KR20080099705A - Spiro type organic material and organic electroluminescent device using same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to spiro type organic materials and organic electroluminescent devices using the same. It relates to a novel spiro-type organic compound of a specific structure that can be. The present invention provides an organic electroluminescent device characterized in that the spiro type organic compound of formula 1 contains at least one layer between the two separated electrodes having a high work function and a low work function. to provide.

[Formula 1]

The compound of Formula 1 may be used as a hole injection and transport material, a light emitting material, an electron injection and transport material constituting the organic electroluminescent device according to the substituent. In particular, as a constituent material of the light emitting material, the number of rings and appropriate substituents may be introduced into a single molecule to impart host to dopant properties such as red, green, and blue. When manufactured, it is possible to improve the driving voltage of the device, the lifetime according to the thermal stability and the luminous efficiency.

Description

Spiro type organic material and organic electroluminescent device using same {Spiro type Organic Light Emitting Materials}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a spiro type organic light emitting material, and is a coating film forming material, in particular, a material having high heat resistance and thin film stability and uniformity, which can greatly improve lifespan and luminous efficiency, and high efficiency using the same. And a long life organic electroluminescent device.

An organic electroluminescent element or organic light emitting diode using an organic material is one of the representative flat panel display devices together with a liquid crystal display (LCD), a plasma display panel (PDP) and a field emission display (FED). The organic electroluminescent device has various advantages in the manufacturing process compared to the conventional flat panel display device, and has high luminance and viewing angle characteristics, fast response speed, and low driving voltage, so that the back light and illumination of a flat panel display or a display such as a wall-mounted TV is low. The development is actively progressed so that it may be used as a light source for advertising billboards.

Organic electroluminescent devices generally recombine holes injected from the anode and electrons injected from the cathode when DC voltage is applied to form exciton, an electron-hole pair, and the excitons return to a stable bottom ecology to emit corresponding energy. It is converted to light by transmitting it to the material. In order to increase the efficiency and stability of organic electroluminescent devices, a low-voltage driving organic electroluminescent device is reported by forming a stacked organic thin film between two opposite electrodes by CW Tang of Eastman Kodak Corporation (CW Tang, SA Vanslyke, Applied Physics). Letters, Vol. 51, p. 913, 1987), studies on organic materials for multilayer thin film organic electroluminescent devices have been actively conducted. The lifespan of such a layered organic electroluminescent device is deeply related to the stability of the thin film, and the crystallization of the material at high temperature or driving temperature causes a shortening of the device life. For example, in the case of the dynaphthylanthracene compound, crystallization occurs easily as the temperature of the device increases because of the molecular structure of right and left symmetry. Recently, the thin film stability has been improved by introducing a spiro structure as a means for preventing such crystallization. For example, US Pat. No. 58,402,17 discloses single molecules such as spiro-sexyphenyl, spiro-DPVBi, and the like, which are derivatives of spirobifluorene, and US Pat. Nos. 5,621,131 and 5763636 are spy repeat units. A polymer containing a compound is disclosed. However, the spyro compound known in the art has a disadvantage in that it is excellent in heat resistance but does not exhibit high driving efficiency or high efficiency of emission, and is mainly limited to a blue region material. The spiro polymer has a disadvantage in that an unreacted residue remains at an impurity or terminal, so that light emission performance is low and film formation by deposition is difficult.

Accordingly, an object of the present invention is to prepare a compound with a novel spy of a symmetrical or asymmetrical form having excellent luminous efficiency and heat resistance in consideration of the problems of the prior art, and to provide an organic electroluminescent device comprising the same. In addition, the present invention is characterized by forming a spiro bond in an asymmetrical form that bonds directly with anthracene rather than a symmetrical form as in the case of conventional spirobifluorene. The compounds disclosed by the present invention can be applied to both the hole injection layer, the hole transport layer, the electron transport layer and the electron injection layer as well as the blue or green and red light emitting materials depending on the type of substituents to be introduced. The bonding-containing compounds have excellent thermal evaporation characteristics, have high solubility in organic solvents, and confirm the merits of wet film formation such as inkjet or spin coating, and have completed the present invention.

That is, the present invention relates to an organic electroluminescent device material represented by a spiro compound of the formula (1).

[Formula 1]

In Formula 1, S ₁ to S ₄ is a carbon, silicon, germanium, phosphorus or sulfur atom capable of spiro bonding.

In the general formula (1), O ₁ to O ₄ is a cyclic structure forming group that spy bonds with S ₁ to S ₄ .

In Formula 1, R ₁ to R ₂ may be a hydrogen atom, have a substituent as specified in Y ₁ to Y ₂ , or have an unsubstituted aromatic group having 6 to 50 nuclear carbon atoms, or have a substituent as specified in Y ₁ to Y ₂ . hwandoen nuclear atoms ventilation of 5 to 50 aromatic hydrocarbon ring, Y ₁ to Y ₂ of the stated substituents or types of substituents indicated in the alkyl group of the unsubstituted carbon atoms of 1 to 50, Y ₁ to Y ₂ in the number of carbon atoms or unsubstituted 2 to 50 alkenyl group, Y ₁ to Y ₂ of the substituents set forth in or unsubstituted of substituents set forth in the alkynyl, Y ₁ to Y ₂ of the ring carbon atoms of 2 to 50, or unsubstituted oxygen, nitrogen, carbon, silicon, Germanium, sulfur atoms and the like. When R ₁ to R ₂ is a hydrogen atom, it is not possible to form a spy bond, and when R ₁ to R ₂ are all hydrogen atoms, they do not correspond to the present invention.

Examples of the unsubstituted aromatic group having 6 to 50 carbon atoms of R ₁ to R ₂ include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1- Pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, etc. are mentioned. Examples of the unsubstituted aromatic heterocyclic group having 5 to 50 atomic atoms of R ₁ to R ₂ include 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, pyrimidyl group, pyridazyl group, 2-pyridine Diary, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3-indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 1-eye Soindolyl group, 2-isoindolyl group, 3-isoindolyl group, 4-isoindolyl group, 5-isoindolyl group, 6-isoindoleyl group, 7-isoindolinyl group, 2-furyl group , 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3 -Isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzofuranyl group, 7-isobenzofuranyl group, quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 6-isoquinolyl group, 7-isoquinolyl group, 8-isoquinolyl group, 2 -Quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-phenanthridinyl group, 2-phenanthridineyl group, 3-phenanthridineyl group, 4-phenanthridineyl group, 6-phenanthridine Diary, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl, 10-phenanthridinyl, 1-acridinyl, 2-acridinyl, 3-acridinyl , 4-acridinyl group, 9-acridinyl group, 1,7-phenanthroline-2-yl group, 1,7-phenanthroline-3-yl group, 1,7-phenanthroline-4-yl group , 1,7-phenanthroline-5-diary, 1,7-phenanthroline-6-diary, 1,7-phenanthroline-8-diary, 1,7-phenanthroline-9-diary, 1 , 7-phenanthroline-10-diary, 1,8-phenanthroline-2-yl, 1,8-phenanthroline-3-yl, 1,8-phenanthroline-4-yl, 1,8 -Phenanthroline-5-diary, 1,8-phenanthroline-6-diary, 1,8-phenanthroline-7-diary, 1 , 8-phenanthroline-9-diary, 1,8-phenanthroline-10-diary, 1,9-phenanthroline-2-yl, 1,9-phenanthroline-3-yl, 1,9 -Phenanthroline-4-yl, 1,9-phenanthroline-5-diary, 1,9-phenanthroline-6-diary, 1,9-phenanthroline-7-diary, 1,9-phenan Trolline-8-diary, 1,9-phenanthroline-10-diary, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1,10-phenanthroline -4-yl, 1,10-phenanthroline-5-diary, 2,9-phenanthroline-1-yl, 2,9-phenanthroline-3-yl, 2,9-phenanthroline-4 -Diary, 2,9-phenanthroline-5-diary, 2,9-phenanthroline-6-diary, 2,9-phenanthroline-7-diary, 2,9-phenanthroline-8-diary , 2,9-phenanthroline-10- diary, 2,8-phenanthroline-1-yl, 2,8-phenanthroline-3-yl, 2,8-phenanthroline-4-yl, 2 , 8-phenanthroline-5-diary, 2,8-phenanthroline-6-diary, 2,8-phenanthroline-7-diary, 2,8-phenanthroline-9-diary, 2,8 -Phenanthroline-10- diary, 2,7-phenanthroline-1-yl, 2,7-phenanthroline-3-yl, 2,7-phenanthroline-4-yl, 2,7 -Phenanthroline-5-diary, 2,7-phenanthroline-6-diary, 2,7-phenanthroline-8-diary, 2,7-phenanthroline-9-diary, 2,7-phenan Trolline-10- diary, 1-phenazine diary, 2-phenazine diary, 1-phenothiazin diary, 2-phenothiazin diary, 3-phenothiazin diary, 4-phenothiazin diary, 10- Phenoxyazine diary, 1-phenoxazine diary, 2-phenoxazine diary, 3-phenoxazine diary, 4-phenoxazine diary, 10-phenoxazine diary, 2-oxazolyl group, 4-oxazolyl group, 5-oxa A sleepy group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, etc. are mentioned.

