JP2003292948A - Red luminescent material and organic electroluminescent element using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a red luminescent material that is inexpensive, can readily be processed to thin film and can be used as an organic electroluminescent element, and provide organic electroluminescent elements using the same. <P>SOLUTION: The red luminescent material comprises at least a phosphorescent substance and a compound bearing a carbazole group. In one example, the phosphorescent substance is a macromolecule bearing a benzophenone group polymer as side chains, or a copolymer from a vinyl monomer bearing the carbazole group and a vinyl monomer. The organic electroluminescent elements according to the invention contains the red luminescent material. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel red light emitting material and an organic electroluminescent device using the same.

[0002]

2. Description of the Related Art Electroluminescent devices include inorganic electroluminescent devices made of inorganic materials and organic electroluminescent devices made of organic materials. In recent years, organic electroluminescent devices have been attracting attention because they can emit high-luminance light at low voltage.

Generally, in an organic electroluminescence device, an organic thin film layer such as a hole transport layer and a light emitting layer is formed on a glass plate on which a thin film of an anode material such as indium tin oxide (ITO) is vapor deposited, and further thereon. It is made by forming a thin film of cathode material on.

Various polymer materials have been developed as hole transport materials and light emitting materials for organic electroluminescence devices. For example, as a hole transport material, a material polymerized with a derivative of triphenylamine (K.Ogino, H.Sato, et al, Macromol. Rapi
d Commun. 20, 103-106 (1999)) is known.
Polymer luminescent materials include polyfluorene-based polymers (M. Inbasekaran, E. Woo, et al, Synth. Metals, 111-
112, 397 (2000), ISMillard, ibid. 111-112, 119 (20
00)) is known. Polyvinylcarbazole has been studied as both a hole transport material and a blue light emitting material (J. Kido, et al, Appl. Phys. Lett. 63, 2627 (199
3)).

Polymers having a long conjugated system such as polyphenylene vinylene are well known (S. Doi et al Synth
etic Matels., 55-57, 4174 (1993)). However, among the polymer materials, polyphenylene vinylene is insoluble in a solvent and cannot be applied as it is. In the case where such a polymer material is insoluble in a solvent, it is necessary to synthesize a precursor, form a thin film by a spin coating method or the like, and then convert it into a target product by heat treatment, which complicates the working process.

DCM and N are used as low-molecular red light emitting materials.
Organic dye compounds such as ile Red are known (C.
W. Tang et al, J. Appl. Phys., 65,3610 (1989))
These compounds do not give a true red color, only an orange-red color. As an Eu complex (tris (1,3-
Diphenyl-1,3-propanedionate))-(1,10
-Phenanthroline) europium (III)) (Eu (TTA) 3 (ph
abbreviated as (enn)) (T. Sano, et al, Jpn. J. Appl. Phy
s., 34, 1883 (1995)) is known. Ir complex (tris (2-phenylpyridine) iridium) or Pt complex (2,3,7,8,12,13,17,18-) as a phosphorescent compound.
Octaethyl-21H, 23H-porphyrinplatinium (II) (abbreviated as PtOEP)) is known and used (Kido, Tanaka, Proceedings of Macromolecular Discussion Group, 13, 3397).
(2001)). There is also a report on a luminescent material composed of these metal complex compounds and a compound that emits phosphorescence (Japanese Patent Laid-open No. HEI-1).
No. 1-256148). However, these organic dye compounds and metal complexes are very expensive, and their price is a major obstacle to industrial use.

[0007]

The red light emitting material has the above problems. Therefore, an object of the present invention is to provide a red light emitting material which can be used for an organic electroluminescent device and which can be manufactured at low cost.

Another object of the present invention is to provide an organic electroluminescent device using such a red coloring material.

[0009]

As a result of intensive studies to achieve the above-mentioned object, the present inventor found that a specific phosphorescent substance,
It has been found that a red light emitting material containing a mixture with a compound containing a carbazole group can be used as a red light emitting material that can be used for an organic electroluminescent device at low cost and can be formed into a thin film.

The present invention has been completed after further studies based on the above findings, and provides the following red luminescent material, a method for producing a thin film containing the red luminescent material, and an organic electroluminescent device. Is.

The present invention relates to a red light emitting material containing at least a phosphor and a compound having a carbazole group. By containing such a substance, a material that emits red light can be provided.

Generally, recombination of holes and electrons produces electrically neutral molecular excitons. Emission occurs via this molecular exciton. The generated singlet excitons and triplet excitons are mixed in the generated molecular excitons,
Singlet excitons and triplet excitons are produced more in triplet excitons at a ratio of 25% to 75%. The excitons that contribute to light emission are singlet excitons, and the triplet excitons are eventually consumed as heat, and the singlet excitons with a low production rate emit light. Therefore, the energy of triplet excitons is a large loss. Therefore, in the present invention, triplet excitons are effectively utilized for light emission by containing a phosphorescent substance and a compound having a carbazole group. The color emitted at this time is
Conventionally, it emits red light, which is difficult to emit and difficult to reproduce vivid colors. In this regard, the present invention
It has a very important significance.

It is preferable that the phosphorescent material has a phosphorescent emission intensity higher than that of benzophenone. This is because it is possible to provide a light emitting material having higher emission intensity. Further, since the phosphorescence is strong, it has a clear triplet level, which means that the energy is less likely to be deactivated by heat due to the existence of an unknown level caused by impurities and the like. Therefore, energy efficiency can be improved.

The phosphor is preferably at least one selected from the group consisting of benzophenone, triphenylacetophenone, benzophenone substituted with an organic residue, and triphenylacetophenone substituted with an organic residue. By using such a phosphorescent substance, organic electroluminescence (EL) capable of obtaining red light emission can be realized.

The phosphor is a side chain of at least one selected from the group consisting of a benzophenone group, a triphenylacetophenone group, a benzophenone group substituted with an organic residue, and a triphenylacetophenone group substituted with an organic residue. It is preferable that it is a polymer. It is possible to provide a material that emits red light not only when benzophenone or the like is used for the main chain but also when a benzophenone group or the like is used for the side chain. Even when a benzophenone group or the like is used for a side chain other than the main chain, it can be used as a red light emitting material, and thus can be applied to an extremely wide range.

The compound having a carbazole group is preferably at least one selected from the group consisting of carbazole, carbazole substituted with halogen and / or organic residue. Accordingly, a material that emits red light can be provided. This is because even if a novel phosphor is discovered, the compound having a carbazole group can promote red light emission.

