JP4623033B2 - Organic electroluminescence device - Google Patents

Description

  The present invention relates to an organic electroluminescence (hereinafter also referred to as organic EL) element, and more particularly to an organic electroluminescence element using an organic electroluminescence element material having excellent emission luminance.

  Conventionally, an inorganic electroluminescence (hereinafter also referred to as “inorganic EL”) element has been used as a planar light source. However, in order to drive the light emitting element, an alternating high voltage is required. A recently developed organic EL device has a structure in which a thin film containing a fluorescent organic compound is sandwiched between a cathode and an anode, and excitons (excitons) are formed by injecting electrons and holes into the thin film and recombining them. And emits light using the emission of light (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a low voltage of several volts to several tens of volts direct current. Since it is a light-emitting type, it is rich in viewing angle dependency, has high visibility, and is a thin-film type complete solid-state device, and thus has attracted attention from the viewpoints of space saving and portability.

  Various organic EL elements have been reported so far. For example, Appl. Phys. Lett. Vol. 51, page 913, or a combination of a hole injection layer described in JP-A-59-194393 and an organic light-emitting layer, hole injection layer described in JP-A-63-295695, and electron injection transport In combination with a layer, Jpn. Journal of Applied Physics, vol 127, no. A combination of the hole transfer layer, the light emitting layer, and the electron transfer layer described on pages 2,269 to 271 is disclosed.

  However, a device with higher luminance is demanded, and further improvement in energy conversion efficiency and light emission quantum efficiency is expected. In addition, a problem that the light emission life is short has been pointed out. The cause of such deterioration in luminance over time has not been completely elucidated, but the electroluminescent device during light emission is decomposed by the organic compound itself that constitutes the thin film by the light emitted by itself and the heat generated at that time, Degradation factors derived from an organic compound as an organic EL element material, such as intramolecular movement, aggregation, orientation, and crystallization of the organic compound in the thin film caused by a high electric field applied to the element, have been pointed out.

  In addition, an EL element accompanied by an organic compound vapor deposition operation has a problem in productivity. From the viewpoint of simplification of the manufacturing process, workability, and increase in area, it is desirable to manufacture an element by a coating method.

  Thus, as an EL element material used in the production of an EL element of a coating method advantageous in productivity, for example, there is an element (Japanese Patent Laid-Open No. 4-212286) in which a low molecular weight dye is dispersed in polyvinyl carbazole. Since the dye type and dye concentration can be changed arbitrarily, it is relatively easy to adjust the color tone and emission intensity. However, since these elements have low molecular weight compounds dispersed in the polymer, a high electric field is applied as described above. Dye aggregation and layer separation are likely to occur, and it is difficult to obtain uniform light emission.

  Similarly, as an EL element material using a coating method, for example, a paraphenylene vinylene polymer is known (Advanced Materials, Item 4, 1992). However, since the polymer main chain has a light emitting portion, the concentration control of the light emitting material is possible. There is a problem that it is difficult to delicately control the color tone and light emission intensity.

  Similarly, as an EL element material using a coating method, a polycarbonate obtained by reacting a bifunctional monomer containing a fluorescent residue such as tetraphenylbenzidine with phosgene, for example (Japanese Patent Laid-Open No. 5-247458) However, in the polymer obtained by such polycondensation, the acid to be eliminated is likely to remain, and the remaining impurities tend to become trap levels and cause deterioration of the device such as generation of dark spots. There is a problem that it is difficult to obtain uniform light emission and the light emission characteristics are not excellent.

  Further, for example, there is a polymer obtained by addition polymerization of a monomer in which a fluorescent residue such as triphenylamine and a vinyl group are linked with a radical initiator or the like (JP-A-7-53953, etc.), Closely linked fluorescent residues interact with each other in the excited state to form an exciplex that stabilizes the light, making the emission longer and facilitating excimer emission with low emission efficiency. Is difficult to control.

  In order to avoid such excimer emission, it is necessary to dilute and disperse the fluorescent residues in the molecule so that the fluorescent residues do not interact with each other in the molecule. As one of the means, a means of copolymerizing a monomer containing a fluorescent residue and a monomer having a structure that hardly interacts with the fluorescent residue can be considered. For example, an organic EL element material obtained by copolymerizing a fluorescent monomer such as vinyl anthracene and a charge transporting monomer such as vinyl carbazole is disclosed (JP-A-8-48726, etc.). Such a technique has the advantage that the dilution ratio can be freely selected depending on the mixing ratio of the monomers before polymerization, but there is a possibility of causing block copolymerization during the polymerization, and the fluorescent residue is expected. Dilution / dispersion is not always possible.

  It is considered that such interaction between fluorescent residues is likely to occur because the fluorescent residues are linked to the vicinity of the polymer main chain and are originally close to each other. Therefore, a method of preventing excimer emission due to the interaction between the fluorescent residues by adjusting the length of the linking group connecting the vinyl group which is a polymerization group and the fluorescent residue is also considered, for example, a methacryloyl group And an organic EL device material in which a coumarin, which is a fluorescent compound, is linked with mono- (or di-) ethylene oxide and the distance between the polymerizable group and the fluorescent residue is increased (Japanese Patent Laid-Open No. 8-157815). issue). However, when the linking group is lengthened in this way, there is a problem that the degree of freedom of movement of the fluorescent residue is increased, and the orientation and aggregation of the arrow-ringed fluorescent residue are liable to occur due to the applied high electric field.

  Accordingly, an object of the present invention is to provide an organic luminescence device containing a polymer having excellent light emission characteristics and processing stability.