In Chemical Formula 1, Y ₁ to Y ₂ each represent a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, substituted or unsubstituted It is a C1-C50 alkyl group and a substituted or unsubstituted C7-C50 aralkyl group. Examples of the substituted or unsubstituted aromatic carbon group having 6 to 50 nuclear atoms of Y ₁ to Y ₂ include a phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 9-anthryl Group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 1-naphthacenyl group, 2-naphthacenyl group, 9-naphthacenyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-biphenylyl group, 3-biphenylyl group, 4-biphenylyl group, p -terphenyl-4-yl group, p -terphenyl-3-yl group , p -terphenyl-2-yl group, m -terphenyl-4-yl group, m -terphenyl-3-yl group, m -terphenyl-2-yl group, o -tolyl group, m -tolyl group, p -tol Aryl group, p - t -butylphenyl group, p- (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4'- Methyl biphenylyl group, 4 " -t -butyl- p -terphenyl-4-yl group, etc. are mentioned. Examples of the substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms of Y ₁ to Y ₂ are 1. Pyrrolyl Group, 2-pyrrolyl group, 3-pyrrolyl group, pyrazinyl group, pyrimidyl group, pyridazyl group, 2-pyridinyl group, 3-pyridinyl group, 4-pyridinyl group, 1-indolyl group, 2-indolyl group, 3- Indolyl group, 4-indolyl group, 5- indolyl group, 6-indolyl group, 7-indolyl group, 1-isoindoleyl group, 2-isoindolinyl group, 3-isoindolinyl group, 4-isoindolinyl group , 5-isoindolyl group, 6-isoindolyl group, 7-isoindolyl group, 2-furyl group, 3-furyl group, 2-benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, 3-isobenzofuranyl group, 4-isobenzofuranyl group, 5-isobenzofuranyl group, 6-isobenzo Furanyl, 7-isobenzofuranyl, quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-iso Teal group, 7-isoquinolyl group, 8-isoquinolyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1-phenanthridineyl group, 2-phenanthridineyl group, 3 -Phenanthridinyl group, 4-phenanthridinyl group, 6-phenanthridinyl group, 7-phenanthridinyl group, 8-phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1- Acridinyl group, 2-acridinyl group, 3-acridinyl group, 4-acridinyl group, 9-acridinyl group, 1,7-phenanthroline-2-yl group, 1,7-phenan Trolin-3-yl, 1,7-phenanthroline-4-yl, 1,7-phenanthroline-5-diary, 1,7-phenanthroline-6-diary, 1,7-phenanthroline -8-diary, 1,7-phenanthroline-9-diary, 1,7-phenanthroline-10-diary, 1,8-phenanthroline-2-yl, 1,8-phenanthroline-3 -Diary, 1,8-phenanthroline-4-yl, 1,8-phenanthroline-5-diary, 1,8-phenanthroline-6-diary, 1,8-phenanthroline-7-diary , 1,8-phenanthroline-9-diary, 1,8-phenanthroline-10-diary, 1,9-phenanthroline-2-yl, 1,9-phenanthroline-3- Group, 1,9-phenanthroline-4-yl, 1,9-phenanthroline-5-diary, 1,9-phenanthroline-6-diary, 1,9-phenanthroline-7-diary, 1,9-phenanthroline-8-diary, 1,9-phenanthroline-10-diary, 1,10-phenanthroline-2-yl, 1,10-phenanthroline-3-yl, 1, 10-phenanthroline- 4-day, 1,10-phenanthroline-5-diary, 2,9-phenanthroline-1-yl, 2,9-phenanthroline-3-yl, 2,9- Phenanthroline-4-yl, 2,9-phenanthroline-5-diary, 2,9-phenanthroline-6-diary, 2,9-phenanthroline-7-diary, 2,9-phenanthrole Lin-8-diary, 2,9-phenanthroline-10-diary, 2,8-phenanthroline-1-yl, 2,8-phenanthroline-3-yl, 2,8-phenanthroline- 4-diary, 2,8-phenanthroline-5-diary, 2,8-phenanthroline-6-diary, 2,8-phenanthroline-7-diary, 2,8-phenanthroline-9- Diary, 2,8-phenanthrolineyl, 2,7-phenanthroline-1-yl, 2,7-phenanthroline-3-yl, 2,7-phenanthroline-4-yl, 2,7 -Phenanthroline-5-diary, 2,7-phenanthroline-6-diary, 2,7-phenanthroline-8-diary, 2,7-phenanthroline-9-diary, 2,7-phenanthroline-10- diary, 1-phenazinyl group, 2-phenazinyl group, 1-phenothiazin diary, 2-phenothiazin diary, 3-phenothiazin diary, 4-phenothiazine Diary, 10-phenoxyazine diary, 1-phenoxazine diary, 2-phenoxazine diary, 3-phenoxazine diary, 4-phenoxazine diary, 10-phenoxazine diary, 2-oxazolyl group, 4-oxazolyl group , 5-oxazolyl group, 2-oxadiazolyl group, 5-oxadiazolyl group, 3-furazanyl group, 2-thienyl group, 3-thienyl group, 2-methylpyrrole-1-yl group, 2- Methylpyrrole-3-yl group, 2-methylpyrrole-4-yl group, 2-methylpyrrole-5-yl group, 3-methylpyrrole-1-yl group, 3-methylpyrrole-2-yl group, 3-methylpyrrole-4- Diary, 3-methylpyrrole-5-yl group, 2- t -butylpyrrole-4-yl group, 3- (2-phenylpropyl) pyrrole-1-yl group, 2-methyl-1-indolyl group, 4-methyl-1 -Indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indolyl group, 2- t -butyl1-indolyl group, 4- t -butyl1-indolyl group, 2- t -butyl3-indole And a 4- t -butyl-3-indolyl group. Examples of the substituted or unsubstituted alkyl group having 1 to 50 carbon atoms of Y ₁ to Y ₂ include methyl group, ethyl group, propyl group, isopropyl group, n -butyl group, sec -butyl group, isobutyl group, t -butyl group, n -pentyl, n-hexyl, n-heptyl, n-octyl group, hydroxymethyl group, 1-hydroxy ethyl, 2-hydroxy ethyl, 2-hydroxy-iso-butyl group, 1,2-dihydroxy Ethyl group, 1,3-dihydroxyisopropyl group, 2,3-dihydroxy- t -butyl group, 1,2,3-trihydroxypropyl group, chloromethyl group, 1-chloroethyl group, 2-chloroethyl group , 2-chloroisobutyl group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro- t -butyl group, 1,2,3-trichloropropyl group, bro Mother methyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyl group, 1,2-dibromoethyl group, 1,3-dibromoisopropyl group, 2,3-dibromo- t- part Group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, 2-iodoisobutyl group, 1,2-diiodoethyl group, 1,3- Diiodoisopropyl group, 2,3-diiodo- t -butyl group, 1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, 2-aminoisobutyl Group, 1,2-diaminoethyl group, 1,3-diaminoisopropyl group, 2,3-diamino- t -butyl group, 1,2,3-triaminopropyl group, cyanomethyl group, 1-between Anoethyl group, 2-cyanoethyl group, 2-cyanoisobutyl group, 1,2-dicyanoethyl group, 1,3-dicyanoisopropyl group, 2,3-dicyano- t -butyl group, 1,2,3-tricyanopropyl group, nitromethyl group, 1-nitroethyl group, 2-nitroethyl group, 2-nitroisobutyl group, 1,2-dynitroethyl group, 1,3-di Nitroisopropyl groups, 2,3 -Dytro- t -butyl group, 1,2,3-trinitropropyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, 1-adamantyl group , 2-adamantyl group, 1-norbornyl group, 2-norbornyl group and the like. Examples of the substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms of Y ₁ to Y ₂ include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylisopropyl group, 2-phenylisopropyl group, phenyl- t -Butyl group, α -naphthylmethyl group, 1- α -naphthylethyl group, 2- α -naphthylethyl group, 1- α -naphthylisopropyl group, 2- α -naphthylisopropyl group, β -naphthyl Methyl group, 1- β -naphthylethyl group, 2- β -naphthylethyl group, 1- β -naphthylisopropyl group, 2- β -naphthylisopropyl group, 1-pyrrolylmethyl group, 2- (1-P Rollyl) ethyl group, p -methylbenzyl group, m -methylbenzyl group, o -methylbenzyl group, p -chlorobenzyl group, m -chlorobenzyl group, o -chlorobenzyl group, p -bromobenzyl group, m -bro Mobenzyl groups, o -bromobenzyl groups, p -iodobenzyl groups, m -iodobenzyl groups, o -iodobenzyl groups, p -hydroxybenzyl groups, m -hydroxybenzyl groups, o -hydroxy Benzyl group, p -aminobenzyl group, m -aminobenzyl Group, o - amino-benzyl, p - nitro Robben chewy, m - nitro Robben chewy, o - nitro Robben chewy, p - cyano benzyl group, m - cyano-benzyl, o - cyano benzyl group, 1-hydroxy A oxy-2- phenyl isopropyl group, a 1-chloro-2- phenyl isopropyl group, etc. are mentioned.

