TW201012898A - Organic light-emitting medium and organic el element - Google Patents

Abstract

Disclosed is an organic light-emitting medium containing a diaminopyrene derivative represented by formula (1) and an anthracene derivative represented by formula (2). (In formula (2), two of the R1-R8 respectively represent a substituted or unsubstituted aryl group having 6-50 nuclear carbon atoms or a substituted or unsubstituted heterocyclic group having 5-50 nuclear atoms.)

Description

201012898 VI. Description of invention: Piece. [Technical Field of the Invention] The present invention relates to an organic light-emitting medium and an organic EL element using the same. [Previously, an electromechanical excitation optical element using an organic compound has been known. The organic EL element has: an L7L member (a plurality of organic thin films in between. In this configuration, when the voltage is applied to the cathode, the anode is erected, and the anode is separated from the anode (7). And the thin film, the light-emitting layer in the organic thin crucible by the injected holes and electrons, and the molecules in the excited state. The energy @ when returning to the substrate state from the excited state will be released in the form of light. An example of a material used for the layer is disclosed in the patent document! The onion body "Aromatic amine" and σ are disclosed. Further, in Patent Documents 2 to 4, a combination of a green onion body and a diamine-based dopant having a specific structure is disclosed. In addition, in the patent documents 5 and 6, the main material of the onion type is disclosed. Patent Document 1 Patent Document 2 Patent Document 3 W02004/018588. WO2004/018587. 曰本开开2004-204238. Patent Document 4: WO2005/108348. Patent Document 5: WO2005/054162. Patent Document 6: WO2005/061656. 201012898 The object of the present invention is to provide an organic EL element and

The organic light-emitting medium of the organic thin film layer of the organic EL element, which has high luminous efficiency, long life, and a combination of a specific main = and dopant material. - The main material of 疋 现 明 明 明 明 明 明 明 明 明 明 明 明 明 明 明 明 明 明 明 明 明 明 。 。 。 。 。 。 。 。藉 By the present invention, the following organic light-emitting media and the like can be provided. An organic light-emitting medium comprising a derivative of the following formula (1), and the following:

=: Two 4' are independently substituted or unsubstituted ring carbon groups of 5 to 50, which are I ^ 50 heterocyclic groups. Aromatic, substituted or unsubstituted ring carbon number i R ' sub (4) Site is a hydrogen atom, substituted or unsubstituted. #童代卞的烧基, substituted or unsubstituted ring carbon number 5~5〇 aromatic / 戈Or an unsubstituted ring carbon number of 6 to 5 、, a phosphorus atomic number of 3 to 50, a substituted alkyl group, a substituted or unsubstituted ring, an alkyl group, a substituted or unsubstituted group, a substituted or unsubstituted carbon number a number of 50 alkoxy rings having a carbon number of 5 to 50 arylamines, aryloxy groups, substituted or unsubstituted arylamino groups, substituted or unsubstituted carbon number U 5, 201012898 heterocyclic groups, substituted An alkylamino group, a substituted or unsubstituted ring carbon number of 5 to 5 fluorene or an unsubstituted fluorenyl group, a cyano group or a dentate atom. Nl~n4 are independently 〇~1〇 ^ When 2 or more, ~24, respectively, can form a saturated or unsaturated ring. - different, but also connected to each other

Ra, a heterocyclic group having a ring carbon number of an aromatic group. 5~50 R, independently substituted or unsubstituted, substituted or unsubstituted, ring carbon number 5~5〇

In the formula (), Ar and Ar' are each independently a substituted or unsubstituted aryl group having 6 to 50 ring carbon atoms or a heterocyclic group having 5 to 5 ring atoms, and R1 to R8 2; a substituted or unsubstituted aromatic group having 6 to 5 ring carbon atoms or a substituted or unsubstituted ring atom having 5 to % ring atoms is a substituted or unsubstituted aromatic group having 6 to 5 ring carbon atoms; Or Ri~ R8 ' other than r1 to r8 of the heterocyclic group having 5 to 50 ring atoms which are substituted or unsubstituted, each independently is an alkyl group selected from a hydrogen atom, a substituted or unsubstituted carbon number, a substituted or unsubstituted group. a cycloalkyl group having a carbon number of 3 to 5 Å, a substituted or unsubstituted alkoxy group having 1 to 50 carbon atoms, a substituted or unsubstituted carbon number of 7 to 5, 201012898, an aryl group, a substituted or an unsubstituted group. An aryloxy group having a ring carbon number of 6 to 5 Å, or an unsubstituted arylthio group having 6 to 50 ring carbon atoms, a substituted or unsubstituted alkoxycarbonyl group having 2 to 50 carbon atoms, a substituted or unsubstituted fluorenyl group, a group of a carboxyl group, a cyano group, a nitro group, and a hydroxy group.) ^ 2. 2. An organic light-emitting medium as described in the above, wherein R, RW, and the above are substituted or unsubstituted rings 1 An aromatic group of hydrazine, or a substituted or unsubstituted ring atomic number of 5 to 50%, and 'R4, ..., and r6, which are substituted or substituted, have a ring carbon number of 6 to 5 Å. Or a substituted or innumerable 5 to 50 heterocyclic group. 3. The organic light-emitting medium according to 2, wherein, 5 is a substituted or unsubstituted ring 6 to 5 〇 aromatic substituted or unsubstituted heterocyclic group having 5 to 5 ring atoms, &quot疋 is a substituted or unsubstituted ring having 6 to 5 ring carbon atoms, 5 groups, and/or R8 unsubstituted heterocyclic groups having 5 to 50 ring atoms. ▲ /疋 replaced or R1, : 2 such as two == among the organic light-emitting media, wherein the above formula (2) is the substitution or unsubstituted ring carbon number 6~ | take: the second 'Γ Further, R3, R4, R, and R6 are those substituted or substituted with an aromatic group having a carbon number of 6 to 5 Å. The organic light-emitting medium of the above formula (7) is such that R in the above formula (7) is Substituted or unsubstituted ring carbon number 6~5〇R and R8 are substituted or unsubstituted ring carbon number 6~5G aromatic ^. Μ and 6r:v take m organic light-emitting medium 'where' above formula (7) In the substituted or unsubstituted ring carbon number 6~5〇 of the aromatic group or, 7 201012898 R and R are substituted or unsubstituted ring male rabbit number 6~50 of the aromatic group. 7. Such as 1~6 And the organic light-emitting medium according to any one of the above, wherein the W in the formula (7) is a substituted or unsubstituted ring atom having a ring number of 5 to 5 q, wherein the organic light is as described in any one of 1 to 6. Media, among them, on

The oxime and oxime in the formula (2) are each independently a substituted or unsubstituted phenyl group. 9·如1~6 中杯一T5 AtL ^ +U ...^ The organic light-emitting medium contained in the item S, wherein the upper and lower ΑΓ and ΑΓ 2 are substituted or unsubstituted ring carbon number 6 An aromatic group of ~ or a stupid group substituted by a substituted or unsubstituted ring atom number. &lt; </ RTI> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; Aromatic base. ':· Such as the organic light-emitting media recorded by the household, among them,

Ar 1 R A r12 ^ . v ; τ is the same base. The organic light-emitting medium as described in 11 'where the above formula is a substituted or unsubstituted 9-phenanthrenyl. The organic light-emitting medium according to 11, wherein, in the above formula (2), r and VIII are substituted or unsubstituted 2-naphthyl groups. 14 ·1 1 Secret ~ | i The organic light-emitting medium contained in 5, wherein the above formulas W and 斛12 are replaced or unsubstituted. () 15 · such as 10 Lu 4 h I, w圮 carried organic light media', where the above-mentioned door Arl1 and gossip are different. 16. For example, the above-mentioned organic light-emitting medium of W s, wherein W and W of 201012898 in the above formula (2) are respectively substituted or unsubstituted 9-phenanthryl group, substituted 1-naphthyl group , substituted or unsubstituted 2_Cai Ji, Yi = 乙合合ϋ基 (fw 崎I), and substituted or unsubstituted $基基, 2 of 0, 17. As in any of 1~6 The organic light-emitting medium according to the above, wherein any one of Ar11 and Ar12 in the formula (2) is a phenyl group which is substituted or unsubstituted, and the other is a substituted or unsubstituted ring carbon number. A condensed aromatic group of 1G to 5(). • wherein 'the above substituted or unsubstituted or unsubstituted 1 wherein 'the above substituted or unsubstituted or unsubstituted 2' wherein 'the above substituted or unsubstituted or unsubstituted C wherein 'the above substituted or unsubstituted or unsubstituted 芘❹ ❿18. The condensed aryl-naphthyl group having a ring carbon number of 10 to 50 substituted by an organic light-emitting medium as described in 17. 19. The condensed aromatic group-naphthyl group having a ring carbon number of 10 to 50 substituted by the organic light-emitting medium according to 17. 2〇. The organic light-emitting medium as described in 17 is substituted with a condensed aromatic group having a ring carbon number of 10 to 50, and is sinter. 21. The organic light-emitting medium according to 17, wherein the condensed aromatic group having a ring carbon number of 10 to 50 is substituted. The organic light-emitting medium contained in the above-mentioned formula (1), wherein Ra, Rb, and V in the above formula (1) are independently substituted or unsubstituted phenyl groups,

A substituted or unsubstituted naphthyl group, or a B-substituted or unsubstituted base. 23. For example, in the middle of the 1st to 22nd, the organic light-emitting medium contained in the member, wherein, the eight of the formula (1)!·1~Ar4 are independently selected from substituted or unsubstituted 9 201012898 The phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted is a substituted or unsubstituted dibenzoxanyl group. Or an organic light-emitting medium according to any one of 1 to 23, wherein the above formula (1) is such that Ar丨~Ar4 s, Dan T ′. In the case of the organic light-emitting medium of any one of the above-mentioned formulas (1), R21 ό 24 , , , &quot;Ρ ' 〜 in the above formula (1) are independently Is a substituted or unsubstituted, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted t: substituted isopropyl, substituted or unsubstituted tertiary butyl, substituted or unsubstituted U ring Anthracenyl, substituted or unsubstituted hexyl, substituted or unsubstituted trimethyl decyl, or cyano. An organic electroluminescence device comprising: an anode and a cathode; and an organic thin film layer of i or more between the anode and the cathode; and at least one layer of the organic thin film layer, comprising an organic light-emitting medium carried in the film 25. The organic electroluminescent device of claim 26, wherein the organic thin film layer of the organic light-emitting medium is a light-emitting layer. According to the present invention, it is possible to provide an organic EL element which can obtain high luminous efficiency, and can be used for the purpose. P, organic light-emitting media. [Organic Light-Emitting Film] [Embodiment] [Organic Light-Emitting Medium] 201012898 The organic light-emitting medium of the present invention contains a specific diamine-based material and a specific onion derivative. The organic light-emitting medium contributes to light emission as a constituent component of the organic thin film layer of the organic rainbow element. For example, when the vaporized mineral is present in the layer and is used in the organic EL element, high luminous efficiency can be obtained. Helps to prolong life. Here, the diamine-based hydrazine derivative and the onion derivative of the present invention will be described. (monoamine-based derivative) The diamine-based hydrazine derivative of the present invention is represented by the following formula (丨).

(R22)n2 ❹ (1) In the formula (1), ΑΑαΑ is independently an aromatic group having a substitution or an unsubstituted ring stone of 5 5G, or a substituted or unsubstituted ring carbon number of 5 to other heterocyclic rings. base. 'R~R , independently, a fluorene atom, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aryl group having 5 to 5 ring carbon atoms, a substituted or unsubstituted ring carbon| 6 to 5G of aromatic, substituted or unsubstituted ring carbon with a carbon number of 3 to 50, substituted or unsubstituted carbon number, alkoxy, substituted or unsubstituted, Wei 5~5〇 An oxy, substituted or unsubstituted stone having an inverse number of 5 50 arylamine groups, a substituted or unsubstituted carbon number (10), an alkylamino group, a substituted or unsubstituted heterocyclic group having a ring carbon number of 5 to 50, and a substitution Or an unsubstituted thiol, cyano or halogen atom. 201012898 ‘仏 is independently an integer of 0~1G, &amp; When 2 or more, Rn~R24 can be divided into n4 knives to lead von 冋 or different, or can form a saturated or unsaturated ring. R and R' are each independently a substituted or unsubstituted aryl group having 5 to 5 ring carbon atoms or a substituted or unsubstituted heterocyclic group having 5 to 5 ring carbon atoms. The monoamine-based derivative is preferably represented by the following formula (1).

