide transparent conductive thin film is preferable, and examples thereof include tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), indium oxide (In ₂ O ₃ ), tin oxide (SnO ₂ ) and zinc oxide ( It is preferable that the main composition is any one of ZnO). These oxides may deviate somewhat from their stoichiometric composition. The mixing ratio of SnO ₂ to In ₂ O ₃ is preferably 1 to 20% by mass, more preferably 5 to 12%.
Mass% is preferred. The mixing ratio of ZnO ₂ to In ₂ O ₃ is preferably 12 to 32 mass%.

The hole injecting electrode has an emission wavelength band, usually 3
50 ~ 800nm, especially the light transmittance for each emitted light is 80
% Or more, particularly preferably 90% or more. Normal,
Since the emitted light is extracted through the hole injecting electrode, if the transmittance thereof is low, the light emission itself from the light emitting layer is attenuated, and the luminance required as a light emitting element tends to be not obtained. However, it is sufficient that the side from which emitted light is extracted is 80% or more.

The thickness of the hole injecting electrode may be a certain thickness or more capable of sufficiently injecting holes, and preferably 5 or more.
The range of 0 to 500 nm, preferably 50 to 300 nm is preferable. The upper limit is not particularly limited, but if it is too thick, peeling or the like may occur. If the thickness is too thin, there are problems in film strength during production, hole transport ability, and resistance value.

A sputtering method is preferable for forming the hole injecting electrode. As the sputtering method, a high frequency sputtering method using an RF power source or the like is possible, but the DC sputtering method is used in consideration of the ease of controlling the film physical properties of the hole injection electrode for film formation, the smoothness of the film formation surface, and the like. It is preferable.

A protective film may be formed if necessary. The protective film can be formed using an inorganic material such as SiO _X or an organic material such as Teflon (registered trademark). The protective film may be transparent or opaque, and the thickness of the protective film is about 50 to 1200 nm. In addition to the reactive sputtering method described above, the protective film may be formed by a general sputtering method, vapor deposition method, or the like.

Further, it is preferable to provide a sealing layer on the element in order to prevent oxidation of the organic layers and electrodes of the element. The sealing layer is an adhesive resin layer such as a commercially available low hygroscopic photocurable adhesive, an epoxy adhesive, a silicone adhesive, a crosslinked ethylene-vinyl acetate copolymer adhesive sheet, etc. for preventing the invasion of moisture. Using, the sealing plate such as a glass plate is adhered and sealed. Besides the glass plate, a metal plate, a plastic plate or the like can be used.

As the substrate material, when the light emitted from the substrate side is taken out, a transparent or semi-transparent material such as glass, quartz or resin is used. Further, the substrate may be provided with a color filter film, a color conversion film containing a fluorescent substance, or a dielectric reflection film to control the emission color. In the case of the reverse lamination, the substrate may be transparent or opaque, and if opaque, ceramics or the like may be used.

As the color filter film, a color filter used in a liquid crystal display or the like may be used, but the characteristics of the color filter are adjusted according to the light emitted by the organic EL to optimize the extraction efficiency and color purity. do it.

Further, if a color filter capable of cutting outside light of a short wavelength which is absorbed by the EL device material or the fluorescence conversion layer is used, the light resistance of the device and the display contrast are improved.

An optical thin film such as a dielectric multilayer film may be used instead of the color filter.

The organic EL device of the present invention is, for example, as shown in FIG. 1, a hole injecting electrode (anode) 2, a hole injecting and transporting layer 3, a light emitting layer 4, an electron injecting and transporting layer 5, an electron injecting electrode on a substrate 1. (Cathode) 6 has a structure in which layers are sequentially laminated. The structure may be reversed from the stacking order, the hole injecting and transporting layer 3 and the electron injecting and transporting layer 5 may be omitted, or the light emitting layer 4 may be omitted.
It may be combined with. These constituent layers may be adjusted to the optimum ones according to the required function of the device.

The organic EL device of the present invention is usually used as a DC drive type or pulse drive type EL device, but it can also be AC driven. The applied voltage is usually 2 to 30.
It is about V.

[0426]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples of the present invention together with comparative examples.

<Synthesis Example 1> 3.Bromo-7,12-diphenylbenzo [k] fluoranthene
Synthesis of diphenylisobenzofuran 5 g (18.5 mmol) and 5-bromoacenaphthylene 4.3 g (18.5 mmol) were stirred in toluene at reflux temperature for 24 hours. After distilling off the solvent under reduced pressure, 500 ml of acetic acid
Dissolved in. 50 cm ³ of 40% aqueous bromic acid solution was added thereto and heated at 80 ° C. for 1 hour. After cooling to room temperature, the precipitate was filtered off and purified by silica gel chromatography using a mixed solvent of toluene and hexane as an extraction solvent to obtain 7 g of yellowish white 3 · bromo · 7,12 diphenylbenzo [k] fluoranthene.

