WO2003050201A1

WO2003050201A1 - Organic electroluminescent materials

Info

Publication number: WO2003050201A1
Application number: PCT/JP2002/012821
Authority: WO
Inventors: Junji Momoda; Yuichiro Kawabata; Toshiaki Otani
Original assignee: Tokuyama Corporation
Priority date: 2001-12-12
Filing date: 2002-12-06
Publication date: 2003-06-19
Also published as: JPWO2003050201A1; AU2002354442A1; KR20040077660A; TW200304939A

Abstract

The invention provides high-purity organic electrolumi- nescent materials permitting spin coating, particularly, an organic electroluminescent material containing a calixarene or calixresorciarene derivative bearing a luminescent organic group and/or a charge transport organic group, for example, a calixarene derivative (1) bearing 4-[1-(2,2-diphenylvinyl)- biphenyl-2-phenylvinyl]phenyl as the luminescent organic group.

Description

Description Organic electorescence luminescent element material Technical field

TECHNICAL FIELD The present invention relates to a novel organic electroluminescent device material (hereinafter, also referred to as “organic EL device material”). Background art

Organic EL devices are expected to be used as inexpensive large-area solid-state color display devices of the solid-state emission type, and are being actively developed. Generally, an organic EL device is composed of a light emitting layer and a pair of opposed electrodes sandwiching the light emitting layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode and holes are injected from the anode. Further, the electrons and holes are recombined in the light emitting layer, and the energy is emitted as light when the energy level returns from the conduction band to valence electrons.

The organic EL element material used for the light emitting layer and the charge transport layer of the organic EL element is required to have characteristics such as high luminance, low driving voltage, and emission of various colors, depending on the application. Therefore, it is necessary to develop materials that meet the requirements. Until now, low molecular weight materials such as copper phthalocyanine (CuPC), star-burst molecules, poly (p-phenylenevinylene) (PPV), polyaniline (PANI), etc. Polymer materials have been developed.

However, there are some inconveniences and problems when thinning these materials and using them as devices. That is, a vacuum evaporation method is used to form an organic thin film using a low molecular material such as CuPc and a star-past molecule, but this method has a problem that it takes time and costs. In addition, the organic thin film formed by the vacuum evaporation method is easily crystallized, which leads to deterioration of the device.

On the other hand, mainly for polymer materials, thinning by spin coating is possible, so that large-capacity thinning can be performed easily and inexpensively in a short time. The use of a polymer-based material also has the advantage that crystallization is unlikely to occur. However, since the polymer has a large molecular weight distribution, there are differences in the emission characteristics depending on the degree of polymerization The disadvantage is that the individual differences are relatively large. In addition, since PPV itself is insoluble in organic solvents, it must be further heated after forming a precursor thin film, and the effects of the polymerization rate and desorbed hydrochloric acid pose problems. ing. Since PAN I alone is not soluble in organic solvents, camphorsulfonic acid must be used. As described above, an organic EL device material that can be easily formed into a thin film by spin coating and has high purity has not yet been provided.

In addition, Japanese Patent Application Laid-Open No. 5-170707 discloses the following formula:

A fluorescent calix [4] arene derivative represented by the formula: This compound has both a luminescent group and a quenching group, and has a void for a metal ion to be captured. If no metal ion is present in the voids of this compound, no light will be emitted due to the short distance between the luminous group and the quenching atomic group. Utilizing the fact that light is emitted due to the distance from the quenching group, this compound is used for the analysis of metal ions. However, the above publication does not disclose at all whether or not this compound is used for an organic electorophore chromic element material. Disclosure of the invention

Accordingly, an object of the present invention is to solve the above-mentioned problems of the prior art, that is, to provide a high-purity organic EL device material that can be spin-coated. The present inventors have conducted intensive studies in order to solve the above-mentioned problems, and as a result, as a organic EL device material, a group consisting of a phyllixarene derivative and a phyxic resorciarene derivative in a molecular skeleton of a light emitting substance or a charge transporting substance. Combines compounds selected from As a result, it has been found that all of the above objects can be achieved, and the present invention has been provided.

That is, the present invention is an organic electroluminescent device material comprising a calix squalene derivative or a physolic resorciarene derivative having at least one of a luminescent organic group and a charge transporting organic group.

The present invention also relates to certain compounds among the above derivatives. BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a ¹ H-nuclear magnetic resonance spectrum of a calixarene derivative according to the present invention, which can be included in the organic electroluminescence device material obtained in Production Example 1. BEST MODE FOR CARRYING OUT THE INVENTION

In the present invention, a calixarene derivative or a carrick resorciarene derivative having at least one of a light-emitting organic group and a charge-transporting organic group used as an organic EL device material (hereinafter, also simply referred to as a force-ricks derivative) A known light emitting substance and a charge transporting substance as an organic EL device material, and a conventionally known calixarene derivative and a calixresorcialane derivative are directly or covalently bonded with or without a divalent organic group. Any compound can be used as long as it is bound.

As such a force lix derivative, for example, compounds represented by the following general formulas (1) and (2) can be suitably used:

In the above formula, n is an integer of 3 to 20, and A, B, D, the same or different atoms or groups, such as a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or the following general formula ( The group represented by 3), wherein a plurality of A, B and D may be different from each other, and at least one of them is a group represented by the general formula (3); When there are a plurality of groups represented by, these may be different from each other

-(L) m- Z (3)

(Where L is a divalent organic group, Z is a luminescent organic group or a charge transporting organic group, and m is 0 or 1).

In the above formula, examples of the halogen atom represented by A, B and D include a chlorine atom, a bromine atom and an iodine atom. As the alkyl group, a group having 1 to 4 carbon atoms such as a methyl group, an ethyl group, a propyl group, and a butyl group is preferable. As the aryl group, a phenyl group, a tolyl group, a xylyl group, A group having 6 to 10 carbon atoms such as a naphthyl group is preferable, and an alkoxy group is a group having 1 to 8 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group and a 2-ethylhexyloxy group. It can be suitably used.

When a plurality of A, B and D are present in a molecule, they may be the same or different, provided that a plurality of A, B and D exist in a molecule. In this case, at least one of them is a group represented by the following formula (3). When a plurality of groups represented by the formula (3) are present in one molecule, they may be the same or different.

― (L) m-Z (3)

In the above formula (3), as the divalent organic group represented by L, a luminescent organic group or a charge transporting organic group and a liques arene derivative or a calixresorcinalene There is no particular limitation as long as it is a group that can be linked to a derivative. The group which can be mentioned as such a linkable group includes, but is not limited to, a group represented by the following formula (wherein, R represents a carbon number of 1 to 12) And n is an integer of 0 to 20.)).

Further, in the above formula (3), the light-emitting organic group and the charge-transporting organic group represented by Z are a residue having a known light-emitting substance or a charge-transporting substance as a skeleton used in a conventional organic EL device. The groups can be used without any restrictions. Both the luminescent organic group and the charge transporting organic group are groups derived from a low molecular weight organic compound or a medium molecular weight organic compound. The molecular weight of the group derived from a medium molecular organic compound is preferably 200 to 400,000 in terms of number average molecular weight, from the viewpoint of purification. The luminescent organic group is a group having a structure capable of emitting fluorescence from an excited singlet or phosphorescence from an excited triplet. The charge transporting organic group is a group having a structure capable of exhibiting hole transporting ability or electron transporting ability, and is classified into a hole transporting organic group and an electron transporting organic group, respectively. These are groups derived from hole and electron transporters, respectively. Some luminescent organic groups exhibit charge transport properties. In that case, there is no particular rule as to which organic group is to be categorized. No gender is observed.

