JP2005179488A - Luminescent material for organic electroluminescent device and organic electroluminescent device using it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a luminescent material for an organic electroluminescent device which has high emission luminance and a long luminescent life and to provide an organic EL device using it. <P>SOLUTION: The luminescent material for the organic electroluminescent device contains a non-conjugated polymer containing units containing the partial structure represented by general formula [1] and units containing the partial structure represented by general formula [2]. In general formula [1] R<SP>1</SP>-R<SP>5</SP>indicate each independently a bonding site, a hydrogen atom or a substituent, R<SP>6</SP>-R<SP>10</SP>indicate each independently a hydrogen atom or a substituent, and R<SP>1</SP>-R<SP>5</SP>and R<SP>6</SP>-R<SP>10</SP>, each bonded with one another, may form a ring. In general formula [2] R<SP>11</SP>-R<SP>17</SP>indicate each independently a bonding site, a hydrogen atom or a substituent, X indicates a direct bonding, -O-, -S-, -Se-, -NH-, -NR<SP>18</SP>- (wherein R<SP>18</SP>is an alkyl group or aryl group), -S(=O)<SB>2</SB>-, -(CO)-, -COO-, -OCO- or -CH<SB>2</SB>-, and R<SP>11</SP>-R<SP>17</SP>, bonded with one another, may form a ring. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a light-emitting material and a high-luminance light-emitting element used for a planar light source, an organic electroluminescence (EL) element used for display, and the like.

  An electroluminescent element using an organic substance is promising for use as a solid light emitting type inexpensive large-area full-color display element, and many developments have been made. In general, an organic electroluminescent element is composed of a light emitting layer and a pair of counter electrodes sandwiching the layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side, holes are injected from the anode side, the electrons recombine with holes in the light emitting layer, and the energy level starts from the conduction band. It is a phenomenon in which energy is released as light when returning to the valence band.

Conventional organic electroluminescent elements have a higher driving voltage and lower luminance and luminous efficiency than inorganic EL elements. Further, the characteristic deterioration has been remarkably not put into practical use.
In recent years, an organic electroluminescent device in which a thin film containing an organic compound having a high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less has been reported and attracted attention (see Non-Patent Document 1). This method uses a metal chelate complex as a light emitting layer and an amine compound as a hole injection layer to obtain high luminance green light emission, and the luminance reaches several thousand cd / m ² at a DC voltage of 6 to 7V. ing. However, the production of an organic electroluminescent element involving an organic compound vapor deposition operation has a problem in productivity, and it is desirable to create a coating method element from the viewpoint of simplifying the manufacturing process and increasing the area.

  A polyphenylene vinylene polymer is known as a light emitting material of an organic electroluminescent element used in the production of an organic electroluminescent element of a coating method advantageous for productivity (see Non-Patent Documents 2 and 3), but a light emitting part. Has a problem in that it is difficult to control the concentration of the light-emitting material and to delicately control the color tone and light emission intensity. Similarly, as an organic electroluminescent element using a coating method, for example, there is an element that disperses a low molecular weight dye or the like in polyvinyl carbazole (see Patent Document 1), but it has been found that there is a problem in characteristics such as low luminous efficiency. It was.

Regarding a light emitting material obtained by copolymerizing a low molecular light emitting material with a polymer, several reports have been made as green to red light emitting materials (see Patent Documents 2 to 6). However, the driving voltage is a polyphenylene vinylene polymer. Higher than organic electroluminescent devices using luminescent materials. This is because the mobility of holes in non-conjugated polymers typified by polyvinylcarbazole is low compared to polyphenylene vinylene-based polymer light-emitting materials. The voltage is considered to have increased.
Applied Physics Letters, 51, 913, 1987 Advanced Materials, Volume 2, Page 4 1992 Advanced Material 9, 551 pages 1997 JP-A-4-212286 JP 07-18834 A Japanese Patent Application Laid-Open No. 08-048726 Japanese Patent Laid-Open No. 11-74077 Japanese Patent Application Laid-Open No. 2000-282025 JP 2001-220410 A

  An object of the present invention is to provide an electroluminescent element material having high emission luminance and a long emission lifetime, and an electroluminescent element using the same.

