JP2001131434A - Photo-denaturable luminescent organic dye and multi-color organic EL device using the same - Google Patents

Abstract

(57) [Problem] To provide a novel light-emitting (photobleaching) luminescent organic dye and an organic EL device using the same. SOLUTION: The following general formula (1): (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 2 carbon atoms, and Ar ¹ and Ar ² are aromatic groups. And an anthracene derivative represented by the following general formula (2): (Wherein, Ar ¹ and Ar ² are each independently selected from the group consisting of an aromatic ring and a heterocyclic ring). Organic dye and multicolor organic EL device using the same.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic EL device and a photo-modifiable luminescent organic dye used therefor.

[0002]

2. Description of the Related Art The present applicant has disclosed in Japanese Patent Application No. Hei 8-144948 (PCT / JP97 / 01626) two or more kinds of organic dyes which can serve as luminescent centers, and the use of such organic dyes.
In the process of manufacturing the L element, the organic light emitting dye layer is partially irradiated with electromagnetic waves (light irradiation) to modify any one or more kinds of dyes by photo-oxidation or photo-decomposition. Function is incapable or inadequate, the emission color is changed to make the emission color of the light-irradiated part different from the emission color of the unexposed part (hereinafter this is referred to as photobleaching). Technology).

In order to develop this technique, it is necessary to enrich the organic dyes (photobleachable organic dyes) which change or lose the luminous ability by exposure.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a novel light-denaturable (photobleachable) luminescent organic dye and an organic EL device using the same.

[0005]

Means for Solving the Problems A first aspect of the present invention is the following general formula (1):

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 2 carbon atoms, and Ar ¹ and Ar ² are aromatic groups. Anthracene derivative represented by the following general formula (2):

Embedded image (Wherein, Ar ¹ and Ar ² are each independently selected from the group consisting of an aromatic ring and a heterocyclic ring), a naphthacene derivative represented by the following general formula (3)

Embedded image (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 2 carbon atoms, and Ar ¹ and Ar ² are aromatic groups. A group independently selected from the group consisting of a ring and a heterocyclic ring, wherein R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are hydrogen, fluorine, a cyano group, a linear or branched C 1-20 group; Alkyl group, linear or branched alkoxy group having 1 to 20 carbon atoms, saturated aliphatic ring having 3 to 6 carbon atoms, aryl group which may have a substituent, linear or branched Mono- or dialkylamino groups, linear or branched mono-, di- or tri-alkylsilyl groups having 1 to 10 carbon atoms, each independently selected from the group consisting of the same or the same ring Two or more bonds in different groups At best, also spiro anthracene derivative represented by may also be) to form a condensed ring between two adjacent carbon atoms, and the following general formula (4)

Embedded image (Wherein, Ar ¹ and Ar ² are each independently selected from the group consisting of an aromatic ring and a heterocyclic ring,
R ¹¹ , R ¹² , R ¹³ and R ^{14 each} represent hydrogen, fluorine, a cyano group, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, A saturated aliphatic ring having 3-6, an aryl group which may have a substituent, a linear or branched mono- or dialkylamino group having 1-8 carbon atoms, a linear or branched mono-alkyl group having 1-10 carbon atoms, Groups independently selected from the group consisting of di- or tri-alkylsilyl groups, which may be bonded to one ring in the form of the same or different groups, and two or more Which may form a condensed ring between two matching carbon atoms), and a light-modifiable luminescent organic dye selected from the group consisting of spiro-based naphthacene derivatives.