In formula (1), when R ₁ to R ₂ is a carbon, silicon, germanium atom, or an unsubstituted aromatic group having 6 to 50 carbon atoms and an aromatic heterocyclic group having 5 to 50 nuclear atoms, Y ₁ to Y ₂ A group represented by OZ ₁ may be introduced and Z ₁ is a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, substituted or unsubstituted a C 1 -C 50 alkyl group, an aralkyl group a substituted or unsubstituted C7 to 50, examples of these embodiments are the same as those described in the examples all the Y ₁ to Y _2. An amino group represented by NZ ₂ Z ₃ may be introduced into Y ₁ to Y ₂ , and Z ₂ to Z ₃ each represent a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, and a substituted or unsubstituted nuclear atom. An aromatic heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, and specific examples thereof include those mentioned in the description of Y ₁ to Y ₂ . The same thing as that can be mentioned. A thio group represented by SZ ₄ may be introduced into Y ₁ to Y ₂ and Z ₄ represents a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, and a substituted or unsubstituted nuclear group having 5 to 50 atoms An aromatic heterocyclic group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, and specific examples thereof include the same as those mentioned in the description of Y ₁ to Y ₂ . have. A carbonyl group represented by COZ ₅ to COOZ ₆ may be introduced into Y ₁ to Y ₂ , and Z ₅ to Z ₆ each represent a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 nuclear atoms, a substituted or unsubstituted group. An aromatic heterocyclic group having 5 to 50 nuclear atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, and as specific examples thereof, in the description of Y ₁ to Y ₂ The same thing as the example is mentioned. A carboxyl group, a halorps atom, a cyano group, a nitro group or a hydroxyl group may be substituted for Y ₁ to Y ₂ .

In the general formula ( ₁ ), _n represented by (Y ₁ ) _n to (Y ₂ ) _n are each independently an integer of 0 to 6, preferably 0 to 2, and each independently to adjacent R ₁ to R ₂ , Y ₁ to It may also form a saturated or unsaturated ring with a group defined by Y ₂ , Z ₁ to Z ₁₂ .

In Chemical Formula 1, X ₁ To X ₂ is a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and As a specific example, the thing similar to what was illustrated by the said description of Y <_1> -Y <_2> is mentioned. A group represented by OZ ₇ may be introduced into X ₁ to X ₂ , and Z ₇ is a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, and a substituted or unsubstituted aromatic hetero atom having 5 to 50 atoms. group, a substituted or unsubstituted C 1 -C 50 alkyl group, a substituted or unsubstituted C7 to an aralkyl group 50, examples of these embodiments are the same as all examples in the description of the Y ₁ to Y _2. An amino group represented by NZ ₈ Z ₉ may be introduced into X ₁ to X ₂ , and Z ₈ to Z ₉ each represent a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, and a substituted or unsubstituted nuclear atom. An aromatic heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, and specific examples thereof include those mentioned in the description of Y ₁ to Y ₂ . And the same thing as that. A thio group represented by SZ ₁₀ may be introduced into X ₁ to X ₂ , and Z ₁₀ is a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, and a substituted or unsubstituted nuclear group having 5 to 50 atoms An aromatic heterocyclic group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, and specific examples thereof include the same as those mentioned in the description of Y ₁ to Y ₂ . have. A carbonyl group represented by COZ ₁₁ to COOZ ₁₂ may be introduced into Y ₁ to Y ₂ , and Z ₁₁ to Z ₁₂ each represent a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 nuclear atoms, a substituted or unsubstituted group, and An aromatic heterocyclic group having 5 to 50 nuclear atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, and as specific examples thereof, in the description of Y ₁ to Y ₂ The same thing as the example is mentioned. X ₁ To X ₂ are a carboxyl group, a halogen atom, a cyano group, a nitro group or a hydroxyl group.

In the general formula ( ₁ ), _n represented by (X ₁ ) _n to (X ₂ ) _n are each independently an integer of 0 to 4, preferably 0 to 2, and each independently to adjacent R ₁ to R ₂ , Y ₁ to It may also form a saturated or unsaturated ring with a group defined by Y ₂ , Z ₁ to Z ₁₂ .

In Chemical Formula 1, R ₁ to R ₂ and Y ₁ to Y ₂ and X ₁ X ₂ is a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, a substituted or unsubstituted carbon atom having 1 to 50 carbon atoms. An alkyl group, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, may include a spiro bond-containing group represented by the formula (1). A substituted or unsubstituted aromatic group having 6 to 50 carbon atoms which may have a vinyl bond of R ₁ to R ₂ and Y ₁ to Y ₂ and X ₁ to X ₂ ; An aromatic heterocyclic group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, is the same as described above in the description of Y ₁ to Y ₂ , and a substituted or unsubstituted group. The vinyl group couple | bonded is mentioned.

As shown in Formula 1 and Formulas 2 to 6 shown below, the number of spiro bonds may have 1 to 4 bonds, preferably 1 to 2. As in Formula 1 and Formulas 3 to 6, compounds having two or more spiro bonds may have different spiro bond structures.

[Formula 2] [Formula 3] [Formula 4]

[Formula 5] [Formula 6]

In formula (1), the bonding structure of the compound having a spiro bond is preferably a bond-containing group represented by formula (7).

[Formula 7]

In Formula 7, L ₁ to L ₂ are a single bond, carbon to heteroatoms included in R ₁ to R ₂ ,-(CR'R '') _e -,-(SiR'R '') _e -,- O-, -CO-, or -NR'-. R 'and R''are each independently a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 atoms, a substituted or unsubstituted carbon atom And an alkyl group of 1 to 50, a substituted or unsubstituted aralkyl group of 7 to 50 carbon atoms, and specific examples thereof include the same as those mentioned in the above description of Y ₁ to Y ₂ . e is an integer from 1 to 10, and R 'and R''may be the same or different.

