JP2012077069A - Bis(aminobiphenyl ethynyl)-based compound, blue fluorescent dye, and organic el element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new compound which gives a blue fluorescent dye having high emission luminance, being robust, and having excellent solubility, and to provide an organic EL element using the blue fluorescent dye.SOLUTION: There are provided a new bis(aminobiphenyl ethynyl)-based compound represented by general formula (1), the blue fluorescent dye composed of the compound, and the organic EL element including the compound. The EL element is utilized for light for display, a display and so on.

Description

The present invention relates to a novel bis (aminobiphenylethynyl) compound, a blue fluorescent dye comprising the compound, and an organic electroluminescence device comprising the compound (hereinafter referred to as “organic EL device”).
The compounds of the present invention are useful as functional dyes, particularly blue fluorescent dyes.
The organic EL element of the present invention can be used for display illumination, display devices, and the like.

Organic EL devices have been put into practical use as small displays such as mobile phones and digital cameras, and there are great expectations for the realization of flexible displays in the future. An organic EL element operates by applying a high electric field to an organic layer that is originally an insulator to inject a high-density charge into the organic thin film. Electrons and holes injected from the outside move in the thin film and recombine with a certain probability on fluorescent or phosphorescent organic molecules, and the energy of this recombination excites the organic molecules and emits light energy. This light energy emission is the same as that of fluorescence or phosphorescence, and the electroluminescence (EL) color matches the color of fluorescence or phosphorescence (photoluminescence, PL).
In this organic EL element, high-density electric charges and excitons coexist, and the organic EL element is used under extremely severe conditions that cannot be considered with an element using a conventional organic material. Therefore, chemical and electrical durability is required for the material used for the organic EL element. Since organic EL devices that are currently in practical use are formed by laminating a carrier transport layer and a light emitting layer by vapor deposition, the carrier transport materials and light emitting materials used have excellent carrier transport capability and In addition to luminous efficiency, sublimation for film formation is also required. Furthermore, in order to put an organic EL element having a large screen into practical use, an expensive large-sized vacuum vapor deposition apparatus is required, which is a great hindrance to the practical application of an organic EL element large screen.

  On the other hand, studies on dye-dispersed polymer organic EL devices that can easily form a thin film with a large area are limited in the number of luminescent dyes that can be used. The polymer organic EL element has higher physical strength than the low molecular weight element, and has an advantage that the element can be easily formed by coating, and a reduction in production cost can be expected. In particular, the dye-dispersed polymer organic EL device is one in which a light-emitting dye is uniformly dispersed and a low-molecular carrier transport material, a dopant, or the like can be used. Moreover, since the freedom degree of the pigment | dye to disperse | distributes regarding a luminescent color is also high, it can implement | achieve each color from blue to red and white. In addition, polymer dispersions were used for low-molecular EL devices formed by vapor deposition, because of problems such as crystallization, which is considered to have an adverse effect on durability, and difficulties in the manufacturing process of high-definition large-sized panels. There is an advantage that can be overcome by adopting a printing process such as an inkjet method or a roll-to-roll method.

The development of a high-brightness and high-efficiency white organic EL element is an example of the problem of the dye-dispersed polymer organic EL element. The white organic EL element can be used for illumination such as mono-color display and backlight, and can also be displayed in color by mounting a color filter on the display device.
As a white organic EL device, for example, US Pat. No. 5,503,910 discloses a device in which a light emitting layer is a laminate of a blue light emitting layer and a green light emitting layer, and a red meter fluorescent compound is added thereto. Japanese Patent No. 5683828 discloses an element having a light-emitting medium in which a boron-based complex which is a red fluorescent compound is added to a blue-green light-emitting layer, and Japanese Patent Laid-Open No. 10-308278 discloses a blue-green light-emitting layer. An element having a light emitting medium to which a benzothioxanthene derivative that is a red fluorescent compound is added is disclosed. Japanese Patent No. 4255610 discloses a blue light-emitting layer containing a blue light-emitting material made of a styryl derivative or an anthracene derivative, and a layer containing a yellow fluorescent compound containing at least one fluoranthene skeleton or pentacene skeleton. A white organic EL element containing the above is disclosed. However, these elements do not sufficiently satisfy practicality in terms of luminous efficiency and lifetime.

On the other hand, one point for obtaining a white light-emitting element with excellent performance lies in the development of a blue light-emitting dye having excellent performance in terms of luminous efficiency, luminance, and lifetime. Compared to other color luminescent dyes, the basic performance of these dyes was inferior with blue luminescent dyes. The blue light-emitting dye is a dichroic white light-emitting element that is combined with a complementary yellow light-emitting dye to form a white light-emitting element, or a blue light-emitting dye, a green light-emitting dye, and a red light-emitting dye are combined to form a white light-emitting element. It can be used as an RGB tricolor white light emitting element. As a blue fluorescent dye for an organic EL element, for example, WO2005 / 033087 discloses a heterocyclic-substituted phenylacetylene compound. Regarding the luminous efficiency, luminance, lifetime, etc. of the organic EL element, Further improvements are awaited.
Further, according to the spin coating method, a light emitting surface having a large area can be easily obtained. However, in order to obtain high luminance and high light emission efficiency, improvement of the solvent dispersibility of the blue fluorescent dye is one of the problems. It is.

US Pat. No. 5,503,910 US Pat. No. 5,683,828 JP-A-10-308278 Japanese Patent No. 4255610 WO2005 / 033087

  An object of the present invention is to improve the above-mentioned problems, to provide a novel compound that gives a blue fluorescent dye having high emission luminance, robustness, and good solubility, and to use the blue fluorescent dye An organic EL device is provided.

The present invention
General formula (1):

[In the formula, each of R ^{1 to} R ²⁰ is the same or different and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkyloxy group having 1 to 10 carbon atoms, or an alkyl having 1 to 10 carbon atoms. A primary or secondary amino group having a group, L is a divalent organic group, and has a general formula (TFD-000 to TFD-004):

[In the formula, each of R ^{20 to} R ⁴⁰ is the same or different and is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyloxy group having 1 to 12 carbon atoms, and each of R ⁴¹ and R ⁴² is Are the same or different and are alkyl groups having 1 to 12 carbon atoms. ]. ]
The bis (aminobiphenylethynyl) type compound represented by these is provided.

The present invention provides a blue fluorescent dye as a fluorescent dye for organic EL comprising the bis (aminobiphenylethynyl) compound.
Moreover, this invention is an organic EL element which has a pair of electrode and the light emitting layer containing the luminescent material which exists between this electrode, Comprising: This luminescent material contains the said bis (aminobiphenyl ethynyl) type-compound. An organic EL element is provided.
The present invention also provides a method for producing an organic EL device, wherein a luminescent layer is formed by a solution coating method using a bis (aminobiphenylethynyl) compound as a luminescent material.

  Furthermore, the present invention provides a dichroic white luminescent material comprising the bis (aminobiphenylethynyl) compound and a luminescent dye having a complementary color relationship. That is, the present invention provides a two-color white light-emitting material comprising a (aminobiphenylethynyl) -based compound as a blue fluorescent dye and a yellow light-emitting dye having a complementary color relationship. For white light emission, ideally both x and y values in the CIE chromaticity coordinates are in the vicinity of 0.31, but some width may be acceptable. The appropriate mixing ratio of the blue fluorescent dye and the yellow fluorescent dye for obtaining white light emission may vary depending on the configuration of the light emitting layer of the EL element (such as the type of hole transporting host material or electron transporting material). The emission color coordinates of the two-color mixed fluorescent dyes having a complementary color relationship move on a line connecting the chromaticity coordinates of the blue and yellow emission dyes, so that the emission color coordinates are x = 0.26 to 0.38, y = The mixing ratio of the dye is determined so as to be 0.26 to 0.38.

  The present invention also provides a three-color white luminescent material comprising the bis (aminobiphenylethynyl) compound, a green luminescent dye, and a red luminescent dye. That is, the present invention provides a three-color white light emitting material comprising a bis (aminobiphenylethynyl) compound as a blue fluorescent dye, a green light emitting dye, and a red light emitting dye. In the case of three-color white light emission, as in the case of the two-color white light emission, an appropriate mixing ratio of blue, green, red, and each fluorescent dye is determined by the configuration of the light-emitting layer of the EL element (hole transport host material or electron). Depending on the type of transport material, etc., in the case of a three-color system, there is a portion where the fluorescence spectrum and absorption spectrum overlap, and energy transfer occurs from blue to green and from green to red. Determine the dye composition. For example, in the case of the bis (aminobiphenylethynyl) tricolor mixture, blue: green: red = 1: 0.002-0.10: 0.002-0.10, preferably 1: 0.01- 0.04: It is the range of 0.01-0.04.

  And this invention is an organic electroluminescent element which has a pair of electrode and the light emitting layer containing the luminescent material which exists between this electrode, Comprising: This luminescent material is the said dichroic or trichromatic white color. An organic EL device including a light emitting material is provided.