The above Ar ¹ and Ar ² are

Embedded image

Embedded imageC₆₀And C₇₀ Independently selected from the group consisting of
The radical¹¹, R¹², R¹³, R¹⁴, R
^Fifteen, R¹⁶, R¹⁷And R¹⁸Is hydrogen, fluorine,
Cyano group, linear or branched alkyl having 1 to 20 carbon atoms
Group, a linear or branched alkoxy group having 1 to 20 carbon atoms,
It may have a saturated aliphatic ring having 3 to 6 carbon atoms and a substituent.
An aryl group, a linear or branched mono- or C1-C8 mono- or
Is a dialkylamino group, a straight or branched chain having 1 to 10 carbon atoms.
Group consisting of various mono-, di- or tri-alkylsilyl groups
Are each independently selected from
Two or more rings in the same or different groups
And condensation between two adjacent carbon atoms
May form a ring,²¹Is hydrogen, fluorine, silicon
An ano group and a linear or branched alkyl having 1 to 20 carbon atoms
A group selected from the group consisting of
Or two or more different groups may be bonded,
R²³Is hydrogen and a straight or branched chain having 1 to 20 carbon atoms
R is a group selected from the group consisting of²⁵
Is hydrogen, linear or branched alkyl having 1 to 20 carbons
, Cyano and alkyl groups having 1 to 2 carbon atoms
A group selected from the group consisting of anoalkyl groups;
³¹And R³²Is hydrogen, halogen, cyano group, carbon
A linear or branched alkyl group having 1 to 20 carbon atoms;
20 straight-chain or branched alkoxy groups having 3 to 6 carbon atoms
Saturated aliphatic ring, aryl group which may have a substituent, charcoal
A linear or branched mono- or di-alkyl group having a prime number of 1 to 8;
Amino groups, straight-chain or branched mono- and di-C 1-10
Or a trialkylsilyl group, each independently.
A group selected from the group consisting of R³¹And R³²Is one
May form a condensed ring with
⁴¹Is hydrogen, fluorine, cyano group, hydroxyl group, carbon number 1
20 linear or branched alkyl groups having 1 to 20 carbon atoms
A straight or branched alkoxy group, a straight chain having 1 to 4 carbon atoms,
Or a branched aralkyl group, a saturated aliphatic ring having 3 to 6 carbon atoms,
An aryl group which may have a substituent, having 1 to 8 carbon atoms
Linear or branched mono- or dialkylamino group, carbon
Linear or branched mono-, di- or tri-a
A group selected from the group consisting of
These may be two or more in the same or different groups in one ring
May be bonded to each other, or between two adjacent carbon atoms.
A condensed ring may be formed between them.

Specific examples of the compounds represented by the general formulas (1) and (2) include a compound group represented by the following formula.

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image (Wherein, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R
¹⁶ , R ¹⁷ and R ¹⁸ are hydrogen, fluorine, a cyano group, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, A saturated aliphatic ring, an aryl group which may have a substituent, a linear or branched mono- or dialkylamino group having 1 to 8 carbon atoms, a linear or branched mono-, di- or tri-alkyl group having 1 to 10 carbon atoms. Groups independently selected from the group consisting of alkylsilyl groups, which may be bonded to one ring in the form of the same or different groups, and two or more A condensed ring may be formed between atoms, and R ²¹ and R ²² are hydrogen, fluorine,
A group selected from the group consisting of a cyano group and a linear or branched alkyl group having 1 to 20 carbon atoms, and two or more of the same or different groups may be bonded to one ring; ²³ is a group selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 20 carbon atoms;
²⁵ and R ²⁶ are each independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyano group, and a dicyanoalkyl group having 1 to 2 carbon atoms in the alkyl group. R ³¹ , R ³² , R ³³ and R ³⁴ are hydrogen, halogen, cyano group, carbon number 1-2.
0 linear or branched alkyl group, 1 to 20 carbon atoms, linear or branched alkoxy group, 3 to 6 carbon atoms, saturated aliphatic ring, aryl group which may have a substituent, 1 to 1 carbon atoms
8 linear or branched mono- or dialkylamino groups,
A group independently selected from the group consisting of linear or branched mono-, di- or tri-alkylsilyl groups having 1 to 10 carbon atoms, wherein R ³¹ and R ³² are united to form a fused ring R ⁴¹ and R
⁴² is hydrogen, fluorine, cyano group, hydroxyl group, carbon number 1
A linear or branched alkyl group having 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, a linear or branched aralkyl group having 1 to 4 carbon atoms, a saturated aliphatic ring having 3 to 6 carbon atoms,
An aryl group which may have a substituent, a linear or branched mono- or dialkylamino group having 1 to 8 carbon atoms, and a linear or branched mono-, di- or tri-alkylsilyl group having 1 to 10 carbon atoms. Groups independently selected from the group consisting of two or more groups which may be bonded to one ring in the form of the same or different groups, and between two adjacent carbon atoms. A condensed ring may be formed. )

A second aspect of the present invention is a multicolor organic EL device having a light-emitting layer containing at least two kinds of organic dyes serving as luminescent centers, wherein at least one of the organic dyes is any one of claims 1 to 3. The present invention relates to a multicolor organic EL device characterized in that the light-emitting organic dye capable of being photo-modified is photo-modified to change the color of light emitted from the device.