  As a result of examining the above problems, the present invention has been completed by finding that it is effective to lengthen the repeating unit of the polymer main chain in order to achieve intramolecular dispersion of the fluorescent residue. It is. That is, in the vinyl group polymer, every two fluorescent residues exist with respect to the polymer main chain, but when the polymerizable group has a cyclic structure, three, four, five It is possible to obtain a polymer material having a fluorescent residue accurately for each of two or more arbitrary repeating units, such as a fluorescent substance at a desired concentration while limiting the degree of freedom of the fluorescent residue. Residues can be dispersed in the polymer, excimer emission based on the interaction between fluorescent residues is prevented, and organic EL element materials with excellent emission characteristics, stability, and processing characteristics are obtained. be able to. In addition, any linking group may be introduced between the polymerizable cyclic structure and the fluorescent residue, and such a polymerizable monomer may be copolymerized with a monomer having an appropriate charge transporting group. In addition, it is possible to design organic EL device materials in a more free range by mixing a dopant in such a polymer at an appropriate concentration, or by adding, condensing, or graft-polymerizing a reactive polymer.

  The object of the present invention is to provide an organic electroluminescent device in which a light emitting layer composed of a single layer or a plurality of layers of organic compound thin film is sandwiched between an anode and a cathode facing each other, and at least one layer of the organic compound thin film has the following general structure: This is achieved by an organic electroluminescence device containing at least one compound having a polymerizable cyclic structure represented by formula (5) or a polymer thereof.

  In addition, although it is an aspect different from this invention, it replaces with the compound which has a polymeric cyclic structure represented by General formula (5), or its polymer, and the following general formula (1)-(4), ( An embodiment containing a compound having a polymerizable cyclic structure represented by any one of 6) or a polymer thereof is also preferable. In addition, the compounds of the general formulas (1) to (6) in which the luminescent compound residue [L] is a monovalent substituent derived from the fluorescent compound represented by the general formula (7) or a polymer thereof are also included. preferable. Furthermore, as represented by the general formula (8), a compound having a luminescent compound residue [L] of the general formula (7) or a polymer thereof, a compound of the general formula (1) to (6) or (8) A polymer obtained by copolymerization with compounds or other monomers, addition reaction, condensation reaction or graft polymerization of the compounds of the general formulas (1) to (8) and a polymer having a reactive group An organic electroluminescence device containing at least one organic compound thin film containing at least one kind is also a preferred embodiment.

  [Wherein X represents a divalent reactive group, -O-, -S-, -NR-, -COO-, -CONR-, -CR = CR-, -O-CR = N- or- O-CR = CR- is shown. R represents a hydrogen atom or a substituent. Z is an aliphatic hydrocarbon chain which may have a substituent, and forms a ring structure together with X. [L] represents a monovalent luminescent compound residue, and [S] represents a linking group that links [L] with the ring formed by X and Z. ]

[In formula (I), Q ₁ is -O -, - S- or -NR ₂₅ - represents, n2 represents an integer of 1 to 5. R ₂₁ , R ₂₂ , R ₂₃ , R ₂₄ and R ₂₅ each represent a hydrogen atom or a substituent, and any one of them is — [S] — [L]. R _{21 to} R ₂₅ may be connected to each other to form a ring structure. [L] and [S] are respectively synonymous with [L] and [S] in the general formula (1). ]

Wherein, Q ₂ is -O- or -NR ₃₅ - represents, n3 is an integer of 1-6. R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ and R ₃₅ each represent a hydrogen atom or a substituent, and any one of them is — [S] — [L]. R _{31 to} R ₃₅ may be connected to each other to form a ring structure. [L] and [S] are respectively synonymous with [L] and [S] in the general formula (1). ]

[Wherein n4 represents an integer of 1 to 5, and R ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ and R ₄₆ each represents a hydrogen atom or a substituent, S]-[L]. R _{41 to} R ₄₆ may be linked to each other to form a ring structure. [L] and [S] are respectively synonymous with [L] and [S] in the general formula (1). ]

Wherein, n5 is _1, each _{R 51, R 52, R 53} , R 54 and _{R 55} represent a hydrogen atom or a substituent, any one can - in [L] - [S] is there. R _{51 to} R ₅₅ may be connected to each other to form a ring structure. [L] represents a monovalent light-emitting compound residue composed of a condensed cyclic aromatic heterocyclic compound , and [S] connects [L] with a ring formed containing N and O in the formula. It represents a divalent group represented by phenylene, ethylene or —CO—, or a linking group in which a plurality of these are connected . ]

[Wherein, R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R ₆₅ and R ₆₆ each represent a hydrogen atom or a substituent, and any one of them is — [S] — [L]. R _{61 to} R ₆₆ may be linked to each other to form a ring structure. [L] and [S] are respectively synonymous with [L] and [S] in the general formula (1). ]

Wherein, R ₇₁ represents a hydrogen atom or a substituent, each A _1, A _2, A ₃ and A _4, C, N, O, S, represents one of the P, A ₁ to A ₄ Are not all C. Y ₁ represents a linking group or a bond, Y ₂ represents a group that forms a 4- to 8-membered ring with A ₁ and A ₂ , and Y ₃ represents a group that forms a 4- to 8-membered ring with A ₃ and A ₄ Represents. ]

[Wherein R ₈₁ , R ₈₂ and R ₈₃ each represent a hydrogen atom or a substituent. [L] and [S] are respectively synonymous with [L] and [S] in the general formula (1). ]
Further, a fluorescent thin film containing at least one compound represented by the general formula (1) or a polymer thereof, an addition reactant, or a condensation reactant is also an embodiment thereof.

  With these configurations, the fluorescent residue can be appropriately dispersed in a state where the degree of freedom is limited every 2 to 7 atoms with respect to the polymer main chain, and the light emission characteristics, stability, processing characteristics Either of these can provide a good organic EL element material.