As a result of intensive studies by the present inventors, in an organic electroluminescent device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes, the light emitting layer has the general formula [1]. By using a light-emitting material for an organic electroluminescent element comprising a non-conjugated polymer containing a unit containing a unit and a unit containing the general formula [2], the light emission starting voltage and luminous efficiency of the electroluminescent element are improved. I found.
That is, the present invention provides an organic comprising a non-conjugated polymer including a unit including a partial structure represented by the following general formula [1] and a unit including a partial structure represented by the following general formula [2]. The present invention relates to a light emitting material for an electroluminescent element.

General formula [1]

[Wherein R ^{1 to} R ⁵ each independently represents a bonding site, a hydrogen atom or a substituent,
R ^{6 to} R ¹⁰ each independently represents a hydrogen atom or a substituent.
R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ may be bonded to each other to form a ring. ]

General formula [2]

[Wherein R ^{11 to} R ¹⁷ each independently represents a bonding site, a hydrogen atom or a substituent,
X is a direct bond, —O—, —S—, —Se—, —NH—, —NR ¹⁸ — (R ¹⁸ represents an alkyl group or an aryl group), —S (═O) ₂ —, — ( CO) -, - COO -, - OCO-, or represents -CH ₂ -.
R ^{11 to} R ¹⁷ may be bonded to each other to form a ring. ]

Moreover, this invention relates to the said light emitting material for electroluminescent elements whose general formula [1] is the following general formula [3].
General formula [3]

[Wherein R ^{19 to} R ²³ each independently represents a bonding site, a hydrogen atom or a substituent,
R ^{24 to} R ³² each independently represent a hydrogen atom or a substituent,
R ³³ represents an aryl group or an alkyl group.
R ^{19 to} R ²³ and R ^{24 to} R ³³ may be bonded to each other to form a ring. ]

  Moreover, this invention relates to the said light emitting material for electroluminescent elements whose general formula [2] is the following general formula [4].

General formula [4]

[Wherein R ^{34 to} R ⁴² represent a bonding site, a hydrogen atom or a substituent. ]
The present invention also relates to an organic electroluminescent device comprising a light emitting layer or a plurality of layers of organic compound thin films including a light emitting layer formed between a pair of electrodes, wherein at least one layer includes the organic electroluminescent device material. The present invention relates to a light emitting element.

  According to the present invention, an organic EL element having a lower driving voltage, higher luminance, and longer life can be obtained.

  In the organic electroluminescence device, the light emitting material in the light emitting layer includes a carrier transportable partial structure represented by the general formula [2] and a styryl group represented by the general formula [1]. And a light-emitting partial structure having a non-conjugated polymer.

  Examples of the unit including the partial structure represented by the general formula [1] of the present invention include the following general formula [5].

General formula [5]

[Wherein, A represents a non-conjugated trivalent organic residue, B represents a direct bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted ethenyl group, and these Represents a divalent organic residue selected from the group consisting of: and C represents a monovalent organic residue represented by the general formula [1]. ]

  Examples of the unit including the partial structure represented by the general formula [2] of the present invention include the following general formula [6].

General formula [6]

[Wherein D represents a non-conjugated trivalent organic residue, E represents a direct bond, a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted ethenyl group, and these Represents a divalent organic residue selected from the group consisting of: F represents a monovalent organic residue represented by the general formula [2]. ]

  In the general formulas [5] and [6], A and D represent any trivalent organic residue capable of forming a non-conjugated main chain skeleton having B, C, and E and F in the side chain. Examples are shown in G-1 to G-12 of Table 1, but are not limited thereto.

Table 1

The polymerization mode of the non-conjugated main chain skeleton monomer when forming the polymer can be polymerized by vinyl polymerization such as radical polymerization, cationic polymerization, anion polymerization, condensation polymerization, ring-opening polymerization, and various polymerization reactions. The method is not particularly limited, but in the present invention, a polymer formation reaction by polymerization of a vinyl polymerization monomer is particularly preferable.
Further, B and / or C in the general formula [5] and E and / or F in the general formula [6] were formed at the non-conjugated main chain skeleton monomer stage even though they were not introduced at the stage of the non-conjugated main chain skeleton monomer. Later, it may be introduced and modified.

  In the general formula [5], B represents a direct bond, a divalent, substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted ethenyl group, or a combination of these groups. Represent. Examples are shown in B-1 to B-15 of Table 2, but are not limited thereto.

Table 2

  In the general formula [6], E represents a direct bond, a divalent, substituted or unsubstituted arylene group and a substituted or unsubstituted heteroarylene group. Examples are shown in E-1 to E-6 of Table 3, but are not limited thereto.