The light emitting layer may be composed of only one layer, or may be composed of a plurality of layers. Electromagnetic wave irradiation (exposure) to one or more light-emitting layers containing an organic dye serving as a light-emitting center can be performed to any one or all layers. In this case, (a) when the irradiation intensity is changed over the entire surface (for example, while changing the irradiation intensity of light generated from a minute light source or exposing through a filter having a partially different transmittance such as a black and white negative film). (E.g., scanning) or (b) partial irradiation by masking. When performing partial exposure, for example, contact exposure is performed using a shadow mask, or projection exposure (partial exposure is performed using light collected by a lens or light generated from a minute light source. , Etc.).

The compound of the general formula (1) can be produced, for example, as in Production Example 2 described below.

The compound of the general formula (2) can be produced, for example, as in Production Example 1 described below.

FIG. 1 is a schematic view showing an embodiment (single-layer type) of an organic EL device according to the present invention. On a glass substrate (transparent substrate) 21, a transparent electrode constituting an anode electrode, for example, an ITO electrode 22, a luminescent layer 23 containing a luminescent dye, and a back electrode 24 serving as a cathode are sequentially laminated. The specific layered structure of the device is not particularly limited, and may be an anode / hole transport layer / light emitting layer / cathode, anode / light emitting layer / electron transport layer / cathode, anode / hole transport. Layer / emission layer / electron transport layer / cathode, anode / hole injection layer / emission layer / cathode, anode / hole injection layer / hole transport layer / emission layer / cathode, anode / hole injection layer / hole transport Layer / emission layer / electron transport layer / cathode.

FIG. 2 is a schematic view showing a method for manufacturing a multicolor organic EL device. Irradiation (exposure) of electromagnetic waves to one or more light-emitting layers containing an organic dye that can be a light-emitting center can be performed on any one or all layers. In this case, (a) when changing the irradiation intensity over the entire surface (for example, by exposing through a filter having a partially different transmittance such as a black and white negative film or changing the irradiation intensity of light emitted from a minute light source) (E.g., scanning) or (b) partial irradiation by masking. In the case of performing partial exposure, for example, contact exposure is performed using a photomask, or projection exposure (partial exposure is performed using light collected by a lens or light generated from a minute light source. , Etc.). Specifically, for example, a 3 mm wide stripe-shaped IT
Sixteen O electrodes (indicated by reference numeral 22 in the figure) are arranged in parallel at equal intervals (see FIG. 2A).
After forming 0 ° (FIG. 2B), the photomask 9 is adhered to the polymer surface, and the PVK layer 23 in which the dye is dispersed is entirely striped at regular intervals in the atmosphere through a filter using a high-pressure mercury lamp. Of the control dye was first denatured (FIG. 2C). Subsequently, the second control dye 6 was also denatured by irradiating a half of the area of the PVK layer 23 in which the specific control dye was denatured with a photomask in a stripe shape (FIG. 2D). . From above, a stripe-shaped Mg: Ag electrode having a width of 1 mm (24 in FIG.
48) were deposited to form a matrix type display element (FIG. 2E).

In an organic EL device, holes are injected from an anode, ie, a hole injection electrode, into an organic layer, and electrons are injected from a cathode, ie, an electron injection electrode, into an organic layer. Both carriers recombine in the organic layer which becomes the light emitting layer to generate excitons, that is, excited molecules. By dispersing a small amount of an organic dye having a lower excitation energy level as a dopant (guest) in the light emitting layer than the compound (host) used in the light emitting layer,
Excitation energy transfer can modulate the emission of the host to that from the dopant dye. In this case, when a plurality of types of dopant dyes are used, the color of light emitted from the device can be controlled by adjusting the concentration of each dopant dye (J. Kido et al., Appl.
hys. Lett. 67 2281, 1995).

In the present invention, in an element having two or more kinds of organic dyes capable of functioning as a plurality of kinds of luminescent centers, a part of any organic dyes, such as ultraviolet light or visible light, may be used. Irradiation of electromagnetic waves degrades only an arbitrary organic dye and modulates the emission color of the exposed portion. In particular, all pixels on the same substrate are red,
Green and blue pigments are included, and red, green,
If a blue light emitting pixel is formed, it can be used as a full color display.