  By polymerizing the luminescent compound, high thermal stability, stability over time and productivity can be obtained. Further, in terms of light emission characteristics, it is possible to obtain an element with good color purity by suppressing the occurrence of excimer light emission without reducing the luminance of the low molecular light emitting compound.

  This will be described in detail below. First, the compounds or substituents represented by the general formulas (1) to (8) will be described.

  In the general formula (1), X is a divalent functional group that reacts with a polymerization initiator such as a radical, a cation, an anion, or a metal complex, and can newly become an active site of the reaction. -S-, -NR-, -COO-, -CONR-, -CR = CR-, -O-CR = N- or -O-CR = CR- (R is a hydrogen atom or a substituent). The aliphatic hydrocarbon chain which may have a substituent represented by Z preferably has 2 to 6 carbon atoms and forms a ring structure together with X.

  [S] is a divalent linking group linking the ring structure formed by X and Z and the monovalent luminescent compound residue [L], such as phenylene, ethylene, -O-, -NR-, -CO. A divalent group such as-(R is a hydrogen atom or a substituent), or a combination thereof. [L] is a monovalent luminescent compound residue, which is obtained by removing one hydrogen atom or substituent from any position of a compound that emits light at room temperature. The “light emission” of the compound that emits light at room temperature may be fluorescence or phosphorescence.

  Luminescent compounds that can serve as luminescent compound residues include fluorescent dyes that absorb in the visible region such as laser dyes, fluorescent compounds that absorb in the ultraviolet region such as fluorescent whitening agents, and platinum in porphyrins. It may be a phosphorescent compound such as a complex or a biacetyl compound. Specifically, it is described on pages 99 to 122 of Kuroo Yagi, Zenichi Yoshida and Toshikazu Ota, “Fluorescence-Theory, Measurement, and Application” (Nanedo). Typical examples thereof include organic fluorescent substances, fluorescent brighteners described on pages 251 to 270, and fluorescent dyes described on pages 274 to 287.

  Among them, preferably, a condensed cyclic aromatic hydrocarbon ring compound typified by triphenylene or perylene; a linear conjugated polycyclic hydrocarbon compound typified by p-terphenyl or quarterphenyl; acridine, quinoline, carbazole, Condensed aromatic heterocyclic compounds represented by carbazone, fluorene, xanthion, alloxazine, acridone, flavone, coumarin, naphthimidazole, benzoxazole and dibenzophenazine; represented by thiazole, oxazole, oxadiazole, thiadiazole and triazole Conjugated aliphatic compounds represented by aminochloromaleic imide, methylaminocitraconic methylimide, decapentaene carboxylic acid, decapentaene dicarboxylic acid, etc .; -Fluorescent dye compounds represented by fluorescein, eosin, rhodamine and benzoflavin; photosensitive dye compounds such as oxacarbocyanine, carbocyanine, thiacarbocyanine and 2- (anilinopolyethynyl) benzothiazole; porphyrin, chlorophyll and Natural pigment compounds typified by riboflavin and the like; diaminostilbene, distyrylbenzene, benzidine, diaminocarbazole, triazole, imidazole, thiazole, oxazole, imidazolone, dihydropyridine, coumarin, carbostyril, diaminodibenzothiophene oxide, siaminofluorene, oxacyanine , Aminonaphthalimide, pyrazoline and oxadiazole-based fluorescent whitening agents, and the like. It may be formed.

  Examples of the substituent include alkyl groups (methyl, ethyl, i-propyl, hydroxyethyl, methoxymethyl, trifluoromethyl, t-butyl, etc.), cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), aralkyl groups (benzyl, 2-phenethyl etc.), aryl groups (phenyl, naphthyl, p-tolyl, p-chlorophenyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, butoxy etc.), aryloxy groups (phenoxy, naphthoxy etc.) etc. It is done. These groups may be further substituted, and as a substituent, a halogen atom, a trifluoromethyl group, a cyano group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a dialkylamino group, A dibenzylamino group, a diarylamino group, etc. are mentioned.

The compound of the general formula (2) is a derivative of a 3-6 membered cyclic ether (Q ₁ ═O), a cyclic sulfide (Q ₁ ═S), and a cyclic imine (Q ₁ ═NR ₂₅ ). Wherein, n2 is 1-5, but R ₂₁ to R ₂₅ represents a hydrogen atom or a substituent, one of these is - [L] - [S]. These may be connected to each other to form a ring structure.

The compound of the general formula (3) is a 4- to 7-membered lactone (Q ₂ ═O) or lactam (Q ₂ ═NR ₃₅ ) derivative. Wherein, n3 is 1-6, but R ₃₁ ~ ₃₅ represent a hydrogen atom or a substituent, one of these is - [L] - [S]. These may be connected to each other to form a ring structure.

The compound of the general formula (4) is a 4- to 7-membered cycloalkene derivative. Wherein, n4 is 1 to 5, R ₄₁ ~ ₄₆ Table nests a hydrogen atom or a substituent, one of these is - [L] - [S]. These may be connected to each other to form a ring structure.

The compound of the general formula (5) is an oxazoline derivative (n = 1) or a dihydrooxazine derivative (n = 2). In the formula, n5 is 1 or 2, and R ₅₁ to ₅₅ each represents a hydrogen atom or a substituent, and one of these is — [S] — [L]. These may be connected to each other to form a ring structure.

The compound of the general formula (6) is a dihydrofuran derivative. R ₆₁ to ₆₆ each represents a hydrogen atom or a substituent, and one of these is — [S] — [L]. These may be connected to each other to form a ring structure.