Table 3

  The arylene group in the general formulas [5] and [6] is preferably a monocyclic or condensed arylene group having 6 to 60 carbon atoms, more preferably 6 to 40 carbon atoms, still more preferably 6 to 30 carbon atoms. An arylene group. Specific examples include phenylene, biphenylene, naphthalenediyl, anthracenediyl, phenanthroline diyl, pyrenediyl, triphenylenediyl, benzophenanthroline diyl, perylenediyl, pentaphenylenediyl, pentacenediyl, and the like. good.

  The heteroarylene group in the general formulas [5] and [6] is preferably a monocyclic or condensed aromatic heterocyclic group having 4 to 60 carbon atoms, more preferably at least a nitrogen atom, an oxygen atom or a sulfur atom. It is a monocyclic or condensed aromatic heterocyclic group having 4 to 60 carbon atoms containing one, and more preferably a 5- or 6-membered aromatic heterocyclic group having 4 to 30 carbon atoms. Specific examples of the aromatic heterocyclic group include pyrrole diyl, furandyl, thienylene, pyridinediyl, pyridazinediyl, pyrimidinediyl, pyrazinediyl, quinolinediyl, isoquinolinediyl, cinnolinediyl, quinazolinediyl, quinoxalinediyl, phthalazinediyl, pteridinediyl, acridinediyl, phenidinediyl Examples thereof include diyl and phenanthroline diyl, and these groups may have a substituent.

  The substituent of the compound in the present invention is a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkylene group, substituted or unsubstituted. Substituted alkoxy group, substituted or unsubstituted thioalkoxy group, cyano group, amino group, mono- or di-substituted amino group, hydroxyl group, mercapto group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted Alternatively, it represents an unsubstituted arylthio group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted heteroaryloxy group, a substituted or unsubstituted heteroarylthio group, and the substituent is substituted with adjacent substituents. Alternatively, an unsubstituted ring may be formed.

  Examples of the substituted or unsubstituted aryl group include phenyl group, biphenylenyl group, triphenylenyl group, tetraphenylenyl group, 3-nitrophenyl group, 4-methylthiophenyl group, 3,5-dicyanophenyl group, o-, m- And p-tolyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, indenyl group, naphthyl group, anthracenyl group, azulenyl group, heptaenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, Anthryl group, anthraquinonyl group, 3-methylanthryl group, phenanthryl group, pyrenyl group, chrysenyl group, 2-ethyl-1-chrysenyl group, picenyl group, perylenyl group, 6-chloroperylenyl group, pentaphenyl group, pentacenyl group, tetra Phenylenyl group, hexaphenyl Group, hexacenyl group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, there is ovalenyl group.

  Examples of the substituted or unsubstituted heteroaryl group include thionyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolyl group, quinolyl group, isoquinolyl group, phthalazinyl group, Quinoxalinyl group, quinazolinyl group, carbazolyl group, acridinyl group, phenazinyl group, furfuryl group, isothiazolyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, 2-methylpyridyl group, 3 -A cyanopyridyl group and the like.

  Mono- or di-substituted amino groups include methylamino, dimethylamino, ethylamino, diethylamino, dipropylamino, dibutylamino, diphenylamino, bis (acetoxymethyl) amino, bis (acetoxy) And ethyl) amino group, bis (acetoxypropyl) amino group, bis (acetoxybutyl) amino group, and dibenzylamino group.

  Substituted or unsubstituted alkyl groups include methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl , Stearyl group, trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, 1,3-cyclohexadienyl group, 2-cyclopenten-1-yl group, 2,4-cyclopentadiene-1-ylidenyl group, etc. There is.

  Examples of the substituted or unsubstituted alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, and vinyl.

  Examples of the substituted or unsubstituted alkoxy group include methoxy group, ethoxy group, propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, 2-ethylhexyloxy group, stearyloxy Group, trifluoromethoxy group and the like.

  Examples of the substituted or unsubstituted thioalkoxy group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.

  Examples of the substituted or unsubstituted aryloxy group include a phenoxy group, a p-tert-butylphenoxy group, and a 3-fluorophenoxy group.

  Examples of the substituted or unsubstituted arylthio group include a phenylthio group and a 3-fluorophenylthio group.

  Preferred substituents are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group. Further, adjacent substituents form an aliphatic, carbocyclic aromatic, heterocyclic aromatic or heterocyclic ring which may contain a 5- to 7-membered oxygen atom, nitrogen atom, sulfur atom, etc. It may also have a substituent at any position of these rings.