In Formula 7, A <_1> -A <_16> respectively independently represents -CR'R "-, -SiR'R"-, -O-, -NR'-, or -CO-. R 'and R''are each independently the same as described above, R' and R '' may be the same or different, and may combine with each other to form a ring structure. In general formula (7), p is an integer of 1-10, and it is preferable if it is 1-5.

In Formula (7), at least two adjacent ones of A ₁ to A ₁₆ are each represented by -CR'R ''-(R 'and R''are the same as described above), and adjacent R's It is preferable that R '' or R 'and R''form a saturated or unsaturated bond to form a C4-C50 ring structure. Examples of the ring structure having 4 to 50 carbon atoms include cycloalkane having 4 to 12 carbon atoms such as cyclobutane, cyclopentane, cyclohexane, adamantane, and norbornene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, C6-C12 cycloalkadienes, such as cycloalkene, cyclohexadiene, cycloheptadiene, and cyclooctadiene, such as cyclooctene, benzene, naphthalene, phenanthrene, anthracene, pyrene, and cryo And C6-C50 aromatic rings such as sen and acenaphthalene.

Hereinafter, although representative examples (1)-(165) of the novel spiro compound of this invention are illustrated, this invention is not limited to these representative examples.

The organic electroluminescent device of the present invention is an organic electroluminescent device having an organic compound film composed of a single layer or a plurality of layers including at least one light emitting layer between a pair of electrodes, wherein at least one layer of the organic compound film is seen. It contains a novel compound of the invention. In the case of a single layer type, a light emitting layer is included between the substrate, the anode, the cathode, and the anode and the cathode. The multilayer organic electroluminescent device has been laminated in a multilayer structure of a substrate, an anode, a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, an electron injection layer and a cathode from below. By forming the organic electroluminescent device having a multilayer structure, it is possible to prevent a decrease in luminance or life due to quenching. At this time, the layer for injecting holes from the anode is called a hole injecting layer and a layer for receiving holes from the hole injecting layer and transporting holes to the light emitting layer. Similarly, the layer which injects electrons from a cathode is called an electron injection layer, and the layer which receives an electron from an electron injection layer and transports an electron to a light emitting layer is called an electron carrying layer. In addition, if necessary, a material capable of simultaneously injecting and transporting holes may be selected without distinguishing between the hole injection layer and the hole transport layer. A hole suppression layer may be provided between the organic light emitting layer and the electron transport layer to prevent movement of the hole to the electron transport layer. It may be formed. The light emitting layer can obtain light emission of blue light, green light, red light or white light by improving the light emission luminance or light emission efficiency by the kind or content of other doping materials. In addition, the organic light emitting layer may be formed in a layer structure of two or more layers, respectively, to obtain the same effects as described above. Each layer is selected and used depending on factors such as energy level of the material, heat resistance, adhesion to an organic compound film or a metal electrode.

Substrates serve as supports in organic electroluminescent devices and generally require flatness and mechanical strength, thermal stability to withstand various processes, no volatile emissions, air and moisture penetration and transparency. However, a device having a high reflectance may be used for a device requiring a cathode direction or side light emission. Transparent materials include glass, quartz, and transparent resin films. Transparent resin films include polyethylene, ethylene-vinyl acetate copolymers, ethylene-vinyl alcohol copolymers, polystyrene, polymethyl methacrylate, polyvinyl chloride, poly Vinyl alcohol, polyvinyl butyral, nylon, polyether ether ketone, polysulfone, polyether sulfone, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, polyvinyl fluoride, tetrafluoro ethylene-ethylene copolymer, Tetrafluoroethylene-hexafluoropropylene copolymer, polychlorotrifluoroethylene, polyvinylidene fluoride, polyester, polycarbonate, polyurethane, polyether imide, polyimide, polypropylene, and the like. . As the substrate material that is not transparent, a silicon wafer, a ceramic, or a metal such as chromium or gold may be used, and the substrate materials may be used in multiple layers.

The anode of the organic electroluminescent device is a conductive material to which a power source can be connected as it exists in a thin film form, and it is suitable to have a relatively high work function (preferably 4 eV or more). Tungsten, silver, gold, platinum, palladium and alloys thereof, metal oxides such as ITO, tin oxide, indium oxide, and organic conductive resins such as polythiophene or polypyrrole may be used. As the conductive material used for the cathode, one having a work function of less than 4 eV is suitable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, aluminum and alloys thereof may be used, but It is not limited. Examples of the alloy include, but are not limited to, magnesium / silver, magnesium / indium, lithium / aluminum, and the like. The proportion of the alloy is controlled by the temperature of the vapor deposition source, the atmosphere, the degree of vacuum and the like, and is selected at an appropriate ratio. The positive electrode and the negative electrode may have a laminated structure of two or more layers as necessary. For efficient light emission, it is preferable that at least one surface of the organic electroluminescent device is sufficiently transparent in the emission wavelength region of the device. The transparent electrode is set to use the above-mentioned conductive material and to ensure a predetermined light transmittance by a method such as vapor deposition or sputtering. It is preferable that the electrode of a light emitting surface has a light transmittance of 10% or more.

It is preferable that the light emitting material of the light emitting layer forms a uniform thin film having extremely high fluorescence quantum efficiency and high charge transport ability. The organic electroluminescent element can be prevented from deterioration in brightness and lifetime due to quenching by having a multilayer structure. If necessary, the novel spiro compound of the present invention may be used alone or in combination of two or more, or may be additionally used as a light emitting host material or a light emitting dopant material cavity. In the preferred use of such a novel spiro compound, it is added at a concentration of 100 to 80% by weight when used as a single light emitting layer material or a host material. In addition, when using as a light emitting dopant material, it is preferable to add in 0.01-20 weight% of concentration. Examples of the light emitting material or the dopant material which can be used in the light emitting layer together with the compound of the formula (1) include, for example, anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, and phthaloperylene , Phthaloperylene, perinone, phthalopelinone, naphthalophenone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine Cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, mellocyanine, imidazole chelation Although an oxynoid compound, quinacridone, rubrene, fluorescent dye, etc. are mentioned, It is not limited to these. When the light emitting material is used as the dopant material, the material selection criteria include: 1) the dopant molecule having high efficiency fluorescence or phosphorescence; And 2) a bandgap that is less than or equal to the bandgap of the host material.

As the hole injection material, a compound having the ability to transport holes, excellent hole injection efficiency from the anode, and excellent thermal stability while maintaining a stable interface with the anode should be used. Therefore, it is possible to use a novel spiro compound of the formula (1) or to use a known material. Known materials include, for example, phthalocyanine derivatives, naphthalocyanine derivatives, porphyrin derivatives, oxazoles, oxadiazoles, triazoles, imidazoles, imidazolones, imidazolthiones, pyrazoline, pyrazolones, tetrahydroimidazoles, hydras Zone, acylhydrazone, polyarylalkane, stilbene, butadiene, benzidine triphenylamine, styrylamine triphenylamine, diamine triphenylamine and the like and derivatives thereof, and polyvinylcarbazole, polysilane And polymer materials such as conductive polymers (PEDOT / PSS), but are not limited thereto. Among the hole injection materials that can be used in the organic electroluminescent device of the present invention, more effective hole injection materials are aromatic tertiary amine derivatives or phthalocyanine derivatives. Specific examples of the aromatic tertiary amine derivatives include triphenylamine, tritolylamine, tolyldiphenylamine, N, N' -diphenyl- N, N ' -(3-methylphenyl) -1,1'-biphenyl-4 , 4'-diamine, N, N, N ', N' -(4-methylphenyl) -1,1'-phenyl-4,4'-diamine, N, N, N ', N' -(4 -Methylphenyl) -1,1'-biphenyl-4,4'-diamine, N, N' -diphenyl- N, N' -dynaphthyl-1,1'-biphenyl-4,4'- Diamine, 4,4'-bis { N- [4- ( N, N -di- m -tolylamino) phenyl] -N -phenylamino} biphenyl, N, N' -diphenyl- N, N ' -Bis- [4- (phenyl- m -tolyl-amino) -phenyl] -biphenyl-4,4'-diamine, N, N ' -(methylphenyl) -N, N' -(4- n -butyl Oligomers and polymers having a skeletal structure of phenyl) phenanthrene-9,10-diamine, N, N -bis (4-di-4-tolylaminophenyl) -4-phenylcyclohexane and the aromatic tertiary amine, It is not limited to these. Specific examples of phthalocyanine (Pc) derivatives include H ₂ Pc, CuPc, CoPc, NiPc, ZnPc, PdPc, FePc, MnPc, ClAlPc, ClGaPc, ClInPc, ClSnPc, Cl2SiPc, (HO) AlPc, (HO) GaPc, VOPc, TiOP Phthalocyanine derivatives such as MoOPc, GaPc-O-GaPc, and naphthalocyanine derivatives, but are not limited thereto.