The compound having a carbazole group is a polymer or copolymer using at least one selected from the group consisting of vinylcarbazole, vinylcarbazole substituted with halogen and / or an organic residue as a monomer. Preferably there is. When forming a thin film containing a red light emitting material, the thin film formed earlier was dissolved in the solvent of the polymer solution to be formed later, and a clean multilayer laminated thin film could not be formed. Therefore, by polymerizing the polymer or copolymer in the solution of the red light emitting material, a clean multilayer thin film can be formed.

The compound having a carbazole group comprises at least one selected from the group consisting of vinylcarbazole, vinylcarbazole substituted with halogen and / or an organic residue, and a vinyl monomer as a monomer. It is preferable that they are united. This makes it easy to form a thin film of the red light emitting material.

The vinyl monomer is preferably an acrylic vinyl monomer substituted with an unsaturated hydrocarbon group. As a result, it has at least two double bonds of the vinylcarbazole group and at least two double bonds of the acrylic vinyl monomer substituted with the unsaturated hydrocarbon group. By irradiating the thin film portion which is gelled by providing the double bond in this way, the thin film is cured and can be insolubilized in an organic solvent such as toluene. This makes it possible to achieve high quality multilayer thin film lamination. Further, a photomask having a predetermined opening pattern, covering the upper portion of the formed thin film, a portion which is insolubilized by light irradiation and a portion which is not insolubilized by light irradiation are selectively formed, A portion which is not insolubilized in the solvent is formed. Since the portion which is not insolubilized by the solvent is dissolved by the solvent, it can be removed by etching to form the opening pattern shape of the mask.

The acrylic vinyl monomer substituted with an unsaturated hydrocarbon group is vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, crotyl acrylate, crotyl methacrylate, cyclopentadienyl acrylate, cyclopentadienyl methacrylate. It is preferably at least one selected from vinyl acrylate and vinyl methacrylate. This can promote the lamination of high-quality multilayer thin films. Further, the red light emitting material can be manufactured very easily.

The compound having a carbazole group is a polymer or copolymer using at least one selected from the group consisting of ethynylcarbazole, ethynylcarbazole substituted with halogen and / or an organic residue as a monomer. Preferably there is. This makes it possible to manufacture the red light emitting material very easily.

The compound having a carbazole group is at least one selected from the group consisting of ethynylcarbazole and ethynylcarbazole having a halogen and / or an organic residue as a substituent, and an ethynyl compound having a substituent other than a carbazole group. It is preferably a copolymer using a monomer as a monomer. By using such a conductive compound, it is possible to provide a red light emitting material that exhibits an extremely bright red color.

The compound having a carbazole group preferably has a number average molecular weight of 1,000 to 1,000,000. By using the polymer material in this range, it is possible to stack high-quality multilayer thin films at low cost.

The organic residue is selected from the group consisting of a hydrocarbon group having 1 to 20 carbon atoms, an ether group having 1 to 20 carbon atoms, an ester group having 1 to 20 carbon atoms, a carbonyl group, a nitrile group and an amino group. It is preferable that at least one selected from the above. As a result, an unsaturated hydrocarbon group or the like can be used in addition to the alkyl group, and a commonly available raw material can be used, so that it is possible to stack a high-quality multilayer thin film at low cost.

The present invention relates to a thin film of a red light emitting material, which comprises the red light emitting material according to any one of claims 1 to 13. Claims 1 to 1
By using the red light emitting material of No. 3, it is possible to form a thin film of the red light emitting material.

The present invention is characterized by emitting blue light by providing a blue light emitting material, a green light emitting material, and a red light emitting material according to any one of claims 1 to 13. The present invention relates to an organic electroluminescence device. Thereby, a brighter full-color organic electroluminescent device can be provided. Further, conventionally, since the emission intensity of red is low, an organic electroluminescence device that emits yellowish white light and an organic electroluminescence device with low emission intensity that suppresses blue and green emission in accordance with red emission are provided. However, since the present invention can provide a red light emitting material that emits bright red light, it is possible to provide an organic electroluminescent element that emits white light with high emission intensity by combining the three primary colors.

In the present invention, the organic electroluminescent device has at least a light emitting layer between an anode and a cathode which face each other.
A layer comprising at least one layer of an organic thin film, wherein the light emitting layer contains the light emitting material according to at least one of claims 1 to 13.
Or the organic electroluminescent element according to any one of 18). As a result, an organic electroluminescent device that emits red light can be provided. Further, it is possible to provide an organic electroluminescent device in which red and other colors are combined.

[0028] The light emitting layer is an organic electroluminescent device characterized by being insolubilized in a solvent by photoreaction. Thereby, the pattern shape of the film formation can be changed to a desired one.

The light emitting material according to the present invention can be formed into a desired thin film to manufacture an element. Especially when at least one of the phosphorescent material which is a contained component and the compound having a carbazole group is a polymer compound, the spin coating method, the dip coating method and the dip coating method are not used when forming the light emitting material of the present invention. A film can be easily formed by a simple coating method such as a coating method or an inkjet printing method.
Furthermore, the film-forming method by such a coating method has a large area,
It is possible to reduce production cost and processability.

The luminescent material of the present invention is 254 nm or 36
Although it does not emit light at all even when excited by 5 nm ultraviolet light, it emits red light with high brightness and no color mixture when energized after the device is manufactured.

[0031]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.

Phosphorescent Substance The phosphorescent substance used in the present invention is a phosphorescent substance having a phosphorescent emission intensity higher than that of benzophenone. Here, the phosphorescence intensity is Au for phosphors,
A light emitting device is manufactured by providing an anode and a cathode of Pt, Ni or the like,
A direct current voltage of about 10 V is applied to cause light emission, and the peak emission intensity due to phosphorescence in this emission spectrum is indicated.

As the phosphor, both low molecular weight compounds and high molecular weight compounds can be used.

Examples of the low molecular weight phosphorescent substance include benzophenone, triphenylacetophenone, benzophenone having a halogen or an organic residue as a substituent, and triphenylacetophenone. These may be used alone. Further, two or more kinds may be mixed and used.

Further, as a phosphorescent substance, benzophenone,
Triphenylacetophenone, and further, a high-molecular polymer having a structure in which a hydrocarbon polymer such as polyethylene, polypropylene or polyacetylene is substituted for benzophenone having a halogen or an organic residue as a substituent, triphenylacetophenone, etc. They may be used alone or in a mixture of two or more.