  The present invention also provides a method for producing a white light-emitting organic EL device, wherein a light-emitting layer is formed by a solution coating method using the white light-emitting material.

The bis (aminobiphenylethynyl) compound of the present invention emits blue light (fluorescence) with high brightness, and is excellent in fastness and solubility. The bis (aminobiphenylethynyl) compound of the present invention has a high fluorescence quantum yield. Since the bis (aminobiphenylethynyl) -based compound of the present invention is easily dissolved in a solvent, a thin film can be easily formed by spin coating or the like. The bis (aminobiphenylethynyl) compound of the present invention can be dispersed in a host (for example, polyvinyl carbazole) made of a polymer material. Bis (aminobiphenylethynyl) compounds emit high light even at low concentrations.
The bis (aminobiphenylethynyl) -based compound of the present invention is a blue fluorescent dye that is used as a light-emitting material that forms a light-emitting layer that exists between a pair of electrodes and the electrodes. A light-emitting organic EL device is provided.
The bis (aminobiphenylethynyl) compound of the present invention is converted into a blue fluorescent dye and combined with a complementary yellow luminescent dye as a dichroic white luminescent material, or combined with a green luminescent dye and a red luminescent dye. A white light-emitting organic EL device having high luminance and high fastness is provided by using the color-based white light-emitting material as a light-emitting material for forming a light-emitting layer existing between a pair of electrodes.

  In an organic EL device, holes and electrons injected from the positive electrode and the negative electrode recombine in the organic light emitting layer, and emitted when the light emitting organic compound excited by the charge recombination energy is deactivated to the ground state. Extracts energy as luminescence. When a light emitting material is applied to an EL element, the light emission quantum yield is extremely high, and a value close to 1 is desirable. Each of the luminescent dyes in the present application has a high emission quantum yield exceeding 0.8, and is useful as a light-emitting material for organic EL.

FIG. 1 is a schematic view showing the structure of an organic EL device produced in Example 7. FIG. 2 shows the chromaticity coordinates of the monochromatic organic EL elements produced in Example 7 and Reference Example 1. FIG. 3 shows a white light emission (EL) spectrum of the dichroic organic EL device produced in Example 8. FIG. 4 shows white light emission (EL) spectra of the two-color and three-color organic EL elements shown in Table 6.

Hereinafter, embodiments for carrying out the invention will be described in detail.
The bis (aminobiphenylethynyl) compound of the present invention has the general formula (1):

It is represented by
In the formula, L is a divalent organic group, which serves as a linker for connecting the aminobiphenylethynyl groups on both sides, and each of R ^{1 to} R ²⁰ is the same or different and includes a hydrogen atom, a carbon number A primary or secondary amino group having an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkyloxy group having 1 to 10 carbon atoms, or an alkyl group having 1 to 10 carbon atoms.
In the alkyl group having 1 to 10 carbon atoms, part or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, and hexyl group. , Isohexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group and other linear or branched alkyl groups, and some or all of the alkyl group hydrogen atoms are replaced by fluorine atoms Fluoroalkyl groups that have been prepared. Preferably, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a trifluoromethyl group, and a trifluoroethyl group are mentioned, and more preferably, a methyl group, an ethyl group, an isopropyl group, and a trifluoromethyl group are mentioned. It is done.
Examples of the halogen atom include fluorine, chlorine, iodine, and bromine, preferably fluorine, chlorine, and more preferably fluorine.
Examples of the alkyloxy group having 1 to 10 carbon atoms include alkyloxy groups derived from the above alkyl groups.
As a primary or secondary amino group which has a C1-C10 alkyl group, the primary or secondary amino group substituted 1 or 2 by the said alkyl group is mentioned, for example. In this case, the substituted alkyl groups may be the same or different. The primary or secondary amino group is preferably a methylamino group, a dimethylamino group, an ethylamino group, a diethylamino group, a propylamino group, a dipropylamino group, a butylamino group, a dibutylamino group, more preferably a dimethylamino group. Group and diethylamino group.

R ^{1 to} R ²⁰ are preferably a hydrogen atom, an alkyl group, or an alkyloxy group. That is, the present invention preferably
General formula (1):

[In the formula, each of R ^{1 to} R ²⁰ is the same or different and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms, wherein L is as defined above. It is. ]
The compound represented by these may be sufficient.

  L is a divalent organic group that serves as a linker that connects the aminobiphenylethynyl groups on both sides, and is represented by the general formula (TFD-000 to TFD-004):

In the formula, each of R ^{21 to} R ⁴⁰ is the same or different and is a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or 1 to 1 carbon atoms. Each of R ⁴¹ and R ⁴² is the same or different and is a linear or branched alkyl group having 1 to 12 carbon atoms.

In the alkyl group having 1 to 12 carbon atoms, part or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, and hexyl group. Straight chain or branched alkyl groups such as isohexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group and dodecyl group, and part or all of hydrogen atoms of alkyl group Is a fluoroalkyl group substituted with a fluorine atom. Preferably, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, decyl group, 2-ethylhexyl group, dodecyl group, trifluoromethyl group and trifluoroethyl group More preferred are methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, trifluoromethyl group and trifluoroethyl group.
Examples of the alkyloxy group having 1 to 12 carbon atoms include alkyloxy groups derived from the above alkyl groups.

Specific examples of bis (aminobiphenylethynyl) compounds include
General formula (1-1):

[Wherein L is as defined above. ]
The compound represented by these is mentioned.

Specifically, for example,
Formula (1-2):

[Wherein, each of R ⁴³ and R ⁴⁴ is the same or different and is an alkyl group having 1 to 12 carbon atoms. ]
Or a compound represented by the general formula (1-3):

[Wherein, each of R ⁴⁵ and R ⁴⁶ is the same or different and is an alkyl group having 1 to 12 carbon atoms. ]
Or a compound represented by the general formula (1-4):

[Wherein, each of R ⁴⁷ and R ⁴⁸ is the same or different and is an alkyl group having 1 to 12 carbon atoms. Or general formula (1-5):

[Wherein, each of R ^{48 (1)} and R ^{48 (2)} is the same or different and is an alkyl group having 1 to 12 carbon atoms. ]
The compound represented by these is mentioned.

^Here, R 43 ^{to R 48} and ^{R 48 (1)} and ^{R 48 (2)} represents an alkyl group having 1 to 12 carbon atoms. In the alkyl group having 1 to 12 carbon atoms, part or all of the hydrogen atoms of the alkyl group may be substituted with a fluorine atom. Examples of the alkyl group having 1 to 12 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, and hexyl group. , Isohexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, etc., some or all of hydrogen atoms of linear or branched alkyl groups and alkyl groups Are substituted with a fluorine atom, preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a decyl group, 2- Ethylhexyl group, dodecyl group, trifluoromethyl group, trifluoro Butyl group, more preferably a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, decyl group, and a trifluoromethyl group and trifluoroethyl group.

More specifically, for example,
Formula (TFD-052):

Or the formula (TFD-070):

Or the formula (TFD-072):

Or the formula (TFD-068):

Or the formula (TFD-095):

And bis (aminobiphenylethynyl) compounds represented by the formula:
The methoxy group (—OCH ₃ ), the trifluoromethyl group, the butoxy group (—OCH ₂ CH ₂ CH ₂ CH ₃ ) and the nC ₈ H ₁₇ group substituted on the linker moiety corresponding to L in the above exemplary compounds are: It is presumed that the solvent solubility or dispersibility of the bis (aminobiphenylethynyl) compound is enhanced.

  The bis (aminobiphenylethynyl) -based compound of the present invention can be produced by a usual method. For example, between a compound having a bisethynyl group or bisiodo group at both ends (or para positions) of an aromatic hydrocarbon corresponding to the linker moiety and an ethynyl group-substituted or iodo-substituted aminobiphenyl group, for example, by a palladium catalyst It can be synthesized by a coupling reaction. The reaction formula is illustrated below:

  The bis (aminobiphenylethynyl) compound of the present invention has a fluorescence emission wavelength in the range of λem = 420 to 470 nm and emits blue fluorescence.

The bis (aminobiphenylethynyl) compound of the present invention can be used as a dye, particularly a blue fluorescent dye.
Since the bis (aminobiphenylethynyl) -based compound of the present invention is easily dissolved in a solvent, particularly an organic solvent, it can be applied by solution (in particular, spin coating). A bis (aminobiphenylethynyl) -based compound layer can be obtained by applying a solution of bis (aminobiphenylethynyl) -based compound (particularly, spin coating) and then removing the solvent.

  As described above, the present invention is an organic EL element having a pair of electrodes and a light-emitting layer containing a light-emitting material existing between the electrodes, and the light-emitting material includes a bis (aminobiphenylethynyl) compound. An organic electroluminescence device is provided. The present invention is also a method for producing the organic EL device, wherein the bis (aminobiphenylethynyl) compound of the present invention is used as a luminescent material to form a light emitting layer by a solution coating method (particularly, a spin coating method). A method for producing an organic electroluminescence element is provided.