<Synthesis Example 2> 7,12 diphenylbenzo [k] fluorantheno-3.boron
Synthesis of acid 3-bromo-7,12 diphenylbenzo [k] fluoranthene
2.5 g was dissolved in 50 cm ³ of THF and cooled to -40 ° C. 5 cm ³ of a hexane solution of butyryllium (1.5 mol / l) was added thereto and reacted for 2 hours. Triethyl borate 1.
5 g was added and reacted for 1 hour. After returning to room temperature, 15 cm ³ of a 5N hydrochloric acid aqueous solution was added, and the mixture was neutralized with sodium hydrogen carbonate. After evaporating THF, the solid matter was filtered off. The residue was washed with distilled water and purified by reprecipitation to obtain 2 g of boronic acid.

<Synthesis Example 3> Synthesis of Exemplified Compound A.2 2 g (4.5 mmol) of boronic acid prepared above and 0.33 g (1.4 mmol) of p-dibromobenzene were dissolved in 50 cm ³ of dimethoxyethane and heated to 80 ° C. Overheated. 50 cm ^{3 of} distilled water and 10 g of sodium carbonate were added thereto. Further, 0.2 g of tetrakistriphenylphosphine palladium (0) was added thereto.

After 3 hours, the target product which had precipitated was recovered.
For purification, silica gel chromatography was used to obtain 1 g of yellowish white crystals.

The obtained compound was identified by means of mass spectrum, infrared absorption spectrum and NMR. Mass spectrum m / e = 883 (M + 1) + Figure 2 Infrared absorption spectrum Figure 3 NMR Figure 4 Glass transition temperature (Tg) 251 ℃

<Synthesis Example 4> Synthesis of Exemplified Compound V. 2 Boronic acid 2 g (4.5 mmol) synthesized above and bis-p-dibromotriphenylamine 0.56 g (1.4 mmol) were dissolved in 50 cm ³ of dimethoxyethane. Overheated to 80 ° C. Distilled water there
50 cm ³ and 10 g of sodium carbonate were added. Further, 0.2 g of tetrakistriphenylphosphine palladium (0) was added thereto.

After 3 hours, the target product which had precipitated was recovered.
Purification using silica gel chromatography, yellow crystals
I got 1g.

The obtained compound was identified by means of mass spectrum, infrared absorption spectrum and NMR. Mass spectrum m / e = 1050 (M + 1) +

Synthesis of Exemplified Compound Z.2 In 50 cm ^{3 of} xylene , 2 g (4.1 mmol) of 3.bromo-7,12 diphenylbenzo [k] fluoranthene synthesized above and 0.13 g (1.4 mmol) of aniline were dissolved. Then, 0.2 g of trisdibenzylideneacetone palladium (0) and 0.5 cm ³ of tri-t-butylphosphine were added, and the mixture was reacted at 130 ° C for 12 hours.

The precipitated target product was recovered and purified by silica gel chromatography to obtain 1 g of yellow crystals.

The obtained compound was identified by mass spectrum, infrared absorption spectrum and NMR. Mass spectrum m / e = 898 (M + 1) +

<Example 1> An ITO transparent electrode thin film having a thickness of 100 nm was formed on a glass substrate by RF sputtering.
Patterned. The glass substrate with the ITO transparent electrode was ultrasonically cleaned with a neutral detergent, acetone, and ethanol, pulled out from boiling ethanol and dried. After the surface of the transparent electrode was washed with UV / O _{3, the} transparent electrode was fixed to a substrate holder of a vacuum evaporation system, and the pressure inside the tank was reduced to 1 × 10 ⁻⁴ Pa or less.

Then, with the reduced pressure maintained, N, N'-diphenyl-N, N'-bis [N- (4-methylphenyl) -N-phenyl- (4-aminophenyl)]-1 having the following structure was obtained. , 1'-biphenyl-4,4'-diamine was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a film thickness of 100 nm to form a hole injection layer.

[0440]

[Chemical 94]

Then, N, N, N ', N'- having the following structures:
Tetrakis (m-biphenyl) -1,1'-biphenyl-4,4'-diamine with a deposition rate of 0.1 nm / sec of 10 nm
To a hole transport layer.