Examples of the halogen as the above substituent include fluorine, chlorine, bromine, iodine and the like.

The organic residue as the above-mentioned substituent is a hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, an ether group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, and 1 to 2 carbon atoms.
There may be mentioned 0, particularly 1 to 10 ester groups, carbonyl groups, nitrile groups and amino groups. These substituents may be present on any benzene ring of benzophenone or triphenylacetophenone, and the number of substituents is 1 to 5, especially 1 to 2 per molecule of benzophenone or triphenylacetophenone. Preferably. When two or more substituents are present, they may be the same or different.

The above-mentioned hydrocarbon group is a linear, branched or cyclic saturated or unsaturated hydrocarbon group,
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group,
An alkyl group such as an ethylhexyl group and an octyl group is preferable.

Examples of the ether group include groups represented by the formula -OR ¹ . In the formula, examples of R ¹ include the hydrocarbon groups having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms. Among these R ¹ , an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, an ethylhexyl group and an octyl group is particularly preferable.

The ester group has the formula --COOR ²
The group represented by can be mentioned. In the formula, R ² can be exemplified by the hydrocarbon groups having 1 to 20 carbon atoms, especially 1 to 10 carbon atoms. Among these R ² , an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, an ethylhexyl group and an octyl group is particularly preferable.

Further, as the phosphorescent substance of the polymer compound,
The above benzophenone group, triphenylacetophenone group, a benzophenone group having an organic residue as a substituent,
Examples thereof include polymers having a side chain of at least one selected from the group consisting of triphenylacetophenone groups having an organic residue as a substituent.

The number average molecular weight of such a polymer is
It can be selected from a wide range, but generally, the number average molecular weight is about 1,000 to 1,000,000, particularly 5,000 to
500,000 polymers are preferred.

The polymer is selected from the group consisting of benzophenone, triphenylacetophenone, benzophenone having an organic residue as a substituent, and triphenylacetophenone having an organic residue as a substituent in the main chain made of hydrocarbon. The polymer may be a polymer in which only at least one side chain (hereinafter referred to as "specific side chain") is bound, or the main chain composed of a hydrocarbon has the above-mentioned specific side chain and other It may be a copolymer in which side chains (for example, phenyl groups) are mixed and bonded.

Among them, a polymer in which a part of the phenyl group which is the side chain of polystyrene is substituted with the above-mentioned specific side chain, particularly a benzophenone group can be preferably used. In such a polymer, the abundance of the specific side chain is 50
It is preferably at least mol%, particularly preferably at least 60 mol%.

To produce such a polymer, for example,
Method of Friedel-Crafts acylation of polystyrene and an acyl halide compound comprising a halogen and a residue obtained by removing the phenyl group from the structure of the specific side chain in the presence of a Lewis acid such as an aluminum chloride catalyst Etc. can be illustrated. An example of the production example is described in Synthesis Example 3 below.

Among the above-mentioned phosphors of low molecular weight and high molecular weight compounds, benzophenone, triphenylacetophenone, and polymers in which a part of the phenyl group which is a side chain of polystyrene is substituted with a benzophenone group are particularly preferable.

Compounds Containing Carbazole Group Examples of the compound having a carbazole group used in the present invention include the following compounds, which may be used either alone or in combination with each other.
A mixture of two or more species can be used. (a) at least one selected from the group consisting of carbazole and carbazole having a halogen and / or an organic residue as a substituent, (b) vinylcarbazole and a vinylcarbazole having a halogen and / or an organic residue as a substituent At least one selected from the group consisting of a polymer or a copolymer using as a monomer, (c) at least one selected from the group consisting of vinylcarbazole and vinylcarbazole having a halogen and / or an organic residue as a substituent. A copolymer of one type and another vinyl monomer,
(d) a polymer or copolymer using as a monomer at least one selected from the group consisting of ethynylcarbazole and ethynylcarbazole having a halogen and / or an organic residue as a substituent, (e) ethynylcarbazole and Examples thereof include a copolymer of at least one selected from the group consisting of ethynylcarbazole having a halogen and / or an organic residue as a substituent and an ethynyl compound monomer.

In the present specification, the ethynyl compound monomer means a compound having an ethynyl group (HC≡C-).

For example, p-fluorophenylacetylene,
p-chlorophenylacetylene, p-bromophenylacetylene, p-iodophenylacetylene, p-cyanophenylacetylene, p-acetoxyphenylacetylene, p-acetophenylacetylene, biphenylacetylene, 1-ethynyl-4-phenylbenzene, 1-ethynyl -4,4'-Bromophenylbenzene, 1-ethynylnaphthalene, 1-ethynyl-8
-Fluoronaphthalene, 1-ethynyl-4-chloronaphthalene, 1-ethynyl-8-bromonaphthalene, 1-ethynyl-4-hexylnaphthalene, 1-ethynyl-4-octylnaphthalene, 1-ethynyl-4-dodecylnaphthalene, 9 -Ethynylanthracene, 9, -ethynyl-4-chloroanthracene, 9-ethynyl-4-octylanthracene, 2-ethynylphenanthrene, 2-ethynylfluorene, 2-ethynyl-9,9-dioctylfluorene, 2- Examples thereof include ethynyl-9,9-dioctyl-6-bromofluorene, 1-ethynylperylene, 1-ethynylrubrene and the like.

When the compound having a carbazole group used in the present invention is a polymer, its number average molecular weight is about 1,00.
0 to 1,000,000, especially 5,000 to 500,0
The range is 00.

When the compound having a carbazole group is a copolymer, the content of the constituent unit having a carbazole group, which is a monomer, in the copolymer is 50 mol% or more, particularly 6%.
It is preferably 0 mol% or more.

Examples of the halogen which may be substituted on the above carbazole, vinylcarbazole or ethynylcarbazole include fluorine, chlorine, bromine and iodine, but bromine is preferable.

The organic residue which may be substituted on the above carbazole, vinylcarbazole or ethynylcarbazole is a hydrocarbon group having 1 to 20 carbon atoms, an ether group,
Examples thereof include ester group, carbonyl group, nitrile group and amino group.

The organic residue may be a hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, or 1 to 20 carbon atoms, particularly 1 to 1 carbon atoms.
Examples thereof include an ether group having 0, an ester group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, a carbonyl group, a nitrile group, and an amino group.