In the present invention, the host compound which disperses a dopant dye which can be used in an organic EL device which exhibits not only full color but also two or several colors of color emission is not limited in emission color. In addition, carrier transportability, electron transportability, hole transportability, or dual carrier transportability may be used, and there is no particular limitation. Examples of the host compound are shown below.

The most common ones are anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene,
Phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene,
Tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, oxine, aminoquinoline, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran,
Examples thereof include polymethine, merocyanine, imidazole chelated oxinoid compounds, quinacridone, rubrene, and derivatives thereof.

Further, silanamine derivatives disclosed in JP-A-6-49079 and JP-A-6-293778, JP-A-6-279322 and JP-A-6-2
No. 79323, polyfunctional styryl compounds disclosed in JP-A-6-107648 and JP-A-6-929.
No. 47 oxadiazole derivatives,
Anthracene compounds disclosed in JP-A-6-206865, oxynate derivatives disclosed in JP-A-6-145146, tetraphenylbutadiene compounds disclosed in JP-A-4-96990, Organic trifunctional compound disclosed in JP-A-296595, coumarin derivatives disclosed in JP-A-2-191694, and JP-A-2-19.
No. 6885, the perylene derivative disclosed in JP-A-2-255789, the naphthalene derivative disclosed in JP-A-2-289676 and JP-A-2-289676.
Phthaloperinone derivatives disclosed in JP-A-8689 and styrylamine derivatives disclosed in JP-A-2-250292.

When intended to be used as a multi-color display of R (red), G (green), and B (blue), for example, a full-color display, it is necessary to emit red, green, and blue primary colors. . Therefore, the organic compound serving as the host material needs to emit blue (or near-ultraviolet light in terms of color) having a higher energy level, which corresponds to a peak wavelength of the emission spectrum of 370 to 500 nm. .

It is necessary that such an organic compound for a full-color display, that is, an organic compound which emits light in the near-ultraviolet to blue-green color and has a carrier transporting property. In this case, the organic compound may have an electron transporting property, a hole transporting property, or a dual carrier transporting property. The following are examples of organic compounds for hosts that satisfy these requirements.

As the organic compound for the host, p-
Polycyclic compounds such as terphenyl and quaterphenyl and derivatives thereof, naphthalene, tetracene, pyrene,
Condensed polycyclic hydrocarbon compounds such as coronene, chrysene, anthracene, diphenylanthracene, naphthacene, phenanthrene and derivatives thereof, phenanthroline, bathophenanthroline, phenanthridine, condensed heterocyclic compounds such as acridine, quinoline, quinoxaline, phenazine and the like Derivatives, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, oxadiazole, triazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, vinyl anthracene, carbazole, and the like and derivatives thereof , 8-quinolinolato or a derivative thereof as a ligand and at least 1
And other metal complexes.

Further, JP-A-5-202011, JP-A-7-179394, and JP-A-7-278124
Oxadiazoles disclosed in JP-A-7-228579, triazines disclosed in JP-A-7-157473, JP-A-6-20396
No. 3 stilbene derivative and distyryl arylene derivative, JP-A-6-132080 and JP-A-6-88072 disclose a styryl derivative, JP-A-6-100857 and JP-A-6-857.
The diolefin derivatives disclosed in JP-A-207170 can be used. As the distyrylbenzene-based compound, for example, those disclosed in European Patent No. 03753582 can be used. Typical examples are 1,4-bis (2-methylstyryl) benzene,
1,4-bis (3-methylstyryl) benzene, 1,4
-Bis (4-methylstyryl) benzene, distilbenzene, 1,4-bis (2-ethylstyryl) benzene,
1,4-bis (3-ethylstyryl) benzene, 1,4
-Bis (2-methylstyryl) -2-methylbenzene,
1,4-bis (2-methylstyryl) -2-ethylbenzene and the like can also be used.

A distyrylpyrazine derivative disclosed in JP-A-2-252793 can also be used as a host material for the light-emitting layer. As a typical example,
2,5-bis (4-methylstyryl) pyrazine, 2,5
-Bis (4-ethylstyryl) pyrazine, 2,5-bis [2- (1-naphthyl) vinyl] pyrazine, 2,5-bis (4-methoxystyryl) pyrazine, 2,5-bis [2- (4 -Biphenyl) vinyl] pyrazine, 2,5-
Bis [2- (1-pyrenyl) vinyl] pyrazine and the like can also be mentioned.