In the formula (1), 'R21 to R24' are each independently a hydrogen atom, a substituted or unsubstituted aromatic group having a ring carbon number of 6 to 5, a substituted or unsubstituted carbon number, and a substituted or substituted alkyl group. Or an unsubstituted ring carbon group of 3 to 50 ring-substituted, substituted, unsubstituted carbon number 7 to 5 芳 aryl group, or substituted or unsubstituted ❹ slave number 3~2〇之石夕基' When there are 1 or 2 groups of adjacent groups on the same benzene ring, the adjacent groups may be bonded to each other to form a substituted or unsubstituted divalent bond group. η Γ 〜 n 4 ' ' are each independently an integer of 1 to 5. R R is independently a substituted or unsubstituted aromatic group having a ring carbon number of ό50. Further, in the present invention, the hydrogen atom also contains a ruthenium atom. In the present invention, "ring carbon" means a carbon atom constituting a saturated ring, an unsaturated ring, and 12 201012898 ^ aromatic ring. The "ring atom" means a carbon atom and a hetero atom constituting a hetero ring (containing a saturated ring, an unsaturated ring, and an aromatic ring). For example, a phenyl group substituted with a naphthyl group is an aromatic group having a ring carbon number of 16 substituted, and a phenyl group substituted with a methyl group, and an aromatic group having a ring carbon number of 6 substituted. In the definition of each formula of the present invention, the "substituted or unsubstituted" substituent may be, for example, an alkyl group, an aromatic group, a cycloalkyl group, an alkoxy group, a heterocyclic group or an aromatic group, which will be described later. The aryloxy group, the arylthio group, the aerobic acid group, the dentate ❹ ', the ruthenium group, the cyano group, the several groups and the like are preferably an alkyl group, an aromatic group, a cycloalkyl group or a heterocyclic group. * Formula (1)_, Ari~Ar4, each independently a substituted or unsubstituted ring having 5 to 5 carbon atoms, or a substituted or unsubstituted heterocyclic group having a ring carbon number of 5% to 5 Å. Specific examples of the aromatic group having an anisotropy of 5 to 50 include, for example, a phenyl 'naphthyl group, an onion group, a condensed tetraphenyl (naphthacenyl) group, a ketone group, an acrylonitrile group, a group (10) ryseny D, a group, and a flower group. (perylenyl), biphenylyl, terphenylyl, anthracenyl or the like is preferably a phenyl group, a naphthyl group or a g group. Specific examples of the aromatic group having 5 to 5 ring carbon atoms substituted may be ethyl stupyl or p-tertiary butyl

Examples of the heterocyclic group of Ar1 to Ar4 include imidazole, benzimidazole, pyrrole, and furan. Sai, stupid and thiophene, hire two saliva, ten, miso. Residues such as pyridinium, porphyrin, isoporphyrin, benzene, pyralozine, snail (1__ gammon piperidine, dibenzofuran, benzofuran, dibenzothiophene, etc.) Preferably, benzimidazole, thiophene, oxazole, dibenzofuran. Preferably, Ari~Ar4 are independently substituted or unsubstituted phenyl, 13 201012898

Substituted or unsubstituted Cai Ji, running skills M ... flat ...: replaced by the base, or substituted or unsubstituted dibenzofuranyl. In the formula (1), R21 to R24 are independently hydrogen atoms, and the substituted carbon number is 1 to 5 Å (preferably carbon number 2 〇, particularly preferably carbon number, substituted or none) Substituted ring carbon number 5~5〇 aromatic group (compared to carbon number 5~2G, especially preferably ring carbon number 6~1()), substituted or unsubstituted ring number 6~50 aralkyl group (helmet earned The ring of the clothing against the soil (more than 6~2〇 for the ring stone), the ring with the carbon number of 3~5G (preferably the ring carbon number 3~12) of the ring or helmet (4),: ❹ Unsubstituted carbon number 1 Alkoxy group of ~50 (preferably _ 代成, 权佳马奴数~6), or an unsubstituted aryloxy hydrazine having a carbon number of 5 to 50 (preferably a ring carbon number of 5 to 18) Substituted ring carbon number 5 to 5 () (preferably ring carbon number 5 amine group, substituted or unsubstituted carbon number 2 () (preferably carbon number Z-based amine group, substituted or unsubstituted ring a heterocyclic group having 5 to 5 carbon atoms (preferably "number W0", a substituted or unsubstituted (tetra), a cyano group or a south atom. The alkyl group of R to R may, for example, be a methyl group, an ethyl group or a propyl group. Base, isopropyl, butyl, secondary butyl, tert-butyl, pentyl, hexyl, heptyl, octyl A, stearyl ' '2-phenyl isopropyl Base, trimethylmethyl, tri-I fluorenyl, benzyl, α-phenoxyl group, ◎-dimethyl nodal, α,α-methylphenyl bis-trimethyl group, triphenyl Methyl group-based oxygen voltaic temple. From the viewpoint of stability, among the above, it is preferably a carbon number of 4, methyl, ethyl, propyl, isopropyl, butyl, two a butyl group and a tributyl group. The aryl group of R21 to R24 may be the same as the above Ar1 to A. 14 201012898 The aralkyl group of R21 to R24 may, for example, be a benzyl group or an i-phenylethyl group. , 2-phenylethyl, 1-phenylisopropyl, 2-phenylisopropyl, phenyl-tertiary butyl, α-naphthylmethyl, 1-α-naphthylethyl, 2- Α-naphthylethyl, 1-α-naphthylisopropyl, 2~α-naphthylisopropyl, cold-naphthylfluorenyl, 1-col-naphthylethyl, 2—cold-naphthyl Base, 1_callyl-naphthylisopropyl, 2-methylphenylisopropyl, 1-hydroxyl-methyl, 2-hydroxyl-ethyl, ethyl, methylbenzyl, cyano, etc. The cycloalkyl group of R21 to R24 may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, an anthranilyl group or a ring. Base, cyclooctyl, cyclodecyl, bicycloheptyl, bicyclooctyl, tricycloheptyl, adamantyl, etc., are cyclopentyl, cyclohexyl, cycloheptyl, bicycloheptyl, bicyclooctyl An adamantyl group, preferably a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cycloheptyl group. The alkoxy group of R21 to R24 may, for example, be a methoxy group, an ethoxy group or a propoxy group. Isopropoxy group, butoxy group, isobutoxy group, secondary butoxy group, tertiary butoxy group, various pentyloxy groups, various hexyloxy groups, etc. R21 to R24 aryloxy group, for example, phenoxy Examples of the arylamine group of the group, the tolyloxy group, and the naphthalene gas R21 to R24 include a diphenylamino group, a diphenylamino group, a 'nanoylamino group, and a decylphenylamino group. The alkylamino group of R21 to R24' may, for example, be a dimethylamino group, a diethyl group or a dihexylamino group. The heterocyclic group of the earth R21, ^R24 R21-^R24 may, for example, be a substituent similar to the above Arl to Ar4, a substituent having a carbon number of 6 to fluorenyl group, and an aromatic group or a carbon number of 14 may be, for example, a carbon number of 1. ~ 2 〇 1 1 ~ 20 alkoxy. The carbon number 1 15 201012898 20 may be exemplified by a base group, an isobutyl group, a secondary butyl group, a propyl 'isopropyl group, a positive number ～5, and a butyl group and a pentyl group. 'It is preferably a pit number of carbon number 丄5. Carbon number 6 to 14 婪 婪 Α 如 苯 苯 苯 、 、 、 萘 萘 萘 、 、 、 、 、 、 、 、 、 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄 龄The base carbon butyl base is preferably an alkoxy group having 1 to 5 carbon atoms. The ruthenium atom of the group R21 to R24 may be, for example, a sulfonium atom, a chlorine atom or a ruthenium atom. Preferably, r21 to r24 are each a substituted or unsubstituted benzene A-substituted or unsubstituted methyl group. You also have a base, a substitution of u η μ or a filamentous [radical, substituted or unsubstituted isopropyl, substituted or unsubstituted tertiary butyl, substituted or cyclopropyl, substituted or unsubstituted cyclopentane A substituted or unsubstituted trimethyl decyl group, or a cyano group, which is substituted, unsubstituted or unsubstituted. The soil is 0 to 5, more preferably 〇~3. Equation (1) Let 'ΓΠ~η4, respectively, represent the integers of 〇~1〇, respectively, 〇~5, 争社〇==ηη4 respectively 2 or more, r21~r24, respectively, the same or different, They can be joined to each other to form a saturated or unsaturated ring. Examples of the ring include a cycloalkane having a carbon number of 4 to 12 such as cyclobutane, cyclopentane or cyclohexane, a cyclopentene, a cyclopentene, a cyclohexene, a cycloheptene, a cyclooctene, and the like. It is called cycloaliphatic diene, cyclohexanyl, cycloheptadiene, cyclooctane dihalide and the like.

The substituted or unsubstituted ring having 5 to 5 Å of a ring having 5 to 5 Å of a substituted or unsubstituted ring carbon having 5 to 5 ring carbon atoms, which may be substituted or substituted, may be the same as the above Arl~. Preferably, 'Ra, Rb are each independently substituted or unsubstituted Ζ 16 201012898 phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted. Substituted or unsubstituted aryl, substituted or unsubstituted cyclyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted aralkyl, substituted or unsubstituted fluorenyl, adjacent The substituted or unsubstituted 2 valent bond groups formed by the alkyl group are also the same as described above. In a preferred aspect of the invention, the formula is represented. -Aminoguanidine derivatives are as follows

❹ 17 201012898

In the above formula, R21 to R24, Ra and Rb are the same as described above. R21 to R24 may be the same or different, respectively, but it is preferred that R21 and R23, and R22 and R24 are respectively the same. Further, Ra and Rb may be the same or different, but are preferably the same. Specific examples of the diamino hydrazine derivative represented by the formula (1) include compounds represented by the following formulas. 18 201012898

❿ 19 201012898

DM-2-4

DM-2-9

DM-2-7

20 201012898

DM-3-7 DM-3-8 DM-3-9 ❹ 21 201012898

22 201012898

❹ 23 201012898

DM-6-4

❿ 24 201012898

25 201012898

DM-8-1 DM-8-2

DM-8-7 DM-8-8 26 201012898

❹ 27 201012898

DM-10-1

28 201012898

DM-11-4 DM-11-5 DM-11-6

29 201012898

30 201012898

31 201012898

DM·14·4 DM-14.9

G

32 201012898

DM-15-1

33 201012898 -〇-κ

N-SiMe3

Me3Si—^^-1

MeaSi.

-SiMe3 N-^^-SiMesQ kMe3siH: y-κ ^ y\ Q-n DM-16-4

Me3Si i-Q-N:

DM-16-7 DM-16-2 SIM«3 DM-16-3 SiMe3

'N-〇·' SiMej DM-16-9

34 201012898

DM-17-6

35 201012898

DM-17-13 DM-17-14 DM-17-15

DM-17-20 DM-17-21 ❹ 36 201012898

Further, in the present invention, the following (1,) may be removed from the diamino hydrazine derivative represented by the formula (1) by the formula m 咚 丁 + w . That is, the hair + praise month may also be expressed by the above formula (1)

The diamine-based hydrazine derivative (in the pot, the slate, the sulphate is removed by the following formula (1)), and the organic light-emitting medium of the onion derivative represented by the above formula (2).