The hole transport layer is provided on the hole injection layer. The hole transport layer receives the holes from the hole injection layer and transports the holes to the organic light emitting layer positioned thereon, has high hole mobility and hole stability, and blocks electrons. In addition to these general requirements, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (T _g ) of 80 ° C. or higher is preferable. Materials satisfying such conditions include novel spiro compounds of formula 1, NPB, spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene , Silicon germanium oxide compounds, silicon arylamine compounds and the like. On the other hand, the organic monomolecular material for the hole transport layer is an arylamine-based material excellent in high hole transport rate and electrical stability. In order to increase the thermal stability of the arylamine-based material, a hole transport material having a naphthyl substituent or a spiro group is used. In the early hole transport layer organic material, N, N' -diphenyl- N, N' -bis (3-methylphenyl) -1,1'-diphenyl-4,4'-diamine (TPD) was commonly used. Unstable at temperatures above 60 ° C, with higher N -naphthyl- N -phenyl-1,1'-diphenyl-4,4'-diamine (NPB) series or more aromatic groups Amines are used. In particular, since the hole transporting layer organic monomolecular material has to have a fast hole moving speed and forms an interface in contact with the light emitting layer, the ionization potential has an appropriate value between the hole injection layer and the light emitting layer in order to suppress the generation of the hole transporting layer and the light emitting layer interface excitation. The ability to properly control the electrons being moved is needed.

As the electron transporting layer material, it has the ability to transport electrons, has an electron injection effect from the cathode, an electron injection effect excellent to the light emitting layer or the light emitting material, prevents excitons generated in the light emitting layer from moving to the hole transporting layer, and further a thin film Compounds that are excellent in their forming ability are preferred. Specifically, the novel spiro compound of the formula (1), fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenili And methane, anthrone and the like, and derivatives thereof and the spiro compound derivatives of the present invention including them, but are not limited thereto.

In the organic electroluminescent device of the present invention, a more effective electron transporting material is a metal complex compound or a nitrogen-containing five-membered ring derivative. Specific examples of the metal complex compound include (8-quinolinol) lithium, bis (8-quinolinol) zinc, bis (8-quinolinol) copper, bis (8-quinolinol) manganese, tris (8- Quinolinol) aluminum, tris (2-methyl-8-quinolinol) aluminum, tris (8-quinolinol) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10- Hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (o-cresolato) gallium, bis (2 -Methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium and the like, but are not limited thereto. In addition, the nitrogen-containing 5-membered derivative is preferably an oxazole, thiazole, oxadiazole, thiadiazole or triazole derivative. Specifically, 2,5-bis (1-phenyl) -1,3,4-oxazole, 2,5-bis (1-phenyl) -1,3,4-thiazole, 2,5-bis ( 1-phenyl) -1,3,4-oxadiazole, 2- (4'- t -butylphenyl) -5- (4 "-biphenyl) -1,3,4-oxadiazole, 2,5 -Bis (1-naphthyl) -1,3,4-oxadiazol, 1,4-bis [2- (5-phenyloxadiazolyl)] benzene, 1,4-bis [2- (5-phenyl Oxadiazolyl) -4- t -butylbenzene], 2- (4'- t -butylphenyl) -5- (4 "-biphenyl) -1,3,4-thiadiazole, 2,5-bis (1-naphthyl) -1,3,4-thiadiazole, 1,4-bis [2- (5-phenylthiadiazolyl)] benzene, 2- (4'- t -butylphenyl) -5- (4 "-biphenyl) -1,3,4-triazole, 2,5-bis (1-naphthyl) -1,3,4-triazole, 1,4-bis [2- (5-phenyl Triazolyl)] benzene, and the like, but is not limited thereto.

In the present invention, an inorganic compound layer may be disposed between the light emitting layer and the electrode in order to improve charge injection property. Examples of the inorganic compound layer, and the like, alkali metal compound (a fluoride, oxide, etc.), an alkaline earth metal compound, specifically, there may be mentioned LiF, Li ₂ O, BaO, SrO, BaF _2, SrF ₂ and the like.

The organic electroluminescent device of the present invention may be protected by forming a protective layer on the surface of the device or by covering the entire device with a silicone oil or a resin in order to improve stability and lifespan for temperature and humidity atmosphere.

Each layer of the organic electroluminescent device can be formed by applying any of a dry film forming method such as vacuum deposition, sputtering, plasma, ion plating, or a wet film forming method such as radiation coating, immersion coating, and flow coating. The film thickness is not particularly limited, but an appropriate film thickness needs to be set. If the film thickness is too thick, high applied voltage is required to obtain a constant light output, resulting in poor efficiency. If the film thickness is too thin, pinholes or the like will occur, and sufficient light emission luminance will not be obtained even when an electric field is applied. Typical film thickness is preferably in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm. In the wet film formation method, a thin film is formed by dissolving or dispersing the material forming each layer in a suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, or the like, but any solvent may be used. In addition, for any organic thin film layer, suitable resins or additives can be used for improving film forming properties, preventing pinholes of films, and the like. Examples of the resin that can be used include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, cellulose, and copolymers thereof; Photoconductive resins such as poly- N -vinylcarbazole and polysilane; And conductive resins such as polythiophene and polypyrrole. Moreover, as an additive, antioxidant, a ultraviolet absorber, a plasticizer, etc. are mentioned.

The organic electroluminescent device of the present invention can be used, for example, in flat light emitting bodies such as flat panel displays of wall-mounted TVs, light sources such as copiers, printers, back light or instrumentation of liquid crystal displays, display panels, beacons, and lighting.

Hereinafter, the configuration of the present invention through the production examples and examples in more detail.

The following Preparation Examples and Examples are intended to specifically illustrate the present invention, whereby the present invention should not be limited.

Preparation Example 1 (see Scheme 1)

1-1. Synthesis of 9-bromo-10-phenylanthracene

Dissolve 45.4 g (135.3 mmol) of 9,10-dibromoanthracene, 15 g (123.0 mmol) of phenyl boronic acid, and 4.2 g (3.6 mmol) of tetrakis (triphenylphosphine) palladium (0) in 300 mL of tetrahydrofuran. 120 mL of 2N -potassium carbonate aqueous solution was added thereto, and the mixture was refluxed at 100 ° C. for 24 hours. After completion of the reaction, the mixture was extracted with ethyl acetate and the organic layer was dried over anhydrous magnesium sulfate, and then purified through a hexane column to obtain 9-bromo-10-phenylanthracene in a yield of 69% (28.2 g).

1-2. Synthesis of 9- (2-bromophenyl) -10-phenylanthracene

Dissolve 20 g (60.0 mmol) of intermediate 9-bromo-10-phenylanthracene, tetrakis (triphenylphosphine) palladium (0), 2.0 g (1.8 mmol) of compound 1 in 300 mL of tetrahydrofuran, 120 mL of N -potassium carbonate aqueous solution is added and refluxed for 1 hour. 12.0 g (60.0 mmol) of 2-bromophenyl boronic acid was added dropwise to 10 tetrahydrofuran, followed by reaction for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate and the organic layer was dried over anhydrous magnesium sulfate and purified through a column (hexane: dichloromethane = 10: 1) to give 9- (2-bromophenyl) -10-phenylanthracene. Obtained in a yield of% (14.0 g).