[0442]

[Chemical 95]

Further, while maintaining the reduced pressure, the anthracene-based host material having the following structure and the dopant of the compound (A-2) of the present invention were mixed at a mass ratio of 98: 2, and the total deposition rate was 0.1.
It was vapor-deposited at a thickness of 1 nm / sec to a thickness of 40 nm to form a light emitting layer.

[0444]

[Chemical 96]

Then, while maintaining the reduced pressure, tris (8-hydroxyquinoline) aluminum (Alq3) was added.
Was evaporated at a deposition rate of 0.1 nm / sec to a thickness of 15 nm to form an electron injecting and transporting layer.

Then, LiF was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a thickness of 0.5 nm to serve as an electron injection electrode, 100 nm of Al was deposited as a protective electrode, and finally glass-sealed to form an organic EL device. Obtained.

A DC voltage was applied to this organic EL element, and the driving voltage was 8.6 V at a current density of 10 mA / cm ² in the initial stage.
, Emission of 730 cd / m ² or more was confirmed. At this time, the peak wavelength is 450 nm, and the chromaticity coordinates are (x, y) = (0.
15, 0.11). 10mA / cm ^{2 for} this element
When a constant current of,
The luminance half-life was 500 hours or more at 0 cd / m ² or more. Therefore, the luminance cd × half time h was 365,000. The emission spectrum is shown in FIG.

<Example 2> In Example 1, N, N '
-Diphenyl-N, N'-bis [N- (4-methylphenyl) -N-phenyl- (4-aminophenyl)]-
1,1'-biphenyl-4,4'-diamine was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a film thickness of 50 nm to form a hole injection layer.

Then, N, N, N ', N'-tetrakis (m-biphenyl) -1,1'-biphenyl-4,4'
-Using diamine as a host material, the compound of the present invention (A-
The dopant of 2) was vapor-deposited in a mass ratio of 98: 2 to a thickness of 30 nm at an overall vapor deposition rate of 0.1 nm / sec to form a hole transport layer / light emitting layer.

Then, while maintaining the reduced pressure, tris (8-hydroxyquinoline) aluminum (Alq3) was added.
Was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a thickness of 40 nm to form an electron injecting and transporting layer.

Then, LiF was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a thickness of 0.3 nm to form an electron injecting electrode, Al was vapor-deposited to 200 nm as a protective electrode, and finally glass-sealed to form an organic EL device. Obtained.

A direct current voltage was applied to the obtained organic EL device, and light emission of a driving voltage of 7.9 V and 780 cd / m ² or more could be confirmed at a current density of 10 mA / cm ² in the initial stage. At this time, the peak wavelength is 450 nm, and the chromaticity coordinates are (x, y) =
It was (0.15, 0.11). 10mA to this element
When a constant current of / cm ² was passed and continuous driving was performed, the initial luminance was 780 cd / m ² or more, and the luminance half-life was 400 hours or more.

<Example 3> In Example 1, N, N '
-Diphenyl-N, N'-bis [N- (4-methylphenyl) -N-phenyl- (4-aminophenyl)]-
1,1'-biphenyl-4,4'-diamine was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a film thickness of 50 nm to form a hole injection layer.

Then, N, N, N ', N'-tetrakis (m-biphenyl) -1,1'-biphenyl-4,4'
-Diamine was vapor deposited at a vapor deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a hole transport layer.

Further, with the compound (A-2) of the present invention as a host material, a naphthacene compound dopant having the following structure was used at a mass ratio of 98: 2 while maintaining a reduced pressure, and the overall deposition rate was 0.1. It was vapor-deposited at a thickness of 1 nm / sec to a thickness of 40 nm to form a light emitting layer.

[0456]

[Chemical 97]

Then, tris (8-hydroxyquinoline) aluminum (Alq3) was added while keeping the reduced pressure.
Was vapor-deposited to a thickness of 30 nm at a vapor deposition rate of 0.1 nm / sec to form an electron injecting and transporting layer.

Next, LiF was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a thickness of 0.3 nm to serve as an electron injection electrode and Al as a protective electrode to a thickness of 150 nm. Finally, glass was sealed to form an organic EL device. Obtained.

A direct current voltage was applied to the obtained organic EL device, and at the initial stage, a driving voltage of 6.3 V and light emission of 900 cd / m ² or more could be confirmed at a current density of 10 mA / cm ² . At this time, the peak wavelength is 560 nm and the chromaticity coordinates are (x, y) =
It was (0.45, 0.55). 10mA to this element
When a constant current of / cm ² was passed and continuous driving was performed, the initial luminance was 900 cd / m ² or more and the luminance half-life was 3000 hours or more.