In addition, dimethylidin derivatives disclosed in European Patent No. 388768 and JP-A-3-231970 can also be used as a material for the organic light emitting layer. As typical examples, 1,4-phenylenedimethylidin, 4,4′-phenylenedimethylidin,
2,5-xylylenedimethylidin, 2,6-naphthylenedimethylidin, 1,4-biphenylenedimethyldin, 1,4-p-terephenylenedimethylidin, 9,
10-anthracene diyl dimethylidin, 4,4'-
(2,2-di-t-butylphenylvinyl) biphenyl, 4,4 '-(2,2-diphenylvinyl) biphenyl and the like, and derivatives thereof, and JP-A-6-4907.
No. 9, JP-A-6-293778, a polyfunctional styryl compound disclosed in JP-A-6-279322, JP-A-6-279323, and JP-A-6-107648. Oxadiazole derivatives disclosed in JP-A-6-92947, anthracene compounds disclosed in JP-A-6-206865, JP-A-6-14514
Oxynate derivatives disclosed in JP-A-6-96990, tetraphenylbutadiene compounds disclosed in JP-A-4-96990, organic trifunctional compounds disclosed in JP-A-3-296595, and 2-
Coumarin derivatives disclosed in 191694,
Perylene derivatives disclosed in JP-A-2-196885, naphthalene derivatives disclosed in JP-A-2-255789, phthaloperinone disclosed in JP-A-2-289676 and JP-A-2-88689 Derivatives, styrylamine derivatives disclosed in JP-A-2-250292, and the like.

Furthermore, arylamine compounds can also be mentioned as organic compounds that can be used as the host material of the light emitting layer. As the arylamine compounds,
Although there is no particular limitation, JP-A-6-25659, JP-A-6-203963, JP-A-6-215874, JP-A-7-145116, and JP-A-7-22
4012, JP-A-7-157473, JP-A-8-48656, JP-A-7-126226, JP-A-7-188130, JP-A-8-409
No. 95, JP-A-8-40996, JP-A-8-1996
Arylamine compounds disclosed in JP-A-40997, JP-A-7-126225, JP-A-7-101911, and JP-A-7-97355 are preferable. For example, N, N, N ', N' -Tetraphenyl-
4,4'-diaminophenyl, N, N'-diphenyl-
N, N'-di (3-methylphenyl) -4,4'-diaminophenyl, 2,2-bis (4-di-p-tolylaminophenyl) propane, N, N, N ', N'-tetra −
p-tolyl-4,4'-diaminobiphenyl, bis (4
-Di-p-tolylaminophenyl) phenylmethane,
N, N'-diphenyl-N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N,
N ', N'-tetraphenyl-4,4'-diaminophenyl ether, 4,4'-bis (diphenylamino) quadriphenyl, 4-N, N-diphenylamino (2
-Diphenylvinyl) benzene, 3-methoxy-4'-
N, N-diphenylaminostilbenzene, N-phenylcarbazole, 1,1-bis (4-di-p-triaminophenyl) -cyclohexane, 1,1-bis (4-di-p-triaminophenyl)- 4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) -phenylmethane, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4'-
[4 (di-p-tolylamino) styryl] stilbene,
N, N, N ', N'-tetra-p-tolyl-4,4'-
Diamino-biphenyl, N, N, N ', N'-tetraphenyl-4,4'-diamino-biphenyl N-phenylcarbazole, 4,4'-bis [N- (1-naphthyl)
-N-phenyl-amino] biphenyl, 4,4 "-bis [N- (1-naphthyl) -N-phenyl-amino] p-
Terphenyl, 4,4'-bis [N- (2-naphthyl)
-N-phenyl-amino] biphenyl, 4,4'-bis [N- (3-acenaphthenyl) -N-phenyl-amino] biphenyl, 1,5-bis [N- (1-naphthyl)
-N-phenyl-amino] naphthalene, 4,4'-bis [N- (9-anthryl) -N-phenyl-amino] biphenyl, 4,4 "-bis [N- (1-anthryl)-
N-phenyl-amino] p-terphenyl, 4,4'-
Bis [N- (2-phenanthryl) -N-phenyl-amino] biphenyl, 4,4'-bis [N- (8-fluoranthenyl) -N-phenyl-amino] biphenyl,
4,4'-bis [N- (2-pyrenyl) -N-phenyl-amino] biphenyl, 4,4'-bis [N- (2-perylenyl) -N-phenyl-amino] biphenyl,
4'-bis [N- (1-colonenyl) -N-phenyl-
Amino] biphenyl, 2,6-bis (di-p-tolylamino) naphthalene, 2,6-bis [di- (1-naphthyl) amino] naphthalene, 2,6-bis [N- (1-naphthyl) -N -(2-naphthyl) amino] naphthalene,
4,4 "-bis [N, N-di (2-naphthyl) amino]
Terphenyl, 4,4'-bis {N-phenyl-N-
[4- (1-naphthyl) phenyl] amino} biphenyl, 4,4'-bis [N-phenyl-N- (2-pyrenyl) -amino] biphenyl, 2,6-bis [N, N-di (2 -Naphthyl) amino] fluorene, 4,4 "-bis (N, N-di-p-tolylamino) terphenyl, bis (N-1-naphthyl) (N-2-naphthyl) amine, etc., and conventionally organic A known device used for manufacturing an EL element can be used as appropriate.

