JP2003313546A - Luminescent composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a material for an organic electroluminescent element, capable of being formed into a film by a coating method, and having excellent luminescent characteristics. <P>SOLUTION: The luminescent composition contains (1) 0.1-90 wt.% of a calixarene derivative represented by the formula or a calyxresorcinarene derivative, having a luminescent organic group or a charge-transporting organic group, and (2) 99.9-10 wt.% of polyvinylcarbazole. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a luminescent composition which can be suitably used in an organic electroluminescence device (hereinafter, also referred to as an organic EL device).

[0002]

2. Description of the Related Art Organic EL devices are promising for use as inexpensive solid-state light emitting large-area full-color display devices, and are under active development. Generally, an organic EL element is composed of a light emitting layer and a pair of counter 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, this is a phenomenon in which electrons and holes are recombined in the light emitting layer, and energy is emitted as light when the energy level returns from the conduction band to valence electrons.

The organic EL device material used for the light emitting layer and the charge transport layer of the above organic EL device depends on its use.
It is required to have characteristics such as high brightness, low driving voltage, and light emission of various colors, and it is necessary to develop materials that meet the requirements. So far, low molecular weight materials such as copper phthalocyanine (CuPc) and star-burst molecules, and poly (p-phenylene vinylene)
Polymer materials such as (PPV) and polyaniline (PANI) have been developed.

However, there are some inconveniences and problems in thinning these materials and using them as devices. That is, the vacuum deposition method is used to form an organic thin film using a low molecular material such as CuPc and starburst molecules, but this method has a problem that it takes time and cost. Further, the organic thin film formed by the vacuum evaporation method is likely to be crystallized, which leads to device deterioration.

On the other hand, mainly in a polymer material, a thin film can be formed by a spin coating method, so that a large-capacity thin film can be easily formed at a low cost. Also,
The use of a polymer material also has an advantage that crystallization is less likely to occur.

It is known that, among polymer materials, polyvinyl carbazole having a hole-transporting property (hereinafter, also referred to as PVK) containing a small amount of a luminescent dye can provide EL light emission. According to Japanese Patent No. 3069139, in a single-layer type device having a device structure consisting of both electrodes and a light emitting layer, the emission efficiency can be improved by containing PVK with an electron transporting compound such as an oxadiazole derivative. It is disclosed. A characteristic of these material systems is that luminescence of various color tones can be obtained by changing the type of luminescent dye, and white luminescence is also possible by containing several types of luminescent dyes (Japanese Patent Laid-Open No. Hei 7 (1998)).
-90260, JP-A-9-63770).

However, few of the combinations of PVK and the luminescent dye have sufficient performance as an organic electroluminescent device, and relatively good performance is obtained when a coumarin derivative or the like is used as the luminescent dye. But not enough. As one of the causes, luminescent dye and PV
Due to insufficient compatibility with K
When attempting to disperse in VK, stacking of low molecular weight dye compounds occurs and the dispersed state in PVK becomes non-uniform, so that the luminous efficiency may decrease. Further, when PVK contains an electron-transporting compound such as an oxadiazole derivative, the Tg of the material itself is lowered, so that there is a problem in heat resistance of the device.

Due to these problems, an organic EL device material using PVK as a host material, which has practically sufficient light emitting characteristics, has not been provided.

[0009]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to solve these problems of the prior art, namely, organic E which can be spin-coated and has excellent emission characteristics.
It is to provide an L element material.

[0010]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have linked a calixarene derivative or a calixresorciarene derivative to the molecular skeleton of a light emitter or a charge transporter. It was found that the above object can be achieved by using a mixture of the compound and PVK as an organic EL device material,
The present invention has been provided.