The structure of the general formula (7) representing the particularly preferred [L] component is a condensed heteroaromatic ring which may have a substituent. In the formula, A _{1 to} A ₄ represent any one of C, N, O, S, and P, but A _{1 to} A ₄ are not all C. Y ₁ is _{-CR 72 -, - N -,} - a linking group or a bond, such as CO-, Y ₂ together with A _1, A _2, Y _3, together with A _2, A _3, respectively 4-8 membered Form a ring. Examples of the 4- to 8-membered ring include an aromatic hydrocarbon ring or an aromatic heterocyclic ring which may have a substituent, such as benzene, naphthalene, anthracene, azulene, phenanthrene, triphenylene, pyrene, chrysene, naphthacene, Perylene, pentacene, hexacene, coronene, trinaphthylene, furan, thiophene, pyrrole, imidazole, pyrazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, thiazole, isoxazole, isothiazole, furazane, pyridine, Pyrazine, pyrimidine, pyridazine, indolizine, quinoline, isoindole, indole, isoquinoline, phthalazine, purine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, phenanthridine, a Lysine, perimidine, phenanthroline, phenazine and the like.

These may each independently have a plurality of arbitrary substituents, and the plurality of substituents may be condensed with each other to further form a ring. These rings may have a substituent. R ₇₁ and R ₇₂ are each a hydrogen atom or a substituent.

  Typical examples of the condensed heteroaromatic ring represented by the general formula (7) are shown below, but are not limited thereto.

The compound of general formula (8) is an ethylene derivative. R _{81 to} R ₈₃ each represent a hydrogen atom or a substituent, one of which is — [S] — [L], and [L] is a heteroaromatic ring represented by the general formula (7). is there.

  Examples of the linking group [S] common to the general formulas (1), (2), (3), (4), (5), (6) and (8) include phenylene (o, p, m) and methylene. , -O-, -N (R)-(wherein R is a hydrogen atom or a substituent), -CO-, and the like, and these composite systems are also included.

  Specific examples of the compounds represented by the general formulas (1) to (8) are shown below, but are not limited thereto. Compounds E-1 to E-12 are represented by the general formula (2), L-1 to L-12 are represented by the general formula (3), and N-1 to N-12 are represented by the general formula (4). 1 to X-6 are representative examples of the general formula (5), F-1 to F-6 are general formulas (6), and V-1 to V-12 are representative examples of the general formula (8).

  Below, the typical synthesis example of an exemplary compound is shown.

  Synthesis example 1

(Synthesis of Compound Q-1)
90.6 g of anthranilic acid methyl ester was reacted with 54 ml of hydrous hydrazine in xylene under heating and refluxing for 9.5 hours. Thereafter, the solvent was distilled off under reduced pressure, and a small amount of ethanol was added to obtain crude crystals. Further recrystallization with ethanol yielded 64.9 g of intermediate (a) (yield 72%).

  Next, 15.0 g of intermediate a and 21.0 g of ethyl benzoyl acetate were reacted in xylene at 120 ° C. for 1 hour, and then further reacted under reflux for 8 hours. At this time, generated water and ethanol were distilled off. After allowing to cool, the precipitated crystals were collected by filtration. By recrystallizing this crystal with a mixed solvent of N, N-dimethylformamide (hereinafter abbreviated as DMF) and methanol, 14.7 g (yield 56%) of Compound (Q-1) was obtained.

  It was confirmed to be Q-1 by NMR and mass spectrum. When this compound Q-1 was irradiated with UV light, it emitted blue-violet fluorescence.

  Synthesis example 2

(Synthesis of Compound E-1)
Compound (Q-1) 1.31 g (5.0 mmol) was reacted with 1.48 g (14 mmol) of potassium carbonate in dimethylacetamide and 0.43 ml (5.5 mmol) of epichlorohydrin at 50 ° C. for 3 hours. Then, it opened in water and neutralized with 1 mol / L hydrochloric acid. The product was collected by filtration and recrystallized from acetonitrile to obtain 0.92 g (yield 58%) of Compound (E-1).

  It was confirmed to be E-1 by NMR and mass spectrum. Moreover, when this compound E-1 was irradiated with UV light, it emitted blue-violet fluorescence.

(Polymerization of E-1)
100 mg of anhydrous iron chloride (III) as a polymerization initiator is placed in a three-necked flask, heated under reduced pressure to completely dehydrate, and then filled with dry nitrogen gas. Under a nitrogen stream, 0.63 g (2 mmol) of E-1 and 10 ml of dehydrated DMF were added and reacted at 100 ° C. for 3 hours. Thereafter, the reaction solvent was poured into a large excess of methanol to obtain a pale yellow precipitate. This precipitate was dissolved in a small amount of tetrahydrofuran (hereinafter abbreviated as THF) and poured into a large excess of hexane to obtain 0.38 g (yield 60%) of a white precipitate (PE-1).

  When this precipitate was measured by GPC, it was confirmed to be a polymer having a number average molecular weight of about 4500. When this polymer PE-1 was irradiated with UV light, blue-violet fluorescence was emitted.

  Synthesis example 3

(Synthesis of Lactone L-0)
6.0 g (25 mmol) of iodoacetic acid-3-butenyl and 2.5 liters of distilled water were placed in a 4 liter four-necked flask, and the inside of the flask was replaced with dry argon. While stirring, 2.5 ml (2.5 mmol) of a 1 mol / L methanol solution of triethylborane was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours and extracted with ethyl acetate. The composition obtained by distilling off ethyl acetate was purified by silica gel column chromatography to obtain 3.3 g (yield 55%) of 3-iodomethyl-δ lactone (L-0).

(Synthesis of Compound L-1)
1.31 g (5.0 mmol) of compound Q-1 was reacted with 1.48 g (14 mmol) of potassium carbonate in dimethylacetamide and 3.4 g (5.5 mmol) of L-0 at 50 ° C. for 3 hours. Thereafter, it was poured into water and neutralized with 1 mol / L hydrochloric acid. The product was collected by filtration and recrystallized from acetonitrile, whereby 1.02 g (yield 55%) of compound (L-1) was obtained.