In other words, the luminescent organic group is linked such that at least four unsaturated bonds constituting the luminescent organic group form a conjugated system, and forms a residue having a luminescent structure. In addition, the charge transporting organic group has at least two unsaturated bonds constituting the charge transporting organic group connected to form a conjugated system, and forms a charge transporting residue. In addition, two or more of these conjugated systems may be present in a single molecule. Here, the structure having a light-emitting property means a structure capable of showing fluorescence emission from an excited singlet or phosphorescence from an excited triplet as described above. The meaning will be clear by referring to organic compounds. In the case where "the four unsaturated bonds form a conjugated system", for example, a benzene ring is recognized as having three unsaturated bonds.

The position of the bond between the light emitting organic group or the charge transporting organic group is not particularly limited as long as the above conjugated system is not adversely affected.

Examples of such a luminescent organic group and a charge transporting organic group include the residues shown in the following i), ii) and iii).

i) at least two unsaturated ring systems, where unsaturated ring systems are nitrogen, oxygen, sulfur or calcium atoms as 5- or 6-membered hydrocarbon rings or ring members; A 5- or 6-membered heterocyclic ring having 1 to 3 carbon atoms, or 2 to 30 of these hydrocarbon rings and / or heterocyclic rings may be condensed; The ring system may be substituted with a substituent, or a saturated ring may be condensed. ) Are condensed or linked to form a conjugated system through a direct bond or an alkenylene group or a nitrogen atom (particularly, a lone electron versus electron of the nitrogen atom). Residues which may be one or more side chains (or pendant groups) of the polymer backbone, and which confer luminescence or charge transport properties to the elixir derivative molecule.

ii) At least two unsaturated ring systems (where the unsaturated ring system is a 5- or 6-membered hydrocarbon ring or a ring-constituting atom containing 1 to 3 nitrogen, oxygen, sulfur, or silicon atoms). A 5- or 6-membered heterocyclic ring, or 2 to 30 of these hydrocarbon rings and / or heterocyclic rings may be condensed, and these unsaturated ring systems are substituted with substituents. Or a saturated ring may be condensed.) To form a ligand, or to form a conjugated system through a direct bond or one C = group or a nitrogen atom. To form a ligand, and, if necessary, together with an oxygen atom bonded to the unsaturated ring system, to form a ligand such as beryllium, aluminum, copper, zinc, ruthenium, europium, and rhodium. , Platinum or silicon A residue derived from a coordination compound having a genus, which imparts luminescence or charge transport properties to a elixir derivative molecule.

iii) at least two unsaturated ring systems (where the unsaturated ring system is a 5- or 6-membered hydrocarbon ring or ring-constituting atom containing 1 to 3 nitrogen, oxygen, sulfur, or silicon atoms). A 5- or 6-membered heterocyclic ring, or 2 to 30 of these hydrocarbon rings and / or heterocyclic rings may be condensed, and these unsaturated ring systems are substituted with substituents. And a saturated ring may be condensed.) Is derived from an organic metal compound in which two or more of the molecular groups to which iridium is condensed or directly bonded to iridium; Residues that impart luminescence or charge transport properties to

In the above i) to iii), examples of the 5- or 6-membered hydrocarbon ring constituting the unsaturated ring system include a benzene ring, and a nitrogen atom, an oxygen atom, a sulfur atom or a nitrogen atom as a ring-constituting atom. A 5-membered or 6-membered heterocyclic ring with 1 to 3 atoms Examples thereof include a pyrroyl ring, a furan ring, a thiophene ring, a pyridine ring, a pyran ring, a thiazole ring, a triazine ring, an oxaziazole ring and the like.

When the above unsaturated ring system is substituted, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; an oxo group; a methyl group, an ethyl group and a t-butyl group. C1-8 alkyl groups such as groups; C1-8 alkoxy groups such as methoxy, ethoxy and propoxy groups; C1-4 halogenated alkyl groups such as chloromethyl and trifluoromethyl An amino group; a cyano group and the like. These may have a plurality of the same or different substituents as long as they do not adversely affect the conjugated system. Here, “has no adverse effect on the conjugated system” means, for example, that the emission wavelength and intensity (or luminance) originally possessed by the corresponding conjugated system are not substantially changed.

Further, the saturated ring fused to the above unsaturated ring includes a saturated hydrocarbon ring having 5 to 6 carbon atoms such as a cyclohexane ring, a piperidine ring, a pyrazoline ring, or a nitrogen atom as a ring-constituting atom. Saturated heterocycles can be mentioned. Two or more of these saturated rings may be fused to the above-mentioned unsaturated rings.

Specific examples of the residues belonging to the above i) to iii) are as follows.

a— 1) Luminescent organic group belonging to i) above:

• Residues derived from distyrylarylene derivatives

'Residues derived from styryl derivatives such as styrylamine derivatives

. Residues derived from nitrogen-containing aromatic heterocyclic derivatives such as imidazole derivatives

. Residues derived from polycyclic aromatic hydrocarbon derivatives such as perylene derivatives

• Residues derived from pigments such as polymethine, coumarin, and quinacridone

(In the formula, p and q are each an integer of 1 to 10 and an integer such that the number average molecular weight of each group takes a value in the range of 20 to 400.)

• Molecular compounds in π-conjugated systems of arylene derivatives such as polyparaphenylene derivatives.

0 Residues derived from molecular compounds in arylenevinylene derivatives such as polyparaphenylenevinylene derivatives

(Where P and Q are the same as above)

In addition to the above-mentioned residues, naphthylene derivatives; anthracene derivatives; xanthones, cyanines, and other dyes; derivatives in which aromatic groups are polysubstituted, such as tetraphenylcyclopentene and tetraphenylbutadiene; Residues derived from π-conjugated middle molecular compounds such as polythiophene derivatives; sigma-conjugated middle molecular compounds such as polysilane; and pendant middle molecular compounds such as poly (meth) acrylylarylamine derivatives.

a— 2) Hole transporting organic groups in the charge transporting organic groups belonging to i) above:

• Residues derived from arylamine derivatives



(Where p and q are the same as above)

In addition to the above-mentioned residues, there can be exemplified residues derived from pyrazoline derivatives; stilbene derivatives.

a— 3) Electron transporting organic groups in the charge transporting organic groups belonging to i) above: • Residues derived from oxadiazole derivatives

14 • Residues derived from triazole derivatives

Other than the above-mentioned residues, there can be exemplified residues derived from anthraquinone dimethane or a derivative thereof; tetracyano anthraquinodimethane or a derivative thereof; a fluorenone derivative; and a diphenoquinone derivative.

b) Residues belonging to ii) above:

6 Among these luminescent organic groups, preferred groups in the present invention include distyrylarylene derivatives, styrylamine derivatives, imidazole derivatives, naphthylene derivatives, anthracene or its derivatives, perylene or its derivatives, and 8-hydroxy Examples thereof include a metal complex of quinoline or a derivative thereof, and a residue derived from a poly (9,9-dialkylfluorene) derivative.

Among the charge-transporting organic groups, an arylamine derivative is used as the hole-transporting organic group, and an oxadiazole derivative, a triazole derivative, a silole derivative, and a metal complex of 8-hydroxyquinoline or a derivative thereof are used as the electron-transporting organic group. Are preferred.