1-3. Synthesis of 9- [2- (10-phenyl-anthracene-9-yl) phenyl] -9 H -fluorene-9-ol

Dissolve 3 g (7.3 mmol) of the intermediate 9- (2-bromophenyl) -10-phenylanthracene of compound 1 in tetrahydrofuran 100 under argon atmosphere, and 4.3 mL (10.9 mmol) of n -butyllithium at -78 ° C. Was added and then stirred for about 1 hour. After stirring, a solution of 9 g (10.9 mmol) of 9-fluorenone dissolved in 5 mL of tetrahydrofuran was slowly added dropwise at the same temperature, followed by stirring for 2 hours, followed by stirring at room temperature for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the solvent was removed under reduced pressure, and the residue was purified through a column (hexane: dichloromethane = 1: 1) to obtain 9- [2- (10-phenyl-anthracene-9-yl) phenyl] -9 H -fluorene-9-ol was obtained in 92% (3.4 g) yield.

1-4. Synthesis of Compound 1

Dissolve 3 g of 9- [2- (10-phenyl-anthracene-9-yl) phenyl] -9 H -fluorene-9-ol, a precursor of compound 1, in 100 mL of acetic acid, and then add 3 mL of hydrochloric acid as a catalyst. To reflux for 12 hours. After completion of the reaction, the solid and solvent were separated using a filter, and the filtered solid was washed with ethanol and distilled water to obtain Compound 1 in a yield of 99% (2.8 g).

Scheme 1

Preparation Example 2 (see Scheme 2)

2-1. Synthesis of 9- (biphenyl-4-yl) -10-bromoanthracene

18.6 g (155.5 mmol) of 9,10-dibromoanthracene, 10 g (50.4 mmol) of 4-biphenyl boronic acid, tetrakis (triphenylphosphine) palladium (0), 1.7 g (1.5) in 300 mL of tetrahydrofuran mmol) was dissolved, and 120 mL of 2N -potassium carbonate aqueous solution was added thereto, followed by refluxing at 100 ° C. for 24 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and purified through a hexane column to obtain 9- (biphenyl-4-yl) -10-bromoanthracene in a yield of 79% (16.0 g). Got it.

2-2. Synthesis of 9- (biphenyl-4-yl) -10- (2-bromophenyl) anthracene

20 g (48.8 mmol) of intermediate 9- (biphenyl-4-yl) -10-bromoanthracene of compound 3 in 300 mL of tetrahydrofuran, tetrakis (triphenylphosphine) palladium (0), 1.6 g (1.4 mmol), and then refluxed for 1 hour by adding 120 mL of 2N aqueous potassium carbonate solution. 9.8 g (48.8 mmol) of 2-bromophenyl boronic acid was added dropwise to 10 mL of tetrahydrofuran and reacted for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate and the organic layer was dried over anhydrous magnesium sulfate, purified through a column (hexane: dichloromethane = 10: 1), and purified by 9- (biphenyl-4-yl) -10- (2- Bromophenyl) anthracene was obtained in a yield of 80% (18.9 g).

2-3. Synthesis of 9- [2- (10-biphenyl-4-yl-anthracene-9-yl) phenyl] -9 H -fluorene-9-ol

Dissolve 3 g (6.1 mmol) of intermediate 9- (biphenyl-4-yl) -10- (2-bromophenyl) anthracene of compound 3 in 100 mL of tetrahydrofuran under an argon atmosphere, and n − at −78 ° C. 3.7 mL (9.2 mmol) of butyllithium were added and then stirred for about 1 hour. A solution of 1.6 g (9.2 mmol) of 9-fluorenone in 5 mL of tetrahydrofuran was slowly added dropwise at the same temperature, followed by stirring for 2 hours, followed by stirring at room temperature for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the solvent was removed under reduced pressure, and purified through a column (hexane: dichloromethane = 1: 1) to obtain 9- [2- (10-biphenyl-4-yl-anthracene-9-yl ) Phenyl] -9 H -fluorene-9-ol was obtained in a yield of 88% (3.1 g).

2-4. Synthesis of Compound 3

9 precursor of compound 3 in 100 mL acetic acid [2- (10-biphenyl-4-yl-anthracene-9-yl) phenyl] - hydrochloride as fluoren-9-ol was dissolved in 3 g catalyst -9 H Add 3 mL to reflux for 12 hours. After the completion of the reaction, the solid and the solvent were separated using a filter, and the filtered solid was washed with ethanol filtered crystals with ethanol and distilled water to obtain Compound 3 in a yield of 90% (2.6 g).

Scheme 2

Preparation Example 3 (see Scheme 3)

3-1. Synthesis of 9-bromo-10- (naphthalen-2-yl) anthracene

In tetrahydrofuran (300 mL) 33.7 g (100.4 mmol) of 9,10-dibromoanthracene, 15.7 g (91.2 mmol) of 2-naphthyl boronic acid, 3.1 g of tetrakis (triphenylphosphine) palladium (0) 2.7 mmol) was dissolved, and 120 mL of 2 N -potassium carbonate aqueous solution was added thereto, followed by refluxing at 100 ° C. for 24 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the organic layer was dried over anhydrous magnesium sulfate, and purified through a hexane column to obtain 9-bromo-10- (naphthalen-2-yl) anthracene in a yield of 72% (25.1 g). .

3-2. Synthesis of 9- (2-bromophenyl) -10- (naphthalen-2-yl) anthracene

20 g (52.1 mmol) of the intermediate 9-bromo-10- (naphthalen-2-yl) anthracene of compound 5 in 300 mL of tetrahydrofuran, 1.8 g (1.5 mmol) of tetrakis (triphenylphosphine) palladium (0) After dissolving, 120 mL of 2 N -potassium carbonate aqueous solution was added thereto, and the mixture was refluxed for 1 hour. 10.4 g (52.1 mmol) of 2-bromophenyl boronic acid was added dropwise to 10 mL of tetrahydrofuran and reacted for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, and then the organic layer was dried over anhydrous magnesium sulfate, purified through a column (hexane: dichloromethane = 10: 1), and purified by 9- (2-bromophenyl) -10- (naphthalene-2 -Yl) anthracene was obtained in a yield of 62% (14.8 g).

3-3. Synthesis of 9- [2- (10-naphthalen-2-yl anthracene-9-yl) phenyl] -9 H -fluorene-9-ol

Dissolve 3 g (6.5 mmol) of intermediate 9- (2-bromophenyl) -10- (naphthalen-2-yl) anthracene of compound 5 in 100 mL of tetrahydrofuran under an argon atmosphere, and n -butyllithium at -78 ° C. 3.9 mL (9.7 mmol) was added and then stirred for about 1 hour. A solution of 1.7 g (9.7 mmol) of 9-fluorenone in 5 mL of tetrahydrofuran was slowly added dropwise at the same temperature, followed by stirring for 2 hours, followed by stirring at room temperature for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate, the solvent was removed under reduced pressure, purified through a column (hexane: dichloromethane = 1: 1), and 9- [2- (10-naphthalen-2-yl anthracene-9-yl) phenyl ] -9 H -fluorene-9-ol was obtained in a yield of 90% (3.2 g).

3-4. Synthesis of Compound 5

Intermediate 9 of compound 5 in 100 mL acetic acid [2- (10-naphthalene-2-yl-anthracene-9-yl) phenyl] -9 H - fluoren-9-ol hydrochloride as a catalyst was dissolved (3 g) Add 3 mL to reflux for 12 hours. After completion of the reaction, the solid and solvent were separated using a filter, and the filtered solid was washed with ethanol and distilled water to obtain Compound 5 in a yield of 98% (2.8 g).