The onion derivative of the present invention is represented by the following (2). 37 201012898

(10) In the formula (2), Ar &amp; Ar, respectively, are independently substituted or unsubstituted, the number of the slaves is 2 to 50, or the heterocyclic group having 5 to 5 ring atoms, / 2 of a substituted or unsubstituted ring carbon number of 6 to 50 = aryl group, or a substituted or unsubstituted ring atom having a ring number of 5 to 5 q, which is a substituted or unsubstituted ring carbon number of 6 to 5 Å. Instead, the number of ring atoms is 5 to 5. The two knives other than r1 to r8 of the heterocyclic group are independently selected from a hydrogen sheet, an atom-substituted or unsubstituted carbon number of 1 to 50 fluorenyl groups, a substituted or unsubstituted ring carbon number of 3 to an unsubstituted carbon number 丨〜5()的和amp;^ Η (4), substituted or aryl ketone alkoxy, substituted or unsubstituted carbon number 7~50 ❹ di- or unsubstituted cyclofilament 6~ other aryloxy Replace

Is: an arylthio group of 6 to 5 G, a substituted or unsubstituted carbon number of 2 cyano group, a wall group, and a hydroxyl group. a carboxy group, a functional atom, or a derivative of the present invention, preferably, R- is a substituted or unsubstituted ring carbon number: and R is a substituted or unsubstituted ring aryl group, or is taken as ~ 6 of which: take: two:: ring;: and, base, or substituted or unsubstituted, the number of 6 to 50 aromatic atoms 5 to 50 heterocyclic groups. 38 201012898 The onion derivative of the present invention, preferably, wherein R1, R2, and rS are substituted or unsubstituted aromatic groups having a ring carbon number of 6 to 5 Å and, wherein r3, RR and R are - It is a substituted or unsubstituted ring carbon number 6 to a square fragrant group. More preferably, '^ and R5 are a substituted or unsubstituted aryl group having a ring carbon number of 6 to 50, or R4 and W are a substituted or unsubstituted ring carbon number (10).曰❹ More preferably, R and R6 are substituted or unsubstituted ring carbon numbers: base, or R1R7 is substituted or unsubstituted ring carbon number 6~5G aromatic 0 benzene di A CM is preferably respectively A phenyl group which is independently substituted or unsubstituted, and is substituted with or without a substituted ring carbon number 6 to a aryl group or a substituted or unsubstituted heterocyclic group having 5 to 30 ring atoms. τ 丁数: &gt; 30 is mixed with the above-mentioned Rl~R8 requirements, preferably _ 卜, the onion derivative of this volume, privately used for the following creatures (A), (B) The organic structure of the £L· component is achieved by Akanishi +, and can be selected according to the characteristics of the composition or the required characteristics. (Onion derivative (A)) The onion derivative 'in the formula (2), the eight or five unsubstituted ring carbon number 10 to 5G "and the minute (four) site is substituted into Α γ11 and Ari2 is, ', D-fragrance. The onion derivative can be used in the case of a condensed aromatic group with c and not deuterated or unsubstituted. ^ The same formula (2) is substituted or "in the case of condensed aromatic group" It is represented by Bu (2_3), which is derived from the derivative of 2010, 201012898, and Aru b in the formula (2), "12 ηη &gt; $, and a different substituted or unsubstituted condensed aromatic onion derivative of Ar. The onion derivative represented by the formula (2 to 1), Ar11 and Ar12 are a substituted or unsubstituted 9-phenanthryl group.

(In the formula (2-1), R1 to R8 are the same as above, and hydrazine is an aromatic group selected from a hydrogen atom, a substituted or unsubstituted ring carbon number ό~50, and a substituted or unsubstituted carbon atom number of 5 to 50. a heterocyclic group, a substituted or a substituted alkyl group having a carbon number of 1 to 5 Å, a substituted or unsubstituted ring carbon number of 3 to % alkyl group, a substituted or unsubstituted alkoxy group having a carbon number of i to 5 Å , substituted or substituted, substituted aralkyl group of 7 to 50, substituted or unsubstituted ring carbon number 6 50 aryloxy group, substituted or unsubstituted ring carbon number 6~5〇 arylthio group, substituted Or unsubstituted money 2~5Q of the oxygen-reduced, substituted or unsubstituted @基H i atom, cyano, schishyl and thiol group, a is an integer of 〇~9, when Wang is an integer of 2 or more When the plural rU is the same or different under the condition that the two substituted or unsubstituted phenanthryl groups are the same, the onion derivative represented by the following formula (2~2), formula (2) Among them, Arll and AjJ2 are substituted or unsubstituted 2-naphthyl groups. 201012898

(2-2) (In the formula (2-2), R1 to only 8 丨b is 1 7 is the same as the above, and is an integer of 1 to 7. When b is 2 or more, they may be the same or different.) Positive number 犄, plural Rn, 葱 The onion represented by the following formula (2~3) is substituted or unsubstituted i-naphthalene. Arl 1 and ΑΓ12 in work (2)

(2-3) ❹ (In the formula (2-3), 'R1 to R8, r, when b is an integer of 2 or more, the same as above except the above formula (2~i)~r) Same or different. JV~3) Table - is the same as in the formula (7) and Aru is the same: the indole derivative, preferably the indole derivative of the indole, and the substituted or unsubstituted propylene in the formula (2) An unsubstituted thiol-based onion derivative. Γ and 8 1&quot;12 are the same substitutions or Ar11 and Αγ!2 in formula (2) are different scented onion derivatives, Ar11 and aa substituted or unsubstituted condensed car 乂 为 为 (2~ 1)~(2~3), 41 201012898 Substituted or unsubstituted 9-phenanthryl, substituted or unsubstituted i-naphthyl, substituted or unsubstituted 2-naphthyl, and substituted or unsubstituted propylene fluorene Any of the bases. Specifically, the case where 'Ar11 is 1—Caiji and Ar12 are 2-naphthyl', where Ar is 1-methyl and Ar12 is 9-phenanthryl, and αγ&quot; is 2~naphthyl and Ar12 is 9 — Fickey's situation. (Onion derivative (B)) The acetyl derivative is one of AriiA Aru in the formula (2) which is a substituted or unsubstituted phenyl group, and the other is a substituted or unsubstituted ring carbon number of 1 〇 5 The condensed aromatic group of hydrazine. Specific examples of the onion derivative include onion derivatives represented by the following formulas (2 to 4) and (2 to 5). The onion derivative represented by the following formula (2-4), wherein Arll in the formula (2) is a substituted or unsubstituted 1-naphthyl group, and Aru is a substituted or unsubstituted phenyl group.

In the formula (2-4), R, r8, R丨丨 and "the same as above, A&quot;6 is a substituted or unsubstituted aryl group having a ring carbon number of 6 to 50, a substituted or a filamentous ring carbon number of 1 ~ County, substituted or unretained ring carbon number 3 50% alkyl, substituted or unsubstituted carbon number 7~5〇 aralkyl, taking: or unsubstituted ring atom number 5~5〇 The ring group, or Αγ6, may also be the same as the eight bonded benzene rings, forming a substituted or unsubstituted base or taking 42 201012898 or unsubstituted R ' may be the same or different, respectively. An onion derivative represented by the following formula (2^5), a formula or a non-substituted 2~ laughing | 12 (wherein Ar is a phenyl group which is a substituted or unsubstituted phenyl group). When b is an integer of 2 or more

(2-5) ❹ (in the formula (2~5), r1~r8, Rll

Ar7 A ft ^ -v and b are the same as above, and are substituted or unsubstituted ring carbon number 丨~ substituted ring carbon number 3~» ϋ alkyl group, substituted or unsubstituted ί 基 group, substituted or unsubstituted a carbon number of 7 to a square alkyl group, a substituted or unsubstituted benzofuran-H, a dihalide atomic number of 5 to 5 fluorene, a dihydrazino group, a dibenzoheptyl group, a dibenzofuran :, or two stupid and biting the "4-base" Ge, Μ This ring together, forming a substitution of (4) m + 〃 the key of the w... The base is either substituted or unsubstituted, L is an integer of 2 or more In the plural, the other J is the same or different.) In addition to the derivative represented by the formulas (I) and (2-5), it is also the Ar/quot; substituted or unsubstituted propylene. The onion derivative in which V is a substituted or unsubstituted base. (Onion derivative (c)) This Huijie creature is represented by the following formula (2-6), specifically, the following is compared with 43 201012898 The derivative of the formula (2-6). 0, (2 ~ 6 - 2) and (2 6 ~ 3) -

(5) (5-6) 'R1~R8 and the same as above, ΑΓ is a substituted or unsubstituted aryl group having a ring carbon number of 6 to 50, substituted with an unsubstituted ring carbon number (9) Or an unsubstituted cycloalkyl group having a ring carbon number of 5 〇, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 5 ring atoms, A〆 and The points I are selected independently.) '

(In the formula (2-6-1), R~R8 are the same as above) 44 201012898

R to R are the same condensed aromatic groups as described above. (in the formula (2~2), or the unsubstituted ring carbon number 1〇a. Ar8 is substituted

The Ύ IV system and the formula (2) phase &amp; and ΑΓ "series are independently substituted or uncondensed aryl groups."

Ring carbon number 10 Aromatic R, ^ and 仏^^" ring carbon number 6~50 :: 香基' can be phenyl, naphthyl, 2-caiji I onion, 2 - : base, 9- Huiji, Bufiji, 2-phenanthryl, 3-phenanthryl, 4-phenanthyl, phenanthrene-phenanthryl, di-tetraphenyl, 2-_thick tetraphenyl, 9-thick tetraphenyl, 2- Biji, 4-Si, 6-Bei, Bu-Bian(4)phenanthren, 2-::(4)phenanthryl, 3-benzo[c]phenanthryl, 4-benzo[c]phenanthryl, 5-benzoic acid And (4) phenanthryl, 6-benzo(4)phenanthryl, phenylephrine, 2~benzo[4) carbyl]~benz[g]m, 4-benzo[g]m, 5-benzo-yl, 6~Benzene (4) disease 45 201012898 Base, Bu stupid [g] child base, 8- stupid [g] child base, 9-stupid [g] child base, ι〇-benzo (tetra) base, η-benzene And _ base, 12~ stupid (four), i3 and [g] child base, 14-benzo[g] carbyl, 丨triphenyl, 2-triphenyl, benzyl, 9,9-dimethyl f 2 —yl, benzodienyl, dibenzoxyl, 2-biphenyl, 3-biphenyl, 4-biphenyl, conjugated tris- 4-3-yl-p-triphenyl-2- Base, interstitial tris--4-yl, m-di-3-yl, m-triphenyl-2-yl, phenyl, tolyl, sub-ben , p-tertiary butylphenyl, p-(2-phenylpropyl)phenyl, 3-methyl-2-naphthyl, 4-methyl-1-mononaphthyl 4-methyl, 4' Methylbiphenyl, 4, '- = *, mono-butyl butyl biphenyl-4-yl, and the like. = is 'unsubstituted phenyl, substituted phenyl and substituted or without % carbon number 1G~14 (for example, naphthyl, 2-naphthyl, 9 =, substituted or unsubstituted ^(2_) ), and substituted or unsubstituted stone mountain ^ 1 base, 2 - Youji, 4 - Youji). The substituted or unsubstituted ring is preferably an aromatic group of ～50, preferably the above group. Ar Al&gt; and Af8 have a condensed aromatic group having a carbon number of 10 to 20, a bis-yl group, a 2-naphthyl group, a 1-onion group, a 2-onion group, a 9-onion group, an i stupid earth 2 phenanthryl group, and 3 - phenanthryl, 4-phenanthyl, 9-phenanthryl, j-thickened four-: broad copper four stupid base, 9-thick tetraphenyl xiaoyouji, 2, 4 ratio: 2 - fluorenyl and the like. In particular, it is preferably a naphthyl group, a 2-naphthyl group, a 9-phenanthryl group, an anthracenyl group (fluorenyl group, a 2-fluorenyl group, a 4-fluorenyl group), and a second group (2). Substituting *red, s ^Hanfu or ‘,,' substituted condensed aromatic group having a ring carbon number of 10 to 2 M M is preferably a base. R to R8, Ar11, Ar12, R11 » At·5 a 7 Ar R and Ar~Ar7 ring number 5, 46 201012898 5 〇 heterocyclic group, which may be 丨-pyrrolyl, 2-pyrrolyl, 3 — Pyrrolyl, i-indenyl, 2-acridinyl, 3-anthra, 4_bite, 丨-吲, 2-t-tyl, 3-mercapto, 4_, fluorenyl, 5—吲哚 base, 6—引引. Woody, 7 吲哚 吲哚, i —isoindolyl, 2 —isoindolyl, 3 —iso-column, 4-iso, fluorenyl, 5-isoindyl, 6-isoindole Sulfhydryl, 7-mercapto, 2-furyl, 3-furanyl, 2-benzofuranyl, 3-benf-folfyl, 4-benzofuranyl, 5-benzofuranyl, 6 ~ benzofuranyl, 7-benzofuranyl, 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-iso Stupid and furanyl, 7-isobenzofuranyl, fluorenyldibenzofuranyl, 2-dibenzofuranyl, 3~~dibenzofuranyl, 4-dibenzofuranyl, quinone diphenyl And thienyl, 2-dibenzothiophenyl, 3-dibenzothiophenyl, 4-dibenzothiophenyl, quinolyl, 3-quinolinyl, 4-quinolinyl, 5-quinolinyl, 6~Quinolinyl, 7-quinolyl, 8-quinolinyl, 1-isoquinolyl, 3-isoquinolinyl, 4-isoquinolyl, 5-isoquinolinyl, 6-isoquine啉 基, 7 — 异 书 琳 、 、, 8 — 啥 啥 啥 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基 基啥 淋 淋 、 、 1 、 、 、 、 、 、 、 、 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋 淋, 3 ~~-pyridinyl, 4-cyridinyl, 6-pyridinyl, 7-cyridinyl, 8-pyridinyl, 9-phenylpyridinyl, indoleyl, acridine Base, 2~bite group, acridinyl group, 4-acridine group, 9-acridinyl group, 1,7-diazaphenanthrenyl group, phenanthroline-3-yl group, 1,7-diaza Phenanthrene-4-yl, '-azaphenanthrene-5-yl, 1,7-diazaphenanthrene-6-yl, 1,7-dinitrogen