The present invention also provides a dichroic white light emitting material comprising the bis (aminobiphenylethynyl) compound of the present invention and a luminescent dye having a complementary color relationship. Specifically, for example,
Formula (TFD-052):

Or the formula (TFD-070):

Or the formula (TFD-072):

Or the formula (TFD-068):

Or the formula (TFD-095):

And a white light-emitting material composed of a bis (aminobiphenylethynyl) -based compound as a blue light-emitting (fluorescent) dye and a light-emitting dye having a complementary color relationship.

  Since the bis (aminobiphenylethynyl) compound of the present invention is a blue fluorescent dye having a fluorescence emission wavelength in the vicinity of λem = 420 to 470 nm, a luminescent dye having a complementary color relationship thereto has an emission wavelength of λem = 560 to 590 nm. A yellow luminescent dye in the vicinity is suitable.

For example, a white light-emitting material combination consisting of a combination having a specific complementary color relationship will be described.
Formula (TFD-052) as a blue luminescent (fluorescent) dye:

Or the formula (TFD-070):

Or the formula (TFD-072):

Or the formula (TFD-068):

Or the formula (TFD-095):

A compound represented by
Formula (TFD-064) as a yellow pigment:

And a white light-emitting material comprising a fluorescent light-emitting dye represented by the formula:
Examples of the more preferred combinations among these are:
Formula (TFD-052):

A bis (aminobiphenylethynyl) -based compound (λem = 457 nm) of a blue fluorescent dye represented by:
Formula (TFD-064):

And a two-color white light-emitting material composed of a yellow fluorescent dye represented by the formula (λem = 573 nm).
Moreover, Formula (TFD-072):

A bis (aminobiphenylethynyl) -based compound (λem = 447 nm) of a blue fluorescent dye represented by:
Formula (TFD-064):

And a two-color white light-emitting material composed of a yellow fluorescent dye represented by the formula (λem = 573 nm).

For example, a white light-emitting material combination composed of a combination having a more specific complementary color relationship will be described.
Formula (TFD-052) as a blue luminescent dye:

Or the formula (TFD-070):

Or the formula (TFD-072):

Or the formula (TFD-068):

Or the formula (TFD-095):

A compound represented by
Formula (TFD-079) as a yellow luminescent dye:

And a white light-emitting material comprising a fluorescent dye represented by the formula:

The present invention also provides a bis (aminobiphenylethynyl) compound as a blue fluorescent dye (λem = 420 to 470 nm), a green fluorescent dye (λem = 500 to 565 nm) and a red fluorescent dye (λem = 590 to λem) of the present invention. And a trichromatic white light-emitting material.
Specifically, for example, the formula (TFD-052) as a blue luminescent dye:

Or the formula (TFD-070):

Or the formula (TFD-072):

Or the formula (TFD-068):

Formula (TFD-095):

A three-color white light-emitting material composed of a bis (aminobiphenylethynyl) -based compound represented by the formula:

Specifically, the formula (TFD-052) as a blue light-emitting dye compound:

Or the formula (TFD-070):

Or the formula (TFD-072):

Or the formula (TFD-068):

Or the formula (TFD-095):

A compound represented by formula (2):

[Wherein, R ⁴⁹ represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may have a substituent. ]
A green luminescent dye represented by formula (3):

[Wherein, each of R ⁵⁰ and R ⁵¹ is the same or different and is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may have a substituent. ]
And a white light-emitting material composed of a red light-emitting dye represented by the formula:

  Here, in the alkyl group having 1 to 16 carbon atoms which may have a substituent in the general formulas (2) and (3), part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms. A part of the methylene chain may be substituted with an oxygen atom. Examples of the alkyl group having 1 to 16 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, and hexyl group. , Straight or branched alkyl groups such as isohexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl And a fluoroalkyl group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and an ether bond-containing alkyl group in which a part of the methylene chain is substituted with oxygen atoms. Preferably, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group and dodecyl group are mentioned, more preferably methyl group , Ethyl group, propyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group and dodecyl group.

More specifically, for example,
Formula (TFD-072):

A bis (aminobiphenylethynyl) -based compound (λem = 447 nm) as a blue fluorescent dye represented by:
Formula (TFD-005):

A green fluorescent dye represented by (λem = 512 nm),
Formula (TFD-006):

And a three-color white light-emitting material comprising a red fluorescent dye represented by the formula (λem = 605 nm).
Moreover, Formula (TFD-072):

A bis (aminobiphenylethynyl) -based compound (λem = 447 nm) as a blue fluorescent dye represented by:
Formula (TFD-082):

A green fluorescent dye represented by (λem = 509 nm),
Formula (TFD-080):

And a three-color white light-emitting material composed of a red fluorescent dye (λem = 607 nm) represented by the formula:
Moreover, Formula (TFD-070):

A bis (aminobiphenylethynyl) -based compound (λem = 449 nm) as a blue fluorescent dye represented by:
Formula (TFD-082):

A green fluorescent dye represented by (λem = 509 nm),
Formula (TFD-080):

And a three-color white light-emitting material composed of a red fluorescent dye (λem = 607 nm) represented by the formula:

As further three-color white light emitting material of the present invention,
General formula (1) of the present invention:

[In the formula, each of R ^{1 to} R ²⁰ is the same or different and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms, wherein L is as defined above. It is. ]
A blue light-emitting dye compound represented by the general formula (2):

[Wherein, R ⁴⁹ represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may have a substituent. ]
A green luminescent dye represented by
A tricolor white light-emitting material composed of a red phosphorescent dye is exemplified.

As further three-color white light emitting material of the present invention,
General formula (1) of the present invention:

[In the formula, each of R ^{1 to} R ²⁰ is the same or different and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms, wherein L is as defined above. It is. ]
A blue light-emitting dye compound represented by the general formula (2):

[Wherein, R ⁴⁹ represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may have a substituent. ]
A green luminescent dye represented by
Formula (Ir-1):

Or formula (Ir-2):

Or formula (Ir-3):

And a white light-emitting material composed of a combination with a red phosphorescent dye represented by the formula:

Specific examples of combinations:
Formula (TFD-052):

Or the formula (TFD-070):

Or the formula (TFD-072):

Or the formula (TFD-068):

Or the formula (TFD-095):

A blue fluorescent compound represented by
Formula (TFD-082):

A green fluorescent dye represented by (λem = 509 nm),
Formula (Ir-1):

Or formula (Ir-2):

Or formula (Ir-3):

And a white light-emitting material composed of a combination with a red phosphorescent dye represented by the formula:

  Here, in the alkyl group having 1 to 16 carbon atoms which may have a substituent in the general formula (2), a part or all of the hydrogen atoms of the alkyl group may be substituted with fluorine atoms, A part may be substituted with an oxygen atom. Examples of the alkyl group having 1 to 16 carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tertiary butyl group, pentyl group, isopentyl group, neopentyl group, cyclopentyl group, and hexyl group. , Straight or branched alkyl groups such as isohexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl and hexadecyl And a fluoroalkyl group in which part or all of the hydrogen atoms of the alkyl group are substituted with fluorine atoms, and an ether bond-containing alkyl group in which a part of the methylene chain is substituted with oxygen atoms. Preferably, methyl group, ethyl group, propyl group, isopropyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, decyl group and dodecyl group are mentioned, more preferably methyl group , Ethyl group, propyl group, butyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group and dodecyl group.

  In these two-color or three-color white light emitting materials, in order to obtain a desired white light emission, the mixing ratio of a blue fluorescent dye and a yellow light emitting dye or a blue fluorescent dye, a green light emitting dye and a red light emitting dye is appropriately set. It needs to be adjusted. The mixed solution thus prepared is applied (or cast) on the substrate, and then the solvent is dried to obtain a coating film. A direct current voltage is applied to analyze the EL emission from the coating film. For white light emission, it is ideal that the x value and y value of the CIE chromaticity coordinates are both in the vicinity of 0.31, but a certain amount of width can be allowed in practice.

  An example of a suitable mixing ratio for obtaining a dichroic white light emitting material is as follows. For example, a bis (aminobiphenylethynyl) compound as a blue fluorescent dye is represented by the formula TFD-052, and a yellow fluorescent dye is represented by the formula In the case of TFD-064, the structure of the light emitting layer of the EL element is that poly (9-vinylcarbazole: PVCz) as a hole transporting host material is 1 and 2- (4-tert-butylphenyl) as an electron transporting material. In an element configuration in which the ratio of −5- (4-biphenylyl) -1,3,4-oxadiazole (PBD) is 0.4, the mixing ratio of TFD-052 is 0.02 to 0.08, and the luminous efficiency is When the blending ratio of TFD-052 is 0.05, the blending ratio of TFD-064 is 0.001 to 0.01, preferably 0.003 to 0.08, more preferably 0.004 to 0. For example, when TFD-052 is 0.05 and TFD-064 is 0.004, the (x, y) value is (0, 0) in the CIE chromaticity coordinates. .28, 0.32), and white light emission can be obtained.