In the liquix derivative used in the present invention, the calixarene structure portion includes a cyclic oligomer formed by condensation of phenol and formaldehyde, a crosslink lixisarean cross-linked through an alkoxy group, thiacalixarene, oxacalixarene, and the like. Any residue that can be derived from a known compound having a pseudocalixcyclooligomer such as calixspirol or calixsilole in its skeleton can be used without any limitation. For example, "Calixarenes" (edited by CD Getti, Royal Society of Chemistry, 1989), "Calixarenes" (J. ゥ ', edited by Ishon et al., Kluwer Academic Publishers, 1991), and the residues derivable from the compounds described in the review of Bema-I (Angew. Chem. Int. Ed, Engl, 34, p713, 1995). .

In the calix derivative used in the present invention, a residue derived from a cyclic oligomer formed by condensation of a resorcinol derivative and formaldehyde can be used without any limitation for the ricris resorciarene structure portion.

In the calix derivative used in the present invention, a plurality of light emitting organic groups or charge transporting organic groups may be present in a molecule. In this case, the types of the luminescent organic group and the charge transporting organic group may be the same or different. Further, among the calix derivatives in the present invention, a calix derivative having both a light-emitting organic group and a charge-transporting organic group in one molecule is a preferable compound in the present invention because of its high emission luminance as an organic EL device material. .

Further, in the present invention, a liquix derivative (X) having a luminescent organic group It is preferable to use the mixture with a force lix derivative (Y) having a charge-transporting organic group as an organic EL element material because a higher emission luminance can be obtained. In this case, the mixing ratio of the elixir derivative (X) having a luminescent organic group and the elixir derivative (Y) having a charge-transporting organic group is not particularly limited, but is generally less than 100 parts by weight of (X). On the other hand, (Y) is preferably blended in the range of 0.1 to 99.9 parts by weight, and more preferably in the range of 1 to 99 parts by weight.

In the present invention, in the litrix derivatives represented by the general formulas (1) and (2), the compound in which the luminescent organic group and the charge transporting organic group are the groups represented by i) and ii) is a novel compound It is.

Specific examples of the calix derivative suitably used in the present invention are as follows.

Replacement paper, mw

20/1 Replacement paper (m)

Replacement paper (m)

The relix derivative used in the present invention has a relatively high glass transition temperature and high thermal stability. The glass transition temperature varies, but is generally around 10 o ° c. For this reason, when the liquid crystal derivative is used as an organic EL device material, the amount of heat generated when a driving voltage is applied can be suppressed. Such thermal stability is considered to be due to the fact that the elixir has a cyclic structure. In addition, calix derivatives have no absorption in the visible region. For this reason, the organic EL device material using the force lix derivative can effectively suppress a decrease in luminous efficiency due to energy transfer or the like.

The method for producing the calix derivative is not particularly limited, and the calix derivative can be produced by appropriately combining commonly used synthesis methods. As a preferred synthesis method, the synthesis method shown in the following scheme can be exemplified.

When synthesizing a elixir derivative, a elixir structure or a lexical resorciarene structure is directly bonded to the luminescent organic group and the charge transporting organic group without using a linking group. Examples of useful reactions that include

(1) Suzu Coupling reaction in which aryl or trifurylaryl is boron-acid-coupled with boronic acid in the presence of Pd (zero valence) and sodium carbonate catalysts

(2) Negishi Coupling reaction in which halogenated aryl and zinc chloride zinc aryl are force-coupled in the presence of Pd (zero valence) and Ni (zero valence) catalysts

(3) Force coupling between aryl halides in the presence of Cu catalyst Ullmann Negism Coupling <DU

(4) Reaction of coupling aryl halide and amino group in the presence of Pd (0 valence), organophosphorus ligand and base

Etc.

In addition, as a reaction to be bonded via a linking group, for example,

(1) Reaction of carboxylic acid and amine to form amide bond

(2) Reaction of chloromethinole group with amine

(3) Wittig reaction to form double bond by reacting phosphorus ylide with carbonyl group

(4) Reaction of phosphoric ester and carbonyl group to form double bond

(5) Reaction of a Grignard reagent with a halogen compound to form a carbon-carbon bond

30 Etc.

Further, the synthesized lelix derivative is purified by recrystallization or column chromatography. As a solvent used for recrystallization, a known organic solvent and a mixed solvent thereof are used, and preferably, ethanol, isopropyl alcohol, acetone, ethyl acetate, acetonenitrile, hexane and heptane are used.

According to the above-mentioned production method, the elixir can be easily purified and isolated. Therefore, as compared with a normal polymer material having a relatively high impurity concentration and a molecular weight distribution, the elixir has a higher utility value as an organic EL device material. As described above, the force lix derivative having a luminescent organic group in the present invention is a luminescent material forming a light emitting layer, and the calix derivative having a charge transporting organic group is a charge transporting material forming a charge transport layer. Is extremely useful.

Regarding the structure of an organic EL device produced using the organic EL device material of the present invention, a light emitting layer or a charge containing the organic EL device material of the present invention is provided between a pair of electrodes, at least one of which is transparent or translucent. There is no particular limitation as long as the transport layer is formed, and a known structure can be employed. For example, a structure having at least one of a pair of transparent or translucent electrodes on both surfaces of a light-emitting layer composed of only a light-emitting body, or a light-emitting layer composed of a mixture of a light-emitting body and a charge transporter, And a layer in which a hole transport layer containing a hole transporter is provided between the cathode and the light emitting layer, and an electron transport layer containing an electron transporter is provided between the cathode and the light emitting layer.

Further, each of the light emitting layer and the charge transport layer may be composed of a plurality of compounds. For example, in the light-emitting layer, by mixing one light-emitting body with another light-emitting body, energy transfer from one light-emitting body to another light-emitting body can be performed, and the other light-emitting bodies can emit light efficiently. The number of compounds to be mixed at this time is not particularly limited, and the compounds may be combined so as to be optimal in terms of the energy relationship between one luminous body and another luminous body to emit light. The concentration of the other luminous body is selected in the range of 0.1 to 50% by weight / ₀ in the total amount with one luminous body. In the charge transport layer, a plurality of compounds can be mixed for the purpose of maintaining a charge injection barrier from the electrode or a charge injection balance of the device. The number of compounds to be mixed is not particularly limited, and the addition concentration can be 0.1 to 50% by weight of other compounds in the proportion of the total amount as in the case of the above-mentioned luminescent material. In addition, multiple light emitters and multiple

Three The light emitting layer may be a mixture of a load transporter.

In addition, the light emitting layer and the charge transport layer may be a single layer, or a plurality of layers may be combined. Further, a luminescent material other than the organic EL device material of the present invention can be mixed and used in the light emitting layer, and a charge transport material other than the organic EL device material of the present invention can be mixed and used in the charge transport layer. Further, the light emitting layer and the charge transport layer may be composed of the organic EL device material of the present invention alone, or may be composed of a medium molecular or high molecular compound dispersed therein.

The known luminescent material that can be used together with the organic EL device material of the present invention is not particularly limited, but a compound represented by the above-mentioned luminescent organic group, for example, distyrino arylene derivative, styrylamine derivative, naphthalene derivative, anthracene Or a derivative thereof, perylene or a derivative thereof, a polymethine-based, xanthene-based, coumarin-based, or cyanine-based dye, a metal complex of 8-hydroxyquinoline or a derivative thereof, a triplet containing europium or iridium, or the like. A metal complex, aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used. Specifically, known materials such as those described in JP-A-57-51781 and JP-A-59-194393 can be used.