At least one substituent selected from the group consisting of these halogens and organic residues, particularly halogen, a hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, and 1 to 10 carbon atoms.
At least one substituent selected from the group consisting of 20, particularly an ether group having 1 to 10 carbon atoms, an ester group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms, a carbonyl group, a nitrile group and an amino group is any of the carbazole skeletons. May be present on the benzene ring, and the number of the substituents is preferably 1 to 5, particularly 1 to 2 per molecule of carbazole, vinylcarbazole or ethynylcarbazole.
When two or more substituents are present, they may be the same or different.

The above hydrocarbon group is a linear, branched or cyclic saturated or unsaturated hydrocarbon group,
Methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, pentyl group, isopentyl group,
An alkyl group such as an ethylhexyl group and an octyl group is preferable.

The ether group is a group represented by the formula --OR ¹ . In the formula, R ¹ is the above-mentioned carbon number 1
-20, especially 1-10 hydrocarbon group etc. can be illustrated. Among these, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, an ethylhexyl group and an octyl group is particularly preferable.

The ester group has the formula --COOR ²
Is a group represented by. In the formula, R ² may be the hydrocarbon group having 1 to 20 carbon atoms, particularly 1 to 10 carbon atoms. Among these, an alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a pentyl group, an isopentyl group, an ethylhexyl group and an octyl group is particularly preferable.

<Component (a)> In the above component (a), at least one selected from the group consisting of carbazole and carbazole having a halogen and / or an organic residue as a substituent is a known compound, or It can be synthesized by a known method.

<Component (b)> In the above component (b), at least one selected from the group consisting of vinylcarbazole and vinylcarbazole having a halogen and / or an organic residue as a substituent is a known compound. Alternatively, it can be synthesized by a known method.

A polymer of a single monomer selected from the group consisting of vinylcarbazole optionally containing at least one selected from the group consisting of halogen and an organic residue as a substituent of the above (b) or a copolymer of a plurality of monomers. The polymer can be produced, for example, by ordinary radical polymerization.

Further, a homopolymer of vinylcarbazole substituted with halogen or a copolymer with vinylcarbazole can be prepared by adding halogen to a solution of polyvinylcarbazole, as shown in Synthesis Example 1 of Example. It can also be produced by halogenating.

<Component (c)> In the component (c), at least one selected from the group consisting of vinylcarbazole and vinylcarbazole having a halogen and / or an organic residue as a substituent is the same as the above component (b). As explained.

As the other vinyl monomer in the component (c), a wide range of vinyl monomers can be used.
An acrylic vinyl monomer having an unsaturated hydrocarbon group is preferable from the viewpoint of curing the thin film by light irradiation for the purpose of stacking the thin films as described below.

As the unsaturated hydrocarbon group, for example, an unsaturated hydrocarbon group having 2 to 5 carbon atoms, particularly a vinyl group,
Examples include allyl group, crotyl group, cyclopentadienyl group and the like.

Examples of the acrylic vinyl monomer having an unsaturated hydrocarbon residue include acrylic acid esters and methacrylic acid esters having the above unsaturated hydrocarbon group in the ester moiety, such as vinyl acrylate, vinyl methacrylate, and the like. Examples thereof include allyl acrylate, allyl methacrylate, crotyl acrylate, crotyl methacrylate, cyclopentadienyl acrylate, cyclopentadienyl methacrylate and the like. Of these, vinyl acrylate and vinyl methacrylate are particularly preferable.

In the above component (c), at least one selected from the group consisting of vinylcarbazole or vinylcarbazole having a halogen and / or an organic residue as a substituent and an acrylic vinyl having the above unsaturated hydrocarbon residue. In the copolymer with the monomer, the content of the acrylic vinyl monomer having an unsaturated hydrocarbon residue is 50 mol% or less, preferably 40 mol% or less.

To produce such a copolymer, polymerization or copolymerization may be carried out by the above-mentioned method.

<Component (d)> In the component (d), at least one selected from the group consisting of ethynylcarbazole and ethynylcarbazole having a halogen and / or an organic residue as a substituent is a known compound. Alternatively, it can be synthesized by a known method.

At least one selected from the group consisting of ethynylcarbazole as the component (d) and ethynylcarbazole having a halogen and / or an organic residue as a substituent.
The production of a polymer or copolymer using a seed as a monomer can be carried out in the same manner as the above known method.

<Component (e)> In the above component (e), at least one selected from the group consisting of ethynylcarbazole and ethynylcarbazole having a halogen and / or an organic residue as a substituent is the above component (d). Is as described above.

In the above-mentioned component (e), the above-mentioned ones can be used as the ethynyl compound monomer.

In the above component (e), the ethynyl compound is a copolymer of at least one selected from the group consisting of ethynylcarbazole and ethynylcarbazole having halogen and / or an organic residue as a substituent. The monomer is preferably present in an amount of 50 mol% or less, particularly 40 mol% or less. The production of such a copolymer can be carried out in the same manner as the above-mentioned known method.

Among the above-mentioned compounds having a carbazole group, brominated polyvinylcarbazole, poly-N-vinylcarbazole, 9- (2-ethylhexyl) -3-ethynylcarbazole polymer, N-vinylcarbazole and vinyl methacrylate Polymers and the like are preferred.

Red Light-Emitting Material and Thin Film Thereof The red light-emitting material of the present invention contains a mixture of the phosphor (I) and the compound (II) having a carbazole group.

In the red light emitting material, the amounts of the phosphorescent substance (I) and the compound (II) having a carbazole group can be appropriately selected from a wide range, but generally, the phosphorescent substance (I) and the carbazole group are generally used. The compound (II) having
It is preferably used in a ratio of 0 to 80, particularly 30 to 70.

The red light emitting material of the present invention can be manufactured by various methods.

When either one or both of the compound having a carbazole group and the phosphorescent substance is a polymer compound, a spin coating method, a bar coating method, a dip coating method, a flow coating method, a screen printing method, an ink jet printing method. The film can be formed by a simple method such as a method.

When both the compound having a carbazole group and the phosphorescent substance are low molecular weight compounds, a thin film can be formed by a vacuum vapor deposition method.

In particular, the luminescent material of the present invention has a high solvent solubility and is dissolved in various solvents to obtain a thin film-forming coating liquid. From the coating liquid, a spin coating method, a bar coating method, a dip coating method,
A thin film can be easily formed by a simple coating method such as a flow coating method, a screen printing method, or an inkjet printing method.