That is, the present invention provides (1) a calixarene derivative or a calixresorciarene derivative having a light-emitting organic group or a charge-transporting organic group.
90% by weight and (2) polyvinylcarbazole 99.
It is a luminescent composition containing 9 to 10% by weight.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION A calixarene derivative or a calixresorciarene derivative having a light-emitting organic group or a charge-transporting organic group used in the light-emitting composition of the present invention (hereinafter, also simply referred to as a calix derivative) is ,
A compound in which a known light emitting material and charge transporting material as an organic EL device material and a conventionally known calixarene derivative and calixresorciarene derivative are directly bonded by a covalent bond with or without a divalent organic group. If so, it can be used without any limitation.

As such a calix derivative, for example, compounds represented by the following general formulas (1) and (2) can be preferably used.

[0014]

[Chemical 2]

(However, the above general formulas (1) and (2)
In the formula, n is an integer of 3 to 20, A, B, and X 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 the following general formula (3). And a plurality of A, B and X are present, at least one of them is a group represented by the general formula (3).

-(Y) mZ (3) (wherein Y is a divalent organic group, Z is a light emitting 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 X include a chlorine atom, a bromine atom and an iodine atom. Further, the alkyl group is preferably a group having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group and butyl group, and the aryl group is phenyl group, tolyl group,
A group having 6 to 10 carbon atoms such as a xylyl group and a naphthyl group is preferable, and as the alkoxy group, 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. Can be preferably used.

Further, in the above formula, the divalent organic group represented by Y is a group capable of connecting a light-emitting organic group or a charge-transporting organic group with a calixarene derivative or a calixresorciarene derivative. There are no restrictions. For example,

[0018]

[Chemical 3]

The following can be mentioned. However, R in the said formula is an alkyl group, and n is an integer of 0-20.

Further, in the above formulas (1) and (2), as the light emitting organic group and the charge transporting organic group, a residue having a known light emitting body or charge transporting body used in a conventional organic EL device as a skeleton is used. The groups can be used without any restrictions. The light emitting organic group or the charge transporting organic group is a group derived from a low molecular weight organic compound or a medium molecular weight organic compound. The number average molecular weight of the group derived from the medium-molecular-weight organic compound is preferably 200 to 4000 in terms of easiness of purification. The luminescent organic group is a group that exhibits fluorescence emission from excited singlet or phosphorescence emission from excited triplet. The charge transporting organic group is a group having a hole transporting ability or an electron transporting ability, and is classified into a hole transporting organic group and an electron transporting organic group, and is derived from the hole transporting body and the electron transporting body. It is a base. Note that some light-emitting organic groups also have a charge-transporting property. In that case, there is no particular agreement on which organic group is classified, and further, there is a common structure between the compounds. unacceptable.

The position of the bond of the light emitting organic group or the charge transporting organic group is not particularly limited.

As the light emitting organic group and the charge transporting organic group, preferred groups in the present invention are shown below.

Examples of the light-emitting organic group include distyrylarylene derivatives, styrylamine derivatives, imidazole derivatives, naphthalene derivatives, anthracene or its derivatives, perylene or its derivatives, polymethine series, xanthene series, coumarin series, cyanine series and the like. Groups derived from organic compounds having a skeleton such as dyes, metal complexes of 8-hydroxyquinoline or its derivatives, aromatic amines, tetraphenylcyclopentadiene or its derivatives, or tetraphenylbutadiene or its derivatives, poly (9, 9-dialkylfluorene)
Derivatives, polyparaphenylene derivatives, polyparaphenylene vinylene derivatives, polythiophene derivatives, etc. π-conjugated medium-molecular compounds, polyvinylcarbazole derivatives, pendant medium-molecular compounds such as poly (meth) acrylarylamine derivatives, σ-conjugated polysilane derivatives, etc. Examples include groups derived from in-system molecular compounds.

Among these luminescent organic groups, preferred groups in the present invention are distyrylarylene derivatives, styrylamine derivatives, imidazole derivatives, naphthalene derivatives, anthracene or its derivatives, perylene or its derivatives, and 8-hydroxyquinoline or Mention may be made of metal derivatives of the derivatives and groups derived from poly (9,9-dialkylfluorene) derivatives.