  Similarly, when the bis (aminobiphenylethynyl) compound as a blue fluorescent dye is a formula TFD-072 and the yellow fluorescent dye is a formula TFD-064, for example, the blending ratio of TFD-072 is 0.1-0.18 is suitable, and when TFD-072 is 0.12, the TFD-064 blending ratio is preferably 0.003-0.0010, more preferably 0.005-0.008. Good white light emission can be obtained, and when the blending ratio of TFD-072 is 0.12 and TFD-064 is 0.06, the CIE chromaticity coordinate (x, y) value is (0.29, 0.00). 32) and white light emission can be obtained.

  Similarly, in a three-color system, for example, a bis (aminobiphenylethynyl) compound as a blue fluorescent dye is a formula TFD-072, a green fluorescent dye is a formula TFD-005, and a red fluorescent dye is TFD-006. The CIE chromaticity coordinate (x, y) value is (0.36, when TFD-072 is 0.12, TFD-005 is 0.003, and TFD-006 is 0.004. 0.36) and the average color rendering index (Ra) is 92, and white light emission excellent in color rendering can be obtained.

The production of the light emitting layer in the production of the organic EL device of the present invention is preferably carried out by a method in which a coloring material is dissolved in a solvent and applied and cast on a substrate, more preferably by a spin coating method.
Examples of solvents include aliphatic hydrocarbons such as pentane, hexane, heptane; aromatic hydrocarbons such as benzene, toluene, xylene; alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, decalin; petroleum solvents such as petroleum Ethers, petroleum benzines; halogenated hydrocarbons such as carbon tetrachloride, chloroform, 1,2-dichloroethane; ethers such as ethyl ether, isopropyl ether, anisole, dioxane, tetrahydrofuran; ketones such as acetone, methyl isobutyl ketone, methyl ethyl ketone, cyclohexanone , Acetophenone, isophorone; esters such as ethyl acetate, butyl acetate; amides such as dimethylformamide; acetonitrile; dimethyl sulfoxide; halogenated benzene, examples Examples include chlorobenzene, dichlorobenzene; alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, and 2-methyl-2-propanol.

The organic layer (for example, hole injection layer, hole transport layer, light emitting layer, electron transport layer, electron injection layer) of the organic EL element can be formed by spin coating. For example, an organic layer is spin-coated on a substrate such as a cathode, an anode, a hole (electron) transport layer, or a hole (electron) injection layer. In the spin coating operation, it is preferable to rotate the substrate at 100 to 10000 rpm, for example, 500 to 4000 rpm, for 0.1 to 30 minutes, for example, 0.5 to 3 minutes. At the time of spin coating, the concentration of the solid (bis (aminobiphenylethynyl) compound or white light emitting material) in the solution is preferably 0.0001 to 10% by weight, for example, 0.001 to 1% by weight. . A film having a thickness of 5 to 500 nm, for example, 25 to 250 nm (film thickness after drying) is formed by spin coating. Compared with vacuum deposition or the like, spin coating has the advantage that the material is not wasted when the material is deposited, and no complicated process is required, and the manufacturing cost is low and can be easily performed.
The removal of the solvent can be performed by drying the solvent at a temperature of 10 to 200 ° C. at 0.00001 to 1 atmosphere.

In an organic EL element having an organic layer between an anode and a cathode facing each other, the organic layer contains a bis (aminobiphenylethynyl) compound or a white light emitting material.
Examples of the organic layer are a light emitting layer, a hole transport layer, an electron transport layer, a hole block layer, an electron block layer, a hole injection layer, and an electron injection layer. The organic layer containing a bis (aminobiphenylethynyl) compound or a white light emitting material is preferably a light emitting layer.
In the present invention, the organic EL element has a substrate, an anode, and a cathode in addition to the organic layer.

A typical layer configuration of the EL element is illustrated below.
(I) Anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (ii) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection transport layer / cathode (iii) Anode / hole injection transport layer / light emitting layer / electron transport layer / electron injection layer / cathode (iv) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode (v) anode / hole injection layer / hole transport layer / Light emitting layer / cathode (vi) anode / light emitting layer / electron transport layer / electron injection layer / cathode (vii) anode / hole injection transport layer / light emitting layer / cathode (viii) anode / light emitting layer / electron injection transport layer / cathode (Ix) Anode / light emitting layer / cathode In the layer configuration, a hole blocking layer and / or an electron blocking layer may be present between the anode and the cathode.

An anode may be formed on the substrate, or a cathode may be formed on the substrate.
The substrate is not particularly limited, but inorganic materials such as zirconia-stabilized yttrium and glass; polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthalate; polyethylene, polycarbonate, polyethersulfone, polyarylate, allyl diglycol carbonate, It may be a polymer material such as polyimide, polycycloolefin, norbornene resin, poly (chlorotrifluoroethylene), polytetrafluoroethylene, polytetrafluoroethylene-polyethylene copolymer. The substrate may be a composite sheet combining these two or more materials. Furthermore, for example, a color filter film, a color conversion film, and a dielectric reflection film can be combined with the substrate to control the emission color. By combining a blue or blue-green light emitting element with a blue color filter and green and red color conversion films, a full-color display of the three primary colors red, green and blue can be realized. The three-color white light-emitting substrate can be used for a backlight of a liquid crystal display because the emission spectrum includes three primary color components of red, green, and blue.

  Examples of the substance used for the anode include metals, alloys, metal oxides, conductive compounds, or two or more of these. Specific examples include gold, platinum, silver, copper, cobalt, nickel, palladium, vanadium, tungsten, tin oxide, zinc oxide, ITO (indium tin oxide), polythiophene, and polypyrrole. The substances used for the anode may be used alone or in combination of two or more. The material used for the anode is selected in consideration of adhesion to adjacent layers, ionization potential, stability, and the like.

  The anode can be formed on the substrate by a method such as vapor deposition or sputtering. Further, the anode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the anode is preferably several hundred Ω / □ or less, more preferably about 1 to 50 Ω / □. The thickness of the anode is generally about 5 to 1000 nm, more preferably about 10 to 500 nm.

  Examples of the substance used for the cathode include metals, alloys, metal oxides, conductive compounds, or two or more of these. Specific examples include alkali metals (eg, Li, Na, K, Cs, etc.) or alkali metal fluorides, organic salts such as naphthol, alkaline earth metals (eg, Mg, Ca, etc.) or alkali earth fluoride metals, gold, Examples thereof include silver, platinum, lead, aluminum, a sodium-potassium alloy, a lithium-aluminum alloy, a magnesium-silver alloy, or an alloy using two or more of these in combination, and rare earth metals such as indium and ytterbium. The substance used for the cathode is selected in consideration of the layer having the function of electron injection and transport, the adhesion between the cathode and the adjacent layer, the ionization potential, the stability, and the like.

A method such as an electron beam method, a sputtering method, a resistance heating vapor deposition method, or a coating method is used for producing the cathode, and a metal can be vapor-deposited alone or two or more components can be vapor-deposited simultaneously. Furthermore, it is also possible to form an alloy electrode by simultaneously depositing two or more kinds of metals. Further, an alloy prepared in advance may be deposited. The sheet resistance of the cathode is preferably low, and more preferably several hundred Ω / □ or less.
Although the thickness of a cathode can be suitably selected according to the substance to be used, the range of 10 nm-5 micrometers is preferable normally, More preferably, it is 50 nm-1 micrometer, More preferably, it is 100 nm-1 micrometer.

The bis (aminobiphenylethynyl) compound or white light emitting material of the present invention is used in an organic layer, particularly a layer having at least one function of hole injection / hole transport / light emission / electron transport / electron injection.
The bis (aminobiphenylethynyl) compound or the white light-emitting material of the present invention has any one of a hole injection / transport function, a light emission function, and an electron injection / transport function.

A compound having a hole injection transport function is used in a layer having a hole injection transport function, such as a hole injection layer, a hole transport layer, and a hole injection transport layer.
In the layer having a hole injecting and transporting function, only the bis (aminobiphenylethynyl) compound or white light emitting material of the present invention, only other compounds, or the bis (aminobiphenylethynyl) compound or white light emitting material and other compounds Use a combination with.
Specific examples of other compounds having a hole injecting and transporting function include phthalocyanine derivatives, triarylmethane derivatives, triarylamine derivatives, oxazole derivatives, hydrazone derivatives, stilbene derivatives, pyrazoline derivatives, polysilane derivatives, polyphenylene vinylene and derivatives thereof, polythiophene And derivatives thereof, poly-N-vinylcarbazole derivatives, and the like. Other compounds having a hole injecting and transporting function may be used alone or in combination of two or more.