Examples of known charge transporters that can be used together with the above-described organic EL device material of the present invention include, as hole transporters, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenylenediamine derivatives, and the like. Examples of electron transporters include oxaziazole derivatives, anthraquinodimethane or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenoquinone derivatives, and metal complexes of 8-hydroxyquinoline or derivatives thereof. Can be mentioned.

Specific examples of these compounds are described in JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209988, JP-A-3-37992, No. 3-152184. Among the above-described charge transporters, the hole transporter is preferably a trifendildiamine derivative, and the electron transporter is preferably an oxadiazole derivative or a metal complex of 8-hydroxyquinoline or a derivative thereof. As for 4,

32 4'-bis (N (3-methylphenyl) -N-phenylamino) biphenyl is an electron transporter with 2- (4-t-butylphenyl) -1,1,3,4-oxadiazole, benzoquinone, anthraquinone, tris ( 8-quinolinol) aluminum is preferred.

Of these, one or both of the hole transporter and the electron transporter can be used simultaneously. Each of these materials may be used alone or in combination of two or more. When a charge transport layer is provided between the light emitting layer and the electrode, the charge transport layer may be formed using the charge transporter described above.

When a charge transporter is used in a mixture with the light-emitting layer, the amount of the charge transporter varies depending on the kind of the compound to be used and the like. It may be determined appropriately in consideration of the situation. Usually, it is preferably 1 to 40% by weight, more preferably 2 to 30% by weight, based on the luminous body.

In the present invention, it is preferable to use polyvinyl carbazole (hereinafter, also referred to as PV κ) in combination with the liquid crystalline derivative, since the emission luminance can be further improved. PVK can be used as it is on the market.

When PVK is used in combination, the content ratio of the calix derivative is in the range of 0.1 to 90% by weight so that the calix derivative's luminescence characteristics and the effect of blending PVK can be fully exhibited. Is preferably 99.9 to 10% by weight. The mixing ratio of the potassium box derivative and P VK, when considering the stability during light emission characteristics and film formation, Calix derivative from 0.5 to 85 weight ^_0/0, PVK ^^ 99. In the range of 5 to 15 wt% More preferably, the weight lix derivative is 1-70 weight. / ₀ , PVK is more preferably in the range of 99 to 30% by weight.

Next, a typical method for producing an organic EL device using the organic EL device material of the present invention will be described. First, an anode is formed on a transparent substrate such as glass or transparent plastic using a transparent or translucent metal oxide or metal thin film. As the material, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, a film (NESA, etc.) made of conductive glass composed of indium tin oxide (ITO), tin oxide, etc., Au, Pt, Ag, Cu, etc. are used. As a manufacturing method, a vacuum evaporation method, a sputtering method, a plating method, or the like is used. Next, a light emitting layer containing the organic EL device material of the present invention is formed on the anode. Way of formation

33 The methods include spin coating, casting, dating, percode, roll coating, gravure coating, flexographic printing, spray coating, and ink jet printing using a melt, solution, or mixture of these materials. It is particularly preferable to form a film by a coating method such as a method.

The thickness of the light emitting layer is preferably 1 nm to 1 Aim, and more preferably 2 nm to 500 nm. In order to increase luminous efficiency by increasing current density, the range of 5 to 200 nm is preferable. When a thin film is formed by a coating method, the solvent is preferably removed under reduced pressure or under an inert atmosphere, preferably at 30 to 300 ° C, more preferably 60 to 200 ° C. It is desirable to heat and dry at a temperature of C.

When the light emitting layer and the charge transport layer are laminated to improve the charge injection efficiency, the charge transport layer having the hole transport property of the present invention is formed on the anode by the same film forming method as described above. Alternatively, a known hole transporter is formed by a known method, and then a light emitting layer of the organic EL device material of the present invention is formed by the above-described film forming method, and a charge exhibiting the electron transporting property of the present invention is further formed thereon. The transport layer is formed by the same film forming method as described above, or a known electron transporter is formed by a known method.

The method of forming a film of the known charge transporter is not particularly limited, but includes a vacuum deposition method from a powder state, a spin coating method after dissolving in a solution, a casting method, a diving method, a bar code method, and a roll coat method. A coating method such as a coating method can be used. The thickness of the charge transport layer is required to be at least such that pinholes do not occur. However, if the thickness is too large, the resistance of the device increases and a high drive voltage is required, which is not preferable. Therefore, the thickness of the charge transport layer is preferably 1 nm to 1 μπχ, more preferably 2 nm to 500 nm, and particularly preferably 5 nm to 200 nm.

Next, a cathode is provided. This electrode becomes an electron injection cathode. The material is not particularly limited, but a material having a small ionization energy is preferable. For example, A1, In, Mg, Ca, Li, Mg-Ag alloy, In-Ag alloy, Mg-In alloy, Mg-Al alloy, Mg_Li alloy, Al-Li alloy, Al — Ca alloy, graphite thin film, etc. are used. As a method for producing the cathode, a vacuum evaporation method, a sputtering method, or the like is used.

Example

34 Hereinafter, the present invention will be described more specifically with reference to specific examples, but the present invention is not limited to these examples.

Production Example 1

Dibromo (tetrapropoxy) force lix [4] arenes and 4- [2- (4-phenoboronic acid) _ 2-phenylvinyl] —4'-i- (2,2-diphenylvinyl) biphenyl Was reacted in a mixed solvent of dimethoxetane ZEtOH in the presence of tetrakistriphenylphosphine.Pd (0 valence) and sodium carbonate to obtain the desired product (CA1) (yield 5%). M + 1610 was confirmed by molecular weight analysis (LC-MS). Table 1 shows the results. Further, elemental analysis (Table 29) and ¹ H-nuclear magnetic resonance spectra—NMR measurements were performed to confirm the structure of the compound. Figure 1 shows the ¹ H—N MR chart.

Production Example 2-19

Except that the raw materials shown in Tables 1 to 10 were used, 〇2- と 19 were synthesized in the same manner as in Production Example 1. The results are shown in Tables 1 to 10, 29 and 30.

Production Example 20

The charge transporters listed in Table 11 were reacted with tetraformyl (tetrapropoxy) carboxylic [4] arene in tetrahydrofuran in the presence of potassium t-butoxy to obtain the desired product (CA20). twenty two%) . The results are shown in Table 11 and Table 30.

Production Examples 21-36

Organic EL element materials CA21 to CA36 were synthesized in the same manner as in Example 9 except that the raw materials shown in Tables 11 to 19 were used. The results are shown in Tables 11 to 19, Table 30 and Table 31.

T ^ shi / ko.

Production Example 37

Tribromo (hexapropoxy) pyrex [6] arene and carpazole were reacted with a copper catalyst in nitrobenzene to obtain the desired product (C A 37) (yield 19%). The results are shown in Table 20 and Table 31.

Production Example 38

Organic EL device material C was prepared in the same manner as in Production Example 37 except that the raw materials shown in Table 20 were used.

35 A38 was synthesized. The results are shown in Table 20 and Table 31.

Production example 39

The target compound (CA39) was obtained by reacting the charge transporter shown in Table 21 with (Hydroxydipropoxy) calix [4] arene with NaH in dimethylformamide (10% yield). . The results are shown in Table 21 and Table 31. Production 40

An organic EL device material CA40 was synthesized in the same manner as in Production Example 39 except that the raw materials shown in Table 21 were used. The results are shown in Table 21 and Table 31.