Among the charge transporting organic groups, examples of the hole transporting organic group include groups derived from a pyrazoline derivative, an arylamine derivative, a stilbene derivative and a triphenyldiamine derivative, and an electron transporting group. Examples of the organic group include a group derived from an oxadiazole derivative, anthraquinone dimethane or a derivative thereof, tetracyanoanthraquinodimethane or a derivative thereof, a fluorenone derivative, a diphenoquinone derivative, and a metal complex of 8-hydroxyquinoline or a derivative thereof. can do.

Among these groups, the hole-transporting organic group is preferably a triphenyldiamine derivative, and the electron-transporting organic group is preferably an oxadiazole derivative, and 8-hydroxyquinoline or a metal complex of the derivative thereof.

Specific examples of the light emitting organic group and the charge transporting organic group are shown below. (A) Luminescent organic group (A-1) Singlet luminescent organic group

[0028]

[Chemical 4]

[0029]

[Chemical 5]

(In the above 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 is in the range of 200 to 4000.) (A-2) Mie Item Luminescent organic group

[0031]

[Chemical 6]

(B) Charge-transporting organic group (B-1) Organic group capable of transporting holes

[0033]

[Chemical 7]

(B-2) electron-transporting organic group

[0035]

[Chemical 8]

In the calix derivative used in the present invention, the calixarene structure portion is a cyclic oligomer produced by condensation of phenol and formaldehyde, a crosslinked calixarene crosslinked through an alkoxy group, a heterocalix such as thiacalixarene or oxacalixarene. Arene or a residue that can be derived from a known compound having a pseudo-calix cyclooligomer such as caricspirol or calixsilole in the skeleton can be used without any limitation. For example, `` Calix Arene (Calix
arenes) "(CD booklet, Royal Society of Chemistry, 1
989), "Calix arenes" (edited by J. Vishon et al., Kluwer Academic Publishers, 1991), and a review by Boehmer (Angew. Chem. Int. Ed, Engl, 34.
Vol., P713, 1995) and the like which can be mentioned as residues derived from the compounds.

In the calix derivative used in the present invention, as the calix resorcialane structure portion, a residue which can be derived from a cyclic oligomer produced by condensation of resorcinol and formaldehyde can be used without any limitation.

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

[0039]

[Chemical 9]

[0040]

[Chemical 10]

[0041]

[Chemical 11]

[0042]

[Chemical 12]

[0043]

[Chemical 13]

By using the luminescent composition of the present invention as a luminescent layer of an organic EL device, as compared with an organic EL device comprising PVK and a known luminescent material or charge transporter,
Luminous properties such as luminous brightness and luminous efficiency are greatly improved. The reasons for this are as follows.

PVK is used as a known luminescent material or charge transport material.
When it is dispersed in PVK, the compatibility with PVK is insufficient, so when trying to disperse a certain amount or more of the light emitter or charge transporter in PVK, stacking of molecules occurs and the dispersion state in PVK is non-uniform. Therefore, the luminous efficiency may be lowered. On the other hand, when a known light emitter or charge transporter molecule is bound to a calixarene derivative,
It is thought that the molecules are unlikely to associate with each other due to the molecular structure that is difficult to stack in three dimensions. As a result, since the calix derivative is uniformly dispersed in PVK, concentration quenching of light emission is less likely to occur, and it is considered that the light emission characteristics are improved.

The calix derivative used in the present invention is
The film forming property is good, and an amorphous thin film can be easily formed by applying a solution of the calix derivative. Further, the glass transition temperature of the amorphous thin film of the calix derivative is relatively high, and it is about 100 ° C. although it varies depending on the kind of the calix derivative. It is considered that such thermal stability is due to the calix derivative having a cyclic structure. Since the calix derivative has such characteristics, even when the calix derivative is dispersed in PVK, it is possible to suppress the decrease in thermal stability that is observed when a low-molecular material is dispersed. For this reason,
When the luminescent composition of the present invention is used as a material for an organic EL device, it is possible to suppress deterioration of the device due to heat generated when a driving voltage is applied.