Miscellaneous -Q ·, ~ base, 1,7-dione phenanthrene-9, 1,7-diazepine-201012898-based, 1,8-diazaphenanthrene-2-yl, 1, 8 _ diazaphenanthrene-3-yl, 1,8-diazaphenanthrene-4-yl, 1,8-phenanthroline-5-yl, 1,8-diazaphenanthrene-yl, 1,8-diazaphenanthrene-7-yl, 1,8-diazaphenanthrene-9-yl, 1,8-diazaphenanthrene-yl, 1,9-diazaphenanthrene-2 1,1,9-diazaphenanthrene-3-yl, 1,9-diazaphenanthrene-4-yl, 1,9-diazaphenanthrene-5-yl, 1,9-diazaphenanthrene 6 —yl, 1,9-diazaphenanthrene-7-yl, 1,9-diazaphenanthrene-yl, 1,9-diazaphenanthrene-yl, 1,10-diaza Phenanthrene-2-yl, 1,10-diazaphenanthrene-3-yl, 1,10-diazaphenanthrene-4-yl, 1,10-diazaphenanthrene-5-yl, 2,9-di Azaphenanthrene-1-yl, 2,9-diazaphenanthrene-3-yl, 2,9-diazaphenanthrene-4-yl, 2,9-diazaphenanthrene-5-yl, 2,9 - diazaphenanthrene-6-yl, 2,9-diazaphenanthrene-7-yl, 2,9-diazaphenanthrene-8 —2,9-diazaphenanthrene-10-yl, 2,8-diazaphenanthrene-yl, 2,8-diazaphenanthrene-3-yl, 2,8-diazaphenanthrene 4-yl, 2,8-diazaphenanthrene-5-yl, 2,8-diazaphenanthrene-6-yl, 2,8-diazaphenanthrene-7-yl, 2,8-diazonium菲菲-9-yl, 2,8-diazaphenanthrene-yl, 2,7-diazaphenanthrene-yl, 2,7-diazaphenanthrene-3-yl, 2,7 — Diazaphenanthrene-4-yl, 2,7-diazepine-5-yl, 2,7-diazaphenanthrene-6,yl 2,7-diazaphenanthrene-yl, 2, 7-diazaphenanthrene-9-yl, 2,7-diazaphenanthrene-yl, phenazinyl, 2-morphinyl, phenothiazinyl, 2 - morphine, 3 - ° non- phenylation, 4 - morphine, thiophene, 10 - thiophene, 1 - phenoxazinyl, 2 - morphine, 3- morphine腭明: base, 4-morphine morphine, 10-brown oleyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-oxadiazolyl, 5-indole Two 48 201012898

Azolyl, 3-furazanyl, 2-thienyl, 3-thienyl, 2-methylpyrrole-yl, 2-methylpyrrole-3-yl, 2-indenyl-di- Mono-, 2-indolylpyrrole-5-yl, 3-~methylpyrrole-j-yl, 3-methylpyrrole-2-yl, 3-methylpyrrole-4-yl, 3-indolylpyrrole-5 — base, 2-tertiary butylpyrrole 4-yl, 3-(2-phenylpropyl)pyrrole-i-yl, 2-methyl-! _ fluorenyl, 4-hydrazino-i-indenyl, 2-indenyl-3-indenyl, 4-methyl-3-indenyl, 2-trino-butyl-indole , 4-tertiary butyl-l-fluorenyl, 2-tri-tert-butyl-3-indolyl, 4-tertiary butyl-3-indolyl, and the like. Preferably, fluorene-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl, 4-dibenzofuranyl, 1-dibenzothiophenyl, 2-di-benzothiophene Base, 3-dibenzothiophenyl, 4-dibenzothiophenyl, 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-oxazolyl, 9-carbazolyl. The substituted or unsubstituted heterocyclic group having 5 to 50 ring atoms is preferably the above group. R to R, R11 and Ar5 to Ar7 have a carbon number of from 1 to 50, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, an isobutyl group, and a second group. Butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, methyl, 1-ethyl, 2-ethyl, 2-isobutyl, 1,2-diethyl , Zhao isopropyl, 2,3-diamino-tert-butyl, 1,2,3-tri-propyl, methoxymethyl, 1-monoethyl, 2-chloroethyl, 2-gas Butyl, 1,2 monoethyl, 1,3 - diisopropyl, 2,3 - digas, tert-butyl, ι, 2,3 - propyl, xi methyl, 1-bromo Base, 2 - oxime, 2 - desert butyl 1, 2 - bis-ethyl, 1, 3 - isopropyl, 2, 3 - dimethyl-tert-butyl, 1, 2, 3 -Tribromopropyl, iodonium, 1 monoiodoethyl, 2 - mothyl, 2 49 201012898 - iodoisobutyl ' 1,2-diiodoethyl, 1,3 -diiodoisopropyl, 2,3—diiodo-tertiary butyl, 1,2,3-triiodopropyl, aminemethyl, decylaminoethyl, 2~amine ethyl, 2-amine isobutyl, 1,2— Diamine ethyl, 1,3_two Isopropyl, 2,3-diamine-tert-butyl butyl, hydrazine, 2,3-triamine propyl, cyanomethyl, summer-cyanoethyl, 2-cyanoethyl, 2-cyano Isobutyl, j'2-dicyanoethyl, 1,3~dicyanoisopropyl, 2,3-dicyano-tertiary butyl, 12,3-dicyanopropyl, nitrate Methyl, 1-nitroethyl, 2-nitroethyl, 2-nitroisobutyl, 1,2-dinitroethyl, hydrazine, 3-dinitroisopropyl, 2,3 _ Dinitro-tertiary butyl, 1,2,3-trinitropropyl and the like. Preferred are methyl group, ethyl group, propyl 'isopropyl group, n-butyl group, second butyl group, isobutyl group, and second butyl group. The substituted or unsubstituted alkyl group having 1 to 50 carbon atoms is preferably the above one. The cycloalkyl group having 3 to 5 ring carbon atoms of the substituent of R1 to R8, R11 and Ar5 to Ar7 may, for example, be a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a 4-methylcyclohexyl group. 1 - adamantyl, 2-adamantyl, anthracene-norbornyl, norbornyl. Preferred is 'cyclopentyl" or cyclohexyl. The substituted or unsubstituted ring is preferably a cycloalkyl group having 3 to 50 carbon atoms, preferably the above. The alkoxy group having 1 to 50 carbon atoms of R R and Rl 1 is a group represented by -〇z, and the Z is selected from the alkyl group having a substituted or unsubstituted carbon number of the above R1 to R8. The arylalkyl group having 7 to 50 carbon atoms of the substituent of RR, R11 and Ar5 to Ar7 (the portion of the aryl group is a carbon number of 6 to 49, and the part of the alkyl group is a carbon number 丄~) may be a benzyl group or a benzene group. Ethyl ethyl, 2-phenylethyl, fluorenyl phenyl isopropenyl isopropyl, phenyl-tertiary butyl, α-naphthyl fluorenyl, 50 201012898 1-—naphthylethyl, 2— 〇:—naphthylethyl, i—“naphthylisopropyl, 2-α-naphthylisopropyl, naphthylmethyl, anthracenyl-naphthylethyl, 2-—3—naphthalene Ethyl ethyl, ;!-n-naphthylisopropyl, 2_cold-naphthylisopropyl, 1-pyrrolylmethyl, 2-0-pyrrolylethyl, p-methylbenzyl, m. Benzyl, o-methylbenzyl, p-chlorobenzyl, m-chlorobenzyl, o-benzyl, p-bromobenzyl, m-bromobenzyl, o-bromobenzyl, p-iodobenzyl, m-iodobenzyl, O-iodobenzyl, p-hydroxybenzyl, m-hydroxybenzyl, o-hydroxybenzyl, p-aminobenzyl, m-aminobenzyl, o-aminobenzyl, p-nitrobenzyl, m-nitrobenzyl , o-nitrobenzyl, p-cyanobenzyl, m-cyanobenzyl, o-cyanobenzyl, 1-hydroxyl 2-Phenylisopropyl, fluorene- 2-2-phenylisopropyl, etc. A substituted or unsubstituted aralkyl group having 7 to 5 carbon atoms is preferred from the above groups. R to R and R11 The aryloxy group and the arylthio group having a ring carbon number of 5050 are respectively represented as a fluorene and -SY, and the γ is selected from the above substituted R1 to R8 substituted or unsubstituted aromatic group having a ring carbon number of 6 to 50. _ R1 The alkoxycarbonyl group having a carbon number of 2 to 50 to R8 and R11 (the alkyl moiety is a carbon number of 1 to 49) is represented by a c〇〇z, and the z is a substituted or unsubstituted carbon number selected from the above r1 to r8. ~49 alkyl.