Production Example 41

The phosphor shown in Table 22 and the resorci [4] arene were reacted in the presence of NaH in tetrahydrofuran (THF) to obtain the desired product (CA41) (yield 1%). M + 4568 was obtained by using TOF-MASS to confirm the molecular weight. The results are shown in Tables 22 and 31.

Production Examples 42 to 46

The procedure was performed in the same manner as in Production Example 41, except that the phosphors and resorcianes shown in Tables 22 to 24 were used instead. The results are shown in Tables 22 to 24 and Table 31.

Production 47

The target substance was obtained by reacting the luminous substance shown in Table 25 with a monochrome mouth carboxyl (octapropoxy) calix [7] arene in a black mouth form (yield 35%). The results are shown in Table 25 and Table 31.

Production Example 48

The calixresorcialane derivative shown in Table 26 and N, N, N, 1-triphenyl 4,4,1-benzidine were combined with xylene in the presence of palladium acetate, tris (t-butyl) phosphine and sodium 1-butoxide. The reaction was carried out in a solvent to obtain CA48 (yield 21%). The results are shown in Table 26 and Table 31.

Production Examples 49-52

CA49-52 were obtained in the same manner as in Production Example 48 except that the raw materials shown in Tables 26 to 28 were used. The results are shown in Tables 26 to 28 and Table 31.

36 Material e Equipment L

CA1

00

-3

CA2

Material E

OA:

00

Material ε

Fee

Calixarene derivative

Or calix resorci luminescent or charge transporter product I yield

LC-MS arene derivative (%)

Table 4 Lumber Equipment L ο

Material F- Mineral calixarene derivative

Or calix resorsi luminous or charge transporter product yield (%) MS arene derivative

Material list Ξ 6

Machine

Calixarene derivative

7

Lumber

Fee

Table 10 Calixarene derivatives

Or calix resorci luminous or charge transporter product

Arene derivative Yield (%) MS

CA19

Table 11

Table 12

Lumber

Table equipment 1 4 Calixarene derivative

Table 16

Table "18

Table 19

Table 20

W1 Calixarene derivative

E or Calix resorsi Emitting substance or charge transporter Product

Materials Arene derivatives-LC-MS

Surface material £ 21

Fee

Calixarene derivative

Or calix resorci luminous or charge transporter composition yield (%) MS arene derivative

Material ε

Front charges 22

Calixarene derivative

Or calix resorci luminescent or charge transporter S product Yield (%) MS arene derivative

Material list a- Equipment fee 23

Calixarene derivative

Material ε

Front charges 24

Calixarene derivative

Material

Fee

Table 25 Calixarene derivatives

Table 28

Dependent Calixarene derivative

E- or calix resorsi luminous or charge transporter product yield (%) MS material arene derivative

CA52 _Br 8 3418

99

lJ8Zl / Z0df / X3d iozoso / εο OAV

ΙΖ8ΖΙ / Ζ0άΐ / L3d T010S0 / C0 OAV

Production Example 53

Calixresorcia lane derivative shown below

And a phosphate derivative represented by the following formula:

Was reacted in the presence of potassium t-butoxide in a THF solvent to obtain a luminescent intermediate (CA53) obtained by the following formula (yield: 50%). M + 3424 was confirmed by molecular weight analysis (TOF-MAS S). ! ! From <56.0 to 9.O ppm at 140 ° derived from aromatic hydrocarbons, δ at 3.0 to 5. From 0 to 3.0 ppm, 24 ° derived from benzyl and alkylene groups was confirmed. Therefore, it was confirmed that the luminescent intermediate obtained by this reaction was a compound shown in Table 32. The results are shown in Tables 32 and 36.

Production Examples 54 to 59

Except for using the raw materials shown in Tables 32 to 35, luminescent intermediates of CA54 to CA59 were obtained in the same manner as in Production Example 53. The results are shown in Tables 32-35 and 36. Production Example 60

The carboxylic acid resorcinol derivative shown in Table 35 and the benzoimidazole derivative were reacted in a nitrobenzene solvent in the presence of copper powder to obtain a luminescent intermediate CA60 (yield 8%). The results are shown in Tables 35 and 36.

69

Table 33

Table 34

Table 35

fL

l0I0S0 / £ 0 OAV <Synthesis of EL device material having light emitting group and charge transport group>

Production example 6 1

CA 53 obtained in Production Example 53 and N, N, N'-triphenyl 4,4'-benzidine were combined with xylene solvent in the presence of palladium acetate, tris (t-butyl) phosphine and sodium 1-butoxide. The reaction was carried out to obtain the desired product CA61 (yield: 24%). M + 4834 was confirmed by molecular weight analysis (TOF-MAS S).

Further, elemental analysis and ¹ H-nuclear magnetic resonance spectrum ( ¹ H-NMR) measurement were performed to confirm the structure of the compound. The results are shown in Table 37 and Table 60.

Production Examples 62-80

CA62 to .CA80 were synthesized in the same manner as in Production Example 61 except that the charge transporters shown in Tables 37 to 46 were used. The results are shown in Tables 37 to 46, Table 60, and Table 61.

Production example 8 1

'' The CA53 obtained in Production Example 53 and 6- (5- (4-t-butylphenyl)-1,2,4-oxaziazol-1-yl) phenylphenolic acid were combined with tetrakis (triphenyl Phosphine) The reaction is carried out in a mixed solvent of 1,2-dimethoxyethane (DME) and ethanol in the presence of palladium (0 value) and sodium carbonate.

A81 was obtained (8% yield). Using molecular weight analysis (TO F-MAS S), Mw + 4518 was obtained. The results are shown in Table 47 and Table 61.

Production Examples 82 to 89

CA82-89 were obtained in the same manner as in Production Example 81 except that the raw materials shown in Tables 47 to 51 were used. The results are shown in Tables 47 to 51 and Table 61.

Production examples 90, 92, 94, 96, 97, 99, 101

CA90, 92, 94, 96, 97, 99 and 101 were obtained in the same manner as in Production Example 61 except that the raw materials shown in Tables 52 to 58 were used. The results are shown in Tables 52 to 58 and Table 62.

Production Examples 91, 93, 95, 98, 100, 102

CA91, 93, 95, 98, 100 and 102 were obtained in the same manner as in Production Example 81 except that the raw materials shown in Tables 52 to 58 were used. The results are shown in Tables 52 to 58 and Table 62.

7 5 Indicated.

Production Example 103

CA53 obtained in Production Example 53 was dissolved in tetrahydrofuran and reacted with Mg to prepare a Grignard reagent. Here, the promodithienosilole derivative of the charge transporter shown in Table 59 and (1,2-bis (diphenylphosphino) ethane) nickel (Π) dichloride were added, and the reaction was carried out at 65 ° C. Obtained (yield 3%). Using molecular weight analysis (TOF-MAS S), Mw + 4984 was obtained. The results are shown in Table 59 and Table 62.