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

In the synthesis of the calix derivative, when the calixarene structure portion or the calixresorsialane structure portion and the light emitting organic group and the charge transporting organic group portion are bonded, it is useful that they are directly bonded without a linking group. As an example of such a reaction, for example, (1) aryl halide or trifuryl aryl and boronic acid are combined with Pd (0
Value), Suzuki Coupling reaction for coupling in the presence of a catalyst of sodium carbonate (2) Pd of aryl halide and zinc aryl chloride
(0 valent), Negishi Coupling reaction for coupling in the presence of Ni (0 valent) catalyst (3) Ullmann Coupling reaction for coupling aryl halides in the presence of Cu catalyst.

Examples of the reaction for coupling via a linking group include (1) a reaction of reacting a carboxylic acid with an amine to form an amide bond (2) a reaction of a chloromethyl group with an amine (3) a phosphorus ylide And the carbonyl group are reacted with each other to form a double bond (4) There is a reaction of reacting a phosphoric acid ester with a carbonyl group to form a double bond.

Further, the synthesized calix derivative is purified by recrystallization or column chromatography. As the solvent used for recrystallization, known organic solvents, mixed solvents thereof are used, but preferably ethanol, isopropyl alcohol, acetone, ethyl acetate,
Acetonitrile, hexane, heptane are used.

The calix derivative used in the present invention is 1
Only one kind or a combination of plural kinds may be used. Further, a combination of the calix derivative having the light emitting organic group and the calix derivative having the charge transporting group can be used without any limitation.

The other component of the luminescent composition of the present invention is polyvinylcarbazole (PVK). PVK
The commercially available product can be used as it is.

The content of the calix derivative in the luminescent composition of the present invention is in the range of 0.1 to 90% by weight.
Is 99.9 to 10% by weight. When the content of the calix derivative is less than 0.1% by weight, sufficient emission brightness cannot be obtained when the calix derivative is used as the light emitting material, and when the calix derivative is used as the charge transporting material, it is not sufficient. It is not preferable because the charge transport ability cannot be obtained. On the other hand, if the content is more than 90% by weight, the content of PVK is relatively lowered, and the hole transport ability of PVK itself is significantly impaired, which is not preferable. The content ratio of the calix derivative and PVK is 0.5 to 85% by weight of the calix derivative and 99.5 to 99.5% of PVK in consideration of the light emitting property and the stability during film formation.
It is preferably in the range of 15% by weight, more preferably 1 to 70% by weight of calix derivative and 99 to 30% of PVK.
It is more preferably in the range of% by weight.

The luminescent composition of the present invention may contain a known luminescent material or charge transport material. The amount of the known luminescent material or charge transporting material used varies depending on the type of the luminescent material or charge transporting material. Therefore, consider them within a range that does not impair sufficient film forming properties and luminescent properties. It may be decided as appropriate.

The known luminescent material contained in the luminescent composition of the present invention is not particularly limited. For example, naphthalene derivative, anthracene or its derivative, perylene or its derivative, polymethine type, xanthene type, coumarin type, cyanine. -Based dyes, metal complexes of 8-hydroxyquinoline or its derivatives, aromatic amines, tetraphenylcyclopentadiene or its derivatives,
Alternatively, tetraphenyl butadiene or its derivative can be used. Specifically, for example, JP-A-57
Known ones such as those described in Nos. -51781 and 59-194393 can be used.

Examples of known charge transporters contained in the luminescent composition of the present invention include pyrazoline derivatives, arylamine derivatives, stilbene derivatives and triphenyldiamine derivatives as hole transporters. As the electron transporter, an oxadiazole derivative, anthraquinodimethane or a derivative thereof, tetracyanoanthraquinodimethane or a derivative thereof, a fluorenone derivative, a diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or a derivative thereof, or the like can be used. Can be mentioned.

Specific examples of these compounds are described in JP-A-63-
70257, 63-175860 and JP-A 2-1.
No. 35359, No. 2-135361, No. 2-2099.
88, No. 3-37992, and No. 3-152184.