Example 4 An organic EL device was obtained in the same manner as in Example 3 except that the naphthacene compound having the following structure was used as the dopant of the light emitting layer.

[0461]

[Chemical 98]

A direct current voltage was applied to the obtained organic EL device, and light emission of a driving voltage of 6.3 V and 910 cd / m ² or more could be confirmed at a current density of 10 mA / cm ² in the initial stage. At this time, the peak wavelength is 560 nm and the chromaticity coordinates are (x, y) =
It was (0.45, 0.55). 10mA to this element
When a constant current of / cm ² was passed and the device was continuously driven, the initial luminance was 910 cd / m ² or more and the luminance half time was 3000 hours or more.

Example 5 Example 3 is different from Example 3 except that the compound of the following structure is used as the dopant of the light emitting layer.
An organic EL device was obtained in the same manner as.

[0464]

[Chemical 99]

A direct current voltage was applied to the obtained organic EL device, and at the initial stage, at a current density of 10 mA / cm ² , a driving voltage of 6.5 V and light emission of 750 cd / m ² or more could be confirmed. At this time, the peak wavelength is 580 nm and the chromaticity coordinates are (x, y) =
It was (0.52, 0.48). 10mA to this element
When a constant current of / cm ² was passed and continuous driving was performed, the initial luminance was 750 cd / m ² or more and the luminance half-life was 3000 hours or more.

Example 6 Example 3 is different from Example 3 except that the compound of the following structure is used as the dopant of the light emitting layer.
An organic EL device was obtained in the same manner as.

[0467]

[Chemical 100]

A direct current voltage was applied to the obtained organic EL device, and light emission of a driving voltage of 6.6 V, 1100 cd / m ² or more could be confirmed at a current density of 10 mA / cm ² in the initial stage. The peak wavelength at this time is 515 nm, and the chromaticity coordinates are (x, y).
= (0.30, 0.65). 10 for this element
When a constant current of mA / cm ² was passed and continuously driven, the initial brightness was 1100 cd / m ² or more, and the brightness half time was 3000.
It was over time.

Example 7 An organic EL device was obtained in the same manner as in Example 3 except that the compound having the following structure was used as the dopant.

[0470]

[Chemical 101]

A direct current voltage was applied to the obtained organic EL device, and light emission of a driving voltage of 6.5 V, 550 cd / m ² or more could be confirmed at a current density of 10 mA / cm ² in the initial stage. At this time, the peak wavelength is 610 nm, and the chromaticity coordinates are (x, y) =
It was (0.65, 0.35). 10mA to this element
When a constant current of / cm ² was passed and the device was continuously driven, the initial luminance was 550 cd / m ² or more and the luminance half-life was 5000 hours or more.

<Embodiment 8> In Embodiment 1, N, N '
-Diphenyl-N, N'-bis [N- (4-methylphenyl) -N-phenyl- (4-aminophenyl)]-
1,1'-biphenyl-4,4'-diamine was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a film thickness of 50 nm to form a hole injection layer.

Then, N, N, N ', N'-tetrakis (m-biphenyl) -1,1'-biphenyl-4,4'
-Diamine was vapor deposited at a vapor deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a first hole transport layer.

Further, the compound (A-2) of the present invention of Example 1 was vapor-deposited at a rate of 0.1 nm / sec while maintaining the reduced pressure.
It was vapor-deposited to a thickness of 0 nm to form a second hole transport layer.

Then, using a compound having the following structure as a host material,

[Chemical 102]

A compound dopant having the following structure was added in a mass ratio of 9:
At 8: 2, the entire vapor deposition rate was 0.1 nm / sec, and vapor deposition was performed to a thickness of 40 nm to form a light emitting layer.

[0477]

[Chemical 103]

Then, while maintaining the reduced pressure, tris (8-hydroxyquinoline) aluminum (Alq3) was added.
Was vapor-deposited to a thickness of 30 nm at a vapor deposition rate of 0.1 nm / sec to form an electron injecting and transporting layer.

Then, LiF was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a thickness of 0.3 nm to serve as an electron injection electrode, Al as a protective electrode was deposited to 150 nm, and finally glass-sealed to form an organic EL device. Obtained.

A direct current voltage was applied to the obtained organic EL device, and light emission of 6.0 V and 820 cd / m ² or more was confirmed at a current density of 10 mA / cm ² in the initial stage. At this time, the peak wavelength is 556 nm, and the chromaticity coordinates are (x, y) =
It was (0.45, 0.55).