The polymer having the unit represented by the general formula [5] of the present invention and the unit represented by the general formula [6] may be a random, block, or graft copolymer. A polymer having an intermediate structure, for example, a random copolymer having a block property may be used.
When the unit represented by the general formula [5] and the unit represented by the general formula [6] are based on vinyl polymerization, styrene and derivatives thereof, acrylic acid and derivatives thereof, maleic acid and components thereof It may be a copolymer with a derivative, an organic acid vinyl ester or the like.

  The partial structure represented by the general formula [1] or the partial structure represented by the general formula [2] may be included in the main chain as long as it is a non-conjugated polymer. For example, it includes an alternating copolymer with a non-conjugated unit, or a case where units such as those shown in Examples 22 and after are bonded with polyester, polyurethane, polyware, or the like.

Although the typical example of the nonconjugated polymer of this invention is specifically shown in Table 4, the nonconjugated polymer of this invention is not limited to the following representative examples. In addition, although it is an exemplary copolymer, it shows only the structure of each unit monomer, and does not show its polymerization form. N and m represent natural numbers.
Table 4

The electron injecting material of the present invention has the ability to transport electrons, has a hole injecting effect from the cathode, an excellent electron injecting effect for the light emitting layer or the light emitting material, and excitons generated in the light emitting layer. Examples thereof include compounds that prevent movement to the hole injection zone and have excellent thin film forming ability. For example,
Oxazole derivatives, triazole derivatives, oxadiazole derivatives, fluorenone derivatives, anthraquinodimethane derivatives, diphenoquinone derivatives, thiopyrandioxide derivatives, imidazole derivatives, perylenetetracarboxylic acid, fluorenylidenemethane derivatives, anthrone derivatives, phthalocyanine derivatives, metals Complexes (metal complexes of 8-quinolinol derivatives, metal phthalocyanines, metal complexes having benzoxazole or benzothiazole as a ligand, etc.) may be mentioned, but are not limited thereto.

  As the polymer film forming method of the present invention, a coating method (for example, an ink jet method, a spray method, a printing method, a spin coating method, a casting method, a dipping method, a bar coating method, a roll coating method, etc.) is used. I can do it. Solvents used in the coating method include organic halogen solvents such as dichloroethane, dichloromethane and chloroform, ether solvents such as tetrahydrofuran and 1.4-dioxane, aromatic hydrocarbon solvents such as toluene and xylene, dimethyl An amide solvent such as formamide and dimethylacetamide, an ester solvent such as ethyl acetate and butyl acetate, or a mixed solvent thereof may be used. Although it depends on the structure and molecular weight of the polymer, the film is usually formed using a solution of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, of a solvent.

An organic EL element is an element in which a single-layer or multilayer organic thin film is formed between an anode and a cathode.
In the case of the single layer type, a light emitting layer is provided between the anode and the cathode. The light emitting layer contains a light emitting material, and in addition, contains a hole injecting material or an electron injecting material in order to transport holes injected from the anode or electrons injected from the cathode to the light emitting material. The multi-layer type includes (anode / hole injection band / light emitting layer / cathode), (anode / light emitting layer / electron injection band / cathode), and (anode / hole injection band / light emitting layer / electron injection band / cathode). There are organic EL elements stacked in a configuration.

As the conductive material used for the anode of the organic EL element, those having a work function larger than 4 eV are preferable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, etc. Further, alloys thereof, ITO substrates, metal oxides such as tin oxide and indium oxide called NESA substrates, and organic conductive resins such as polythiophene and polypyrrole are used.
As the conductive material used for the cathode, those having a work function smaller than 4.0 eV are preferable. Magnesium, barium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, etc. and alloys thereof However, it is not limited to these. If necessary, the anode and the cathode may be formed of two or more layers.

Hereinafter, the present invention will be described in more detail based on production examples and examples. In the description, parts represent parts by weight and% represents% by weight.
Production Example 1
Synthesis method of compound (2) in Table 4

Under a dry nitrogen stream, N-ethylcarbazole-3-carboxaldehyde (4.46 g 0.02 mol), compound (A) (6.5 g 0.021 mol) and dehydrated DMF (100 ml) were added and stirred at 0 ° C. for 1 hour. did. To this solution, a solution of KOBu ^t (5 g, 0.044 mmol) dissolved in dehydrated DMF (80 ml) was added dropwise over 1 hour. The color of the reaction solution turns white and the viscosity is improved. In this state, stirring is performed for 5 hours. After completion of the reaction, the reaction mixture was poured into 500 ml of water, and the precipitate was filtered and dried at 70 ° C. to obtain a crude product, which was then isolated and purified by silica gel column chromatography to obtain compound (B). Yield 80%.