A compound having a light emitting function is used in the light emitting layer. In the light emitting layer, a combination of the bis (aminobiphenylethynyl) compound and the yellow light emitting material or the bis (aminobiphenylethynyl) compound and the green light emitting material and the red light emitting material or other compound which is the blue fluorescent dye of the present invention. use.
Examples of the compound having a light emitting function other than the bis (aminobiphenylethynyl) compound or the bis (aminobiphenylethynyl) compound of the present invention and the yellow light emitting material or the white light emitting material combining green light emission and red light emission include, for example, an acridone derivative Quinacridone derivatives, diketopyrrolopyrrole derivatives, polycyclic aromatic compounds, triarylamine derivatives, compounds having an enamine structure, organometallic complexes, stilbene derivatives, pyran derivatives, oxazone derivatives, benzothiazole derivatives, benzoxazole derivatives, benzimidazoles Derivatives, pyrazine derivatives, cinnamic acid ester derivatives, poly-N-vinylcarbazole and its derivatives, polythiophene and its derivatives, polyphenylene and its derivatives, polyfluorene and its derivatives, polyphen Vinylene and derivatives thereof, poly biphenylene vinylene and derivatives thereof, poly terpolymers phenylene vinylene and derivatives thereof, poly naphthylene vinylene and derivatives thereof, polythienylenevinylene and a derivative thereof. These compounds having a light emitting function may be used alone or in combination of two or more.

Examples of the polycyclic aromatic compound include rubrene, anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, and 9,10-bis. (Phenylethynyl) anthracene, 1,4-bis (9′-ethynylanthracenyl) benzene, 4,4′-bis (9 ″ -ethynylanthracenyl) biphenyl and the like can be mentioned.
The organic layer containing the bis (aminobiphenylethynyl) compound or bis (aminobiphenylethynyl) compound of the present invention and a yellow light emitting material or a white light emitting material in which a green light emitting material and a red light emitting material are combined is a light emitting layer. It is preferable that

A compound having an electron injection / transport function is used in a layer having an electron injection / transport function such as an electron injection layer, an electron transport layer, and an electron injection / transport layer.
In a layer having an electron injecting and transporting function, only the bis (aminobiphenylethynyl) compound or white light-emitting material of the present invention, only another compound, or a bis (aminobiphenylethynyl) compound or bis (aminobiphenylethynyl) compound And a yellow fluorescent material or a combination of a white light emitting material obtained by combining a green light emitting material and a red light emitting material and another compound.
Examples of other compounds having an electron injecting and transporting function include, for example, organometallic complexes, oxadiazole derivatives, triazole derivatives, triazine derivatives, perylene derivatives, quinoline derivatives, diphenylquinone derivatives, nitro-substituted fluorenone derivatives, thiopyrandioxide derivatives, Examples thereof include quinoxaline derivatives and benzimidazole derivatives.

In the organic EL device of the present invention, the organic layer contains a bis (aminobiphenylethynyl) compound or a white light emitting material. When other compounds (for example, other compounds having a light emitting function or a hole (electron) injecting and transporting function) are used in combination, the ratio of the bis (aminobiphenylethynyl) compound or the white light emitting material in the organic layer is preferably Is 0.001% by weight or more, more preferably 0.1 to 99.9% by weight, for example 0.1 to 99% by weight, in particular 0.2 to 30% by weight, especially 0.5 to 20% by weight. .
In the organic layer, other compounds (having a light emitting function or a hole (electron) injecting and transporting function) as described above other than the bis (aminobiphenylethynyl) compound or the white light emitting material of the present invention may be used. . The amount of other compounds may be 0.01 to 99.9% by weight, for example 0.1 to 99.9% by weight, in particular 1 to 99.9% by weight, based on the organic layer.

  When an organic layer (especially, a light emitting layer) is formed by a solution coating method, only a compound having a light emitting function or a hole (electron) injecting and transporting function, or by dissolving or dispersing these compounds and a binder polymer in a solvent, To do. Examples of the binder polymer include poly-N-vinylcarbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl acrylate, polymethyl methacrylate, polyether, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, Polyethylene ether, polypropylene ether, polyphenylene oxide, polyether sulfone, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polyphenylene ethynylene and derivatives thereof, polyfluorene and derivatives thereof, polythienylene vinylene and derivatives thereof, etc. The high molecular compound of these is mentioned. The binder polymer may be used alone or in combination of two or more. The amount of binder polymer may be 1-99% by weight of the organic layer, for example 10-80% by weight.

The formation method of the organic layer (for example, a layer having a hole injecting and transporting function, a light emitting layer, and a layer having an electron injecting and transporting function) is not particularly limited, and a vacuum deposition method, an ionization deposition method, a solution coating method (for example, , Spin coating method, casting method, dip coating method, bar coating method, roll coating method, Langmuir-brozzet method, ink jet method, and the like). In the present invention, the organic layer is preferably formed by a spin coating method.
A white light-emitting material obtained by combining a bis (aminobiphenylethynyl) compound or a bis (aminobiphenylethynyl) compound and a yellow light-emitting material or a green light-emitting material and a red light-emitting material of the present invention has high solubility in a solvent. Since it dissolves well in a solvent in a uniform dispersion state, a good organic thin film layer can be obtained by solution coating (particularly, spin coating).
The thickness of each organic layer is preferably 5 to 500 nm, for example 25 to 250 nm, in particular 50 to 150 nm.

In the organic EL element, a protective liquid and a protective layer (sealing layer) may be provided. This prevents the organic EL element from coming into contact with oxygen, moisture, or the like. The protective liquid may be an inert liquid such as paraffin, liquid paraffin, silicone oil, fluorocarbon oil, or zeolite-containing fluorocarbon oil. The protective layer may be, for example, an organic polymer material (for example, a photocurable resin) or an inorganic material.
The voltage applied to the organic EL element is, for example, 0.1 to 50V.

  The organic EL element of the present invention can be suitably used for display elements, displays, backlights, electrophotography, illumination light sources, recording light sources, exposure light sources, reading light sources, signs, signboards, interiors, optical communications, and the like.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to the following examples.

Synthesis example 1
[Precursor synthesis]

2.2 g of N- (4′-iodo-4-biphenyl) -N- (3-tolyl) phenylamine (hereinafter abbreviated as “iodine”), 0.56 g of trimethylsilylacetylene, 0.07 g of copper iodide, 0.14 g of catalyst PdCl ₂ (PPh ₃ ) ₂ and 25 ml of triethylamine were mixed and reacted by stirring at room temperature for 4 hours under a nitrogen atmosphere. After separation of the reaction solution, the crude product was purified by column chromatography to obtain 2.5 g of a reaction product. 2.5 g of the obtained reaction product, 1 g of potassium carbonate and 35 ml of methanol were mixed and stirred at room temperature for 7 hours. The reaction solution was subjected to liquid separation treatment and purified by column chromatography to obtain N- (4′-ethynyl-4-biphenyl) -N- (3-tolyl) phenylamine (hereinafter abbreviated as “acetylene body”). . The formation of acetylene was confirmed by IR, 1H-NMR and 13C-NMR analyses.

Example 1
[Synthesis of Compound TFD-070]

Using the acetylene compound produced in Synthesis Example 1 and the diiodo compound, the following formula:

The compound TFD-070 was synthesized by performing the coupling reaction as follows.

0.16 g of acetylene, 0.12 g of 1,4-diiodo-2,5-dioctylbenzene, 4 mg of catalyst copper iodide, 8 mg of catalyst PdCl ₂ (PPh ₃ ) ₂ and 5 ml of triethylamine were mixed under a nitrogen atmosphere. The reaction was stirred at room temperature for 3 hours. The reaction solution was discharged into water and extracted with chloroform. The crude product obtained by concentration was purified by column chromatography to obtain 0.17 g of TFD-070. From the following analytical data, it was confirmed that the obtained product was TFD-070.
Explanation of analytical data: Proton NMR ( ¹ H-NMR) was measured at 300 MHz in a deuterated p-dioxane (C ₄ D ₈ O ₂ ) solvent using a λ-300 nuclear magnetic resonance apparatus manufactured by JEOL. Mass spectrometry was measured using an AXIMA MALDI-TOFMS analyzer manufactured by Shimadzu Corporation or an LCMS-2010EV liquid chromatograph mass spectrometer (LC-Mass) manufactured by Shimadzu Corporation. IR was measured using an IR-Prestage-21 type infrared spectrometer manufactured by Shimadzu Corporation. The ultraviolet / visible light (UV / Vis) electron absorption spectrum was measured in a chloroform solvent using a V-560 type electron spectrometer manufactured by JASCO Corporation.
TFD-070: 1H-NMR (300 MHz, C4D8O2) δ: 0.87 (t, 6H), 1.25-1.51 (m, 20H), 1.70-1.82 (m, 4H), 2.25 (s, 6H), 2.87 (t , 4H), 6.85-7.68 (m, 36H); TOF-MS (m / z) 1016 (M +); IR: νmax / cm-1 3032, 2922, 1585.; UV / Vis (CHCl3): λmax (ε ) 378nm (101000).