Further, those in which the above-mentioned organic compounds are dispersed in a polymer or those in which a polymer is formed can be used, and polymers of poly (N-vinylcarbazole) and polysilanes can also be used.

Also, distyrylpyrazine derivatives disclosed in JP-A-2-252793 can be used as organic dyes. Typical examples are 2,5-
Bis (4-methylstyryl) pyrazine, 2,5-bis (4-ethylstyryl) pyrazine, 2,5-bis [2-
(1-Naphthyl) vinyl] pyrazine, 2,5-bis (4
-Methoxystyryl) pyrazine, 2,5-bis [2-
(4-biphenyl) vinyl] pyrazine, 2,5-bis [2- (1-pyrenyl) vinyl] pyrazine and the like.

Examples of the fluorescent whitening agent used together with the luminescent dye for improving the efficiency of the organic EL device of the present invention include benzoxazole-based, benzothiazole-based and benzimidazole-based brighteners, for example, disclosed in JP-A-59-194393. What is disclosed is mentioned. As a typical example,
2,5-bis (5,7-di-t-pentyl-2-benzooxazolyl) -1,3,4-thiazole, 4,4'-
Bis (5,7-t-pentyl-2-benzooxazolyl) stilbene, 4,4'-bis [5,7-di- (2-
Methyl-2-butyl) -2-benzoxazolyl] stilbene, 2,5-bis (5,7-di-t-pentyl-2)
-Benzoxazolyl) thiophene, 2,5-bis [5
-(Α, α-dimethylbenzyl) -2-benzoxazolyl] thiophene, 2,5-bis [5,7-di- (2-
Methyl-2-butyl) -2-benzoxazolyl]-
3,4-diphenylthiophene, 2,5-bis (5-methyl-2-benzooxazolyl) thiophene, 4,4 ′
-Bis (2-benzoxazolyl) biphenyl, 5-methyl-2- {2- [4- (5-methyl-2-benzooxazolyl) phenyl] vinyl} benzoxazole, 2
-[2- (4-chlorophenyl) vinyl] naphtho (1,
2-d) benzoxazoles such as oxazole,
Benzothiazoles such as 2,2 '-(p-phenylenedivinylene) -bisbenzothiazole, 2- {2- [4
A fluorescent whitening agent such as a benzimidazole-based fluorescent agent such as-(2-benzimidazolyl) phenyl] vinyl} benzimidazole and 2- [2- (4-carboxyphenyl) vinyl] benzimidazole can also be used.

As the distyrylbenzene compound as a fluorescent whitening agent, for example, European Patent No. 037358
No. 2 can be used. Typical examples are 1,4-bis (2-methylstyryl) benzene, 1,4-bis (3-methylstyryl) benzene, 1,4-bis (4-methylstyryl) benzene, distyrylbenzene, , 4-bis (2-ethylstyryl) benzene, 1,4-bis (3-ethylstyryl) benzene, 1,4-bis (2-methylstyryl)
-2-methylbenzene, 1,4-bis (2-methylstyryl) -2-ethylbenzene and the like.