<Example 9> In Example 1, N, N '
-Diphenyl-N, N'-bis [N- (4-methylphenyl) -N-phenyl- (4-aminophenyl)]-
1,1′-biphenyl-4,4′-diamine was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a film thickness of 90 nm to form a hole injection layer.

Then, N, N, N ', N'-tetrakis (m-biphenyl) -1,1'-biphenyl-4,4'
-Diamine was vapor deposited at a vapor deposition rate of 0.1 nm / sec to a thickness of 10 nm to form a hole transport layer.

Further, the compound (A-2) of the present invention was vapor-deposited to a thickness of 10 nm at a vapor deposition rate of 0.1 nm / sec while maintaining a reduced pressure to form a second hole transport layer.

Then, using the compound of Example 8 as a host material, the compound (A-2) of the present invention was added in a mass ratio of 9
At 8: 2, the entire vapor deposition rate was 0.1 nm / sec, and vapor deposition was performed to a thickness of 40 nm to form a light emitting layer.

Then, while maintaining the reduced pressure, tris (8-hydroxyquinoline) aluminum (Alq3) was added.
Was evaporated at a deposition rate of 0.1 nm / sec to a thickness of 15 nm to form an electron injecting and transporting layer.

Then, LiF was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a thickness of 0.5 nm to form an electron injection electrode, Al was vapor-deposited to 100 nm as a protective electrode, and finally glass-sealed to form an organic EL device. Obtained.

A direct current voltage was applied to the obtained organic EL device, and at the initial stage, a driving voltage of 8.0 V and light emission of 700 cd / m ² or more could be confirmed at a current density of 10 mA / cm ² . At this time, the peak wavelength is 450 nm, and the chromaticity coordinates are (x, y) =
It was (0.15, 0.11). 10mA to this element
When a constant current of / cm ² was passed and continuous driving was performed, the initial luminance was 700 cd / m ² or more, and the luminance half-life was 1000 hours or more.

<Example 10> In Example 1, N,
N'-diphenyl-N, N'-bis [N- (4-methylphenyl) -N-phenyl- (4-aminophenyl)]
-1,1'-Biphenyl-4,4'-diamine was vapor-deposited at a vapor deposition rate of 0.1 nm / sec to a film thickness of 10 nm to form a hole injection layer.

Then, N, N, N ', N'-tetrakis (m-biphenyl) -1,1'-biphenyl-4,4'
-Diamine was vapor deposited at a vapor deposition rate of 0.1 nm / sec to a thickness of 20 nm to form a hole transport layer.

Then, N, N, N ', N'-tetrakis (m-biphenyl) -1,1'-biphenyl-4,4'
A mass ratio of 49: 49: 2 using a diamine, a compound of Chemical formula 70, and a compound of Chemical formula 69 as dopants, respectively.
Then, it was vapor-deposited to a thickness of 15 nm at a total vapor deposition rate of 0.1 nm / sec to form a first light emitting layer (red).

Then, N, N, N ', N'-tetrakis (m-biphenyl) -1,1'-biphenyl-4,4'
A mass ratio of 49: 49: 2 using a diamine, a compound of Chemical formula 70, and a compound of Chemical formula 68 as dopants, respectively.
Then, it was vapor-deposited to a thickness of 20 nm at a total vapor deposition rate of 0.1 nm / sec to form a second light emitting layer (green).

Furthermore, N, N, N ', N'-tetrakis (m-biphenyl) -1,1'-biphenyl-4,4'.
-Using a diamine, a compound of Chemical formula 70, and the compound (A-2) of the present invention as a dopant, the mass ratio is 49:
49: 2, overall deposition rate 0.1 nm / sec 20 nm
To a second light emitting layer (blue).

Others were the same as in Example 1 to obtain an organic EL device.

A direct current voltage was applied to the obtained organic EL device, and at an initial stage, a current density of 10 mA / cm ² and a driving voltage of 8.5 V and light emission of 750 cd / m ² or more were confirmed. The overall emission color is (x, y) = (0.30, 0.3) in chromaticity coordinates.
3), and a color tone close to white was obtained.

[Example 11] An organic EL device was obtained in the same manner as in Example 1 except that the dopant of the light emitting layer was changed to the following structure (Type BBB-9).

[0496]

[Chemical 104]

A direct current voltage was applied to this organic EL device, and the driving voltage was 8.6 V at a current density of 10 mA / cm ² in the initial stage.
, Emission of 800 cd / m ² or more was confirmed. The beak wavelength at this time is 452 nm, and the chromaticity coordinates are (x, y) = (0.
15, 0.11).