Example 2
[Synthesis of Compound TFD-072]

Using the acetylene compound produced in Synthesis Example 1 and the diiodo compound, the following formula:

The compound TFD-072 was synthesized by carrying out a coupling reaction as follows.
0.16 g of acetylene, 0.14 g of 2,7-diiodo-9,9-dioctylfluorene, 4 mg of catalyst copper iodide, 8 mg of catalyst PdCl ₂ (PPh ₃ ) ₂ and 5 ml of triethylamine were mixed under nitrogen atmosphere. The reaction was stirred at room temperature for 2 hours. The reaction solution was discharged into water and extracted with chloroform. The crude product obtained by concentration was purified by column chromatography to obtain 0.19 g of compound TFD-072. From the following analytical data, it was confirmed that the obtained product was TFD-072.
Analytical data: TFD-072: ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 0.55-0.70 (m, 4H), 0.77-0.86 (m, 6H), 1.04-1.30 (m, 20H), 1.95-2.04 (m, 4H), 2.28 (s, 6H), 6.85-7.70 (m, 40H); TOF-MS (m / z) 1106 (M +); ν _max / cm ^-1 3032, 2924, 1593 .; UV / Vis (CHCl ₃ ): λmax (ε) 381nm (123000).

Example 3
[Synthesis of Compound TFD-052]

The following reaction formula:

TFD-052
According to the above, compound TFD-052 was synthesized by a coupling reaction of iodine and a diacetylene derivative.

1.0 g of iodine body, 0.16 g of 2,5-diethynyl-1,4-dimethoxybenzene (“diacetylene derivative”), 0.022 g of copper iodide, 0.037 g of PdCl ₂ (PPh ₃ ) ₂ as a catalyst, The mixture was mixed with 15 ml of triethylamine and stirred for 30 hours at 40 ° C. under a nitrogen atmosphere. The reaction solution was filtered, and the resulting crude product was purified by column chromatography to obtain 0.43 g of the desired product. The formation of TFD-052 was confirmed by ¹ H-NMR, -MS, IR, and UV / Vis analysis.
Analytical data: TFD-052: ¹ H-NMR (300 MHz, CDCl ₃ ) δ2.28 (s, 6H), 3.93 (s, 6H), 6.86-7.30 (m, 24H), 7.48-7.63 (m, 12H ); LC-MS (m / z) 853 (M +); ν _max / cm ^-1 3034, 2953, 2853, 2201 .; UV / Vis (CHCl ₃ ): λmax (ε) 390 nm (80400) .λem 457 nm (λex 390nm)

Example 4
[Synthesis of Compound TFD-095]

The following reaction formula:

Then, a coupling reaction was performed using the acetylene body produced in Synthesis Example 1 and the diiodo compound to synthesize Compound TFD-095.

Acetylene compound 0.10 g, 4,4′-diiodo-3,3′-bistrifluoromethylbiphenyl 75 mg, catalyst copper iodide 2 mg, catalyst PdCl ₂ (PPh ₃ ) ₂ mg and triethylamine 2 ml were mixed, and nitrogen was mixed. The reaction was stirred for 6 hours at room temperature under atmosphere. The reaction solution was discharged into water and extracted with chloroform. The crude product obtained by concentration was purified by column chromatography to obtain 0.10 g of Compound TFD-095. From the following analytical data, it was confirmed that the obtained product was TFD-095.
Analytical data: TFD-095: ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 2.29 (s, 6H), 6.87-7.94 (m, 40H); LC-MS (m / z) 1004 (M +); ν _max / cm ^-1 3034, 2920, 1593 .; UV / Vis (CHCl ₃ ): λmax (ε) 368 nm (86500).

Example 5
[Synthesis of Compound TFD-068]

  Compound TFD-068 was synthesized in the same manner as in Example 3, except that 2,5-diethynyl-1,4-dibutoxybenzene was used instead of 2,5-diethynyl-1,4-dimethoxybenzene in Example 3. did.

Synthesis example 2
[Synthesis of Compound TFD-064]

The following reaction formula:

According to the above, Compound TFD-064 was synthesized as follows.

0.66 g of the benzoxazine derivative was dissolved in 5 ml of acetic anhydride, 0.45 g of 4-trifluorobenzaldehyde was added, and the reaction was stirred at 100 ° C. for 16 hours. The mixture was returned to room temperature, discharged into a mixed solvent of chloroform and water, neutralized with alkali, and extracted with chloroform. After the solvent was distilled off, the residue was purified by column chromatography to obtain 0.13 g of compound TFD-064. From the following analytical data, it was confirmed that the obtained product was TFD-064.
Analytical data: TFD-064: ¹ H-NMR (300 MHz, CDCl ₃ ) δ: 1.94-2.03 (m, 4H), 2.77-2.87 (m, 4H), 3.28-3.34 (m, 4H), 7.13 (s , 1H), 7.47 (d, J = 6.3Hz 1H), 7.60 (d, J = 8.3Hz 2H), 7.68 (d, J = 8.3Hz 2H), 7.87 (d, J = 6.3Hz 1H); LCMS ( m / z) 413 (MH +); ν: max / cm ^-1 2943, 2851, 1724, 1626 .; UV / Vis (Toluene): λmax (ε) 499nm (55000).

Example 6
The fluorescence characteristics of the bis (aminobiphenylethynyl) compounds TFD-052, TFD-070, and TFD-072 obtained in Examples 1 to 3 were measured on a quartz substrate in a chloroform solution and a solution in which a luminescent material was dissolved. It was measured in the state of a thin film spin-coated. The measurement was performed with a FluoraMax-4P spectrophotometer manufactured by Horiba. The obtained results are shown in Table 1.
Table 1 Fluorescence emission characteristics of bis (aminobiphenylethynyl) compounds

Each notation in the table is as follows:
Dye: Bis (aminobiphenylethynyl) compound λmax: Maximum absorption wavelength of molecular absorption spectrum (nm)
ε: Molecular extinction coefficient λem: Maximum fluorescence emission wavelength (nm)
λex: Excitation wavelength (nm)

Example 7
[Production of monochromatic organic EL device using bis (aminobiphenylethynyl) compound]
An organic EL element having the structure shown in FIG. 1 was produced by the following method.
The organic EL element configuration was ITO (anode) / PEDOT: PSS (hole injection layer) / PVCz: PBD: Dye (light emitting layer) / CsF (electron injection layer) / Al (cathode).
A 150 nm thick indium tin oxide (ITO) transparent conductive film deposited on a glass substrate (manufactured by Sanyo Vacuum Co., Ltd .; sheet resistance 10Ω, 20 mm (horizontal) × 25 mm (vertical) × 0.7 mm (glass film thickness)) Was patterned into a stripe having a width of 5 mm using a normal photolithography technique and zinc-hydrochloric acid etching to form an anode. After cleaning with zinc-hydrochloric acid, the patterned ITO substrate was cleaned in the order of ultrasonic cleaning with chloroform, cleaning with neutral detergent, water cleaning with pure water, ultrasonic cleaning with ethanol and acetone, and Soxhlet cleaning with isopropyl alcohol. Dry with nitrogen blow. Finally, after surface hydrophilization by ozone treatment, it was placed in a spin coater.
On top of that, poly (ethylenedioxythiophene): poly (styrene sulfonic acid) (PEDOT: PSS) was spin-coated (thickness 30 nm). The spin coating was performed at 25 ° C. under conditions of 1500 seconds / minute for 2 seconds and then 3000 rpm / minute for 60 seconds.
The structural formula of PEDOT: PSS is shown below.

PEDOT: PSS

  Next, bis (aminobiphenylethynyl) compound and 2- (4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole (PBD, Tokyo Chemical Industry Co., Ltd.) A toluene solution dispersed in carbazole (PVCz, Sigma-Aldrich Co., Ltd.) was filtered through a microfilter and then spin-coated to prepare a dye thin film (120 nm). The spin coating was performed at 25 ° C. under the condition of 1000 rpm for 3 seconds and then 3000 rpm for 30 seconds. Examples of structural formulas of PVCz, PBD, and bis (aminobiphenylethynyl) compounds are shown below.

PVCz

PBD

Here, the device on which the spin coating was applied was used as a mask for cathode vapor deposition, and a 2 mm wide stripe-shaped shadow mask was brought into close contact with the device so as to be orthogonal to the ITO ITO stripe and installed in a vacuum vapor deposition apparatus. The inside was evacuated until the degree of vacuum became 1 × 10 ⁻⁶ Torr or less. Subsequently, cesium fluoride was deposited using a tungsten boat to a thickness of 1.0 nm, and an electron injection layer was produced. Furthermore, aluminum was vapor-deposited using a tungsten boat so as to have a film thickness of 200 nm to produce a cathode. The degree of vacuum during vapor deposition was 4 × 10 ⁻⁶ Torr. The substrate temperature during cathode deposition was kept at room temperature. As described above, an organic EL element having a light emitting area portion having a size of 5 mm × 2 mm was obtained. The outline of the obtained organic EL element is shown in FIG.