As the solvent, ketones such as acetone and methyl ethyl ketone, ethers such as dibutyl ether and tetrahydrofuran, ethyl acetate, butyl acetate, 2
-Esters such as ethyl ethylhexanoate, amides such as formamide, N, N-dimethylformamide, N, N-dimethylacetamide, aliphatic hydrocarbons such as hexane, heptane, octane and cyclohexane, benzene, toluene, xylene, etc. Aromatic hydrocarbons, chloroform, dichloromethane, halogenated hydrocarbons such as 1,2-dichloroethane, amide compounds represented by N, N-dimethylacetamide, N, N-dimethylformamide, 1-methoxy-2-propanol, Alcohols such as methoxyethanol and phenoxyethanol are available. It is also possible to use a mixture of these solvents.

The molecular weight of the luminescent material used, the kind of the substituent,
The best solvent is selected depending on the structure and the like. The thin film-forming coating liquid may have various viscosities, but since the solution viscosity differs depending on the coating method, it is necessary to prepare a solution having a viscosity suitable for the coating method.

After selecting and dissolving these optimum solvents, a thin film can be prepared by the above method and dried at room temperature or under heating under normal pressure or reduced pressure to prepare a thin film having an arbitrary thickness. The drying conditions can be appropriately selected depending on various conditions such as the compound to be used and the solvent, but in general,
The pressure during drying can be atmospheric pressure or reduced pressure.

Further, the film thickness of the thin film after drying can be appropriately selected according to the element used and the like.

A known organic fluorescent material may be added to the red light emitting material of the present invention to adjust the emission color. A typical example of the organic fluorescent material is coumarin as a green fluorescent material.
6. Perylene and rubrene are used as blue fluorescent materials such as quinacridone, and europium diketone complex is used as red fluorescent materials, but are not limited to these compounds.

The amount of these organic fluorescent materials to be used varies depending on the compound, but is 5% or less, especially 0. 0%, based on the total weight of the phosphor of the present invention and the compound having a carbazole group.
It is about 001 to 5%. The addition of 0.001% or more improves the emission efficiency, but if it exceeds 5%, the emission efficiency tends to decrease due to concentration quenching. It is preferably in the range of 0.01 to 3%.

The above organic fluorescent material can be added to the light emitting material of the present invention by various methods. For example, the above organic fluorescent material is added to the thin film forming coating solution and dissolved to form a thin film. An example of the method for forming

If necessary, the light emitting material of the present invention can be used as a host material and doped with a triplet light emitting material. As the triplet light emitting material, for example, an iridium complex or a platinum complex is used. An iridium complex or a porphyrin platinum complex having phenylpyridine, thiophenylpyridine, or a derivative thereof as a ligand is used as a ligand, but is not particularly limited to these compounds.

The amount of these triplet light emitting materials used varies depending on the compound, but is 10% by weight or less based on the total weight of the phosphor of the present invention and the compound having a carbazole group.
Particularly, it is about 0.01 to 10% by weight. 0.01% by weight
By adding the above, the luminous efficiency is further improved, and when it exceeds 10% by weight, the luminous efficiency is lowered due to concentration quenching. It is preferably in the range of 0.05 to 5% by weight.

Furthermore, 2- (4-t-butylphenyl) -5
-(4-biphenyl) -1,3,4-oxadiazole,
2,5-di (1-naphthyl) -1,3,4-oxadiazole or 2,5-di (1-naphthyl) -1,3,4-
An electron transfer agent such as oxadiazole is added. When the electron transfer agent is used, the amount used is 10 to 90% by weight, particularly 20 to 8% by weight based on the compound having a carbazole group.
It is preferably 0% by weight.

<Solvent insolubilization> When a thin film of the copolymer of the present invention is produced and an attempt is made to further laminate a thin film on it, when laminating by a usual method, the previously produced thin film will be formed later. It dissolves in the solvent of the polymer solution, and a clean multilayer thin film cannot be formed. In order to solve this problem, a photopolymerization initiator is added to the solution of the red light emitting material,
By irradiating the formed thin film with light, it can be cured and insolubilized in a solvent.

More specifically, as the compound (I) having a carbazole group, at least a component (c) selected from the group consisting of vinylcarbazole and vinylcarbazole having a halogen and / or an organic residue as a substituent is selected. A copolymer of one and an acrylic unsaturated vinyl monomer having an unsaturated hydrocarbon residue is used. At that time, the content of the acrylic unsaturated vinyl monomer having an unsaturated hydrocarbon residue is preferably in the range of 10 to 30 mol%, and 1
The range of 5 to 30 mol% is more preferable.

A thin film is formed by a coating method such as spin coating using the coating solution for forming a thin film containing the red light emitting material of the present invention containing the above copolymer (component (c)) and a phosphor. The thin film is dried if necessary, and then the thin film is cured by irradiation with light. By this method, high quality multi-layer thin film stacking can be achieved.

Here, the light irradiation mainly means the irradiation of ultraviolet rays, but it is not limited to ultraviolet rays and includes visible light. Particularly preferable light is 200 to 450 nm,
Preferably, ultraviolet rays of 240 to 380 nm can be exemplified.
The time of light irradiation is not limited and can be appropriately selected depending on various conditions such as the thickness of the thin film to be produced, the compound used and the solvent, but is usually 5 seconds to 1 hour, preferably 10
For example, seconds to 50 minutes can be exemplified.

The solvent-insolubilized thin film is not dissolved by the solvent of the solution even if a solution of the light-emitting material of the present invention or another material is applied onto the thin film. It is possible to manufacture a layered structure having a thickness.

Further, by applying the above-mentioned solvent insolubilization method,
Pattern formation can also be performed. For example, when a photomask having a predetermined opening pattern was covered over the produced thin film of the present invention and irradiated with light, the solvent was selectively insolubilized by light irradiation and the solvent was not insolubilized because light was not irradiated. When a portion is formed and the portion which is not insolubilized with the solvent is removed by etching with a solvent, a pattern corresponding to the opening pattern shape of the mask can be formed.

Examples of the photopolymerization initiator usable in the present invention include carbonyl compounds such as aromatic ketones such as benzophenone and thioxanthone, acetophenone and 2-
Hydroxy-2-methyl-propiophenone, 2,2-
Acetophenones such as dimethoxy-2-phenylacetophenone and benzoin ether; diketones such as benzyl and methylbenzoylformate; acylphosphine oxides such as 2,4,6-trimethylbenzoylphosphine oxide; and sulfur compounds such as tetramethylthiuram disulfide. , Organic peroxides such as benzoyl peroxide, and azo compounds such as azobisisobutyronitrile. Preferred examples include acetophenones and diketones.