When a constant current of 10 mA / cm ² was passed through this device and it was continuously driven, the luminance half time was 1200 hours or more at the initial stage of 800 cd / m ² or more. Therefore, the brightness cd
× The half-life was 960000. The emission spectrum is shown in FIG.

[Example 12] An organic EL device was obtained in the same manner as in Example 1 except that the dopant of the light emitting layer was changed to the following structure (Type V-2).

[0500]

[Chemical 105]

A direct current voltage was applied to this organic EL element, and the driving voltage was 8.6 V at a current density of 10 mA / cm ² in the initial stage.
, Emission of 900 cd / m ² or more was confirmed. At this time, the peak wavelength is 473 nm, and the chromaticity coordinate is (x, y) = (0.1
4, 0.27)).

A constant current of 50 mA / cm ² was passed through this element,
When continuously driven, the initial luminance was 4,500 cd / m ² or more, and the luminance half time was 500 hours or more. Therefore, the brightness cd
× The half-life was 22500000. The emission spectrum is shown in FIG.

Example 13 An organic EL device was obtained in the same manner as in Example 1 except that the structure (Type Z-2) shown below was used instead of the dopant of the light emitting layer.

[0504]

[Chemical formula 106]

A direct current voltage was applied to this organic EL device, and the driving voltage was 8.6 V at a current density of 10 mA / cm ² in the initial stage.
Light emission of 1100 cd / m ² or more was confirmed. At this time, the peak wavelength is 518 nm, and the chromaticity coordinate is (x, y) = (0.2
It was 8, 0.61).

When a constant current of 50 mA / cm ² was passed through this element and continuously driven, at an initial stage of 5500 cd / m ² or more,
The luminance half-life was 500 hours or more. Therefore, the luminance cd × half-life time was 27500000. The emission spectrum is shown in FIG.

Comparative Example 1 An organic EL device was obtained in the same manner as in Example 1 except that the light emitting layer was not doped with a dopant.

When a DC voltage was applied to this organic EL device, the driving voltage was 6.5 V and 180 cd / m ² or less at the initial current density of 10 mA / cm ² . At this time, the peak wavelength is 440 nm and the chromaticity coordinates are (x, y) =
It was (0.16, 0.07). 10mA to this element
When a constant current of / cm ² was passed and the device was continuously driven, the initial luminance was 180 cd / m ² and the luminance half-life was 250 hours or less. Therefore, the luminance cd × half time h was 4500. From this, it can be seen that the device of Example 1 can emit light with a brightness of 4 times or more as compared with this device, and has a life of 8 times or more with the same light emission brightness.

<Comparative Example 2> An organic EL device was obtained in the same manner as in Example 1 except that the compound of the following structure was used as the dopant for the light emitting layer.

[0510]

[Chemical formula 107]

When a DC voltage was applied to this organic EL device, initially, the current density was 10 mA / cm ² , and the driving voltage was 6.6 V and 700 cd / m ² . At this time, the peak wavelength is 465 nm, and the chromaticity coordinates are (x, y) = (0.20,
0.20) and the emission color deviated from blue to the long wavelength side. When a constant current of 10 mA / cm ² was passed through this device and the device was continuously driven, the initial brightness was 700 cd / m ² and the brightness half-life was 500 hours.

Comparative Example 3 An organic EL device was obtained in the same manner as in Example 1, except that the compound of the following structure was used as the dopant for the light emitting layer.

[0513]

[Chemical 108]

When a DC voltage was applied to this organic EL device, initially, the current density was 10 mA / cm ² , and the driving voltage was 6.5 V and 180 cd / m ² . At this time, the peak wavelength is 440 nm, and the chromaticity coordinates are (x, y) = (0.16,
0.07). A constant current of 10 mA / cm ² was passed through this element for continuous driving, and an initial luminance of 180 cd /
At m ² , the luminance half-life was 250 hours.

[0515]

As described above, according to the present invention, it is possible to obtain light emission with sufficient luminance, particularly light emission at a long wavelength, and to obtain excellent color purity, particularly color purity sufficient for use in a full-color display, Further, it is possible to provide a compound for an organic EL device having excellent durability in which good light emitting performance is maintained for a long period of time, and an organic EL device.

[Brief description of drawings]

FIG. 1 is a schematic cross-sectional view showing the basic structure of an organic EL element of the present invention.

FIG. 2 is a diagram showing a mass spectrum.

FIG. 3 is a diagram showing an infrared absorption spectrum.

FIG. 4 is a diagram showing an NMR spectrum.

5 is a diagram showing an emission spectrum of the device of Example 1. FIG.

6 is a diagram showing an emission spectrum of the device of Example 11. FIG.