In FIG. 1, an organic EL device includes a substrate 11, an ITO anode 12, a poly (ethylenedioxythiophene): poly (styrene / sulfonic acid) (PEDOT: PSS) layer 13, a bis (aminobiphenylethynyl) compound and a PBD. Are dispersed in PVCz, an electron injection layer (CsF) 15, and a cathode (aluminum) 16. Layer 13 serves as a hole injecting and transporting layer, and layer 14 serves as a light emitting layer.
The luminance of this organic EL element was measured. The obtained results are shown in Table 2, and the chromaticity coordinates are shown in FIG. Maximum luminance of the organic EL device, when the light-emitting material is a TFD-072, if the 9534cd ^/ m 2, TFD-070 at 12.5 V, when the 9258cd ^/ m 2, TFD-052 at 12V, 6348Cd in 11.5V / M ² .
Table 2 Characteristics of organic EL light emitting devices in single color

The element structure is ITO (anode) / PEDOT: PSS (hole injection layer) / PVCz: PBD: Dye (light emitting layer) / CsF (electron injection layer) / Al (cathode).
Each notation in the table is as follows:
Blue, Green, Yellow, Red: Fluorescent color of fluorescent dye used Dye: Bis (aminobiphenylethynyl) compound (blue fluorescent dye) number or other fluorescent dye number x: Content ratio of fluorescent dye to PVCz = 1 (weight) ratio)
Voltage: Applied voltage (V)
Chromaticity coordinates: (x, y) value EL wavelength: light emission maximum wavelength (nm)

Reference example 1
[Characteristics of monochromatic organic EL devices using yellow fluorescent dye, green fluorescent dye or red fluorescent dye]
In combination with the blue fluorescent bis (aminobiphenylethynyl) compound of the present invention, a yellow light emitting material having a complementary color relationship giving a two-color white light emitting material, a green light emitting material giving a three color white light emitting material, or For each of the red light emitting materials, the organic EL characteristics in a monochromatic system were measured according to Example 7. The obtained results are shown in Table 2 together with the results of Example 5.
Moreover, the position of the chromaticity coordinate of each fluorescent dye of Table 2 is shown in FIG.

  The structural formulas of the luminescent materials used in Example 7 and Reference Example 1 are shown below:

Example 8
[Characteristics of two-color white light emitting device using TFD-052 as a blue fluorescent dye and TFD-064 as a yellow fluorescent dye having a complementary color relationship therewith]
Based on the chromaticity coordinates shown in Table 2 and FIG. 2, TFD-052 was used as a blue fluorescent dye, and TFD-064 was selected as a yellow fluorescent dye complementary to the blue fluorescent dye. The amount of dispersion with respect to polyvinyl carbazole was studied. The device configuration is the same as the configuration studied in the single color of Example 7, ITO (anode) / PEDOT: PSS (hole injection layer) / PVCz: PBD: Dye (light emitting layer) / CsF (electron injection layer) / Al (cathode). ). The dispersion amount of the blue fluorescent dye TFD-052 was fixed to the optimum dispersion amount of 0.05 alone, and the configuration of emitting white light was examined by changing the dispersion amount of the yellow fluorescent dye TFD-064. The results are shown in Table 3.
Table 3 Dichroic white light emitting device characteristics (1)

The notation in the table is as follows:
x: Content ratio (weight ratio) of blue fluorescent dye TFD-052 to PVCz = 1
y: Content ratio (weight ratio) of yellow fluorescent dye TFD-064 to PVCz = 1
Voltage: Applied voltage (V)
Chromaticity coordinates: (x, y) value EL wavelength: light emission maximum wavelength (nm)

  FIG. 3 shows an electroluminescence (EL) spectrum when examined as a dichroic white light-emitting element. As the amount of yellow component dispersion (y) increases, the intensity of the yellow light-emitting portion in the EL spectrum increases, and it can be seen that the amount of dispersion with respect to polyvinylcarbazole is important when producing a white color. From the results of both the chromaticity coordinate (x, y) values and the EL spectrum in Table 3, it can be seen that the combination ratio of Entry 3 and Entry 4 has good characteristics as a white light-emitting element.

Example 9
[Two-color white light emitting device characteristics using TFD-072 as a blue fluorescent dye and TFD-064 as a yellow fluorescent dye having a complementary color relationship therewith]
The EL element configuration is the same as in Example 8, and the dispersion amount of the blue light-emitting dye TFD-072 is fixed to the optimum dispersion amount of 0.12 alone, and further, the dispersion amount of the yellow light-emitting dye TFD-064 is changed to change the white color. The configuration for emitting light was studied. The examination results are shown in Table 4.
Table 4 Dichroic white light emitting device characteristics (2)

The notation in the table is the content ratio (weight ratio) of the blue fluorescent dye TFD-072 to x: PVCz = 1.
Other than that, it is synonymous with Table 3.

Even when TFD-072 is used as the blue fluorescent dye, it has been found that there is an optimum amount of dispersion. For example, Entry 4 provides a white light emitting device having a luminance of 17060 cd / m ² at an applied voltage of 11 V. It was.

Example 10
In the dichroic white light-emitting element, a configuration that emits white light was examined using the same method as in Example 9 except that TFD-070 was used as the blue light-emitting material and TFD-079 was used as the yellow light-emitting material. When an energization test was performed on these, a white light emitting element having a luminance of 12490 cd / m ² with an applied voltage of 13 V was obtained.

Example 11
In the dichroic white light-emitting element, a configuration that emits white light was studied using the same method as in Example 9 except that TFD-072 was used as the blue light-emitting material and TFD-079 was used as the yellow light-emitting material. When an energization test was performed on these, a white light emitting element having a luminance of 16520 cd / m ² with an applied voltage of 12 V was obtained.

Example 12
[Trichromatic white light emitting device characteristics using TFD-072 as a blue fluorescent dye, TFD-005 as a green fluorescent dye, and TFD-006 as a red fluorescent dye]
As in Example 5, the EL device configuration was ITO (anode) / PEDOT: PSS (hole injection layer) / PVCz: PBD: Dye (light emitting layer) / CsF (electron injection layer) / Al (cathode). TFD-072 was used as the blue fluorescent dye, TFD-005 was selected as the green fluorescent dye, and TFD-006 was selected as the red fluorescent dye, and optimization of the dispersion amount of each of the three color dyes was examined. To proceed with the study, we first studied the optimal amount of dispersion to create white by mixing the two colors of blue and green fluorescent dyes (Entry 1 and 2), and then added red to the dispersion concentration. The approach to consider (Entry 3 and 4) was adopted. The results obtained are shown in Table 5.
Table 5 Three-color white light emitting device characteristics using blue fluorescent dye (TFD-072), green fluorescent dye (TFD-005) and red fluorescent dye (TFD-006)

The notation in the table is
x: Content ratio (weight ratio) of blue fluorescent dye TFD-072 to PVCz = 1
y: Content ratio (weight ratio) of green fluorescent dye TFD-005 to PVCz = 1
z: Content ratio (weight ratio) of red fluorescent dye TFD-006 to PVCz = 1
Other than that, it is synonymous with Table 3.

In chromaticity coordinates (0.36, 0.36), it succeeded in extracting almost white light emission. Therefore, Entry 4 is optimal as a three-color white light emitting element. As a first step, in the mixed dispersion element of the blue fluorescent dye and the green fluorescent dye, an element exceeding 25000 cd / m ² was obtained with light emission in the vicinity of the target chromaticity coordinate (Entry 1). By adding a red fluorescent dye, the target white emission spectrum was obtained, but the luminance was slightly reduced to 14780 cd / m ² (Entry 4). The main reason for the EL characteristics in the monochromatic system is that the luminance (2922 cd / m ² ) of the red fluorescent dye TFD-006 used is lower than that of the blue fluorescent dye or the green fluorescent dye. If limited to this example, it is suggested that the selection of the red fluorescent dye is important for improving the characteristics of the three-color white light emitting device.

Example 13
In the three-color white light-emitting element, a structure that emits white light using the same method as in Example 12 except that TFD-072 is used as a blue light-emitting material, TFD-082 is used as a green light-emitting material, and TFD-006 is used as a red light-emitting material. It was investigated. When an energization test was performed on these, a white light emitting device having a luminance of 21300 cd / m ² with an applied voltage of 13 V was obtained.

Example 14
In the three-color white light-emitting element, a structure that emits white light using the same method as in Example 12 except that TFD-072 is used as the blue light-emitting material, TFD-082 is used as the green light-emitting material, and TFD-080 is used as the red light-emitting material. It was investigated. When an energization test was performed on these, a white light emitting device having a luminance of 17570 cd / m ² with an applied voltage of 12.5 V was obtained.

Example 15
In the three-color white light-emitting element, a structure emitting white light using the same method as in Example 12 except that TFD-070 is used as the blue light-emitting material, TFD-082 is used as the green light-emitting material, and TFD-080 is used as the red light-emitting material. It was investigated. When an energization test was performed on these, a white light emitting device having a luminance of 12000 cd / m ² with an applied voltage of 14 V was obtained.

Example 16
In the three-color white light emitting device, a structure emitting white light using the same method as in Example 12 except that TFD-072 is used as a blue light emitting material, TFD-082 is used as a green light emitting material, and Ir-1 is used as a red light emitting material. It was investigated. When an energization test was performed on these, a white light emitting device having a luminance of 14330 cd / m ² at an applied voltage of 13.5 V was obtained.