When a photopolymerization initiator is used, the photopolymerization initiator absorbs light to generate radicals, so that the type of light source and the absorption region of the compound are well matched, and the curing rate is high. It is preferable to select it in consideration of good compatibility with the polymer solution and low cost. The amount of the photopolymerization initiator used is about 0.5 to 20%, preferably 1 to 10%, based on the copolymer.

If necessary, a crosslinking auxiliary agent can be used in order to accelerate the curing speed and enhance the adhesion to the substrate. As a crosslinking aid, unsaturated hydrocarbon residue, azide group,
A polyfunctional monomer having an azo group, a nitrile group, a cinnamic acid group, or the like is used. Specific examples thereof include a bifunctional styrene derivative, a bifunctional vinyl ether, an aromatic divinyl compound, an aromatic bisdiazide, and diazonaphthoquinone. Preferably, divinylbenzene, diallyl phthalate, 3,3'-diazidophenylsulfolane, 4,
4'-diazide-2,2'-dimethoxybiphenyl and the like. The amount of the crosslinking aid used can be appropriately selected from a wide range, but is generally 0.1 to 10 wt% with respect to the photopolymerization initiator.
%, Particularly preferably 0.5 to 5 wt%.

Organic Electroluminescent Device Next, the structure of the organic electroluminescent device of the present invention will be described. The organic electroluminescent element of the present invention has a structure in which one or more organic thin film layers including a light emitting layer are laminated between an anode and a cathode, and the organic thin film contains the red light emitting material of the present invention.

For example, a structure in which a substrate / anode / light emitting layer / cathode is sequentially stacked, a structure in which a substrate / anode / hole transport layer / light emitting layer / cathode are sequentially stacked, substrate / anode / buffer layer / light emitting layer / Examples thereof include a structure in which a cathode is sequentially stacked, a structure in which a substrate / anode / hole transport layer / buffer layer / light emitting layer / cathode are sequentially stacked.

The substrate is preferably a glass plate or a plastic sheet, for example, a highly transparent plastic sheet such as polycarbonate, polystyrene, polymethacrylate or nylon.

The anode supplies holes to the hole transport layer, the light emitting layer, etc., and is formed on a substrate such as glass.
The anode material used in the present invention is not particularly limited, and specific examples thereof include conductive metal oxides such as indium tin oxide (ITO) and tin oxide, and metals such as gold, silver and platinum. Further, a commercially available glass with ITO can be used. Commercially available glass with ITO is usually used after being washed with a detergent, a solvent, or a UV ozone irradiation device or a plasma irradiation device.

As a hole injecting layer, a hole injecting agent (mixture of PEDOT / PSS, trade name Baytron P) manufactured by Bayer was used.
It can also be used as a thin film of 0 to 100 nm.

The hole-transporting layer used in the present invention is not particularly limited, and any of those generally used as a hole-transporting material can be used. However, from the viewpoint of workability, a thin film can be formed by a coating method. What is possible is preferable. For example, polymer materials such as polyamide, polythiophene, and triphenyldiamines are preferably used.

In addition, the organic electroluminescent device according to the present invention is
It is preferable to form a buffer layer between the light emitting layer and the anode or between the light emitting layer and the hole transport layer in order to improve the coating characteristics of the light emitting layer during film formation and form a uniform thin film. .

As the buffer layer, an organic solvent-soluble metal complex is used, and preferably an organic solvent-soluble low molecular weight organic metal complex is used.

The cathode supplies electrons to the light emitting layer, and the cathode material used in the present invention is not particularly limited, and any commonly used material may be used. Specific examples thereof include metals such as Mg, Ag, Ca and Al and alloys thereof, for example, Mg-Ag alloy and Mg-A.
1 alloy, LiF, and other compounds.

In the organic electroluminescent device of the present invention, the method of forming each organic thin film layer is not particularly limited, and spin coating, bar coating, dip coating, flow coating, screen printing, etc. are commonly used. The film can be easily formed by various methods. Here, when a laminated structure is produced by a coating method, when the upper layer is formed,
Care must be taken not to dissolve the solvent in the lower layer by using the solvent-insolubilized thin film or by using a different solvent.

The organic electroluminescent element of the present invention can also emit white light by further including a blue light emitting material and a green light emitting material in addition to the red color forming material of the present invention. For example, the red light emitting material of the present invention may be mixed with a blue light emitting material and a green light emitting material, and an organic thin film layer containing the blue light emitting material and the green light emitting material may be newly provided and used. .

As the blue light emitting material and the green light emitting material, materials known in the field of organic electroluminescent devices can be appropriately selected from a wide range.

[0112]

EXAMPLES Next, the present invention will be described more specifically by way of examples, but the present invention is not limited to the description of the following examples.

Synthesis Example 1 Synthesis of brominated polyvinylcarbazole 2.0 g of polyvinylcarbazole (Wako, reagent having a molecular weight of 10,000) was placed in a 500 ml three-necked flask containing a rotor, and 200 ml of chloroform was added and dissolved in a nitrogen atmosphere. . A solution prepared by dissolving 2 g of bromine in 20 ml of chloroform was added dropwise to a 50 ml dropping funnel. 1
After stirring for 5 hours, a 5% aqueous solution of sodium carbonate was added, the mixture was separated with a separating funnel, washed with water, and the chloroform solution was dried with anhydrous sodium sulfate. Chloroform was removed with an evaporator to obtain a powder. It was dissolved in THF and added to a solution of methanol / water = 3/1 to obtain a white precipitate. After filtration and drying, 2.5 g of white powder was obtained.

Since the amount of bound bromine in the obtained brominated polyvinylcarbazole was 62.5 mol%, it was found that a copolymer of vinylcarbazole and brominated vinylcarbazole was formed.