Scheme 3

The maximum absorption wavelength (UV-Vis spectrum), maximum emission wavelength (Photoluminescence), glass transition temperature (T _g ) and melting point (T _m ) of the spiro compound obtained in Preparation Examples 1 to 3 are shown in Table 1 below. Indicated.

compound UV-Vis (nm) PL (nm) T _g (℃) T _m (℃) Preparation Example 1 444 469 157 302 Preparation Example 2 445 473 173 367 Preparation Example 3 445 475 179 347

Example 1 (Manufacture of Organic Electroluminescent Device)

The substrate cut to ITO (indium tin oxide) transparent electrode having a thin film thickness of 100 nm in size of 40 mm × 40 mm × 0.7 mm was ultrasonically cleaned in distilled water dissolved in detergent for 10 minutes, and Washing was repeated several times. After the distilled water was washed, solvents such as isopropyl alcohol, acetone, and methanol were sequentially washed with ultrasonic waves and dried. After dry cleaning using oxygen / argon plasma after wet cleaning, a glass substrate having transparent electrode lines is mounted on the substrate holder of the vacuum deposition apparatus, and the transparent electrode is first placed on the side of the side where the transparent electrode lines are formed. N, N' -diphenyl- N, N' -bis- [4- (phenyl- m -tolylamino) phenyl] -biphenyl-4,4'-diamine membrane having a film thickness of 60 nm (hereinafter, DNTPD membrane). The DNTPD film functions as a hole injection layer. Next, a 4,4'-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl film (hereinafter referred to as NPB film) having a thickness of 30 nm was formed on the DNTPD film. This NPB membrane functions as a hole transport layer. Next, the compound 1 having a film thickness of 30 nm was deposited on the NPB film alone to form a film. This compound 1 film functions as a layer. A tris (8-quinolinol) aluminum film (hereinafter referred to as Alq film) having a film thickness of 30 nm was formed on the film. This Alq film functions as an electron transport layer. Next, LiF was deposited to form an electron injection layer film. Metal aluminum was deposited on the LiF film to form a metal cathode, thereby manufacturing an organic electroluminescent device.

As a result of measuring at a voltage of 5 V on the organic electroluminescent device manufactured as described above, the current density was formed to 8.19 mA / cm ^2, where is 456 cd / corresponding to x = 0.247, y = 0.486 based on 1931 CIE color coordinates A spectrum of m ² brightness was observed and the efficiency was 5.57 cd / A.

Example 2

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the thicknesses of the compounds 1 and Alq were formed at 40 nm and 20 nm, respectively.

As a result of measuring the voltage of 5 V in the organic electroluminescent device manufactured as described above, the current density was formed to 7.69 mA / cm ² , wherein the emission is 423 cd corresponding to x = 0.242, y = 0.481 based on the 1931 CIE color coordinates A spectrum of / m ² brightness was observed and the luminous efficiency was 5.51 cd / A.

Example 3

An organic electroluminescent device was manufactured in the same manner as in Example 1 except for using Compound 3 as a light emitting material instead of Compound 1.

As a result of measuring the voltage of 5 V on the organic electroluminescent device manufactured as described above, the current density was formed to 5.57 mA / cm ² , wherein the emission was 258 cd corresponding to x = 0.187 and y = 0.439 based on the 1931 CIE color coordinate. / m ² brightness spectrum was observed and the luminous efficiency was 4.63 cd / A.

Example 4

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the thicknesses of the compounds 3 and Alq were formed at 40 nm and 20 nm, respectively.

As a result of measuring the voltage of 5 V in the organic electroluminescent device manufactured as described above, the current density was formed to 4.56 mA / cm ² , wherein the emission is 230 cd corresponding to x = 0.181, y = 0.426 in 1931 CIE color coordinates A spectrum of / m ² brightness was observed and the luminous efficiency was 5.04 cd / A.

Example 5

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Compound 5 was used as the light emitting material instead of Compound 1.

As a result of measuring the voltage of 5 V in the organic electroluminescent device manufactured as described above, the current density was formed to 6.28 mA / cm ² , wherein the emission is 268 cd corresponding to x = 0.201, y = 0.441 based on 1931 CIE color coordinates / m ² brightness spectrum was observed and the luminous efficiency was 4.27 cd / A.

Example 6

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the thicknesses of the compounds 5 and Alq were formed at 40 nm and 20 nm, respectively.

As a result of measuring the voltage of 5 V in the organic electroluminescent device manufactured as described above, the current density was formed to 5.36 mA / cm ² , wherein the emission is 191 cd corresponding to x = 0.220, y = 0.475 based on the 1931 CIE color coordinates / m ² brightness spectrum was observed and the luminous efficiency was 3.57 cd / A.

Example 7

Deposition thickness of DNTPD film and NPB film at 60 nm and 30 nm, respectively, on wet and dry cleaned ITO transparent substrates in the same manner as in Example 1, followed by simultaneous compound 1 and C-545T in a weight ratio of 100 to 1 It formed into a film and formed the light emitting layer film of 40 nm. Compound 1 functions as a host of the light emitting layer, and C-545T functions as a dopant of the light emitting layer. An Alq film was then deposited to a thickness of 20 nm and LiF deposited. Metal aluminum was deposited on the LiF film to form a metal cathode, thereby manufacturing an organic electroluminescent device.

As a result of measuring the voltage of 5 V in the organic electroluminescent device manufactured as described above, the current density was formed to 7.20 mA / cm ^2, where the emission is 614 cd corresponding to x = 0.255, y = 0.603 based on the 1931 CIE color coordinates A spectrum of / m ² brightness was observed and the luminous efficiency was 8.54 cd / A.

Example 8

An organic electroluminescent device was manufactured in the same manner as in Example 7, except that Compound 3 was used as a host material of the emission layer instead of Compound 1.

As a result of measuring the voltage of 5 V in the organic electroluminescent device manufactured as described above, the current density was formed to 5.81 mA / cm ² , wherein the emission is 470 cd corresponding to x = 0.233, y = 0.584 in 1931 CIE color coordinates A spectrum of / m ² brightness was observed and the luminous efficiency was 8.07 cd / A.

Example 9

An organic electroluminescent device was manufactured in the same manner as in Example 7, except that Compound 5 was used as the host material of the emission layer instead of Compound 1.

As a result of measuring the voltage of 5 V in the organic electroluminescent device manufactured as described above, the current density was formed to 6.02 mA / cm ² , the emission is 413 cd corresponding to x = 0.256, y = 0.594 based on the 1931 CIE color coordinates / m ² brightness spectrum was observed and the luminous efficiency was 6.86 cd / A.

Comparative Example 1

In the same manner as in Example 1, the DNTPD film and the NPB film were deposited on wet and dry cleaned ITO transparent substrates at 60 nm and 30 nm, respectively, and Alq was formed to form a thickness of 60 nm. Alq functions as a light emitting layer and an electron transporting layer. Next, LiF was deposited, and metal aluminum was deposited on the LiF film to form a metal cathode, thereby manufacturing an organic electroluminescent device.

As a result of measuring the voltage of 5 V on the organic electroluminescent device manufactured as described above, the current density was formed to 4.82 mA / cm ² , wherein the emission was 136 cd corresponding to x = 0.326 and y = 0.535 in 1931 CIE color coordinates. A spectrum of / m ² brightness was observed and the luminous efficiency was 2.82 cd / A.

Comparative Example 2

Deposition film thickness of DNTPD film and NPB film on wet and dry cleaned ITO transparent substrate in the same manner as in Example 1 at 60 nm and 30 nm, respectively, and simultaneously forming Alq and C-545T at a weight ratio of 100 to 1 To form a 40 nm light emitting layer film. Alq functions as a host of the light emitting layer, and C-545T functions as a dopant of the light emitting layer. An Alq film was then deposited to a thickness of 20 nm and LiF deposited. Metal aluminum was deposited on the LiF film to form a metal cathode, thereby manufacturing an organic electroluminescent device.

As a result of measuring the voltage of 5 V in the organic electroluminescent device manufactured as described above, the current density was formed to 4.08 mA / cm ² , wherein the emission is 371 cd corresponding to x = 0.290, y = 0.630 based on the 1931 CIE color coordinates / m ² brightness spectrum was observed and the luminous efficiency was 9.09 cd / A.

The results of the organic electroluminescent devices manufactured in Examples and Comparative Examples are shown in Table 2 below.