  It was confirmed by NMR and mass spectrum that it was the target compound. When this compound L-1 was irradiated with UV light, it emitted blue-violet fluorescence.

(L-1 polymerization)
Triethylaluminum was dissolved in dehydrated toluene to make a 3% solution, and this solution was used as an initiator. Further, 18 ml of a reaction solvent in which 0.2 ml of distilled water was added to 2 liters of dehydrated THF was poured into a 50 ml three-necked flask, and further 0.93 g (2.5 mmol) of Compound L-1 and 3 of the above triethylaluminum. 0.4 ml (0.1 mmol: 4.0 mol%) of a% toluene solution was added at 0 ° C. Thereafter, THF was refluxed for 4 days. After completion of the reaction, the reaction solution is poured into a large amount of diethyl ether, and the precipitated white solid is filtered off, washed with a 0.1 mol / L hydrochloric acid solution, dissolved in chloroform, poured into a large amount of hexane and reprecipitated. And 0.41 g (44% yield) of white precipitate (PL-1) was obtained.

  When this precipitate was measured by GPC, it was confirmed to be a polymer having a number average molecular weight of about 5400. When this polymer PL-1 was irradiated with UV light, it emitted blue-violet fluorescence.

  Synthesis example 4

(Synthesis of Compound N-1)
1.31 g (5.0 mmol) of compound Q-1 was reacted with 1.48 g (14 mmol) of potassium carbonate and 0.78 g (5.5 mmol) of 4-chloromethylnorbornene in dimethylacetamide at 50 ° C. for 3 hours. Thereafter, it was poured into water and neutralized with 1 mol / L hydrochloric acid. The product was collected by filtration and recrystallized from acetonitrile, whereby 0.85 g (yield 46%) of compound (N-1) was obtained.

  By NMR and mass spectrum, it was confirmed to be Compound N-1. Further, when this compound N-1 was irradiated with UV light, it emitted blue-violet fluorescence.

(Polymerization of N-1)
0.74 g (2.0 mmol) of Compound N-1 and 71 mg (0.02 mmol, 1.0 mol%) of iridium (III) chloride trihydrate were dissolved in 20 ml of i-propanol and refluxed for 8 hours. As a result, a gray insoluble material was deposited as an insoluble material. This composition was filtered off, washed with acetone, dissolved in hot toluene, reprecipitated with a large excess of methanol, and 0.43 g (yield 58%) of a light gray polymer (PN-1) was obtained. Obtained.

  When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 5400. When this polymer PN-1 was irradiated with UV light, it emitted blue-violet fluorescence.

  Synthesis example 5

(Synthesis of Compound X-1)
1.31 g (5.0 mmol) of compound Q-1 was reacted with succinyl dichloride 0.78 g (5.0 mmol) and triethylamine 1.5 ml (11 mmol) in dimethylacetamide at room temperature for 3 hours. After allowing to cool, a solution of ethyleneimine 0.3 ml (5.5 mmol) in diethyl ether (3 ml) was added and reacted at 50 ° C. for 5 hours. After allowing to cool, the precipitated triethylamine hydrochloride was filtered off, and 1.48 g (14 mmol) of potassium carbonate was added to the solution and reacted at 50 ° C. for 3 hours. Thereafter, it was poured into water and neutralized with 1 mol / L hydrochloric acid. The product was collected by filtration and recrystallized from acetonitrile to obtain 1.20 g (yield 61%) of compound (X-1).

  It was confirmed to be X-1 by NMR and mass spectrum. When this compound X-1 was irradiated with UV light, it emitted blue-violet fluorescence.

(Polymerization of X-1)
A 2% acetonitrile solution of p-chlorophenyloxazolinium perchlorate is prepared as a polymerization initiator. 0.77 g (2.0 mmol) of Compound X-1 was dissolved in 10 ml of dimethylacetamide, 0.1 ml was added under a nitrogen atmosphere, and the mixture was reacted at 120 ° C. for 18 hours. After completion of the reaction, the solution was poured into a large excess of methanol to obtain a white precipitate. This white solid was dissolved again in THF and reprecipitated in a large excess of diethyl ether to obtain 0.59 g (77%) of a white solid (PX-1).

  When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 6600. When this polymer PX-1 was irradiated with UV light, it emitted blue-violet fluorescence.

  Synthesis Example 6

(Synthesis of Compound F-0)
1.31 g (5.0 mmol) of Compound Q-1 was reacted with 1.47 g (5.5 mmol) of 4-iodobenzoyl chloride and 0.8 ml (6.0 mmol) of triethylamine in dimethylacetamide for 3 hours at room temperature. It was. After allowing to cool, the precipitated hydrochloride of triethylamine was filtered off, the solution was partitioned with ethyl acetate, the organic layer was dehydrated with sodium sulfate, and the solvent was distilled off to obtain a crude product. By recrystallization from acetonitrile, 2.26 g (yield 91%) of a white solid (F-0) was obtained.

  NMR and mass spectrum confirmed that it was F-0. Further, this compound F-0 was irradiated with UV light, but no fluorescence emission was observed.

(Synthesis of Compound F-1)
1.96 g (4.0 mmol) of the compound F-0 was mixed with 22.4 mg (0.01 mmol, 2.5 mol%) of palladium (II) acetate and 26.2 mg (0.01 mmol, triphenylphosphine) in dimethylformamide. 2.5 mol%), 0.43 g (4.0 mmol) of butylammonium chloride and 1.18 g (12 mmol) of potassium acetate, and reacted at 80 ° C. for 24 hours. After allowing to cool, the solution was separated with ethyl acetate, the organic layer was dehydrated with sodium sulfate, and the solvent was distilled off to obtain a white crude product. By recrystallizing the composition with acetonitrile, 1.26 g (yield 73%) of Compound (F-1) was obtained.