76 Table 37

Table 38

Material E fee ''

CA63

CA64

Table 39

Luminescent intermediate Charge transporter Product MS Material J n

Table 40

Table 42 Luminescent intermediate materials E

CA71 CA53

00

05

CA72 CA53

Table 43

Table 44

Table 45

Table 46 Luminescent intermediate materials available ε

CA79 CA53

00

CA80 CA53

Table 47

Table 48

Table 4 £

Yes

E Luminescent intermediate Charge transport material

CA85 CA53

GO CD

CA86 CA53

Table 50

Table 51

E luminous intermediate charge transporter yield

Product MS material (%)

CA89 CA53 2 5095

Table 52

Table 54

Table 55

Table 56

Table 57

Table 58

Table 59

οοτ

09 Halla

ΐί8Ζΐ / Ζ0 <ΙΓ / Χ3 <Ι iozoso / εο OA TOT

TZ8Zl / r0df / X3d l0Z0S0 / £ 0 OAV

zm

l0Z0S0 / £ 0 OAV Example 1

The organic EL device material obtained in Production Example 1 was dissolved in black hole form to obtain a 1% by weight black form solution. Approximately 2 g of this solution was applied to a 2 mm thick glass surface using a MI KASA spin-co 1H-DX2 for 10 seconds at a rotational speed of 4 Or.pm-2 seconds at 500 rpm → 200 Or.pm Spin coating was performed under the condition of 45 seconds. Further, the spin-coated glass was heated at 8 O: to remove the solvent to form a thin film. When the formed thin film was observed using an optical microscope, no crystals were found. Further, the crystallinity of this thin film was evaluated by an X-ray diffraction method, but no crystal reflection was obtained. From the above, it was found that a thinner version of the compound of Example 1 exhibited amorphous properties and gave good film forming properties. When the film forming properties of the compounds of Production Examples 2 to 103 were evaluated in the same manner, thin films showing good amorphous properties were obtained in all cases.

Example 2 '

Fluorescent characteristics>

When the CA 1 spin-coated thin film obtained in Example 1 was irradiated with ultraviolet light having a main maximum at 35 Onm, blue fluorescence was confirmed. It was measured using a spectrophotometer (Instant Multi-Channel Photo Detector MCPD 1000: Otsuka Electronics Co., Ltd.), and a spectrum showing an emission maximum at 460 nm was obtained. <EL emission characteristics 1>

A transparent support substrate was prepared by forming an IT〇 film with a thickness of 150 nm on a 2.5 mm × 2 Omm × 0.8 mm glass substrate. After etching and washing the transparent support substrate, about 2 g of the above-mentioned 1% by weight solution of CA1 in chloroform was spun onto a 2 mm thick glass surface using MIKASA spino 1H-DX2. Spin coating was performed under the following conditions: 10 seconds at 4 Or.pm → 2 seconds at 50 Or.pm → 45 seconds at 2000 rpm. The film was further heated at 80 ° C. under a nitrogen atmosphere to remove the solvent and form a thin film. On top of this, 20 nm of BCP (2,9-dimethyl-4,7-diphenyl-1,10 phenanthroline) is used as a hole blocking layer, and 50 nm of tris (8-quinolinol) aluminum is used as an electron transport layer. The deposition was performed at a deposition rate of 0.1 nmZ seconds using a deposition apparatus manufactured by ULVAC (EBV-6DA). Finally, an organic EL device is formed by depositing 100 nm of Ag: Silver = 10: 1 as a cathode on it.

03 did. The degree of vacuum in vapor deposition were all less than 1 X 10- ⁵ To rr. When a voltage of 12 V was applied to the element and the fluorescence was measured using a spectrophotometer (MCPD 1000: Otsuka Electronics Co., Ltd.), the blue fluorescence having a maximum emission wavelength at 470 nm was measured. Was observed.

Example 3

1% by weight of CA24 obtained in Production Example 24 and 0.5% of N, N′-bis (3-methylphenyl) -1-N, N, diphenyl [1,1′-biphenyl] —4,4,1-diamine A coating solution was prepared by dissolving the solution in benzene at a concentration of weight%. A 150 mm thick IT film formed on a 25 mm X 1 O mm X 0.7 mm glass substrate was used as a transparent support base.This transparent support base was etched and washed, and then the coating solution prepared above was adjusted to about 0. 4 g was spin-coated on a glass substrate surface for 60 seconds at 1500 rpm using a MI KASA spin coater 1H-D7. This substrate was heated to 100 ° C. in a nitrogen atmosphere to remove the solvent, and a thin film was formed. Further, using a vacuum deposition apparatus EBV-6DA manufactured by ULVAC, an organic EL element was prepared by depositing 40 nm of calcium and then 60 nm of aluminum as a cathode. The degree of vacuum in vapor deposition was 1 X 10- ⁶ To rr below. When a DC voltage was applied to this device, a blue surface emission with an emission luminance of 600 cdZm ² was obtained at 12.5 V. This emission was measured using a spectrophotometer (Instant Multi-Channel Photodetector M CPD 1000: Otsuka Electronics), and the maximum emission wavelength was 460 nm. The results are shown in Table 63.

Examples 4 to 36

The EL characteristics were evaluated in the same manner as in Example 3, except that the organic EL materials shown in Table 63 were used. The results are shown in Table 63.

104 Table 63

105 Example 37

CA61 obtained in Production Example 61 was dissolved in xylene at a concentration of 1% by weight to prepare a coating solution. A transparent support base was prepared by forming an ITO film with a thickness of 150 nm on a 25 mm X 10 mm X 0.7 mm glass substrate.This transparent support base was etched and washed, and then the coating solution prepared above was adjusted to about 0. 4 g was spin-coated on the surface of a glass substrate for 60 seconds at a rotation speed of 1,500 rpm using a MI KAS A spin controller 1H-D7. The substrate was heated to 100 ° C. in a nitrogen atmosphere to remove the solvent and form a thin film. Further, using a vacuum deposition apparatus EBV-6DA manufactured by ULVAC, calcium was deposited as a cathode at 40 nm and then aluminum was deposited at 60 nm to produce an organic EL device. The degree of vacuum at the time of vapor deposition was 1 × 10 ⁶ To rr or less. When a DC voltage was applied to this device, a blue surface emission with an emission luminance of 800 cd / m ² was obtained at 12.5 V. This emission was measured using a spectrophotometer (Instant Multi-Channel Photodetector MCPD 1000: Otsuka Electronics), and the maximum emission wavelength was 460 nm. The results are shown in Table 64.

Examples 38 to 84

The EL characteristics were evaluated in the same manner as in Example 37 except that the organic EL materials shown in Table 64 were used. The results are shown in Table 64.

06 Table 64

107 Example 85

A mixture of CA61 and CA81 (weight ratio 50/50) was dissolved in xylene at a concentration of 1% by weight to prepare a coating solution. A transparent support substrate was prepared by forming an ITO film with a thickness of 150 nm on a 25 mmX 10 mmX 0.7 mm glass substrate, and after etching and washing the transparent support substrate, the coating solution prepared above was adjusted to approximately 0. Using 4 g of MIKAS A spinco 1H-D7 on the glass substrate surface

Spin coating was performed at 500 rpm for 60 seconds. The substrate was heated to 100 ° C. in a nitrogen atmosphere to remove the solvent and form a thin film. Furthermore, using a ULVAC vacuum evaporation system E BV-6DA, 40 nm of calcium was used as the cathode, followed by aluminum.

An organic EL device was prepared by vapor deposition at 60 nm. The degree of vacuum in vapor deposition was less than 1 X 10- ⁶ T orr. When a DC voltage was applied to this device, a blue surface emission with an emission luminance of 1800 cdZm ² was obtained at 12.5 V. This emission was measured using a spectrophotometer (Instant Multi-Channel Photodetector MCPD 1000: Otsuka Electronics), and the maximum emission wavelength was 460 nm. The results are shown in Table 65. Example 86-: L 25

The EL characteristics were evaluated in the same manner as in Example 85, except that the organic EL materials were mixed at the composition ratios shown in Table 65. The results are shown in Table 65.