Among the above-mentioned charge transporters, the hole transporter is preferably a triphenyldiamine derivative, the electron transporter is preferably an oxadiazole derivative, or a metal complex of 8-hydroxyquinoline or a derivative thereof. As a transporter, 4,4′-bis (N (3-methylphenyl) -N-phenylamino) biphenyl is
2- (4-t-butylphenyl)-as an electron transporter
Preference is given to 1,3,4-oxadiazol, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum.

Of these, either one or both of the hole transporter and the electron transporter can be used at the same time. Each of these materials may be used alone or in combination of two or more.

Regarding the structure of an organic EL device produced by using the luminescent composition of the present invention, a luminescent layer containing the luminescent composition of the present invention is provided between a pair of electrodes, at least one of which is transparent or semitransparent. Is not particularly limited as long as it is formed,
A known structure can be adopted. For example, a structure having a pair of transparent or semi-transparent electrodes on at least one of both surfaces of a light emitting layer consisting of a light emitting body or a light emitting layer consisting of a mixture of a light emitting body and a charge transporting body, and further an anode and a light emitting body. Examples thereof include a layer in which a hole transport layer is stacked between layers, a layer in which an electron transport layer is stacked between a cathode and a light emitting layer, and a layer in which both a hole transport layer and an electron transport layer are stacked. The light emitting layer and the charge transport layer may be one layer, and
It is also possible to combine a plurality of layers. When the charge transport layer is provided between the light emitting layer formed of the light emitting composition of the present invention and the electrode, the charge transport layer may be formed using the charge transport material described above. In addition to the charge transport materials exemplified above, as the hole transport layer, pigments such as copper phthalocyanine derivative and indanthrene derivative, conductive polymers such as polyaniline derivative and polythiophene derivative, molybdenum oxide, silicon dioxide, etc. As the electron transport layer, oxides such as lithium oxide, magnesium oxide, and aluminum oxide, fluorides such as lithium fluoride and magnesium fluoride, lithium compounds such as lithium acetylacetonate, and 8-quinolinol lithium. Can be used. Next, a typical method for producing an organic EL element using the organic EL element 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 semitransparent metal oxide or a metal thin film.
A conductive metal oxide film, a semitransparent metal thin film, or the like is used as the material. Specifically, indium tin
A film (NESA or the like) formed using conductive glass made of oxide (ITO), tin oxide or the like, Au, Pt,
Ag, Cu or the like is used. As a manufacturing method, a vacuum deposition method, a sputtering method, a plating method, or the like is used.

Next, a light emitting layer containing the light emitting composition of the present invention is formed on this anode. As a forming method, a melt coating solution, a solution or a mixed solution of the luminescent composition is used, a spin coating method, a casting method, a dipping method, a bar code method, a roll coating method, a gravure coating method, a flexographic printing method, a spray coating method. It is particularly preferable to form the film by a coating method such as an inkjet printing method.

The solvent for applying the solution of the luminescent composition of the present invention is not particularly limited as long as it is a good solvent for the luminescent composition. Suitable solvents include chloroform, tetrahydrofuran, dichloroethane and chlorobenzene. Etc. can be illustrated.

The thickness of the light emitting layer is preferably 1 nm.
˜1 μm, more preferably 2 to 500 nm. To increase the current density and luminous efficiency, 5 to 200n
A range of m is preferred. In the case of forming a thin film by a coating method, it is preferable to heat and dry under reduced pressure or in an inert atmosphere at a temperature of preferably 30 to 300 ° C, more preferably 60 to 200 ° C in order to remove the solvent. desirable.

When a light emitting layer and a charge transporting layer are laminated in order to improve the charge injection efficiency, a luminescent composition of the present invention showing a hole transporting property is formed on the anode in the same manner as described above. It is formed by a film method or a known hole transporter is formed by a known method, and then the luminescent composition of the present invention exhibiting luminescent property is formed by the above-mentioned film forming method, and the electron transporting property is formed thereon. The luminescent composition of the present invention showing the above is formed by a film forming method similar to the above, or a known electron transporter is formed by a known method.