In addition, dimethylidene derivatives disclosed in European Patent No. 388768 and JP-A-3-231970 can be used as a material for the organic light emitting layer. As typical examples, 1,4-phenylenedimethylidin, 4,4′-phenylenedimethylidin,
2,5-xylylenedimethylidin, 2,6-naphthylenedimethylidin, 1,4-biphenylenedimethylidin, 1,4-p-terephenylenedimethylidin, 9,
10-anthracene diyl dimethylidin, 4,4'-
(2,2-di-t-butylphenylvinyl) biphenyl, 4,4 '-(2,2-diphenylvinyl) biphenyl, and the like, and derivatives thereof.

As the metal chelated oxanoid compound, for example, those disclosed in JP-A-63-295695 can be used. Representative examples are tris (8-quinolinol) aluminum, bis (8-quinolinol) magnesium, bis [benzo (f) -8-quinolinol] zinc, bis (2-methyl-
8-quinolinolate) aluminum oxide, tris (8-quinolinol) indium, tris (5-methyl-8-quinolinol) aluminum, lithium 8-quinolinol, tris (5-chloro-8-quinolinol) gallium, bis (5-chloro- 8-quinolinol) calcium, poly [zinc (II) -bis- (8-hydroxy-5)
-Quinolinonyl) methane] and dilithium epindridione.

The dopant is not particularly limited as long as it is a fluorescent organic compound. In addition to the above-mentioned electron transporting material, hole transporting material and light emitting material, coumarin derivatives and dicyanomethylene pyran derivatives known as laser dyes are used. And dicyanomethylenethiopyran derivatives, fluorescein derivatives, perylene derivatives, and porphyrin derivatives.

As the organic compound that can be used as the electron transporting layer, an organic compound having an electron transporting property among the above-mentioned host materials for the light emitting layer can be used.
695, JP-A-8-22557 and JP-A-8
In the metal chelate complex compounds disclosed in JP-A-81472, JP-A-5-9470 and JP-A-5-17764, particularly, metal chelated oxide compounds, tris (8-quinolinolato) aluminum and bis (8- Quinolinolato) magnesium, bis [benzo (f) -8-quinolinolato] zinc, bis (2-methyl-
8-quinolinolato) aluminum, tris (8-quinolinolato) indium, tris (5-methyl-8-quinolinolato) aluminum, 8-quinolinolatolithium, tris (5-chloro-8-quinolinolato) gallium, bis (5-chloro) -8-quinolinolato) 8 such as calcium
-A metal complex having at least one quinolinolato or a derivative thereof as a ligand is preferably used.

For the hole transporting layer, a hole transporting organic compound such as arylamine among the above-mentioned host materials for the light emitting layer can be used. Those in which the above-mentioned organic compounds are dispersed in a polymer or those which are polymerized can also be used. A so-called π-conjugated polymer such as polyparaphenylenevinylene and derivatives thereof and a polyalkylthiophene derivative, a hole-transporting non-conjugated polymer represented by poly (N-vinylcarbazole), and a sigma-conjugated polymer of polysilanes can also be used.

The hole injecting layer is not particularly limited, but metal phthalocyanines such as copper phthalocyanine and metal-free phthalocyanines, carbon films, and conductive polymers such as polyaniline can be suitably used. Further, a Lewis acid may be allowed to act on the above-mentioned arylamines as an oxidizing agent to form radical kaotin and be used as a hole injection layer.

As the electromagnetic wave irradiation method (exposure method), a known exposure method such as laser beam scanning can be used in addition to a contact exposure method using a photomask and a projection exposure method.

As the electromagnetic waves, those having an appropriate energy level such as visible light, ultraviolet light, X-rays, and γ-rays can be used.

As the various organic films used in the present invention, known thin film forming methods such as a vacuum evaporation method, a sputtering method, and a coating method can be used.

In the multi-color organic EL device according to the present invention, pixels emitting three kinds of light of red, green and blue are used side by side by modification. In the case of laminating, it is conceivable to perform lamination, but in the case of lamination, for example, it is necessary to perform lamination of electrode / red organic layer / electrode / green organic layer / electrode / blue organic layer / electrode, Compared to a separate process for each layer, if they are arranged in parallel, it is only necessary to arrange three types of light sources, red, green, and blue, and to provide electrodes on them, and the number of processes is extremely small, which is very advantageous. is there.