108

^ Examples 126 to 147

The EL characteristics were evaluated in the same manner as in Example 85, except that the organic EL materials were mixed at the composition ratios shown in Table 66. The results are shown in Table 66. Table 66

Example 148

A 150-nm-thick ITO film was formed on a glass substrate of 2.5 mm X 2 O mm X 0.8 mm as a transparent support substrate. After etching and washing this transparent support substrate, about 2 g of the above-mentioned 1% by weight solution of CA2 in chloroform was applied to a 2 mm-thick glass surface using a MIKASA spino 1H-DX2 for 4 revolutions or more. Spin coating was performed under the conditions of 10 seconds at .pm → 2 seconds at 50 Or.pm and 45 seconds at 200 Or.pm. The film was further heated at 80 ° C. under a nitrogen atmosphere to remove the solvent and form a thin film. Tris (8-quinolinol) aluminum 60 nm was deposited thereon as a light emitting layer and an electron transporting layer at a deposition rate of 0: nm / sec using a ULVAC (EBV-6DA) deposition apparatus. Finally, on top of that, as a cathode, magnesium: silver =

1 10 10: 1 was vapor-deposited at 170 nm to produce an organic EL device. The degree of vacuum in vapor deposition was all 1x10- ⁵ To rr below. When a DC voltage was applied to the device, a green surface emission with an emission luminance of 400 cd / m ² was obtained at 12 V. This emission was measured using a spectrophotometer (MCPD 1000, an instantaneous multi-channel photodetector: manufactured by Otsuka Electronics). The maximum emission wavelength was 52 Onm. The results are shown in Table 67.

Example 149 ~: L 51, Comparative Example 1

The EL characteristics were evaluated in the same manner as in Example 148 except that the organic EL materials shown in Table 67 were replaced. The results are shown in Table 67.

Table 67

The organic EL device material of the present invention can be spin-coated and can be easily formed. Further, according to the present invention, an organic EL device material can be easily obtained with high purity. Therefore, the organic EL device material of the present invention is extremely useful as a luminous body and a charge transporter constituting the organic EL device.

Example 152

EL EL characteristics 5>

CA 24 obtained in Production Example 24 was dissolved in chlorobenzene at a concentration of 0.5% by weight and PVK at a concentration of 2% by weight to prepare a coating solution. A transparent support substrate was prepared by forming an ITO film with a thickness of 150 nm on a 25 mm X 10 mm X 0.7 mm glass substrate.After etching and washing the transparent support substrate, about 0.4 g of the coating solution prepared above was applied. Using a spinco 1H-D7 manufactured by MI KASA, spin coating was performed on the glass substrate surface at a rotation speed of 1500 rpm for 60 seconds. Place this substrate in a nitrogen atmosphere 1 The solvent was removed by heating to 0 ° C to form a thin film. At this time, the content of CA24 in the formed organic thin film was 20% by weight. Further, using a vacuum deposition apparatus EBV-6DA manufactured by ULVAC, calcium was vapor-deposited as a cathode at 40 nm and then aluminum was vapor-deposited at 60 nm to produce an organic EL device. The degree of vacuum at the time of vapor deposition was 1 × 10 ¹⁶ To rr or less. When a DC voltage was applied to this device, a blue surface emission with an emission luminance of 5700 cdZm ² was obtained at 12.5 V. This emission is measured with a spectrophotometer

The maximum emission wavelength was 46 Onm when measured using an instantaneous multi-channel photodetector MCPD 1000 (manufactured by Otsuka Electronics).

Example 153

A device was fabricated in the same manner as in Example 152 except that the concentration of CA24 was changed to 0.04% by weight. At this time, the content of CA 24 in the formed organic thin film was 2% by weight. When a DC voltage was applied to this device, a blue surface emission with a light emission luminance of 2400 cdZm ² was obtained at 12.5 V. The maximum emission wavelength of light emission was 460 nm.

Example 154

In Example 152, the concentration of octane was 1.5% by weight, A device was produced in the same manner as in Example 152 except that the concentration of 1 was changed to 1.5% by weight. At this time, the content of CA24 in the formed organic thin film was 50% by weight. When a DC voltage was applied to this device, a blue surface emission with an emission luminance of 4400 cdZm ² was obtained at 12.5 V. The maximum emission wavelength of light emission was 460 nm.

Example 155

In Example 152, the concentration of CA 24 was 2.8% by weight,? Concentration. A device was prepared in the same manner as in Example 152 except that the content was changed to 0.7% by weight. At this time, the content of CA24 in the formed organic thin film was 80% by weight. When a DC voltage was applied to this device, a blue surface emission with an emission luminance of 1800 cdZm ² was obtained at 12.5 V. The maximum emission wavelength of light emission was 46 Onm.

Examples 156 to 187

A device was produced in the same manner as in Example 152, except that the compounds shown in Table 68 were used instead of C A24 used in Example 152. Table 68 shows the result of applying a DC voltage of 12.5 V to this device.

112 Table 68

113 Examples 188 to 193

A coating solution was prepared by dissolving 2.7% by weight of CA24 and the charge transporter shown in Table 69 at a concentration of 0.3% by weight in benzene with a black mouth. Thereafter, a device was manufactured in the same manner as in Example 152. Table 69 shows the results of applying a DC voltage of 12.5 V to this device.

14 Table 6 9

115 Replacement Form (Rule 26) Table 69 continued

115/1 Replacement sai (ailJ26) Example 194

CA61 obtained in Production Example 61

Azole derivatives

Was dissolved in xylene at a concentration of 0.8% by weight to prepare a coating solution. A transparent support substrate was prepared by forming an ITO film with a thickness of 150 nm on a 25 mm × 1 Omm × 0.7 mm glass substrate. After etching and washing the transparent support substrate, a 1.56% aqueous solution of polyethylene dioxythiophene (PEDT) and polystyrene sulfonic acid (PSS), Baytron P (trade name, manufactured by Bayer AG) was added to MIKASA Subinco Evening 1 H—D7 was used for spin coating at a rotation speed of 1000 rpm for 60 seconds. This substrate was heated at 200 ° C. for 1 hour using a hot plate. Approximately 0.4 g of the coating solution prepared above was spin-coated on the substrate at 4000 rpm for 30 seconds, and heated to 10 ot under a nitrogen atmosphere to remove the solvent, thereby forming a thin film. Further, using a vacuum deposition apparatus EBV-6DA manufactured by ULVAC, calcium was deposited as a cathode at 40 nm and then aluminum was deposited at 80 nm to produce an organic EL device. The degree of vacuum deposition vapor is was 1 X 10- ⁶ To rr below. When a DC voltage was applied to this device, blue light emission with a luminance of 900 cd / m ² was obtained at 8 V. This emission was measured using a spectrophotometer (Instant Multi-Channel Photo Detector MCPD 1000: Otsuka Electronics), and the maximum emission wavelength was 460 nm.

Examples 195 to 215

Instead of CA61 used in Example 194, the compounds shown in Table 70 synthesized in Production Examples 62 to 75 and Production Examples 90, 92, 94, 96, 97, 99, and 101 were used.

116 A device was produced in the same manner as in Example 1924 except for the above. Table 70 shows the results of applying a DC voltage of 8 V to this element.