  A four-necked flask was fitted with a condenser, and compound (B) (2.2 g, 5.8 mmol), 4-vinylphenylboronic acid (1.04 g 7.03 mmol), dehydrated tetrahydrofuran (40 ml), 2M aqueous potassium carbonate solution (40 ml), tetrakis (triphenylphosphine) palladium (O) (0.12 g) was added thereto, and the mixture was heated and stirred at the boiling point for 6 hours. After completion of the reaction, the mixture was cooled to room temperature, extracted with toluene, and further purified by column chromatography and methanol reprecipitation to obtain compound (C). The yield was 82%.

  A Schlenk flask was charged with 4-vinyl-biphenyl-N-carbazole (0.95 g) and 0.05 g of compound (C), and vacuum deaeration was repeated several times. Azobisisobutyronitrile (0.04 g) and THF (3 ml) were added thereto, and the mixture was stirred at 70 ° C. for 8 hours. The reaction liquid has become viscous. After completion of the reaction, the reaction mixture was poured into methanol, and the precipitated white solid was filtered off and purified by reprecipitation of methanol to obtain compound (2). The yield was 95%.

Example 1
On the washed glass plate with an ITO electrode, PEDOT was formed into a film thickness of 50 nm by a spin coat method, and vacuum-dried at 100 ° C. Further, a solution prepared by mixing the compound (1) shown in Table 4 and the following compound (31) at a weight ratio of 60:40 and dissolving in 1,2-dichloroethane at a concentration of 0.75 wt% was spin-coated. By this method, a light-emitting layer was obtained by forming a film with a thickness of 80 nm on the previously prepared PEDOT layer. An electrode was formed on the coated substrate by a vacuum deposition method with a film thickness of Ca of 40 nm and Al of 120 nm to produce an organic EL element 1.

Compound (31)

Example 2
On the washed glass plate with an ITO electrode, PEDOT was formed into a film thickness of 50 nm by a spin coat method, and vacuum-dried at 100 ° C. Further, a solution prepared by mixing the compound (2) shown in Table 4 and the following compound (32) in a weight ratio of 60:40 and dissolving in 1,2-dichloroethane at a concentration of 0.75 wt% was spin-coated. By this method, a light-emitting layer was obtained by forming a film with a thickness of 80 nm on the previously prepared PEDOT layer. An electrode was formed on the coated substrate by a vacuum deposition method with a film thickness of Ca of 40 nm and Al of 120 nm, thereby producing an organic EL element 2. The EL spectrum of this device is shown in FIG.

Compound (32)

Example 3
On the washed glass plate with an ITO electrode, PEDOT was formed into a film thickness of 50 nm by a spin coat method, and vacuum-dried at 100 ° C. Further, a solution prepared by mixing the compound (3) and the compound (32) shown in Table 4 in a weight ratio of 60:40 and dissolving in 1,2-dichloroethane at a concentration of 0.75 wt% was obtained by spin coating. Thus, a light emitting layer was obtained by forming a film with a thickness of 80 nm on the previously prepared PEDOT layer. An electrode was formed on the coated substrate by a vacuum vapor deposition method with a film thickness of Ca of 40 nm and Al of 120 nm to produce an organic EL element 3.

Comparative Example 1
On the washed glass plate with an ITO electrode, PEDOT was formed into a film thickness of 50 nm by a spin coat method, and vacuum-dried at 100 ° C. Furthermore, the following compound (33), the above compound (32), and the following compound (34) were mixed at a weight ratio of 60: 37: 3 and dissolved in 1,2-dichloroethane at a concentration of 0.75 wt%. The solution was formed into a film having a thickness of 80 nm on the previously prepared PEDOT layer by a spin coating method to obtain a light emitting layer. An electrode was formed on the coated substrate by a vacuum deposition method with a film thickness of Ca of 40 nm and Al of 120 nm, thereby producing an organic EL element 4.