The substituted fluorenyl group of R1 to R8 and R11 may, for example, be a trimethyl sulfonium group, a triethylene sulfanyl group, a tertiary butyl dimethyl fluorenyl group, a vinyl fluorenyl group, a propyl fluorenyl group or a triphenyl fluorene group. Base. The above-mentioned "substituted or unsubstituted" means that the substituents may further have an alkyl group, a cycloalkyl group, an alkoxy group, a cyano group, a decyl group, an aryl group, a heterocyclic group or a halogen atom. The substituent is preferably an alkyl group, 51 201012898 cycloalkyl, an aromatic I, a heterocyclic group, more preferably an aromatic group or a heterocyclic group. Specific examples of such substituents are as described above. The dentate atoms of R to R8 and R11 may be fluorine gas, moisture or hydrazine. The onion derivative of the present invention' is preferably a '(4) organism in which the substituent is composed only of an aromatic group and/or a group, and most preferably, the substituent is composed of an aromatic group. The hydrogen atom bonded to the onion derivative of the present invention may also be used. Specific example 2 of the onion street creature represented by the formula (7) of the present invention

52 201012898

❹ 53 201012898

54 201012898

55 201012898

56 201012898

57 201012898

❿ 58 201012898

59 201012898

60 201012898

❹ 61 201012898

62 201012898

❹ 63 201012898

64 201012898 201012898

❿ 66 201012898

67 201012898

68 201012898

69 201012898

70 201012898

71 201012898

72 201012898

73 201012898

74 201012898

75 201012898

76 201012898

77 201012898

78 201012898

❹ 79 201012898

80 201012898

81 201012898

82 201012898

83 201012898

84 201012898

85 201012898

86 201012898 201012898

88 201012898

89 201012898

90 201012898

91 201012898

92 201012898

93 201012898

94 201012898

95 201012898 The diamine-based derivative represented by the formula (1), for example, can be used to introduce a substituent by a known method after the bromination of a commercially available ruthenium bromide. , bromination again under the metal catalyst, and the oblique reaction, thereby synthesizing. Further, in the above formula (7), the onion derivative represented by the second-order amine compound 1 to fly () can be synthesized, for example, by the method described in WO2004/018587 - the organic light-emitting medium of the present invention (1) It is indicated that the diamine group is a coexisting bear with the onion derivative represented by the formula (2).质量 The mass ratio of the diamine-based derivative represented by the formula (1) to the two compounds represented by the formula (2) is preferably 50: 50 to 〇1 〜, and the butyl is more preferably 20: 80 to i · yy 〇 [organic EL Element] The organic EL element of the present invention is an element of an organic thin film layer of a complex: layer of an anode and a cathode. When the organic thin film layer is a plurality of layers, the layer becomes a light-emitting layer. When the organic thin film layer is layered to the anode = there is a light emitting layer as an organic thin film layer. Organic film ❹ illuminating medium: Γ Γ is a luminescent layer) 'includes the organic zan 蜾 body of the present invention, in order to transfer the injected electrons injected from the anode to the luminescent material; . The organic light-emitting medium of the present invention has a high incidence:::. Electrically, the organic EL element of the present invention is an organic thin film layer composed of an anode and a cathode gate sandwiching a luminescent layer of a layer of 3 or more layers, wherein r is preferably between the anode and the luminescent layer. Organic: medium, more than the transport layer. Organic layer. The organic layer can be referred to as a hole injection layer, and the hole is transmitted. 96 201012898 The organic thin layer of the present month is a plurality of layers (anode/hole injection & organic EL element's light layer/electron injection layer/risk# The optical layer/cathode) and the (anode/layer/electron injection layer (anode/hole injection layer/light-emitting I' cathode) are laminated. In the plural layer, in addition to the organic light-emitting medium of the present invention. In addition, it is also possible to further use the well-known illuminating illuminating or electron injecting material. The organic EL V material and the hole injecting material are 70 ,t, by making the organic thin enamel layer into a plurality of layers. It can prevent quenching (_η ❹: if necessary, luminescent material, doping two == combined use. Also, by doping the material, it can obtain red or blue luminescence with improved illuminance or efficiency. The hole injection layer, the first layer, and the electron injection layer may be formed by layer formation of two or more layers. At this time, in the case of the hole injection layer, the layer in which the electrode is injected into the hole is referred to as a hole injection layer. Receiving a hole from the hole injection layer and then transmitting the hole to the light emitting layer The layer is called a hole transport layer. Similarly, in the case of an electron injection layer, a layer in which electrons are injected from an electrode is called an electron injection layer, and a layer in which electrons are transferred from an electron injection layer and then transmitted to a light-emitting layer is called an electron. The transport layer can be selected according to the main factors such as the energy level of the material, the heat resistance, and the adhesion to the organic layer or the metal electrode. It can be used together with the organic light-emitting medium of the present invention in the light-emitting layer. The host material or the doping material may be naphthalene, phenanthrene, rubrene, onion, tetracene, perylene, chrysene, decacyclene, orthoquinone (decacyclene). Coronene), tetraphenylcyclopentadiene, pentaphenylcyclodecadiene, anthracene, spiro, 9,10-diphenyl onion, 9,10-bis(phenylacetylene 97 201012898) onion, 1 , 4-bis(9,1-ethynyl onionyl)benzene and other condensed aromatic compounds and the specific biological, ginseng (8-jing Jilin)|Lu, Shuangyi (2 - fluorenyl-8) Organometallic complexes such as quinoline)-tetra-(phenylphenolate) aluminum, triarylamine derivatives, Ethylamine derivative, diphenylethylene derivative, coumarin derivative, piperan derivative, oxaz〇ne derivative, benzothiazole derivative, benzozazole 〇xaz〇le) derivative, stupid imidazole derivative, pyrazine derivative, cinnamic acid ester derivative, diketopyrrolopyrrole derivative, acridonone derivative, quinacrid a ketone (qUinacrid〇ne) derivative, etc., but not limited to such. The hole injecting material 'preferably has the ability to transport holes, has a hole injection effect by the anode, has a light-emitting layer or an organic light-emitting medium Excellent hole injection effect, a compound that prevents excitons generated in the light-emitting layer from moving toward the electron injection layer or the electron injecting material and has excellent film forming ability. Specifically, for example, a phthalocyanine derivative, a naphthalocyanine derivative, a p〇rphyrin derivative, an oxazole, an oxadiazole, or an oxadiazole may be mentioned. ), three β sitting, taste β sitting, n meters. Ketone, rice sputum is IL ketone, 0 is pyraz〇lin, η is pyraz〇i〇ne, tetrahydro imi. Sitting, sturdy, hiring diazole, hydrazone, hydrazine, polyarylalkane, stilbene, butadiene, benzidine triphenylamine, styrylamine triphenylamine, diamine triphenylamine, etc. And such derivatives, and polymer materials such as polyvinyl carbazole, polyfluorene, and conductive polymers, but are not limited thereto. The hole injecting material used in the organic EL device of the present invention can be more effective. The hole injecting material is an aromatic tertiary amine derivative and a derivative of phthalocyanine 98 201012898. Aromatic tertiary amine derivatives, for example, triphenylamine, trimethylamine, phenyldiphenylamine, N,N'-diphenyl-N,N'-(3-mercapto-phenyl, 4-biphenyl-4, 4'-Diamine, N,N,N',N,-(4-mercaptophenyl)-M,-phenyl-4,4'-diamine, N,N,N',N'- 4-nonylphenyl-biphenyl-4,4-amine, N,N'-diphenyl-N,N'-di-naphthyl-[, hydrazine, monobiphenyl-4,4' Diamine, N, N'-(methylphenyl)-N,N,-(4-n-butylphenyl)-phenanthrene-9,1-diamine, N,N-bis(4-di- 4-monophenylamine phenyl)-tetraphenyl-cyclohexane or the like, or an oligomer or polymer having the aromatic tertiary amine skeleton, etc., but is not limited thereto. Eryion (Pc) derivative For example, there are H2pc, CuPc, c〇pc, ZnPc, PdPc, FePc, MnPc, clA1Pc, cmapc, CUnpc, cisnpc,

Cl2SiPc, (HO)AlPc, (H0)GaPc, v〇Pc, Ti〇Pc, M〇〇pc,

An anthraquinone derivative such as GaPc-O-GaPc or a naphthophthalocyanin derivative, but is not limited thereto.

Further, the organic EL device of the present invention is preferably formed between the light-emitting layer and the anode, and is formed with a layer containing the aromatic second face, which is derived from the scorpion sulphate, and/or the anthraquinone derivative. For example, the hole transport layer or the hole injection layer. The electron injecting material, 敕佳 A, preferably has the ability to transport electrons, has an electron injection effect from the cathode, and has a superior electron injection effect on the precursor layer or the luminescent material, and can prevent tI φ ^ A compound that excites the exciton generated by the first layer to move toward the hole injection layer and has excellent film forming ability. A metal ruthenium of a specific example of the electron injecting material, a metal sterol D of 8-hydroxyquinoline or a derivative thereof, or a diazole derivative is preferred. A specific example of the 8-hydroxyquinoline or a metal complex thereof of 99 201012898 Ho can be used for metal chelation of a chelate containing Osin (general quinolinol or 8-hydroxyquinoline) Chemical gas = / (〇Xyn〇id) compound (for example, ginseng (8-quinolinic acid) aluminum) as an electronic § German material.卞〉Main material, on the other hand, the compound of the quinone derivative, which can be exemplified by the following formula:

Ar5

-Ar7—Ο-Ar®——Ar® 矣- (In the above formula, Αγ1, Αγ2, Αγ3, Αγ5, Α/4Αγ^α: 4 or unsubstituted aryl groups, respectively, may be the same or different. Do not indicate the substituted or unsubstituted arylene group for the 22nd and 78th series, or the 'electron injection material', which can be expressed by the following general formula (8)~(F)

Formula (A) and peak) m ^ nitrogen-containing ring derivatives

100 201012898 Carbon in the general formulae (A) and (8), the Arl~Ar3 series are independently substituted by a nitrogen atom or an e Ar '-substituted or unsubstituted ring carbon number of 6~, and the number of ring atoms is 2 or unsubstituted. a heterocyclic group of 5 to 6 fluorene, i or ai #', a substituted or unsubstituted ring carbon group, a substituted or unsubstituted ring atom number of 60, a substituted carbon number, or a :::=, superseded or absent--, or the 2: of them: substituted or unsubstituted... Bu 60 is the second of them - the 'substitution or substitution of ring carbon number (\ is a substituted or unsubstituted ring atomic number 5~60 of the early (m〇n〇hetero) condensed ring group. Number two, Λ:: 独独亚芳Λ The number of substituted or unsubstituted ring atoms 5~60 Heteroarylene, or Huorenylene., substituted substituent R, a hydrogen atom, a substituted or unsubstituted ring carbon number 6~6〇 substituted or unsubstituted ring atom The number of 5 to 6 alumina, the carbon number of the alkyl group, or the substitution = the unsubstituted alkoxy group 'η is an integer of 〇~5, ',,, and the substituted U 1~20 may be the same or phase different Alternatively, when it is adjacent to J, the plural number of rings forms a carbocyclic aliphatic ring or a carbocyclic aromatic number R group is bonded to each other R1, which is a hydrogen atom, a substituted or unsubstituted = group, a substituent or Unsubstituted ring carbon number 3~6 Anti-6~60 square scent substituted carbon number U sylylene diisoaryl, substituted or non-flyer 疋 substituted or unsubstituted carbon number 1 101 201012898 ~20 alkoxy a nitrogen-containing heterocyclic derivative represented by the formula (C): HAr-L1-Ar1-Ar2 (c) having a carbon number of 3 to 40 (wherein the 'HAr' system Further, it may have a substituent heterocyclic ring, an aromatic group having a ring carbon number of 6 to 60, a heteroarylene group having 6 Å, or a ring atom which may have a L-type single bond or may have a substituent or a substituent. a number of substituted thiol groups, which may also have a substituent of a ring carbon number of 6 hydrocarbon groups, a 60-valent aromatic

The A fluorene group may have an aromatic group having a ring carbon number of 6 to 60 or a heterocyclic group having a ring number of 5 to 60 which may have a substituent. () kg represents the cyclopentadiene derivative (silacycl〇pentadiene):

(wherein X and Y are independently saturated or unsaturated in each of the numbers 1 to 6; alkoxy, alkoxy, diloxy, alkynyloxy, hydroxy, substituted or unsubstituted aryl, substituted or unsubstituted a substituted heterocyclic ring or a structure which is bonded to γ to form a saturated or unsaturated ring, R to R, each independently being hydrogen, a halogen atom, a substituted or unsubstituted alkyl group having a carbon number of 1 i 6 , an alkoxy group Base, aryloxy, perfluoroalkyl, total gas 102 201012898 alkoxyamino, alkylcarbonyl, arylfan A pin 篡 篡 slave from w aryl aryl group, alkoxycarbonyl, aryloxy group, azo Base, alkylcarbonyl 枭^^^ oxy, aryl carbonyloxy, decyloxy, aryloxycarbonyloxy, subsupply sulphide, sulphide, sulfonyl, sulphonyl, tetrahydroanthracene Base, amine carbonyl, aryl, heterosulfide heterocyclyl, alkenyl, alkynyl, nitro, formyl, nitroso, methyloxy, τ, cyano, cyanate, isocyanate The structure of a condensation group of a thiol group, a thiocyanate group, and an isothiocyanate' substituted ring. t is substituted for the boron-burned derivative represented by the formula (8):