A known method for forming a film of a charge transporter is not particularly limited, but a vacuum deposition method from a powder state or a spin coating method after casting in a solution, a casting method, a dipping method, a bar code method, a roll method. A coating method such as a coating method can be used.

Regarding the thickness of the charge transport layer, at least a thickness that does not cause pinholes is required, but if it is too thick, the resistance of the device increases and a high driving voltage is required, which is not preferable. Therefore, the thickness of the charge transport layer is preferably 1 nm to 1 μm, more preferably 2 n.
m to 500 nm, particularly preferably 5 nm to 200 nm.

Next, a cathode is provided. This electrode becomes the electron injection cathode. The material is not particularly limited, but a material having low ionization energy is preferable. For example, Al, In, Mg, Ca, Li, Mg-Ag alloy,
In-Ag alloy, Mg-In alloy, Mg-Al alloy, M
A g-Li alloy, an Al-Li alloy, an Al-Ca alloy, a graphite thin film or the like is used. As a method of manufacturing the cathode, a vacuum vapor deposition method, a sputtering method, or the like is used.

[0068]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Production Example 1 Dibromo (tetrapropoxy) calix [4] arene and 4- [2- (4-boronic acid phenyl) -2-phenylvinyl], 4 '-(2,2-diphenylvinyl) biphenyl were tetrakised. Triphenylphosphine Pd (0
Value), in the presence of sodium carbonate, dimethoxyethane / E
The reaction was carried out in a tOH mixed solvent to obtain the target product (CA1) (yield 5%). M + 161 by molecular weight analysis (LC-MS)
0 was confirmed. The results are shown in Table 1. Further, elemental analysis (Table 20) was performed to confirm the structure of the compound.

Production Examples 2 to 8 CA2 to CA8 were synthesized in the same manner as in Production Example 1 except that the raw materials shown in Tables 1 to 4 were used. The results are shown in Tables 1 to 4 and Table 20.

Production Example 9 The charge transporter shown in Table 5 was reacted with tetraformyl (tetrapropoxy) calix [4] arene in tetrahydrofuran in the presence of potassium t-butoxide to obtain the desired product (yield 22 %). The results are shown in Table 5 and Table 20.

Production Examples 10 to 12 Organic EL device materials CA10 to CA12 were synthesized in the same manner as in Production Example 9 except that the raw materials shown in Tables 5 to 6 were used. The results are shown in Tables 5 to 6 and Table 20.

Production Example 13 Tribromo (hexapropoxy) calix [6] arene and carbazole were reacted with a copper catalyst in nitrobenzene to obtain the desired product (yield 19%). The results are shown in Tables 7 and 20.

Production Example 14 Organic EL device material CA14 was synthesized in the same manner as in Production Example 13 except that the raw materials shown in Table 7 were used. The results are shown in Tables 7 and 20.

Production Example 15 The charge transporter shown in Table 8 and (dihydroxy-dipropoxy) calix [4] arene were reacted with NaH in dimethylformamide to obtain the desired product (yield 10%). The results are shown in Tables 8 and 20.

Production Example 16 The target compound was obtained by reacting the luminescent material shown in Table 8 with monocarboxy (octapropoxy) calix [7] arene in chloroform (yield 35%). The results are shown in Tables 8 and 20.

Production Example 17 The target compound was obtained by reacting the luminescent material shown in Table 9 and tetrahydroxy-tetramethoxy-resorcy [4] arene with NaH in dimethylformamide (yield 3%). The results are shown in Table 9 and Table 20.

Production Example 18 The luminescent material shown in Table 9 and diformyl (dimethoxy) calix [4] arene were reacted in tetrahydrofuran in the presence of potassium t-butoxide to obtain the desired product (yield 10%). The results are shown in Table 9 and Table 21.