Example 17
In the three-color white light-emitting element, a structure emitting white light using the same method as in Example 12 except that TFD-072 is used as a blue light-emitting material, TFD-082 is used as a green light-emitting material, and Ir-2 is used as a red light-emitting material. It was investigated. When an energization test was performed on these, a white light emitting device having a luminance of 19120 cd / m ² at an applied voltage of 14.5 V was obtained.

Example 18
In the three-color white light emitting device, a structure emitting white light using the same method as in Example 12 except that TFD-072 is used as a blue light emitting material, TFD-082 is used as a green light emitting material, and Ir-3 is used as a red light emitting material. It was investigated. When an energization test was performed on these, a white light emitting device having a luminance of 17090 cd / m ² with an applied voltage of 13.5 V was obtained.

The results of the above-described characteristics of the two-color and three-color white light emitting elements are summarized in Table 6, and the TFD-52 / TFD-064 mixed system, TFD-072 / TFD-064 mixed system, and TFD-072 / FIG. 4 shows an EL spectrum of the TFD-005 / TFD-006 mixed system.
Table 6 Summary of characteristics of dichromatic and trichromatic white light emitting devices

Of the notations in the table, Ra represents the average color rendering index, and the other notations are as defined above.
Here, the average color rendering index is an index representing how accurately the sample light source reproduces the test colors R1 to R8 compared to the reference light, and Ra = 100 is the same as the reference light. Thus, the closer to Ra = 100, the better the color rendering. The formula is as follows:
Ra = Σ (i = 1-8) Ri × 1/8
Ri = 100−4.6 × ΔEi
ΔEi is the color difference in the CIE1964 uniform color space

From Table 6, the two-color system and the three-color system succeeded in extracting white light emission exceeding 12000 cd / m ² , and the drive voltage (applied voltage) was also reduced. Although the luminance and chromaticity coordinates are not so different between the two-color system and the three-color system, the average color rendering index (Ra) is greatly different, and Ra exceeds 90 in all compositions of the three-color white light emitting element. High color rendering was obtained. For trichromatic white light emitting elements, red light emitting materials are dispersed, so there is light emission in the long wavelength region and a broad EL spectrum compared to the dichroic system, and it is possible to emit light in a wider wavelength region. It seems to have a positive effect on sex. As a white light-emitting element, it was desirable that the light-emitting element was composed of three colors.

  The novel compound of the present invention that provides a blue fluorescent dye that has high emission luminance, is robust, and has good solubility provides a highly functional white organic EL device using the blue fluorescent dye, such as a mobile phone or a digital camera. It can be used as a small display. In the future, it can also be used for flexible displays.

The description of symbols in the EL element of FIG. 1 is as follows:
DESCRIPTION OF SYMBOLS 11 Board | substrate, 12 Anode, 13 PEDOT: PSS layer, 14 Light emitting layer, 15 Electron injection layer, 16 Cathode

Claims (26)

General formula (1):
[In the formula, each of R ^{1 to} R ²⁰ is the same or different and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a halogen atom, an alkyloxy group having 1 to 10 carbon atoms, or an alkyl having 1 to 10 carbon atoms. A primary or secondary amino group having a group,
L is a divalent organic group having a general formula (TFD-000 to TFD-004):
[In the formula, each of R ^{21 to} R ⁴⁰ is the same or different and is a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkyloxy group having 1 to 12 carbon atoms, and each of R ⁴¹ and R ⁴² is Are the same or different and are alkyl groups having 1 to 12 carbon atoms. ]
A bis (aminobiphenylethynyl) compound represented by the formula: Each of R ^{1 to} R ^{20 in} the general formula (1) is the same or different and is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or an alkyloxy group having 1 to 10 carbon atoms. The described compound. The compound is represented by the general formula (1-1):
[Wherein L is as defined above. ]
The compound of Claim 1 or 2 which is represented by these. The compound has the general formula (1-2):
[Wherein, each of R ⁴³ and R ⁴⁴ is the same or different and is an alkyl group having 1 to 12 carbon atoms. ]
The compound according to any one of claims 1 to 3, which is represented by: The compound has the general formula (1-3):
[Wherein, each of R ⁴⁵ and R ⁴⁶ is the same or different and is an alkyl group having 1 to 12 carbon atoms. ]
The compound according to any one of claims 1 to 3, which is represented by: The compound has the general formula (1-4):
[Wherein, each of R ⁴⁷ and R ⁴⁸ is the same or different and is an alkyl group having 1 to 12 carbon atoms. ]
The compound according to any one of claims 1 to 3, which is represented by: The compound is represented by the general formula (1-5):
[Wherein, each of R ^{48 (1)} and R ^{48 (2)} is the same or different and is an alkyl group having 1 to 12 carbon atoms. ]
The compound according to any one of claims 1 to 3, which is represented by: The compound has the formula (TFD-052):
Or the formula (TFD-070):
Or the formula (TFD-072):
Or the formula (TFD-068):
Or the formula (TFD-095):
The compound as described in any one of Claims 1-7 which is represented by these.   The compound according to any one of claims 1 to 8, wherein the compound is a blue fluorescent dye.   The compound according to any one of claims 1 to 8, wherein the compound is a fluorescent dye for organic electroluminescence.   It is an organic electroluminescent element which has a pair of electrode and the light emitting layer containing the luminescent material which exists between this electrode, Comprising: This luminescent material contains the compound as described in any one of Claims 1-8. Organic electroluminescence device.   It is a manufacturing method of the organic electroluminescent element which has a pair of electrode and the light emitting layer containing the luminescent material which exists between this electrode, Comprising: Bis (aminobiphenyl ethynyl) as described in any one of Claims 1-8, ) A light emitting layer is formed by a solution coating method using a compound based on a light emitting material, and a method for producing an organic electroluminescent element.   A dichroic white light-emitting material comprising the compound according to any one of claims 1 to 8 and a luminescent dye having a complementary color relationship.   A dichroic white light-emitting material comprising at least one compound according to claim 8 and a luminescent dye having a complementary color relationship. A compound (TFD-064) having a complementary color relationship with at least one compound according to claim 8:
The dichroic white light-emitting material according to claim 13 or 14, comprising a fluorescent dye represented by the formula: A compound (TFD-079) having a complementary color relationship with at least one compound according to claim 8:
The dichroic white light-emitting material according to claim 13 or 14, comprising a fluorescent dye represented by the formula:   A three-color white luminescent material comprising the compound according to any one of claims 1 to 8, a green luminescent dye, and a red luminescent dye.   A three-color white light-emitting material comprising at least one compound according to claim 8, a green light-emitting dye, and a red light-emitting dye. At least one compound according to claim 8 and the general formula (2):
[Wherein, R ⁴⁹ represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may have a substituent. ]
A green luminescent dye represented by formula (3):
[Wherein, each of R ⁵⁰ and R ⁵¹ is the same or different and is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may have a substituent. ]
The trichromatic white light-emitting material according to claim 17 or 18, comprising a red light-emitting dye represented by the formula: Formula (TFD-072):
A compound represented by
Formula (TFD-005):
A green fluorescent dye represented by
Formula (TFD-006):
The trichromatic white light-emitting material according to claim 17, comprising a red fluorescent dye represented by the formula: Formula (TFD-072):
A compound represented by
Formula (TFD-082):
A green fluorescent dye represented by
Formula (TFD-080):
The trichromatic white light-emitting material according to claim 17, comprising a red fluorescent dye represented by the formula: Formula (TFD-070):
A compound represented by
Formula (TFD-082):
A green fluorescent dye represented by
Formula (TFD-080):

The trichromatic white light-emitting material according to claim 17, comprising a red fluorescent dye represented by the formula: A compound according to any one of claims 1 to 7 and a general formula (2):
[Wherein, R ⁴⁹ represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may have a substituent. ]
The trichromatic white luminescent material according to claim 18 or 19, comprising a green luminescent dye represented by the formula (1) and a red phosphorescent dye. A compound according to any one of claims 1 to 8 and the general formula (2):
[Wherein, R ⁴⁹ represents a hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may have a substituent. ]
A green luminescent dye represented by
Formula (Ir-1):
Or formula (Ir-2):
Or formula (Ir-3):
The three-color white luminescent material according to any one of claims 17, 18 and 23, comprising a red phosphorescent dye represented by the formula:   It is an organic electroluminescent element which has a pair of electrode and the light emitting layer containing the luminescent material which exists between this electrode, Comprising: This luminescent material is a white luminescent property as described in any one of Claims 13-24. A white light-emitting organic electroluminescence device including a material.   It is a manufacturing method of the organic electroluminescent element which has a pair of electrode and the light emitting layer containing the luminescent material which exists between this electrode, Comprising: The white luminescent material as described in any one of Claims 13-24 is used. A method for producing a white light-emitting organic electroluminescent device, characterized in that a light-emitting layer is formed by a solution coating method.