  It was confirmed to be F-1 by NMR and mass spectrum. When this compound F-1 was irradiated with UV light, it emitted blue-violet fluorescence.

(F-1 polymerization)
0.86 g (2.0 mmol) of Compound F-1 was added to 8.4 mg (0. 0) of hexafluoroantimonic acid 4-methoxy-2-oxo-2,2,6,6-tetramethylpiperidinium in dimethylacetamide. 02 mmol, 1.0%) was added under nitrogen and allowed to react for 4 hours at room temperature. The obtained reaction solution was reprecipitated in a large excess of methanol to obtain 0.61 g (yield 71%) of a white solid (PF-1).

  When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 5300. When this polymer PF-1 was irradiated with UV light, blue-violet fluorescence was emitted.

  Synthesis example 7

(Synthesis of Compound V-1)
A methanol solution of Compound Q-1 (1.31 g, 5.0 mmol) was dropped into a methanol / sodium methoxide 28% solution and reacted at room temperature for 3 hours, and then the solvent was distilled off. The obtained gray solid was dissolved again in 30 ml of methanol, and 5 ml of THF solution in which 0.8 ml (5.5 mmol) of 4-chloromethylstyrene was dissolved was added dropwise at 0 ° C. After stirring for 3 hours, the solvent was distilled off, and the white solid was reacted with 1.48 g (140 mmol) and epichlorohydrin 0.51 g for 3 hours at 100 ° C. Thereafter, it was poured into water and neutralized with 1 mol / L hydrochloric acid. The product was collected by filtration and recrystallized from acetonitrile to obtain 1.73 g (yield 92%) of compound (V-1).

  It was confirmed to be V-1 by NMR and mass spectrum. When this compound V-1 was irradiated with UV light, it emitted blue-violet fluorescence.

(Polymerization of V-1)
0.75 g (2.0 mmol) of the above compound V-1 was dissolved in THF, and azobisisobutyronitrile (AIBN, 0.1 mmol, 5 mol%) was added at 0 ° C. under a nitrogen atmosphere. Reflux for a period of time. After allowing to cool, the reaction solution was precipitated in a large excess of methanol to obtain 0.66 g (yield 88%) of a white solid (PV-1).

  When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 7300. When this polymer PV-1 was irradiated with UV light, blue-violet fluorescence was emitted.

  Synthesis Example 8

(Copolymerization of X-1 and γ-propiolactone)
0.39 g (1.0 mmol) of the compound X-1 was dissolved in DMF, and 6.3 ml (1.0 mmol) of a 1.0% DMF solution of γ-propiolactone was added at 0 ° C. under a nitrogen atmosphere. Then, the reaction was carried out at 100 ° C. for 10 hours. After allowing to cool, the reaction solution was precipitated in a large excess of methanol to obtain 0.40 g (yield 87%) of a white solid (PLX-1).

  When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 6100. When this polymer PLX-1 was irradiated with UV light, it emitted blue-violet fluorescence.

Synthesis Example 9
(L-1 graft copolymerization)
J. et al. Polymer Sci. 34,309 (1959), styrene and methacryloylcaprolactam were polymerized with AIBN to obtain a copolymer (PMS) of poly (methacryloylcaprolactam) and poly (styrene) (yield 27%). When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 130,000. 1.0 g of this polymer and 1.0 g of the compound L-1 were graft-polymerized in toluene at 95 ° C. using sodium caprolactone as a polymerization initiator. Since gelation occurred during the reaction, the mixture was allowed to cool, filtered, washed, and dried to obtain 1.42 g (yield 71%) of white solid PGL-1.

  When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 170,000. When this polymer PGL-1 was irradiated with UV light, it emitted blue-violet fluorescence.

  The organic EL device of the present invention basically has a structure in which a light emitting layer is held between a pair of electrodes, and a hole injection layer or an electron injection layer is interposed as necessary. Specifically, (i) anode / light emitting layer / cathode, (ii) anode / hole injection layer / light emitting layer / cathode, (iii) anode / light emitting layer / electron injection layer / cathode, (iv) anode / positive There are structures such as hole injection layer / light emitting layer / electron injection layer / cathode.

  The light emitting layer has (1) an injection function capable of injecting holes from an anode or a hole injection layer when an electric field is applied, and (2) an injected charge. It has a transport function that moves (electrons and holes) by the force of an electric field, and (3) a light-emitting function that provides a field for recombination of electrons and holes inside the light-emitting layer and connects it to light emission. However, there may be a difference in the ease of hole injection and the ease of electron injection, and the transport function represented by the mobility of holes and electrons may be large or small, but at least either Those having a function of moving one charge are preferable.

  There is no restriction | limiting in particular about the kind of luminescent material used for this light emitting layer, The conventionally well-known thing can be used as a luminescent material in an organic EL element. Such a light-emitting material is mainly an organic compound, and may have a desired color tone, for example, Macromol. Symp. 125, pages 17-26.

  As a method for forming a light emitting layer using the above material, for example, it can be formed by thinning by a known method such as a vapor deposition method, a casting method, or an LB method. It is preferable to form a solution by dissolving in a solvent and then forming a thin film by spin coating or the like. There is no restriction | limiting in particular about the film thickness of the light emitting layer formed in this way, Although it can select suitably according to a condition, Usually, it is the range of 5 nm-5 micrometers.

As the anode in the EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode substances include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , and ZnO. The anode may be formed by forming a thin film from these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or (100 μm) when pattern accuracy is not so high. As described above, a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, the transmittance is desirably greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.