Production Examples 19-21, 25-27, 30, 3
6 In the same manner as in Production Example 18 except that the luminescent materials shown in Table 10, Table 11, Tables 13 to 15 and Table 18 were replaced with calixarene or resorcialane. In addition, TOF-MASS was used for confirmation of the molecular weight. The results are shown in Table 10,
The results are shown in Table 11, Tables 13 to 15, Table 18, Table 21 and Table 22.

Production Example 22 The phosphor shown in Table 11 and dibromocalix [4] arene were added to tetrakistriphenylphosphine Pd (0
Value), in the presence of sodium carbonate, dimethoxyethane / E
The desired product was obtained by reacting in a tOH mixed solvent (yield 2
%). 1860 using TOF-MASS for confirmation of molecular weight
Got The results are shown in Tables 11 and 21.

Production Examples 23, 24, 32, 37, 38 The same procedure as in Production Example 22 was repeated except that the luminescent materials shown in Table 12, Table 16 and Table 19 were replaced with calixarene or resorcialane. Table 12, Table 16, Table 1
9, shown in Table 21 and Table 22.

Production Example 28 The luminescent material and resorcy [4] arene shown in Table 14 were converted to Na.
The reaction was carried out in tetrahydrofuran (THF) in the presence of H to obtain the desired product (yield 1%). TOF for confirmation of molecular weight
Using MASS, 4568 was obtained. The results are shown in Tables 14 and 21.

Production Examples 29, 31, 33 to 35 The same procedure as in Production Example 28 was carried out except that the luminescent materials and resorcialane shown in Table 15, Table 16, Table 17 and Table 18 were used. The results are shown in Table 15, Table 16, Table 17, Table 18, and Table 2.
1 and Table 22.

[0084]

[Table 1]

[0085]

[Table 2]

[0086]

[Table 3]

[0087]

[Table 4]

[0088]

[Table 5]

[0089]

[Table 6]

[0090]

[Table 7]

[0091]

[Table 8]

[0092]

[Table 9]

[0093]

[Table 10]

[0094]

[Table 11]

[0095]

[Table 12]

[0096]

[Table 13]

[0097]

[Table 14]

[0098]

[Table 15]

[0099]

[Table 16]

[0100]

[Table 17]

[0101]

[Table 18]

[0102]

[Table 19]

[0103]

[Table 20]

[0104]

[Table 21]

[0105]

[Table 22]

Example 1 <Evaluation of EL characteristics> The CA18 obtained in Production Example 18 was evaluated as 0.
Chlorobenzene at a concentration of 5% by weight and PVK at 2% by weight
A coating solution was prepared by dissolving. 25 mm x 10 mm x
ITO film 150nm thick on 0.7mm glass substrate
The transparent support base is the transparent support substrate
After etching and cleaning the board, the coating solution prepared above is approx.
0.4 g of MIKASA spin coater 1H-D7
Using the glass substrate surface 60 rpm at 1500 rpm
Spin coated for seconds. This substrate is placed under a nitrogen atmosphere for 10
The solvent was removed by heating to 0 ° C. to form a thin film. This and
The content of CA18 in the formed organic thin film is 20
The amount is%. In addition, ULVAC vacuum deposition equipment EBV-
Using 6DA, 40nm calcium as the cathode, then
Aluminum is vapor-deposited with 60 nm to make an organic EL device.
It was The degree of vacuum during vapor deposition is 1 × 10 ^-6Below Torr
Met. When a DC voltage was applied to this element, 1
Luminance of 5700 cd / m at 2.5V^TwoOf blue
A surface emission was obtained. This emission is measured by a spectrophotometer
Channel Photo Detector MCPD1000: Otsuka Electronics
The maximum emission wavelength is 460n.
It was m.

Example 2 An element was prepared in the same manner as in Example 1 except that the concentration of CA18 was changed to 0.04% by weight. At this time, the content rate of CA18 in the formed organic thin film is 2% by weight. Applying DC voltage to this device 1
A blue surface emission having an emission luminance of 2400 cd / m ² was obtained at 2.5V. The maximum emission wavelength of light is 460 nm.
Met.