Compound (33)

Compound (34)

Comparative Example 2
On the washed glass plate with an ITO electrode, PEDOT was formed into a film thickness of 50 nm by a spin coat method, and vacuum-dried at 100 ° C. Furthermore, the following compound (33), compound (32), and the following compound (35) were mixed at a weight ratio of 60: 37: 3 and dissolved in 1,2-dichloroethane at a concentration of 0.75 wt%. Was formed into a film having a thickness of 80 nm on the previously prepared PEDOT layer by a spin coating method to obtain a light emitting layer. On this coated substrate, an electrode was formed with a film thickness of Ca of 40 nm and Al of 120 nm by a vacuum deposition method, and an organic EL element 5 was produced.
Compound (35)

Table 5 shows the EL characteristics of Examples 1 to 3 and Comparative Examples 1 and 2.

  The organic EL device of the present invention achieves low driving voltage, light emission efficiency, and light emission brightness, and is used together with a light emitting substance, a light emission auxiliary material, a hole transport material, an electron transport material, and a sensitizer. However, the resin, the electrode material, etc. and the device manufacturing method are not limited.

  As is apparent from Table 6, the compound (34) and the compound (35), which are materials that are not a copolymer with an electroluminescent element (element 1, element 2, element 3) using the organic electroluminescent element material of the present invention. When the used electroluminescent elements (element 4 and element 5) are compared, it can be confirmed that the former has lower driving voltage and higher efficiency light emission.

  When all the organic EL devices shown in this example were continuously emitted, a luminance of 50% or more of the initial luminance could be observed for 1000 hours or more. However, the device of Comparative Example 1 was allowed to continuously emit light under the same conditions. As a result, the luminance was 50% or less of the initial luminance in 20 hours, and the number of dark spots was extremely large. Since the hole transport material of the present invention has a high molecular weight, the heat resistance as an organic EL device is extremely improved. All of the compounds of the present invention have glass transition temperatures and melting points of 100 ° C. or more, indicating that the luminescent material of the present invention is greatly improved.

  The organic EL device of the present invention achieves improvement in luminous efficiency, luminous luminance and longevity, and is used together with a luminescent substance, a luminescent auxiliary material, a hole transport material, an electron transport material, a sensitizer, The resin, the electrode material, etc. and the element manufacturing method are not limited.

  The organic EL device of the present invention can be applied to flat panel displays such as wall-mounted TVs, flat light emitters, light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display boards, and indicator lights. The industrial value is very large.

Emission spectrum of the device of Example 2

Claims (4)

Luminescent material for organic electroluminescence device comprising a non-conjugated polymer comprising a unit comprising a partial structure represented by the following general formula [1] and a unit comprising a partial structure represented by the following general formula [2] .
General formula [1]

[Wherein R ^{1 to} R ⁵ each independently represents a bonding site, a hydrogen atom or a substituent,
R ^{6 to} R ¹⁰ each independently represents a hydrogen atom or a substituent.
R ^{1 to} R ⁵ and R ^{6 to} R ¹⁰ may be bonded to each other to form a ring. ]

General formula [2]

[Wherein R ^{11 to} R ¹⁷ each independently represents a bonding site, a hydrogen atom or a substituent,
X is a direct bond, —O—, —S—, —Se—, —NH—, —NR ¹⁸ — (R ¹⁸ represents an alkyl group or an aryl group), —S (═O) ₂ —, — ( CO) -, - COO -, - OCO-, or represents -CH ₂ -.
R ^{11 to} R ¹⁷ may be bonded to each other to form a ring. ] The light emitting material for electroluminescent elements according to claim 1, wherein the general formula [1] is the following general formula [3].
General formula [3]
[Wherein R ^{19 to} R ²³ each independently represents a bonding site, a hydrogen atom or a substituent,
R ^{24 to} R ³² each independently represent a hydrogen atom or a substituent,
R ³³ represents an aryl group or an alkyl group.
R ^{19 to} R ²³ and R ^{24 to} R ³³ may be bonded to each other to form a ring. ]
The light emitting material for electroluminescent elements according to claim 1 or 2, wherein the general formula [2] is the following general formula [4].
General formula [4]
[Wherein R ^{34 to} R ⁴² represent a bonding site, a hydrogen atom or a substituent. ] In the organic electroluminescent element formed by forming the light emitting layer or a plurality of layers of organic compound thin films including the light emitting layer between the pair of electrodes, at least one layer contains the material for an organic electroluminescent element according to any one of claims 1 to 3. Organic electroluminescent device.