On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron injectability and durability against oxidation, a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixtures, magnesium / indium mixtures, aluminum / aluminum oxide (Al ₂ O ₃ ) mixtures, lithium / aluminum mixtures and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 1 μm, preferably 50 to 200 nm. In order to transmit light, if either the anode or the cathode of the organic EL element is transparent or translucent, the light emission efficiency is improved, which is convenient.

  Next, the hole injection layer provided as necessary has a function of transmitting holes injected from the anode to the light emitting layer, and the hole injection layer is interposed between the anode and the light emitting layer. In addition, many holes are injected into the light emitting layer with lower electric field strength, and the electrons injected from the cathode or the electron injection layer into the light emitting layer are barriers to electrons present at the interface between the light emitting layer and the hole injection layer. Thus, an element having excellent light emission performance such as accumulation at the interface in the light emitting layer and improvement in light emission efficiency is obtained. The material of the hole injection layer (hereinafter referred to as the hole injection material) is not particularly limited as long as it has the above-mentioned preferable properties. Any one of commonly used ones and known ones used for the hole injection layer of EL elements can be selected and used.

  The hole injection material has either hole injection or electron barrier properties, and may be either organic or inorganic. Examples of the hole injection material include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives. Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. As the hole injecting material, those described above can be used, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Representative examples of the aromatic tertiary amine compound and styrylamine compound include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N ′. -Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1- Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl, 1,1-bis (4-di-p- Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N -Di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadri Phenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenyl Amino- (2-diphenylvinyl) benzene, 3-methoxy-4′-N, N-diphenylaminostilbenzene, N-phenylcarbazole, and two condensations described in US Pat. No. 5,061,569 Having an aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308688 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (m-TDATA), etc., in which three triphenylamine units are linked in a three star burst type Is mentioned.

  Also, inorganic compounds such as p-type-Si and p-type-SiC can be used as the hole injection material. The hole injection layer can be formed by thinning the hole injection material by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of a positive hole injection layer, Usually, it is about 5 nm-5 micrometers. The hole injection layer may have a single-layer structure composed of one or more of the above materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions. Furthermore, the electron injecting layer used as necessary may have a function of transmitting electrons injected from the cathode to the light emitting layer, and any material selected from conventionally known compounds can be selected as the material. Can be used.

  Examples of materials used for the electron injection layer (hereinafter referred to as electron injection materials) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene; carbodiimides , Fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like. In addition, a series of electron transport compounds described in JP-A-59-194393 is disclosed as a material for forming a light emitting layer in the publication, but as a result of studies by the present inventors, as an electron injection material. It turns out that it can be used. Furthermore, in the oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron injection material.

  Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg, Cu , Ca, Sn, Ga, or Pb can also be used as the electron injection material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron injection material. Further, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as the electron injecting material. Similarly to the hole injecting layer, inorganic semiconductors such as n-type-Si and n-type-SiC can be used as the electron injecting material. Can be used as

  This electron injection layer can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. The thickness of the electron injection layer is not particularly limited, but is usually selected in the range of 5 nm to 5 μm. This electron injection layer may have a single layer structure composed of one or more of these electron injection materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.

  Next, a suitable example for producing the organic EL element will be described. As an example, a method for producing an EL device comprising the above-mentioned anode / hole injection layer / light emitting layer / electron injection layer / cathode will be described. First, a thin film made of a desired electrode material, for example, a material for an anode, on a suitable substrate. Is formed by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm, to produce an anode. Next, a thin film made of materials of a hole injection layer, a light emitting layer, an electron injection layer, and a cathode layer, which are element materials, is sequentially formed thereon.

Examples of the thinning method include a spin coating method, a casting method, and a vapor deposition method. Considering productivity, the spin coating method is preferable as described above, but low molecular compounds, metal electrodes, and the like cannot be formed at present under the spin coating method. For the formation of these thin film layers, vacuum vapor deposition is preferred from the standpoint that a compound-homogeneous film is easily obtained and pinholes are not easily generated. When this vapor deposition method is employed for thinning, the vapor deposition conditions vary depending on the type of compound used, the target crystal structure of the molecular deposition film, the association structure, etc., but generally the boat heating temperature is 50 to 450 ° C. It is desirable that the degree of vacuum is 10 ⁻⁶ to 10 ⁻³ Pa, the deposition rate is 0.01 to 50 nm / second, the substrate temperature is −50 to 300 ° C., and the film thickness is 5 nm to 5 μm.

  In the case where a DC voltage is applied to the EL element thus obtained, light emission can be observed by applying a voltage of about 3 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this.

Example 1
(Production of organic EL element)
After patterning on a substrate (NH Techno Glass Co., Ltd .: NA-45) having a film of 150 nm of ITO (supra) formed on glass as an anode, the transparent support substrate provided with this ITO transparent electrode was converted to i-propyl alcohol. Was subjected to ultrasonic cleaning, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes. On this transparent support substrate, 20 mg of polymer PE-1 was dissolved in 3 ml of THF, and spin-coated under conditions of 1000 rpm and 3 sec. The film thickness of the purified organic thin film was about 100 nm.

After fixing this substrate to a substrate holder of a commercially available vacuum deposition apparatus, the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, then the heating boat containing Alq3 was energized and heated to 250 ° C., and the deposition rate An electron injection layer having a thickness of 20 nm was provided by vapor deposition on the light emitting layer at 0.1 nm / sec. In addition, the substrate temperature at the time of vapor deposition was room temperature. Furthermore, lithium and aluminum are co-deposited from different vapor deposition sources at a vapor deposition rate of 1.5 to 2.0 nm / sec at a mass ratio of 6: 1 to form a counter electrode composed of the mixture of lithium and aluminum. Thus, an organic EL element DE-1 was produced.