7 is a diagram showing an emission spectrum of the device of Example 12. FIG.

8 is a diagram showing an emission spectrum of the device of Example 13. FIG.

[Explanation of symbols]

1 substrate 2-hole injection electrode 3 Hole injection transport layer 4 Light emitting layer 5 Electron injection transport layer 6 Electron injection electrode

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) C09K 11/06 620 C09K 11/06 620 635 635 645 645 645 690 690 H05B 33/14 H05B 33/14 B 33 / 22 33/22 BD (72) Inventor Tetsuji Inoue 1-13-1 Nihonbashi, Chuo-ku, Tokyo Inside TDC Corporation

Claims (30)

[Claims] 1. Having a basic skeleton represented by the following formula (1):
A compound for organic EL devices. Xn-Y (1) [In the formula (1), X represents a compound represented by the following formula (2).
However, they may be the same or different. Y is also a single bond
Or a substituted or unsubstituted aryl group or heterocyclic group
And represents an integer of 2 or 3.
However, Y is R ₇ And R₇ , R₈ And R₈ Or R₇ And R₈ 
When combining with the combination of positions, a single bond and
The compounds represented by the formulas (11) and (12) are not included. ] [Chemical 1] [In the formula (2), R₁ ~ R₈ And a to d are hydrogen and alk
Group, an aryl group which may have a substituent, and a substituent
Allyl group which may have or may have substituent group
It may have a heterocyclic group, an amino group, or a substituent.
Represents any of the arylamino groups. ] 2. The compound for an organic EL device according to claim 1, wherein the Y is one selected from the following compounds. [Chemical 2] 3. The compound for an organic EL device according to claim 1, wherein n is 2. 4. The method according to claim 1, which is used as a dopant.
3. The compound for organic EL device according to any one of 3 5. The compound for an organic EL device according to claim 1, which is an electron transport material. 6. The compound for organic EL device according to claim 1, which is a hole injecting or transporting material. 7. A basic skeleton represented by the following formula (3a) is included.
The compound for an organic EL device according to claim 1. [Chemical 3] [In Formula (3a), R₁ ~ R₈ And a₁ ~ D₁ , R₁₁ 
~ R₁₈ And a₂ ~ D ₂ Is hydrogen, alkyl group, substituted
Optionally having an aryl group, having a substituent
Good allyl group, a heterocyclic group which may have a substituent,
Amino group, arylamino group which may have a substituent
Represents either Y is a substituted or unsubstituted phenyle
N, biphenylene, naphthacene, perylene, pyrene, fu
Enanthrene, thiophene, pyridine, pyrazine, tri
Azine, amine, triarylamine, pyrrole derivative
Body, thiazole, thiadiazole, phenanthroline,
Linkage consisting of either quinoline or quinoxaline
Represents a group. ] 8. A basic skeleton represented by the following formula (3b) is included.
The compound for an organic EL device according to claim 1. [Chemical 4] [In Formula (3b), R₁ ~ R₈ And a₁ ~ D₁ , R₁₁ 
~ R₁₈ And a₂ ~ D ₂ Is hydrogen, alkyl group, substituted
Optionally having an aryl group, having a substituent
Good allyl group, a heterocyclic group which may have a substituent,
Amino group, arylamino group which may have a substituent
Represents either Y is a single bond, a substituted or unsubstituted a
It represents a linking group composed of a reel group or a heterocyclic group. ] 9. A basic skeleton represented by the following formula (3c) is included.
The compound for an organic EL device according to claim 1. [Chemical 5] [In Formula (3c), R₁ ~ R₈ And a₁ ~ D₁ , R₁₁ 
~ R₁₈ And a₂ ~ D ₂ Is hydrogen, alkyl group, substituted
Optionally having an aryl group, having a substituent
Good allyl group, a heterocyclic group which may have a substituent,
Amino group, arylamino group which may have a substituent
Represents either Y is a single bond, a substituted or unsubstituted a
It represents a linking group composed of a reel group or a heterocyclic group. ] 10. The compound for organic EL device according to claim 1, which has a basic skeleton represented by the following formula (A). [Chemical 6] [In the formula (A), R _{1 to} R ₇ and R _{11 to} R ₁₇ represent hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. ] 11. The compound for organic EL device according to claim 1, which has a basic skeleton represented by the following formula (B). [Chemical 7] [In the formula (B), R _{1 to} R ₇ and R _{11 to} R ₁₇ represent hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. ] 12. The compound for organic EL device according to claim 1, which has a basic skeleton represented by the following formula (E). [Chemical 8] [In the formula (E), R _{1 to} R ₈ and R _{11 to} R ₁₈ represent hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. ] 13. The compound for an organic EL device according to claim 1, which has a basic skeleton represented by the following formula (H). [Chemical 9] [In the formula (H), R _{1 to} R ₈ and R _{11 to} R ₁₈ represent hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. ] 14. The compound for an organic EL device according to claim 1, which has a basic skeleton represented by the following formula (X). [Chemical 10] [In the formula (X), R _{1 to} R ₈ and R _{11 to} R ₁₈ represent hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. ] 15. The compound for an organic EL device according to claim 1, which has a basic skeleton represented by the following formula (Z). [Chemical 11] [In the formula (Z), R _{1 to} R ₇ and R _{11 to} R ₁₇ R represent hydrogen, an alkyl group, a substituted or unsubstituted aryl group, or a heterocyclic group. ] 16. The compound for an organic EL device according to claim 1, which has a basic skeleton represented by the following formula (AAA ′). [Chemical 12] [In Formula (AAA '), R < ₁ > -R < ₈ >, and R < ₁₁ > -R < ₁₈ >.
Is hydrogen, an alkyl group, an aryl group which may have a substituent, an allyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, a substituent It represents any of the arylamino groups which may be possessed. ] 17. The compound for an organic EL device according to claim 1, which has a basic skeleton represented by the following formula (BBB ′). [Chemical 13] [In Formula (BBB '), R < ₁ > -R < ₈ >, and R < ₁₁ > -R < ₁₈ >.
Is hydrogen, an alkyl group, an aryl group which may have a substituent, an allyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, a substituent It represents any of the arylamino groups which may be possessed. ] 18. The compound for organic EL device according to claim 1, which has a basic skeleton represented by the following formula (CCC ′). [Chemical 14] [In Formula (CCC '), R < ₁ > -R < ₈ >, and R < ₁₁ > -R < ₁₈ >.
Is hydrogen, an alkyl group, an aryl group which may have a substituent, an allyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, a substituent It represents any of the arylamino groups which may be possessed. ] 19. The compound for an organic EL device according to claim 1, which has a basic skeleton represented by the following formula (DDD ′). [Chemical 15] [In Formula (DDD '), R < ₁ > -R < ₈ >, and R < ₁₁ > -R < ₁₈ >.
Is hydrogen, an alkyl group, an aryl group which may have a substituent, an allyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, a substituent It represents any of the arylamino groups which may be possessed. ] 20. The compound for organic EL device according to claim 1, which has a basic skeleton represented by the following formula (EEE ′). [Chemical 16] [In Formula (EEE '), R < ₁ > -R < ₈ >, and R < ₁₁ > -R < ₁₈ >.
Is hydrogen, an alkyl group, an aryl group which may have a substituent, an allyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, a substituent It represents any of the arylamino groups which may be possessed. ] 21. The compound for organic EL device according to claim 1, which has a basic skeleton represented by the following formula (RRR ′). [Chemical 17] [In Formula (RRR '), R < ₁ > -R < ₈ >, and R < ₁₁ > -R < ₁₈ >.
Is hydrogen, an alkyl group, an aryl group which may have a substituent, an allyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, a substituent It represents any of the arylamino groups which may be possessed. ] 22. The compound for organic EL device according to claim 1, which has a basic skeleton represented by the following formula (SSS ′). [Chemical 18] [In Formula (SSS '), R < ₁ > -R < ₈ >, and R < ₁₁ > -R < ₁₈ >.
Is hydrogen, an alkyl group, an aryl group which may have a substituent, an allyl group which may have a substituent, a heterocyclic group which may have a substituent, an amino group, a substituent It represents any of the arylamino groups which may be possessed. ] 23. An organic EL device according to claim 1, which has at least one organic layer involved in at least a light emitting function between a pair of electrodes, and at least one layer of the organic layers. EL device containing one or more compounds for use. 24. The organic EL device according to claim 23, which further contains one or more anthracene compounds in addition to the compound for organic EL device. 25. The organic EL device according to claim 24, which contains the anthracene derivative as a host material of a light emitting layer. 26. The organic E according to claim 23, which contains the compound for an organic EL device as a dopant.
L element. 27. The organic EL device according to claim 23, wherein the organic EL compound is contained in a light emitting layer. 28. The organic EL device according to claim 23, wherein the compound for organic EL is contained in an electron transport layer. 29. The organic EL device according to claim 23, wherein the compound for organic EL device is contained in a hole injecting and transporting layer. 30. The organic EL device according to claim 23, which has two or more types of emission maximum wavelengths of two or more types of light emitting materials.