7 日 丞 丞 丞 丞 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环 杂环An aryl group, a heterocyclic group, a substituted amino group, an alkoxy group or an aryloxy group, and the substituents of B1 and Z2 may be bonded to each other to form a condensed ring, and n represents an integer of i3, and when π is 2 or more'匕 can also be different. And, in the case where ^^ and ^ are methyl groups and the heart is a nitrogen or a substituted boron boron group, and 4 3 and Ζ is a methyl group). 103 201012898

(P) expressed by the general formula (G) [wherein, Q1 and Q2 independently represent the lower ligand,

L represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted ring group, an OR1 (R1 hydrogen atom, substituted or unsubstituted) An alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group.) or a 0-Ga-Q3 (Q4) (Q3 and q4, with 屮And the same ligand as shown in Q2). ]

[In the formula, the rings A1 and A2 are a 6-membered aromatic ring structure which may have a mutual condensation of substituents. ] σ This metal complex has strong properties as an n-type semiconductor and has a large electron injecting ability. Further, since the formation energy at the time of formation of the complex compound is also low, the bond between the metal of the metal complex formed and the ligand is also strong, so that the fluorescence quantum efficiency as a light-emitting material is also large. In the hole injection material, the hole transmission material, and the electron injection 104 201012898, the alkyl group, the formula (10) =, the heterocyclic group, and the like described in the present invention can be applied to the above chemical examples. Or the above-mentioned chemical formula (7), R to R8, the preferred or difficult organic layer of the organic EL device of the present invention or the boundary between the cathode and the organic layer is preferably formed at a region where electrons are transported, and is reductively doped. The substance, the tomb is made into _ this substance. Therefore, the mouth of the ancient 4 can reduce the electron-transporting compound to the west, and only have a variety of Ning +, the market, for example, better, the sex can be used, the use of various rare earth metals, metal oxidation Free metal, geotechnical metal, oxide, alkaline earth metal, toothed material, alkaline earth metal metal, metal carbonate == oxide or rare earth metal organic compound, test Soil metal: at least one of the metal carbonates, the complexes formed by the organic complexes, and the rare earth metals. And 'more specifically' the preferred reduction function: ,, Κ (work function: 2.28ev) has two (power and Cs (work function: 1.9 city) mountain number. (4)) or ca (work function: 2.9eV In the middle of the 〉, - alkali metal, Μ work function: 2. coffee) at least _ secret +), and work function of 2.9eV or less is particularly good. Preferably, the preferred metal &apos; impurity is selected from the group consisting of (10) and ~ to a small-reducing blend, more preferably, or Cs, most preferably Cs.乂 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种 种Also, (9) seeking organic

The following reducing dopants may also be a group of two or more metal detectors such as 2.9 eV. 2010 20109898 〇Specially including a combination of Cs, for example, preferably Cs and Na, cs and s and Rb or Cs The combination of Na and K. By combining the inclusion of Cs, the reducing ability can be efficiently exhibited, and by adding the electron injecting region, the luminance of the organic rainbow element can be improved and the life can be extended. In the winter month, an electron injecting layer composed of a semiconductor or a semiconductor may be further provided between the cathode and the organic layer. At this time, % can be effectively prevented; (^ CUrrent), and electron injectability can be improved. Such an insulator is at least one metal compound selected from the group consisting of a metal compound such as a chaic genide, a test metal-based compound, an alkali metal compound, and an alkaline earth metal. . If the electron injecting layer is formed of such a metal chalcogenide or the like, the electron injectability can be further improved, which is preferable.

G is eight-body. Preferably, the alkali metal chalcogenide is, for example, Li2〇, K2〇, Na2S, Na2Se&amp; Na2〇, preferably a soil metallurgical compound, such as Ca〇, Ba〇, (4), Be〇, BaS'. And CaSe. Further, preferred examples of the alkali metal compound include LiF, NaF, KF, CsF, LiC, KC1, and Naci. Further, as a preferred embodiment of the soil-measuring metal, for example, a 2' BaF2, a ring, a ton or the like, or a halide other than a fluoride may be added. Further, a semiconductor constituting the electron injection layer may be included

Yb'Al, Ga, In, Ti, M〇λ λ ^ L! Na, Cd, Mg, Si, Ta, Sb, and Ζη = a single element of an oxide, a salt or an oxynitride, etc. - a combination of the above. Further, the inorganic compound constituting the electron injecting layer is preferably a microcrystalline or amorphous insulating film. If the electron injecting layer is composed of the insulating film of the above 4, a more homogeneous film can be formed, so that pixel defects such as less dark spots can be reduced by 106 201012898. Further, examples of such an inorganic compound include the above-mentioned alkali metal chalcogenide, soil-measuring metal chalcogenide, metallization metallization, and soil-measuring metal halide. Next, as the electrode, a metal having a small work function (4 eV or less), an alloy, a conductive compound, and a mixture thereof are used as the electrode material. Specific examples of such an electrode material are sodium, sodium-potassium alloy, magnesium, lithium, planer, magnesium-silver alloy, and oxidation/oxidation! S, A1//Li2〇, A1/Li〇, Ai/LiF, Mingzhong alloy, indium, rare earth metal, etc. &quot;Hai cathode' can be produced by forming the electrode material by vapor deposition or sputtering. Here, in the case where the light emitted from the light-emitting layer is emitted from the cathode, the transmittance of the light emission of the cathode is preferably greater than 10%, and the sheet resistance of the cathode is preferably several hundred Ω/ϋ or less. Further, it is usually from 1 nm to bm, preferably from 50 to 20 nm. ^, and the 5' organic EL element is a pixel defect due to leakage or short circuit due to the application of an electric field to the ultra. In order to prevent H, an insulating film layer can be inserted between the counter electrodes. The materials used in the layer of the inner layer of the bell can be oxidized, fluorinated clock, oxygen clock, gasification hammer, cerium oxide, oxidized lock, calcium hydride, aluminum hydride, titanium oxide, chaotic molybdenum oxide, oxidation Antimony, antimony oxide, antimony nitride, boron nitride, layer. Vanadium oxide, etc. It is also possible to use the mixture or the environment == obtained organic EL element for temperature, humidity, or a protective layer on the surface of the element, or a protective element such as 油 107 201012898 oil or resin. The conductive material used for the anode of the organic EL element of the present invention preferably has a work function of more than 4 eV, and can use carbon 'Ming, Syria, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium. Such an alloy, an iodine substrate, an oxidized metal such as tin oxide or indium oxide used in the NESA substrate, and an organic group-like 导电1 11 虿 conductive resin such as polythiophene and a polypyr. The conductive material used for the cathode is preferably a work function having a work function of less than 4 eV, and may be used for the alloy, the alloy, the tin, the titanium, the titanium, the bell, the bell, the bell, the fluorinated bell, and the like. ❹ But not limited to these. Heming, | Lifting lock / silver, town / indium, clock / Shao, etc. 1 乍 is a representative example, but not limited to these. The ratio of the alloy is controlled by the steam source Z degree, the ambient atmosphere, the true enthalpy, etc., and the ratio of the appropriate t is selected. The anode and the cathode ' may be formed in two or more layers as needed. In the organic EL device of the present invention, in order to efficiently emit light, it is preferable that at least one of the faces is sufficiently transparent in the light-emitting wavelength region of the element. The substrate is also preferably transparent. The transparent I-weight ^ φ edge-electrode is set to use the above-mentioned conductive material to ensure a predetermined light transmittance by vapor deposition or bismuth ❹ umbrella I 瑕 method. The electrode of the surface is preferably a light transmittance of 10% or more. The substrate is not particularly limited as long as it has several mechanical strengths and thermal strengths and is transparent, and J has a glass substrate and a transparent resin film. The transparent resin film may, for example, be a polyethylene, a material, or a mixture of ethylene-vinyl acetate, a copolymer of a vinyl alcohol, a poly(vinyl alcohol) copolymer, a poly(meth) methacrylate, a polyethene, a polymethyl methacrylate. Brewed, gasified ethylene, polyvinyl ether age apl, knowing, polyvinyl butyral, nylon, polymer, π* ethylene-perfluoroalkyl vinyl ether copolymerization

Polyethylene, tetrafluoroethylene, ethylene, ethylene, hexafluorene, hexafluoro, hexafluoro, hexafluoro, polytetrafluoroethylene, polyfluorene Vinegar, polyurethane, styrene, polyacrylamide, polyimine, polypropylene, etc. In the organic EL device of the present invention, the formation of each layer of the π2, 1 dry layer can be carried out by dry film formation such as vacuum evaporation, (10), plasma, ion (tetra)-platlng or spin coating, dipping, flow coating. S-method of iso-wet film formation method. The film thickness is not particularly limited and must be set to an appropriate film thickness. If the film thickness is too thick, the light output obtained ’ must be applied with a large voltage, which deteriorates the efficiency. If the film thickness is too thin, pinholes or the like are generated, and π does not have sufficient light-emitting luminance even if an electric field is applied. The film thickness of the pass f is preferably in the range of 5 nm to 1 Gp, and more preferably in the range of 10 nm to 〇.2 #m. In the case of the wet film formation method, the material for forming each layer of the ruthenium or ruthenium is dissolved or dispersed in a suitable solvent such as ethylene glycol, chloroform, tetrahydrogen, or hydrazine to form a film, and the solvent may be any. Further, in the organic thin film layer, an appropriate resin or additive for improving the film formability and preventing pinholes of the film or the like can be used. Resins which can be used include polystyrene, polycarbonate, polyarylate, polyester, polyamine, melamine polycondensate, decyl acrylate, polymethyl acrylate And a conductive resin such as a cellulose resin or the like, a copolymer of the above, a photoconductive resin such as poly-N-vinylcarbazole or polydecane, or a polypyrene or polypyrrole. The human, the additive may, for example, be an antioxidant, an ultraviolet absorber, a plasticizer or the like. The organic EL device of the present invention can be used for a light source such as a flat panel display such as a flat panel display of a wall-mounted television, a photocopying machine, a printer, a backlight of a liquid crystal display, a light source, a display panel, an indicator light, etc. 109 201012898 The material 'can be used not only for organic EL elements, but also for electrophotographic photoreceptors, photoelectric conversion elements, solar cells, image sensors, and the like. [Examples] Next, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited thereto. Further, in the following examples and comparative examples, 'compounds 3-7 to 5 3' refer to the following compounds. These compounds are synthesized by reference to International Publication WO2003/060956.

110 201012898

111 201012898

112 201012898 Synthesis Example 1 Dm 1 7 -1 of the dopant was synthesized by the following reaction.