Synthesis Example 2 9- (2-ethylhexyl) -3
Polymerization of ethynylcarbazole In a 100 ml flask containing a rotor was added 1 g of 9- (2-ethylhexyl) -3-ethynylcarbazole (3.1
5 mmol) was added and the atmosphere was sufficiently replaced with nitrogen. In a nitrogen atmosphere, 50 ml of dimethylformamide as a solvent and 10 mg of [Rh (norbornadiene) Cl] 2 as a catalyst were added.
(0.022 mmol) and 222 mg (2.2 mmol) of triethylamine as a co-catalyst were added, and the mixture was stirred at 30 ° C. for 2 hours.
Polymerization was carried out by stirring for a time. After the completion of the polymerization, it was poured into 500 ml of methanol to obtain a powdery polymer. After filtering, washing with methanol, and vacuum drying at 50 ° C. for 3 hours. 0.9 g
To give an orange polymer. The polymerization yield was 90%. The number average molecular weight was 170,000.

Synthesis Example 3 Synthesis of Partially Benzoylated Polystyrene 2 g of polystyrene (degree of polymerization 3000) and 1.3 g of anhydrous aluminum chloride were dissolved in 100 ml of carbon disulfide in a 300 ml three- necked flask containing a rotor under a nitrogen atmosphere. Using a dropping funnel, 1.7 g of benzoyl chloride was dissolved in 50 ml of carbon disulfide and added dropwise. The mixture was reacted under reflux for 3 hours. 50 ml of water containing 50 ml of chloroform and 2.5 ml of concentrated hydrochloric acid was added and stirred. After separating the organic layer, the solvent was distilled off to obtain 3.4 g of a pale yellow powder.

As a result of elemental analysis, a polymer in which 70 mol% of polystyrene phenyl groups were benzoylated, that is,
It was found that the polymer has a benzophenone group and a phenyl group in the side chain.

Synthesis Example 4 Synthesis of Copolymer of N-Vinylcarbazole and Vinyl Methacrylate 12 g of N-vinylcarbazole was added to a 300 ml flask.
(63 mmol) and 2.7 g of vinyl methacrylate (24
mmol) and 0.5 g of azobisisobutyronitrile, and 240 ml of toluene was added and dissolved. After sealing, the mixture was allowed to stand in an atmosphere of 60 ° C. for 48 hours for copolymerization.
It was poured into 1000 ml of methanol, filtered, washed with methanol, and vacuum dried at 50 ° C. to obtain 14.4 g (yield 98.
%) White powder was obtained.

As a result of the analysis, the vinyl group of N-vinylcarbazole and the methacrylic group of vinyl methacrylate were polymerized,
It was found to be a copolymer in which the vinyl group of vinyl methacrylate exists as a side chain. The number average molecular weight was 15,000. The content of N-vinylcarbazole in the copolymer was 82%.

Example 1 An organic electroluminescent device was produced as follows. A hole-injecting material (PED) manufactured by Bayer Co., Ltd. is placed on a commercially available glass with ITO (15 Ω / □ or less; manufactured by Central Glass Co., Ltd.) that has been washed.
An equal volume of OT / PSS mixture, trade name Baytron-P)
A solution diluted with -methoxy-2-propanol was used for spin coating at 3000 rpm for 25 seconds. 1
It was dried under reduced pressure at 20 ° C. for 1 hour.

Then, poly-N-vinylcarbazole 50 was added.
mg, 2- (4-t-butylphenyl) -5- (4-biphenyl) -1,3,4-oxadiazole 40 mg, triphenylacetophenone 50 mg are dissolved in toluene 5 ml and a 20 micron membrane filter is used. And filtered to obtain a light emitting layer solution. The solution was spin-coated at a rotation speed of 2000 rpm and vacuum dried at 50 ° C. for 30 minutes.

Next, using a vacuum vapor deposition device, L was used as a cathode.
About 10 angstrom of iF and 1500 angstrom of Al were vapor-deposited.

The light emitting device thus produced was sealed with epoxy resin using a cover glass containing CaO under nitrogen. When a luminescent brightness was measured by applying a DC voltage, red luminescence with a brightness of 11 cd / m ² was exhibited at a driving voltage of 13V. The emission spectrum is shown in FIG.

Example 2 An organic electroluminescent device was produced as follows. Instead of 2- (4-t-butylphenyl) -5- (4-biphenyl) -1,3,4-oxadiazole used in Example 1, 2,5
2-di (1-naphthyl) -1,3,4-oxadiazole
A light emitting device was produced in the same manner as in Example 1 except that 0 mg was used. When a luminescent brightness was measured by applying a DC voltage, red luminescence with a brightness of 12 cd / m ² was exhibited at a driving voltage of 13V.

Example 3 An organic electroluminescent device was produced as follows. Instead of the poly-N-vinylcarbazole used in Example 1, the brominated poly-N-vinylcarbazole shown in Synthesis Example 1 was used.
A light emitting device was produced by performing the same operation as in Example 1 except that mg was used. When a luminescent brightness was measured by applying a DC voltage, red luminescence with a brightness of 9 cd / m ² was exhibited at a driving voltage of 13V.

Example 4 An organic electroluminescent device was produced as follows. The same operation as in Example 1 was carried out except that 79 mg of the polymer of 9- (2-ethylhexyl) -3-ethynylcarbazole shown in Synthesis Example 2 was used instead of the poly-N-vinylcarbazole used in Example 1. Then, a light emitting device was manufactured. A direct current voltage was applied and the emission luminance was measured. It was 9c at a driving voltage of 13V.
It showed red light emission with a brightness of d / m ² .

Example 5 An organic electroluminescent device was produced as follows. 35 g of partially benzoylated polystyrene shown in Synthesis Example 3 instead of 50 mg of triphenylacetophenone used in Example 1
A light emitting device was produced in the same manner as in Example 1 except that g and 25 mg of triphenylacetophenone were used.

When a direct current voltage was applied and the light emission luminance was measured, red light emission with a luminance of 6 cd / m ² was shown at a driving voltage of 13V.

Example 6 An organic electroluminescent device was produced as follows. 200 mg of the copolymer of N-vinylcarbazole and vinyl methacrylate synthesized in Synthesis Example 4 and 2,2 as a photopolymerization initiator
Dimethoxy-2-phenylacetophenone (10 mg) was dissolved in toluene (5 ml), and the solution of polyvinylcarbazole used in Example 1 was used instead of spin coating to form a thin film, which was dried under reduced pressure.

Attaching a photomask, 254 to 365n
m was irradiated with ultraviolet rays having a dominant wavelength, and the obtained thin film was cured into a predetermined pattern of a photomask to make it insoluble in a solvent. Next, the partially cured thin film was immersed in a toluene solvent and etched to obtain a mask-patterned light emitting layer having a film thickness of 60 nm. Next, a cathode was produced in the same manner as in Example 1.