Example 3 In Example 1, the concentration of CA18 was 1.5% by weight and P
An element was produced in the same manner as in Example 1 except that the VK concentration was 1.5% by weight. At this time, the content rate of CA18 in the formed organic thin film is 50% by weight. When a DC voltage was applied to this element, blue surface emission with an emission luminance of 4400 cd / m ² was obtained at 12.5 V. The maximum emission wavelength of emitted light was 460 nm. Example 4 In Example 1, the concentration of CA18 was 2.8% by weight, P
An element was produced in the same manner as in Example 1 except that the VK concentration was 0.7% by weight. At this time, the content rate of CA18 in the formed organic thin film is 80% by weight. When a DC voltage was applied to this element, blue surface emission with an emission luminance of 1800 cd / m ² was obtained at 12.5 V. The maximum emission wavelength of emitted light was 460 nm.

Examples 6 to 36 Example 1 was repeated except that the compound shown in Table 23 synthesized in Preparation Examples 1 to 38 was used in place of CA18 used in Example 1.
An element was produced in the same manner as in. The results of applying a DC voltage to this element are shown in Table 23.

[0110]

[Table 23]

Comparative Example 1 Instead of CA18 used in Example 1, bis-4,4′- was used.
A device was produced in the same manner as in Example 1 except that (2,2-diphenylethen-1-yl) biphenyl was used. When a DC voltage was applied to this element, blue surface emission with an emission luminance of 1500 cd / m ² was obtained at 12.5 V. The maximum emission wavelength of emitted light was 460 nm.

Comparative Example 2 In Example 1, coumarin 6 was used as a coating solution in an amount of 0.
04% by weight, 2- (4-biphenylyl) -5- (4-t
-Butylphenyl) -1,3,4-oxadiazole was prepared in the same manner as in Example 1 except that a chlorobenzene solution containing 0.6% by weight of PVK and 2% by weight of PVK was used. When a DC voltage was applied to this element 12.
At 5 V, green surface emission with an emission luminance of 400 cd / m ² was obtained. The maximum emission wavelength of emitted light was 520 nm.

Comparative Example 3 A device was manufactured in the same manner as in Example 1 except that the concentration of CA18 was 0.001% by weight and the concentration of PVK was 2% by weight. At this time, the content rate of CA18 in the formed organic thin film is 0.05% by weight. When a DC voltage was applied to this element, blue surface emission with an emission luminance of 80 cd / m ² was obtained at 12.5 V. The maximum emission wavelength of emitted light was 460 nm. Comparative Example 4 In Example 1, the concentration of CA18 was 3.8% by weight, P
An element was manufactured in the same manner as in Example 1 except that the VK concentration was 0.2% by weight. At this time, the content rate of CA18 in the formed organic thin film is 95% by weight. When a DC voltage was applied to this device, the emission brightness was 1 at 12.5V.
A blue surface emission of 70 cd / m ² was obtained. The maximum emission wavelength of emitted light was 460 nm.

[0114]

When the luminescent composition of the present invention is used as an organic EL device material, it is possible to form a film by a coating method, and compared with a light emitting device in which a known luminescent material or charge transport material is dispersed in PVK. Excellent light emission characteristics. Therefore, the luminescent composition of the present invention is extremely useful as an organic EL device material.

Claims (2)

[Claims] 1. A calixarene derivative or a calixresorciarene derivative having a light-emitting organic group or a charge-transporting organic group, 0.1 to 90% by weight, and (2).
A luminescent composition comprising 99.9 to 10% by weight of polyvinylcarbazole. 2. A calixarene derivative or a calixresorciarene derivative having a light-emitting organic group or a charge-transporting organic group is represented by the following general formula (1) or (2): (However, in the general formulas (1) and (2), n is 3 to
Is an integer of 20, and A, B and X 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). A, B and X, which are present in plural numbers, are at least one of these groups represented by the general formula (3). -(Y) mZ (3) (wherein Y is a divalent organic group, Z is a light emitting organic group or a charge transporting organic group, and m is 0 or 1). The luminescent composition according to claim 1, which is a compound to be described.