Examples 2-8
In Example 1, instead of PE-1, each of SP-1, PN-1, PX-1, PF-1, PV-1, PLX-1, and PGL-1 was used to spin coat to a thickness of 100 nm Then, organic EL elements DL-1, DN-1, DX-1, DF-1, DV-1, DLX-1, and DGL-1 were produced in the same manner as in Example 1 except that the light emitting layer was used.

Example 9
In Example 1, 0.2 mg of 4-dicyanomethylene-2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM1) was dissolved in 20 mg of the polymer PE-1 to be spin-coated and 3 ml of THF. Organic EL element DD-1 was produced in exactly the same manner except that spin coating was performed under the conditions of 1000 rpm and 3 sec.

Comparative Example 1
After patterning on a substrate (NA-45: supra) with ITO deposited on glass as an anode at 150 nm, the transparent support substrate provided with this ITO transparent electrode was ultrasonically cleaned with i-propyl alcohol and dried nitrogen After drying with gas, UV ozone cleaning was performed for 5 minutes.

After fixing this transparent support substrate to a substrate holder of a commercially available vacuum deposition apparatus, the vacuum chamber was depressurized to 4 × 10 ⁻⁴ Pa, and then 4,4 ′, 4 ″ -tris (-N- (m-tolyl). ) -N-phenylamino) triphenylamine (m-TDATA) was deposited at a deposition rate of 0.2 nm / sec to a thickness of 40 nm to form a hole injection layer, and then N, N'-diphenyl-N, N ' -Di (m-tolyl) -4,4'-diamino-1,1'-biphenyl (TPD) was vapor-deposited to a thickness of 35 nm at a vapor deposition rate of 0.2 nm / sec. Further, while maintaining the reduced pressure, tris (8-quinolinolato) aluminum (Alq3) was deposited to a thickness of 50 nm at a deposition rate of 0.2 nm / sec to form an electron transport layer. Aluminum with different deposition sources The organic EL device DT-1 for comparison is made by co-evaporating at a vapor deposition rate of 1.5 to 2.0 nm / sec at a mass ratio of 6: 1 to form a counter electrode made of a mixture of lithium and aluminum. Produced.

Comparative Example 2
In Comparative Example 1, an organic EL device DQ-1 was produced in exactly the same manner as in Example 1 except that Compound Q-1 was used instead of TPD to form a hole transport layer / light-emitting layer.

(Characteristic evaluation of EL element)
Source EL unit DE-1, DL-1, DN-1, DX-1, DF-1, DV-1, DLX-1, DGL-1, DD- using source measure unit 2400 type manufactured by Toyo Technica 1 and comparative organic EL elements DT-1 and DQ-1 were made to emit light by applying a direct current of 10 V using the ITO electrode of the element as an anode and a counter electrode made of lithium and aluminum as a cathode, and the luminance was made by Topcon Corporation BM-8 and the emission wavelength were measured using a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics.

  First, in Comparative Example DT-1, surface emission was uniformly blue, and no dark spots were observed in the initial state, but 10 to 15 dark spots with a diameter of 100 μm or less were confirmed after driving for 1 hour.

  Next, in Comparative Example DQ-1, it was confirmed that surface emission was uniformly blue-white, and no dark spots were observed in the initial state, but after driving for 1 hour, dark spots with a diameter of 100 μm or less were 1 to 4 Confirmed. In addition, when the electroluminescence spectrum is measured, there are emission peaks at 424 nm and 454 nm, and some interaction is caused in the m-TDATA layer interface, the Alq layer interface, or the light emitting layer, resulting in a dichroic spectrum. understood.

  On the other hand, in Example DE-1, the surface emission was uniformly blue-violet, and the occurrence of dark spots was not confirmed even after driving for 1 hour in the initial state. Further, when the electroluminescence spectrum was measured, the confirmed emission peak at 454 nm disappeared in DQ-1, and a spectrum having only an emission wavelength of 425 nm was observed. Table 1 summarizes the results of this element and the elements according to other examples, DL-1, DN-1, DX-1, DF-1, DV-1, DLX-1, DGL-1, and DD-1. .

  As shown in Table 1, it was possible to obtain high thermal stability, stability over time and productivity by polymerizing the luminescent compound. Further, in terms of light emission characteristics, it is possible to obtain an element with good color purity by suppressing the occurrence of excimer light emission without reducing the luminance of the low molecular light emitting compound.

Claims (3)

In an organic electroluminescence device in which a light emitting layer composed of a single-layer or multiple-layer organic compound thin film is sandwiched between an anode and a cathode facing each other, at least one layer of the organic compound thin film is represented by the following general formula (5). An organic electroluminescence device comprising at least one compound having a polymerizable cyclic structure or a polymer thereof.

Wherein, n5 is _1, each _{R 51, R 52, R 53} , R 54 and _{R 55} represent a hydrogen atom or a substituent, any one can - in [L] - [S] is there. R _{51 to} R ₅₅ may be connected to each other to form a ring structure. [L] represents a monovalent light-emitting compound residue composed of a condensed cyclic aromatic heterocyclic compound , and [S] connects [L] with a ring formed containing N and O in the formula. It represents a divalent group represented by phenylene, ethylene or —CO—, or a linking group in which a plurality of these are connected . ] 2. The organic electroluminescence device according to claim 1, wherein at least one organic compound thin film containing at least one copolymer containing at least one compound selected from the compound represented by the general formula (5) as a monomer is used. the organic electroluminescent device characterized Rukoto to Yusuke. 3. The organic electroluminescence device according to claim 1, wherein at least one compound selected from the compounds represented by the general formula (5) and a polymer having a reactive group are subjected to an addition reaction, a condensation reaction, or a graft. An organic electroluminescence device comprising at least one organic compound thin film containing at least one polymer compound obtained by polymerization .