(1) Synthesis of intermediate Μ-1 In a 200 ml three-necked flask, 2-amino- 9,9-diindenyl 36.6 mmol (7.66 g), dibenzylideneacetone dipalladium was placed. 0.28 mmol (0.25 g), 2,2'-bis(diphenylphosphino)-indole, quinone-binaphthyl (BINAP) 0.5 6 mmol (0.35 g) and tertiary sodium butoxide 37.5 mmol (3.61 g), The system was depressurized and subjected to two nitrogen substitutions. Next, 30 ml of toluene and 18.8 mmol (3.74 g) of 3,4,5-trimethylbromobenzene were placed, and the mixture was reacted under reflux for 7 hours. The insoluble matter was filtered off from the obtained reaction solution, and washed with benzene. The filtrate was washed with 200 ml of a saturated aqueous solution of sodium chloride, and then the organic layer was dried over magnesium sulfate. The residual oil after removal of the solvent was subjected to oxidization of the oxidized stone column (hexane/chlorodecane = 9/1 to 8/2) to obtain (M-1)3,7g 113 201012898 (yield 67%) ). (2) Synthesis of DM17-1 In a 200 ml three-necked flask, iota, 6-dibromo-3,8-di(2,1-naphthalene-grade sodium butoxide 10.2 mmol (0.98 g) was placed, and the system was depressurized. And nitrogen substitution was carried out twice. Then, 6〇ml of toluene and 0.51mmoK0.10g of tris(tert-butyl)phosphine and (M-1) U.2mm〇1 (37g) were placed, and 8 反应c was reacted. hour. The terpene was removed from the resulting heterogeneous solution, methanol was added, and the dissolved matter was filtered off. Wash with water and sterol. The insoluble material was recrystallized by repeating with toluene to obtain the target compound (3 g) (yield: 55%). The result of mass spectrometry is the target, relative to the molecular weight! 1〇4 54, m/ e = 1 1 04. Synthesis Example 2 Dm 17-2 of the dopant was synthesized by the following reaction. 114 201012898

Br Pd2(dba)3/BINAP/NaOtBu

(BrPyr)

Pd(OAc)2/P(tBu)3/NaOtBu

DM 17-2 In the synthesis of DM17-1, 3,4,5-tridecylaniline was substituted for 2-amino-1,9-dimethylindole, and 3,4,5-triethylbenzene was used. Instead of 3,4,5-tridecylbromobenzene, it was synthesized in the same manner. As a result of mass spectrometry, it was a target, m/e = 1040 with respect to a molecular weight of 1040.60. Synthesis Example 3 DM DM17-3 was synthesized by the following reaction. 115 201012898

Pd2(dba)3/BINAP/NaOtBu

In the synthesis of DM17-1, 3,4,5-trimethylbromobenzene was replaced with 3,4,5-triethylbenzene, and then synthesized in the same manner. As a result of mass spectrometry, it was a target, relative to a molecular weight of 1 1 88.63, m/e = 1 188. Synthesis. Example 4 The DM17-4 of the dopant was synthesized by the following reaction.

116 201012898 In the synthesis of DM17-1, 3,4,5-trimethylaniline was substituted for 2-amino-1,9-dimethylindole, and 2-bromodibenzofuran was used instead of 3,45. Dimethyl group is then synthesized in the same way. As a result of mass spectrometry, it was the target ' relative to the molecular weight n36 53, m/e = 1136. Example 1 A glass substrate (manufactured by Ge〇matec Co., Ltd.) containing an IT0 transparent electrode (anode) of 25 mm x 75 mm x 1 mm thick was ultrasonically washed in isopropyl alcohol for 5 minutes, and then subjected to UV ozone washing for 30 minutes. The glass substrate having the transparent electrode line after the cleaning is mounted on the substrate holder of the vacuum vapor deposition apparatus. First, the film thickness of the compound A-1 is formed on the surface on the side where the transparent electrode line is formed. Covering the transparent electrode. After the film formation of the A-germanium film, A_h having a film thickness of 20 nm is formed on the A-1 film, and a film thickness ratio of 40:2 and a total film thickness of 4 Å are formed on the a-2 film. The host material compound 37 of the present invention and the dopant materials DM1 to 丨 are formed as a green light-emitting layer.

On the film, an electron transport layer having a film thickness of 2 〇 nm was formed by vapor deposition. Thereafter, a 150 nm metal A-electrode EL light-emitting element was deposited on the thick film.

Alq of the following construction. In the LiF, I formed a 117 201012898

Example 2 to 64

In the first embodiment, the organic EL device was produced in the same manner by using the host material _ impurity material shown in Tables 1 and 2 instead of the host material compound 1637 and the dopant material surface. Comparative Example 1 In Example 1, an organic EL device was produced in the same manner by substituting the host compound H-oxime for the host compound 37 and using the dopant materials DM2 - 4 and __ instead of the dopant material DM ~ 1 '.

Comparative Example 2 Substituted host material composite material DM1 - 1, In the same manner as in Example 1, an organic EL device was produced in the same manner as in the case of using the compound Hi material 37 and the dopant material DM10-4. Comparative example 3

VIII: In the implementation of "You", the following compound Η-2 was used to replace the main phase (9), and the following compound D-1 was used instead of the dopant material DM 118 201012898 1, and an organic EL device was produced in the same manner.

Comparative example 4

In the first embodiment, the following corps is used. Η% 3 Substituting the host material Compound 37, an organic EL device was produced in the same manner using the following compound D-2 as the 擦n wipe material DM 1 - 1 '.

In Example 1, an organic EL device was produced in the same manner as in the following compound 37 using Compound D-2. The compound H-5 is substituted for the host material, and the dopant material DM 1 — 1 is replaced by 119 201012898

The light-emitting efficiency and the half-life of the initial luminance of 1000 cd/m2 of the organic EL devices obtained in Examples 1 to 64 and Comparative Examples 1 to 5 are shown in Tables 1 and 2. ®

120 201012898 [Table 1] Example No. Body material dopant material Luminous efficiency [cd/A] Half-life life [hr] 1 Compound 37 DM1-1 20 57000 2 Compound 38 DM1-1 20 60000 3 Compound 39 DM1- 1 20 60000 4 Compound 40 DM1-1 20 60000 5 Compound 41 DM1-1 20 60000 6 Compound 42 DM1-1 20 60000 7 Compound 43 DM1-1 20 60000 8 Compound 44 DM1-1 20 47000 9 Compound 37 DM2 —1 21 57000 10 Compound 38 DM2-1 21 60000 11 Compound 39 DM2 —1 21 60000 12 Compound 40 DM2-1 21 60000 13 Compound 41 DM2—1 21 60000 14 Compound 42 DM2—1 21 60000 15 Compound 43 DM2-1 21 60000 16 Compound 44 DM2 - 1 21 47000 17 Compound 37 DM3-8 21 57000 18 Compound 38 DM3-8 21 60000 19 Compound 39 DM3-8 21 60000 20 Compound 40 DM3-8 21 60000 21 Compound 41 DM3-8 21 60000 ' 22 Compound 42 DM3 —8 21 60000 23 Compound 43 DM3 —8 21 60000 24 Compound 44 DM3-8 21 47000 25 Compound 37 DM 2—4 22 58000 26 Compound 38 DM2-4 22 61000 27 Compound 39 DM2-4 22 61000 28 Compound 40 DM2 -4 22 61000 29 Compound 41 DM2 -4 22 61000 30 Compound 42 DM2—4 22 61000 31 Compound 43 DM2-4 22 61000 32 Compound 44 DM2—4 22 48000 33 Compound 37 DM9-1 22 58000 34 Compound 38 DM9-1 22 61000 35 Compound 39 DM9-1 22 61000 36 Compound 40 DM9-1 22 61000 37 Compound 41 DM9-1 22 61000 38 Compound 42 DM9-1 22 61000 39 Compound 43 DM9-1 22 61000 40 Compound 44 DM9-1 22 48000 121 201012898 [Table 2] Examples No. Bulk material dopant material Luminescence efficiency [cd/A] Half-life life [hr] 41 Compound 37 DM10-1 23 59000 42 Compound 38 DM10-1 23 62000 43 Compound 39 DM10-1 23 62000 44 Compound 40 DM10- 1 23 62000 45 Compound 41 DM10-1 23 62000 46 Compound 42 DM10-1 23 62000 47 Compound 43 DM10-1 23 62000 48 Compound 44 DM10-1 23 49000 49 Compound 37 DM11-8 23 59000 50 Compound 38 DM11-8 23 62000 51 Compound 39 DM11-8 23 62000 52 Compound 40 DM11-8 23 62000 53 Compound 41 DM11-8 23 62000 54 Compound 42 DM11-8 23 62000 55 Compound 43 DM11-8 23 62000 56 Compound 44 DM11-8 23 49000 57 Compound 37 DM10-4 24 60000 58 Compound 38 DM10-4 24 63000 59 Compound 39 DM10-4 24 63000 60 Compound 40 DM10-4 24 63000 61 Compound 41 DM10-4 24 63000 62 Compound 42 DM10-4 24 63000 63 Compound 43 DM10-4 24 63000 64 Compound 44 DM10-4 24 50000 Comparative Example 1 H-1 DM2-4 18 28000 Comparative Example 2 H-1 DM10-4 18 30000 Comparative Example 3 H-2 D-1 18 25000 Comparative Example 4 H-3 D-2 4 5000 Comparative Example 5 H-5 D-2 6.4 9000

Example 65 A glass substrate (manufactured by Geomatec Co., Ltd.) of 25 mm x 75 mm x l mm thick ITO transparent electrode (anode) was ultrasonically washed in isopropyl alcohol for 5 minutes, and then subjected to UV ozone washing for 30 minutes. The washed glass substrate containing the transparent electrode wire is mounted on the substrate holder of the vacuum vapor deposition apparatus. First, the compound A-3 having a film thickness of 65 nm 122 201012898 is formed on the surface on the side on which the transparent electrode line is formed. It covers the transparent electrode. Thereafter, the above-mentioned A-2 having a film thickness of 65 nm was formed on the A-3 film. On the film-forming A-2 film, the host material compound 37 and the doping material DM]-1, which are formed by the film thickness ratio of 19:1 and having a total film thickness of 2 〇nm, are green-emitting. Floor.

A-3 On the film, -2 of the following structure having a film thickness of 4 〇 nm was formed by vapor deposition as an electron transport layer. After that, w is formed to have a film thickness. On the UP film, a metal A of 1 〇 nm was vapor-deposited to form a metal cathode to form an organic EL light-emitting element.

Examples 66 to 1 34 Comparative Examples 6 to 8 Organic elements were produced in the same manner as in Example 65 except that the host material and the dopant material were changed to the compounds shown in Tables 3 and 4. 123, 2010, and Table 4, showing the luminous efficiency of the organic EL device obtained in Examples 65 to 134 and Comparative Examples 6 to 8, and the half life of the initial luminance of 1000 cd/m2 and the emission wavelength.

124 201012898 [Table 3] Main body dopant luminous efficiency [cd/A] emission wavelength (nm) half-life life [hr] Example 65 Compound 37 DM2-1 34 504 80000 Example 66 Compound 45 DM2-1 35 504 70000 Example 67 Compound 46 DM2-1 35 504 70000 Example 68 Compound 47 DM2-1 35 504 70000 Example 69 Compound 48 DM2-1 35 504 70000 Example 70 Compound 49 DM2-1 34 504 70000 Example 71 Compound 50 DM2 -1 34 504 65000 Example 72 Compound 51 DM2 - 1 34 504 65000 Example 73 Compound 52 DM2-1 34 504 65000 Example 74 Compound 53 DM2 - 1 34 504 70000 Example 75 Compound 37 DM10-1 35 515 85000 Example 76 Compound 45 DM10-1 36 515 75000 Example 77 Compound 46 DM10-1 36, 515 75000 Example 78 Compound 47 DM10-1 36 515 75000 Example 79 Compound 48 DM10-1 36 515 75000 Example 80 Compound 49 DM10 -1 35 515 75000 Example 81 Compound 50 DM10-1 35 515 70000 Example 82 Compound 51 DM10-1 35 515 70000 Example 83 Compound 52 DM10-1 35 515 70000 Example 84 Compound 53 DM10-1 35 515 75000 Example 85 Compound 37 DM10-4 37 519 90000 Example 86 Compound 45 DM10-4 38 519 80000 Example 87 Compound 46 DM10-4 38 519 80000 Example 88 Compound 47 DM10-4 38 519 80000 Example 89 Compound 48 DM10-4 38 519 80000 Example 90 Compound 49 DM10-4 37 519 80000 Example 91 Compound 50 DM10-4 37 519 75000 Example 92 Compound 51 DM10-4 37 519 75000 Example 93 Compound 52 DM10-4 37 519 75000 Example 94 Compound 53 DM10-4 37 519 80000 Example 95 Compound 37 DM17-1 38 523 90000 Example 96 Compound 45 DM17-1 39 523 80000 Example 97 Compound 46 DM17-1 39 523 80000 Example 98 Compound 47 DM17-1 39 523 80000 Example 99 Compound 48 DM17-1 39 523 80000 Example 100 Compound 49 DM17-1 38 523 80000 Example 101 Compound 50 DM17-1 38 523 75000 Example 102 Compound 51 DM17-1 38 523 75000 Example 103 Compound 52 DM17-1 38 523 75000 Example 104 Compound 53 DM17-1 38 523 80000 125 201012898 [Table 4] Main body dopant luminous efficiency [cd/A] Luminescence wavelength (nm) Half-life life [hr] Example 105 Compound 37 DM17-2 37 519 90000 Example 106 Compound 45 DM17-2 38 519 80000 Example 107 Compound 46 DM17-2 38 519 80000 Example 108 Compound 47 DM17-2 38 519 80000 Example 109 Compound 48 DM17-2 38 519 80000 Example 110 Compound 49 DM17-2 37 519 80000 Example 111 Compound 50 DM17-2 37 519 75000 Example 112 Compound 51 DM17-2 37 519 75000 Example 113 Compound 52 DM17-2 37 519 75000 Example 114 Compound 53 DM17-2 37 519 80000 Example 115 Compound 37 DM17-3 38 523 90000 Example 116 Compound 45 DM17-3 39 523 80000 Example 117 Compound 46 DM17-3 39 523 80000 Example 118 Compound 47 DM17-3 39 523 80000 Example 119 Compound 48 DM17-3 39 523 80000 Example 120 Compound 49 DM17-3 38 523 80000 Example 121 Compound 50 DM17-3 38 523 75000 Example 122 Compound 51 DM17-3 38 523 75000 Example 123 Compound 52 DM17-3 38 523 75000 Example 124 Compound 53 DM17-3 38 523 80000 Example 125 Compound 37 DM17-4 38 515 85000 Example 126 Compound 45 DM17-4 39 515 75000 Example 127 Compound 46 DM17-4 39 515 75000 Example 128 Compound 47 DM17-4 39 515 75000 Example 129 Compound 48 DM17-4 39 515 75000 Example 130 Compound 49 DM17-4 38 515 75000 Example 131 Compound 50 DM17- 4 38 515 70000 Example 132 Compound 51 DM17-4 38 515 70000 Example 133 Compound 52 DM17-4 38 515 70000 Example 134 Compound 53 DM17-4 38 515 75000 Comparative Example 6 Η-2 D — 1 30 528 10000 Comparison Example 7 Η-3 DM2-1 30 504 40000 Comparative Example 8 Compound 37 D-1 33 528 15000