EXAMPLES Comparative Example Host ^* Dopant ^** Emission wavelength (nm) @ 5V Luminance (cd / m ² ) @ 5V Luminous Efficiency (cd / A) @ 5V Color coordinates @ 5V Kinds thickness Kinds Example 1 Compound 1 30 - (475) 518 ^*** 456 5.57 x = 0.247 y = 0.486 Example 2 Compound 1 40 - (475) 518 ^*** 423 5.51 x = 0.242 y = 0.481 Example 3 Compound 3 30 - 485 258 4.63 x = 0.187 y = 0.439 Example 4 Compound 3 40 - 485 230 5.04 x = 0.181 y = 0.426 Example 5 Compound 5 30 - 484 268 4.27 x = 0.201 y = 0.441 Example 6 Compound 5 40 - 484 191 3.57 x = 0.220 y = 0.475 Example 7 Compound 1 40 C-545T 504 614 8.54 x = 0.255 y = 0.603 Example 8 Compound 3 40 C-545T 504 470 8.07 x = 0.233 y = 0.584 Comparative Example 1 Alq 30 - 520 136 2.82 x = 0.326 y = 0.535 y = 0.594

* When the thickness of the host is 30 nm, the film thickness of Alq, which is an electron transport layer, is 30 nm. When the thickness of the host is 40 nm, the film thickness of Alq, an electron transport layer, is 20 nm.

 ** Dopant concentration is 1%.

*** There are two characteristic peaks.

As described in detail above, the organic electroluminescent device using the novel spiro compound of the present invention has excellent heat resistance, high stability of the thin film constituting the device, long life, high luminous efficiency and high luminous luminance, and low voltage driving. This is possible. For this reason, the organic electroluminescent element of the present invention can be used in various organic electroluminescent elements such as flat panel displays such as wall-mounted TVs, illumination or back light of displays.

Claims (13)

An organic electroluminescent device material represented by a spiro compound of Formula 1 [Formula 1]

In Chemical Formula 1, each component is as follows. S ₁ to S ₄ are carbon, silicon, germanium, phosphorus or sulfur atoms, O ₁ to O ₄ is a cyclic structure former that spy bonds with S ₁ to S ₄ , R ₁ to R ₂ are hydrogen atoms, Y ₁ to Y of the substituents set forth in the _second or beach of the substituents set forth in the aromatic group of the ring nucleus carbon atoms of 6 to 50, Y ₁ to Y ₂ or nuclear atoms an unsubstituted An aromatic heterocyclic group having 5 to 50 carbon atoms having ₁ to Y ₂ substituents or unsubstituted alkyl groups having 1 to 50 carbon atoms, and having ₁ to Y ₂ having substituents or unsubstituted alkenyl groups having 2 to 50 carbon atoms. , Y ₁ to Y of the substituents set forth in the _second or unsubstituted C2 to 50 alkynyl, Y ₁ of the substituents set out in to Y ₂ or unsubstituted oxygen, nitrogen, carbon, silicon, and germanium or a sulfur atom , R ₁ to R ₂ are not all hydrogen atoms. In addition, Y ₁ to Y ₂ are each a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 atomic atoms, a substituted or unsubstituted carbon atom 1 to A 50 alkyl group, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, When R ₁ to R ₂ is a carbon, silicon or germanium atom, an unsubstituted aromatic group having 6 to 50 carbon atoms or an aromatic heterocyclic group having 5 to 50 nuclear atoms, Y ₁ to Y ₂ are represented by OZ ₁ . A group, an amino group represented by NZ ₂ Z ₃ , a thio group represented by SZ ₄ , a carbonyl group represented by COZ ₅ to COOZ ₆ , a halogen atom, a cyano group or a nitro group may be substituted. Where Z ₁ To Z ₆ represents a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, substituted Or an unsubstituted aralkyl group having 7 to 50 carbon atoms. In addition, _n represented by (Y ₁ ) _n to (Y ₂ ) _n are each independently an integer of 0 to 6, and each may independently form a saturated or unsaturated ring with R, X, and Z groups. X ₁ To X ₂ is a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, and OZ ₇ And a group represented by NZ ₈ Z ₉ , an amino group represented by SZ ₁₀ , a thio group represented by SZ ₁₀ , a carbonyl group represented by COZ ₁₁ to COOZ ₁₂ , a halogen atom, a cyano group, and a nitro group. ₇ to Z ₁₂ is a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 carbon atoms, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, Or a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms. _N represented by (X ₁ ) _n to (X ₂ ) _n are each independently an integer of 0 to 4, and each may independently form a saturated or unsaturated ring with R, Y, and Z groups. The method of claim 1, Material for an organic electroluminescent device wherein the spiro compound of Formula 1 is a compound represented by any one of the following Formulas 2 to 6 [Formula 2] [Formula 3] [Formula 4]

     [Formula 5] [Formula 6]

The method of claim 1, An organic electroluminescent device material, wherein the spiro compound of Formula 1 is a compound represented by the following Formula [Formula 7]

In Formula 7, L ₁ to L ₄ are a single bond, carbon to heteroatoms included in R ₁ to R ₂ , independently-(CR'R '') _e -,-(SiR'R '') _e -, -O-, -CO- or -NR'-. Wherein R ′ and R ″ are each independently a hydrogen atom, a substituted or unsubstituted aromatic group having 6 to 50 nuclear carbon atoms, a substituted or unsubstituted aromatic heterocyclic group having 5 to 50 nuclear atoms, substituted or unsubstituted An alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, e is an integer from 1 to 10, and R 'and R' 'may be the same or different. In addition, A ₁ to A ₁₆ each independently represent -CR'R ''-, -SiR'R ''-, -O-, -NR'- or -CO-, Wherein R 'and R' 'may be the same or different, and may combine with each other to form a ring structure. p is an integer from 1 to 10. Further, at least two adjacent ones of A ₁ to A ₁₆ are each represented by -CR'R ''-(R 'and R''are the same as described above), and R's adjacent to each other R''R' or R 'and R' may be saturated or unsaturated to form a ring structure having 4 to 50 carbon atoms. In the organic electroluminescent device which is located between the anode and the cathode, the organic thin film layer composed of a single layer or a plurality of layers having at least one light emitting layer is sandwiched, At least one layer of the said organic thin film layer contains the organic electroluminescent element material of any one or more of Claims 1-3. The method of claim 4, wherein An organic electroluminescent device in which the light emitting layer contains a spiro compound represented by the formula (1) as a main component. The method of claim 4, wherein An organic electroluminescent device comprising as a host a spiro compound represented by Formula 1 using a dopant material in addition to the light emitting layer. The method of claim 4, wherein An organic electroluminescent device comprising as a dopant a spiro compound represented by the formula (1) using a host material in addition to the light emitting layer. The method of claim 6, As the light emitting material or dopant material, as an condensed polycyclic aromatic, anthracene, naphthalene, phenanthrene, pyrene, tetracene, pentacene, coronene, chrysene, fluorescein, perylene, rubrene and derivatives thereof, phthalo Perylene, Naphthaloperylene, Perinone, Phthaloperinone, Naphthalophenone, Diphenylbutadiene, Tetraphenylbutadiene, Coumarin, Oxadiazole, Aldazine, Bisbenzoxazolin, Bisstyryl , Pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazole An organic electroluminescent device containing a chelated oxynoid compound, quinacridone, stilbenes and derivatives thereof. The method of claim 7, wherein Examples of the light emitting material or host material include condensed polycyclic aromatics, anthracene, naphthalene, phenanthrene, pyrene, tetracene, pentacene, coronene, chrysene, fluorescein, perylene, rubrene and derivatives thereof, and phthalope Reylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperin, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, Pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazole chelate An organic electroluminescent device containing a oxidized oxynoid compound, quinacridone, stilbene and derivatives thereof. The method of claim 4, wherein An organic electroluminescent device, wherein the plurality of hole injection layers contain a spiro compound represented by the formula (1) as a main component. The method of claim 4, wherein An organic electroluminescent device, wherein the plurality of hole transport layers contain a spiro compound represented by the formula (1) as a main component. The method of claim 4, wherein An organic electroluminescence device, in which the electron transport layer of the plurality of layers contains a spiro compound represented by the formula (1) as a main component. The method of claim 4, wherein An organic electroluminescent device, wherein said plurality of electron injection layers contain, as a main component, a spiro compound represented by formula (1).