When a direct current voltage was applied and the emission luminance was measured, red emission with a luminance of 8 cd / m ² was shown at a driving voltage of 13V.

Example 7 An organic electroluminescent device was produced as follows. Instead of the light emitting layer solution used in Example 1, 170 mg of poly-N-vinylcarbazole, 2- (4-t-butylphenyl)-
5- (4-biphenyl) -1,3,4-oxadiazo-
140 mg, triphenylacetophenone 23.4
mg, perylene 1.27 mg, coumarin-6 0.0
A light emitting device was produced in the same manner as in Example 1 except that 42 mg was dissolved in 15 ml of toluene and the light emitting layer solution prepared by filtering with a 20 micron membrane filter was used.

When a luminescent brightness was measured by applying a DC voltage, white luminescence with a brightness of 15 cd / m ² was exhibited at a driving voltage of 9V. The emission spectrum is shown in FIG.

[0134]

As a red light emitting material of organic EL, DCM is used.
Organic dye compounds such as Nile Red and Nile Red are known, but these compounds do not give a true red color but only an orange red color. Further, Eu complex and Pt complex are known. However, these organic dye compounds and metal complexes are very expensive, and their price is a major obstacle to industrial use.

The red light emitting material of the present invention comprises at least a compound having a carbazole group and a phosphorescent material having a phosphorescent light emission intensity higher than that of benzophenone, and a red light emitting material using the same. It is an electroluminescent device, has a light emission brightness comparable to the above-mentioned known compounds, is a very inexpensive compound, and has industrial advantages.

[Brief description of drawings]

FIG. 1 is an emission spectrum characteristic diagram obtained by using the organic electroluminescence device manufactured in Example 1.

FIG. 2 is an emission spectrum characteristic diagram obtained by using the organic electroluminescence device manufactured in Example 7.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) H05B 33/14 H05B 33/14 BF term (reference) 3K007 AB02 AB04 AB18 DB03 FA01 4J002 BC12W BQ00X EE036 EU027 FD206 FD207 GP00

Claims (20)

[Claims] 1. A red light-emitting material containing at least a phosphor and a compound having a carbazole group. 2. The red light emitting material according to claim 1, wherein the phosphorescent material has a phosphorescent light emission intensity higher than that of benzophenone. 3. The phosphor is at least one selected from the group consisting of benzophenone, triphenylacetophenone, benzophenone substituted with an organic residue, and triphenylacetophenone substituted with an organic residue. The red light emitting material according to claim 1 or 2. 4. The at least one phosphor selected from the group consisting of a benzophenone group, a triphenylacetophenone group, a benzophenone group substituted with an organic residue, and a triphenylacetophenone group substituted with an organic residue. A polymer having a side chain, which is characterized in that
Or the red light emitting material according to 2. 5. The compound having a carbazole group is at least one selected from the group consisting of carbazole and carbazole having a halogen and / or an organic residue as a substituent. The red light-emitting material according to at least any one of 1. 6. A polymer or copolymer in which the compound having a carbazole group uses as a monomer at least one selected from the group consisting of vinylcarbazole and vinylcarbazole having a halogen and / or an organic residue as a substituent. 5. A polymer, which is a polymer.
The red light-emitting material according to at least any one of 1. 7. A compound having a carbazole group, wherein at least one selected from the group consisting of vinylcarbazole and vinylcarbazole having a halogen and / or an organic residue as a substituent, and a vinyl monomer are used as monomers. The red light emitting material according to any one of claims 1 to 4, wherein the red light emitting material is a copolymer. 8. The red light emitting material according to claim 7, wherein the vinyl monomer is an acrylic vinyl monomer substituted with an unsaturated hydrocarbon group. 9. The acrylic vinyl monomer substituted with an unsaturated hydrocarbon group is vinyl acrylate, vinyl methacrylate, allyl acrylate, allyl methacrylate, crotyl acrylate, crotyl methacrylate, cyclopentadienyl acrylate, cyclopentadiene. 9. The red light emitting material according to claim 8, wherein the red light emitting material is at least one selected from the group consisting of enylmethacrylate, vinyl acrylate and vinyl methacrylate. 10. The compound having a carbazole group is
Ethynylcarbazole and halogen and / or as a substituent
Alternatively, it is a polymer or copolymer using at least one selected from the group consisting of ethynylcarbazole having an organic residue as a monomer.
5. The red light emitting material according to at least any one of 1 to 4. 11. The compound having a carbazole group is
Ethynylcarbazole and halogen and / or as a substituent
Alternatively, at least one selected from the group consisting of ethynylcarbazole having an organic residue and an ethynyl compound monomer are used as a monomer, and the copolymer is a copolymer. The red light-emitting material according to the item. 12. The red light emitting material according to claim 6, wherein the compound having a carbazole group has a number average molecular weight of 1,000 to 1,000,000. 13. The organic residue has 1 to 20 carbon atoms and is at least one selected from the group consisting of a hydrocarbon group, an ether group, an ester group, a carbonyl group, a nitrile group and an amino group. 3. The method according to claim 3, wherein
2. The red light emitting material according to at least any one of 2. 14. A thin film of a red light emitting material, comprising at least the red light emitting material according to claim 1. 15. A method for producing a luminescent material, which comprises applying a solution containing a luminescent material to form a film, wherein the luminescent material comprises the phosphorescent substance according to at least any one of claims 1 to 13 and a carbazole group. 15. The method for producing a thin film of a red light emitting material according to claim 14, wherein at least one of the phosphorescent substance and the compound having a carbazole group is a polymer compound. . 16. The compound having a carbazole group is composed of a copolymer of monomers having an unsaturated group, and after applying a solution containing the red light emitting material, the solvent is insolubilized by a photoreaction. Item 15. A method for producing a thin film of a red light emitting material according to Item 14. 17. An organic electroluminescent device comprising the light emitting material according to claim 1. 18. An organic electric field comprising a blue light-emitting material, a green light-emitting material, and the red light-emitting material according to any one of claims 1 to 13 to emit white light. Light emitting element. 19. The organic electroluminescent device comprises a layer composed of at least one organic thin film having at least a light emitting layer between an anode and a cathode facing each other, and the light emitting layer comprises: The organic electroluminescent element according to claim 17, which comprises the light emitting material according to at least one of 1 to 13. 20. The organic electroluminescent device according to claim 19, wherein the light emitting layer is insolubilized in a solvent by photoreaction.