Table 70

1 1 7 Example 2 1 6

The coating solution was prepared by dissolving CA 81 obtained in Production Example 81 at a concentration of 0.9% by weight and polyvinylcarbazole at a concentration of 2.1% by weight in benzene at a concentration of 0.1% by weight. Thereafter, a device was manufactured in the same manner as in Example 194. Table 71 shows the results of applying a DC voltage of 8 V to this device.

'Example 2 Γ 7 ~ 2 2 9

In Example 2 16 instead of CA81, the compound shown in Table 71 synthesized in Production Examples 82 to 89 and 93, 95, 98, 100, 102 was prepared. A device was produced in the same manner as in Example 216 except that the device was used. Table 71 shows the results of applying a DC voltage of 8 V to this device. Table 71

118

Claims

The scope of the claims

1. An organic electroluminescent device material comprising a dexararene derivative or a calixresorcialane derivative having at least one of a luminescent organic group and a charge transporting organic group.

2. The compound according to claim 1, wherein the liquisqualene derivative or the calixresorcialane derivative having at least one of a luminescent organic group and a charge transporting organic group is a compound represented by the following general formula (1) or (2). Organic electorescence luminescence element material.

In the above formula, n is an integer of 3 to 20, and A, B, and D are the same or different atoms or groups, and are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group, or A group represented by the formula (3), a plurality of A, B and D may be different from each other, and at least one of them is a group represented by the general formula (3); When there are a plurality of groups represented by the formulas, these may be different from each other:

-(L) m- Z (3)

1 1 9

3. The organic electroluminescent device according to claim 1, wherein the luminescent organic group is linked so that at least four unsaturated bonds constituting the luminescent organic group form a conjugated system, and forms a luminescent residue. Luminescent device material.

4. The organic charge-transporting organic group according to claim 1, wherein the at least two unsaturated bonds constituting the charge-transporting organic group are linked so as to form a conjugated system, and form a residue having a charge-transporting property. Electroluminescent device materials.

5. The organic electroluminescent element material according to claim 1, wherein the luminescent organic group and the charge transporting organic group are selected from the group consisting of residues represented by the following i), ϋ) and iii):

i) at least two unsaturated ring systems (where the unsaturated ring system is a 5- or 6-membered hydrocarbon ring or 1-3 membered nitrogen, oxygen, sulfur or silicon atoms) A 5- or 6-membered heterocyclic ring, or 2 to 30 of these hydrocarbon rings and / or heterocyclic rings may be condensed, and these unsaturated ring systems are substituted with substituents. , Or may be condensed with a saturated ring force, or is connected to form a conjugated system through a direct bond or an alkenylene group or a nitrogen atom. And the unsaturated ring system may be one or more side chains (or pendant groups) of a polymer main chain, and a residue that imparts luminescence or charge transport to a calix derivative molecule; '

ii) at least two unsaturated ring systems (where the unsaturated ring system is a 5- or 6-membered hydrocarbon ring or a ring-constituting atom containing 1 to 3 nitrogen, oxygen, sulfur, or silicon atoms). A 5- or 6-membered heterocyclic ring, or 2 to 30 of these hydrocarbon rings or heterocyclic rings may be condensed, and these unsaturated ring systems may have a substituent May form a ligand, or at least two of the above unsaturated ring systems may be a direct bond or a C-group or nitrogen. Are linked to form a conjugated system via an atom to form a ligand, and, if necessary, to form a ligand together with an oxygen atom bonded to the unsaturated ring system; beryllium, aluminum, copper , Zinc, ruthenium, you

1 2 0 A residue derived from a coordination compound having palladium, rhodium, platinum or silicon as a central metal and imparting luminous or charge transporting properties to the elixir derivative molecule; and

iii) at least two unsaturated ring systems (where the unsaturated ring system is a 5- or 6-membered hydrocarbon ring or ring-constituting atom containing 1 to 3 nitrogen, oxygen, sulfur, or silicon atoms). A 5- or 6-membered heterocyclic ring, or two to thirty of these hydrocarbon rings and heterocyclic rings may be condensed, and these unsaturated ring systems are substituted with substituents. Or a saturated ring may be condensed), and is derived from an organometallic compound in which two or more of the molecular groups directly bonded to the compound and iridium are bonded, and the luminescent or derivative molecule has a luminescent or Residues that impart charge transport properties.

6. The luminescent organic group is a distyryl arylene derivative, a styryl amine derivative, an imidazole derivative, a naphthalene derivative, an anthracene derivative, a perylene derivative, a polymethine derivative, a xanthone derivative, a coumarin derivative, a cyanine derivative, a quinatalidone derivative, or a bery. Lithium, aluminum, copper, zinc, ruthenium, europium, rhodium as the central metal, coordination complexes, organometallic compounds containing iridium, etc., pentaphenyltetracyclyl pentagen, tetrafuylbutadiene, poly (9,9 dianolequinole phenololenolene) derivatives , Polyparaphenylene derivatives, polythiophene derivatives, polyparaffinylene vinylene derivatives, arylene vinylene derivatives, polyvinylcarbazole derivatives, poly (meth) acrylarylamine derivatives and A residue derived from a compound selected from the group consisting of silanes, wherein the charge-transporting organic group is a bilazoline derivative, an arylamine derivative, a stilbene derivative, or a trif; a phenyldiamine derivative; Derived from a compound selected from the group consisting of dimethane or its derivative, tetracyanoanthraquinodimethane or its derivative, fluorenone derivative, diphenoquinone derivative, silole derivative 8-hydroxyquinoline or its metal complex 2. The organic electroluminescent element material according to claim 1, which is a residue to be obtained.

7. — Calixa with both luminescent and charge-transporting organic groups in the molecule

Two 2. The organic electroluminescent device material according to claim 1, comprising a lane derivative or a calixresorcialane derivative.

8. A compound represented by the formula (X), wherein a dicarboxylic acid derivative having a luminescent organic group or a dicarboxylic resin derivative (X) and a calixarene derivative or a calixresorcialane derivative having a charge-transporting organic group are represented by (X) An organic electroluminescent device material comprising a composition containing (Y) in a range of 0.1 to 99.9 parts by weight per 100 parts by weight.

9. An organic electroluminescent device material containing a calixarene derivative or a calixresorcialane derivative having at least one of a luminescent organic group and a charge transporting organic group, and polyvinyl carbazole.

10. An organic electorescent luminescent device material comprising a elixirene derivative or a calixresorsialene derivative having a luminescent organic group and a charge transporting compound.

11. An organic electroluminescent device comprising a light emitting layer or a charge transport layer containing the organic electroluminescent device material according to claim 1 between an anode and a cathode.

12. Compounds represented by the following general formulas (1) and (2):

122

In the above formula, n is an integer of 3 to 20, and A, B, and D are the same or different atoms or groups, and are a hydrogen atom, a halogen atom, an alkyl group, an aryl group, an alkoxy group or A group represented by the following general formula (3), and a plurality of A, B and D may be different from each other, and at least one of them is a group represented by the general formula (3); 3) When there are a plurality of groups represented by the formula, these may be different from each other

-(L) m-Z (3)

Here, L is a divalent organic group, Z is a luminescent organic group or a charge transporting organic group selected from the group consisting of residues represented by the following formulas, and m is 0 or 1. RU:

(Where p and q are each an integer of 1 to 10 and are integers such that the number average molecular weight of each group takes a value in the range of 00 to 400);

(Where T) and q are the same as above);

twenty five

26

2 7

129

130