The onion derivative and the diamine hydrazine derivative of the present invention have high efficiency and a very long life compared with the conventional combination. In particular, in the host material, when the comparative compound is Η-1, Η-2, Η-3, compared with the 4-substituted onion derivative of the present invention, it is understood that the efficiency is particularly high and the life is long. It is presumed that 126 201012898 is such that the number of substituents of ruthenium is changed from two to four, and the wavelength of the light emitted by the main body itself is wavelength-', and energy transfer is likely to occur between the green dopant and the green dopant. Further, by changing the number of substituents from two to four, the energy gap of the host material is reduced, whereby the energy applied to the material at the time of energization is reduced, so that the life is prolonged. On the other hand, the diamine hydrazine derivative of the dopant material has a very long life compared to the conventional lysine derivative. The diamino hydrazine derivative has a shorter wavelength with respect to the luminescence wavelength required for the application of a television or the like, but can be long-wavelength by introducing a thiol group such as DM17-i or DM17_3. [Industrial Applicability] The organic EL element using the organic light-emitting medium of the present invention is, for example, a light source such as a backlight of a wall-mounted television or a backlight of a liquid crystal display. The contents of the references described in the present specification are hereby incorporated by reference in their entirety. ❹ [Simple diagram description] None [Main component symbol description] None 127

Claims (1)

201012898 VII Patent Application Range: Amine 1. An organic light-emitting medium comprising the following formula (base derivative, and onion derivative represented by the following formula (7); 0) _ (In the formula (1), 'Ar 1 to Ar4, sub-K丨丨3® a jj* :* H...Λ The only part of the stone that is substituted or unsubstituted is 5~50. The +/1_1^ heterocyclic group; a aryl group substituted or unsubstituted ring carbon number 5 to 5 〇, R21 to R24, each independently a hydrogen atom, a substituted or unsubstituted alkyl group of 50, substituted or absent Substituted ring carbon number 5~5〇 aroma = unsubstituted ¥ carbon number 6~5G aromatic, substituted or unsubstituted ring = 5G cycloalkyl, substituted or unsubstituted carbon number U alkoxy a substituted or unsubstituted carbon number of 5 to 5 方, a aryloxy group, a substituted or unsubstituted number of 5 to 5 arylamino groups, a substituted or unsubstituted carbon number, a aryl group, a substituted group Or a substituted ring carbon of 5 to 5 g of a heterocyclic group or an unsubstituted fluorenyl group, a cyano group or a south atom; the substituents nl to n4' are each independently an integer of 0 to 10, and when nl to n4 are respectively higher or higher When R21 R R24, respectively, may be the same or different, or may be connected to each other, 'Ό to form a saturated or unsaturated ring; # RR is independently substituted or unsubstituted ring carbon number 5~50 aromatic Base, substitution or no Instead money 5~5 ring () of the heterocyclyl); 128 (2) 201 012 898 And Ar (in the formula (2), the ring carbon number of Ari 6~5〇η__ is independently a substituted or unsubstituted R1 to a aryl group, or a heterocyclic group having a ring number of 5 to 50, ❹ ❹ aryl group Or a substituted or unsubstituted ring carbon number of 6 to 50 „ ^ substituted or unsubstituted ring atomic number 5 to 50 heterocyclic ring -, or substituted or unsubstituted ring carbon number ό ~ 50 Aromatic sputum, red: a ring of unsubstituted or unsubstituted ring, or taken as ~R8' is independently selected from "the base of R, R, R, R, R, R, 2, or unsubstituted carbon number 1~5〇戈 or..., substituted ring carbon number 3~5〇 unsubstituted carbon number 1~50 of its w 1 alkyl group, substituted or if it produces its unsubstituted or unsubstituted carbon number 7~ The formula of 50, the substituted or unsubstituted ring carbon number (a) number 7 or the unsubstituted ring carbon number 6~5〇 minus, the substitution of ~50 is the negative thiol, substituted or unsubstituted Pit oxygen with a carbon number of 2 〇 "base, substituted or unsubstituted carbon number cyano, stone succinyl and (d) base).竣 自 自 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. 2. Take profit: two: substituted ring ~50 heterocyclic group, and, ..., ..., ^ two substituted ring atom number ^ or unsubstituted ring carbon number 6 ~ 50 aromatic group, or: the replacement A heterocyclic group having 5 to 50 ring atoms. Deuterated or unsubstituted 129 201012898 3 · The organic light-emitting medium of claim 2, wherein R1 and R5 in the formula (2) are substituted or unsubstituted ring carbon number 6 to an aromatic group, or ^ Is a substituted or unsubstituted heterocyclic group having a ring number of 5 to 5 Å, or R and R 8 are a substituted or unsubstituted aryl group having a ring carbon number of 6 to 5 Å, or a substituted or unsubstituted ring atom. A heterocyclic group of 5 to 5 Å. 4. The organic light-emitting medium of claim 1, wherein one of R, R2, R7 and r8 in the formula (2) is a substituted or unsubstituted aromatic group having a ring carbon number of 6 to 50, And, R3, r4,. And one of R6 is a substituted or unsubstituted aromatic group having a ring carbon number of ό50. 5. If you apply for a patent! The organic light-emitting medium of the fourth aspect, wherein R and R in the formula (2) are a substituted or unsubstituted aromatic group having 6 to 5 carbon atoms, or R and R are a substituted or unsubstituted ring carbon number 6 to 5 〇 aromatic base. 6. The organic light-emitting medium of claim 4, wherein R in the formula is a substituted or unsubstituted aromatic group having a ring carbon number of 6 to 5 G, or R and R7 are substituted or unsubstituted ring carbons. A few 6 to 5 芳香 aromatic groups. The organic light-emitting medium of any one of the claims 1 to 6 wherein the Αγη in the formula (7) is a substituted or unsubstituted heterocyclic group of ～50. 8. The scope of the patent application, wherein the substituted phenyl group in the formula (2). The organic light-emitting media ι·11 and Α〆2 of any one of items 1 to 6, respectively, are independently substituted or π-free, and the organic hair body of any of the items of the patent range is... Arl, Arl, ring carbon number 6~30 Α Α ^ 无 无 之 、, or by substituted or unsubstituted ring 130. 201012898 5 to 30 substituted by a heterocyclic group of phenyl . Body, in which Shen Erzhu:: Ar and Ar12 in the organic light-emitting medium of the i- to 6th---------------------------- An aromatic group. Gogo is airless (2) Π: The organic light-emitting medium of claim 10, wherein Ar&quot; and Αγ12 in the formula (2) are the same base. 11 organic light-emitting media, wherein the substitute or Unsubstituted 9 12. For example, the Ar11 and Ar12 (phenanthrenyl) in the formula (2) of the patent application. 13. The organic light-emitting medium of claim ii, wherein the Al-&quot; And a substituted or unsubstituted 2_naphthyl group. The organic light-emitting medium of claim 11, wherein the Al- and Arl2 in the formula (2) are substituted or unsubstituted tea bases. 15. For the organic light-emitting media of the first paragraph of the patent scope, the Ar&quot; and Aru in the cough type (2) are different. 16_ The organic light-emitting medium of claim 15 of the patent patent, wherein Ar and Ari2 in the formula (2) are substituted or unsubstituted 9-phenanthryl, substituted or unsubstituted 1 naphthalene Any of 2,naphthyl, substituted or unsubstituted propylene fluorenyl, and substituted or unsubstituted fluorenyl, substituted or unsubstituted. The organic light-emitting medium according to any one of claims 1 to 6, wherein in the formula (2), Arn and ^12 are substituted or unsubstituted phenyl, and the other is substituted. Or an unsubstituted condensed aromatic group having a ring carbon number of 1 〇 to 5 Å. 131 201012898 18. If the scope of the patent application is substituted or unsubstituted, the ring carbon number is 1 〇 substituted 1 is naphthyl. 17 organic light-emitting media, wherein the 50-terminal aromatic group is substituted or absent. 19. For example, the substituted or unsubstituted ring carbon number 丨〇~5 〇 substituted 2-naphthyl group. An organic light-emitting medium, wherein the terminal aromatic group is substituted or not. 20. The substituted carbon number of the substituted or unsubstituted ring as claimed in the patent application. 17th organic light-emitting medium, wherein the 50-condensed aromatic group is substituted or absent 21. If the scope of the patent application is substituted or unsubstituted, the carbon number of the ring is substituted. Item 17 of the organic light-emitting medium, wherein the 10 to 50 condensed aromatic group is substituted or not 22. As claimed in the first aspect of the invention, wherein Ra in the formula (1), substituted phenyl, substituted Or an unsubstituted sulfhydryl group. The organic light-emitting media R ’ of any of the six items are independently substituted or not taken, or replaced or unsubstituted. 23. For example, in the scope of the patent application, the organic light-emitting medium of the term "Essence of the first element", in which the Ur1~A〆 in the formula (1) are independently selected from substituted or unsubstituted A phenyl, substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted dibenzofuranyl group. The organic light-emitting medium according to any one of claims 1 to 6, wherein at least one of Ar! to Ar4 in the formula (1) is a substituent or a substituted group of blood. The illuminating medium is as described in any one of claims 1 to 6 of the invention, wherein there is a lining, a substituted or an unsubstituted phenyl group, a substituted or unsubstituted group of the formula (1); : independently, substituted or unsubstituted isopropyl, or unsubstituted ethyl, or unsubstituted cyclopropyl, substituted Ge: unsubstituted tertiary butyl, substituted for... substituted or unsubstituted a cyclopentyl group, a substituted or I-substituted hexamethylene group, a substituted or unsubstituted trichosting group, or an aryl group. 26, an organic electroluminescent device anode and cathode heart! Products, systems, with anodes and cathodes, and what? The organic thin film layer of the organic thin film layer is an organic light-emitting medium containing the item of any one of claims 1 to 25. φ 27· The organic electroluminescence device of claim 26, wherein the organic thin film layer-based light-emitting layer containing the organic light-emitting medium. Eight, schema: no ❽ 133