One pixel is composed of three types of RGB,
In an element where those pixels are arranged horizontally in parallel,
An image is formed by time-divisionally driving one of the two electrodes as a signal electrode and the remaining electrode as a scanning electrode to form a so-called passive matrix type RGB dot matrix display or a full color display.

Further, by adding an active element such as a transistor to each pixel of the RGB multi-color element to have a memory function, an active matrix type RG is provided.
It can be a B dot matrix display and a full color display.

According to the present invention, an organic layer having two or more kinds of dyes that can be luminescent centers is irradiated with light during the device manufacturing process to degrade any dye and modulate the color of light emitted from the device. By partially irradiating light, elements having different emission colors can be extremely easily arranged on the same substrate, and can be widely used for a multi-color display element and the like.

In particular, by arranging three layers of light-emitting pixels of red, green and blue as one pixel on a substrate, it can be widely used as a multi-color or full-color display.

[0044]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited thereby.

Production Example 1 (Synthesis of DPN) (1) Synthesis of 5,12-diphenylnaphthacene-6,11-dione (DPNO)

Embedded image In a 1-liter four-necked flask, 8.4 g (0.031 mol) of 1,3-diphenylisobenzofuran and 1,4-diphenylisobenzofuran were added.
5.2 g (0.031 mol) of naphthoquinone is added and dissolved in 265 ml of dichloromethane. This is stirred at room temperature for 20 hours under a nitrogen stream. Next, the flask was cooled in a dry ice-acetone bath, and 535 m
31 ml (0.33 mol) of boron tribromide diluted to 1
Is slowly dropped. After the dropwise addition, the mixture is brought to room temperature and further distilled on a hot water bath for 4 hours. After returning to room temperature, the reaction solution is poured into 500 ml of water in a 2 liter beaker. The solution is separated and the aqueous layer is extracted twice with 200 ml of dichloromethane. Combine the dichloromethane layers and wash with saturated saline. Thereafter, the solvent is recovered under reduced pressure. 5,12 obtained
-Diphenylnaphthacene-6,11-dione (DPN
O) was used for the next reaction without purification.

(2) 5,12-diphenylnaphthacene-
Synthesis of 6,11-diol (DPND)

Embedded image In a 500 ml four-necked flask, 150 ml of well-dried tetrahydrofuran (THF) was mixed with 5,12 previously synthesized.
-Diphenylnaphthacene-6,11-dione (DPN
O) 10 g (24.4 mmol) is added, and the mixture is stirred under a nitrogen stream. This solution contains lithium aluminum hydride.
5 g (66 mmol) are added slowly. Since it generates initial heat, cool it down with water. After the addition, the reaction is carried out at room temperature for 1 hour. Then, the reaction solution is poured into 500 ml of a saturated saline solution in a 1 liter beaker. The aqueous layer and the oil layer are separated, and the aqueous layer is extracted twice with 200 ml of dichloromethane. The obtained oil layer and dichloromethane layer are combined into one, and the solvent is recovered under reduced pressure. 5,12-diphenylnaphthacene-6,11-diol obtained (DPND)
Was used for the next reaction without purification.

(3) Synthesis of 5,12-diphenylnaphthacene (DPN)

Embedded image In a 1 liter four-necked flask, add tetrahydrofuran 3
8 ml of the previously synthesized 5,12-diphenylnaphthacene-6,11-diol (DPND) (19.4 m
mol) and adjust the distillation temperature. When the distillation begins gently, 240 ml of 57% hydroiodic acid are added dropwise. Thereafter, a post-reaction is carried out for 2 hours under distillation. It is then cooled to room temperature and poured into 1 liter of aqueous sodium persulfate in a 2 liter beaker. The solution is then extracted three times with 300 ml of ether. The ether layer is neutralized with a saturated aqueous sodium hydrogen carbonate solution and then dried over anhydrous sodium sulfate. After filtration, the solvent is recovered under reduced pressure. Further, the obtained residue is added to 1 liter of cyclohexane, heated together with clay, and subjected to hot filtration. The resulting cyclohexane solution is recovered under reduced pressure to obtain crude 5,12-diphenylnaphthacene (DPN). This crude product is recrystallized from acetic acid to obtain the desired 5,12-diphenylnaphthacene (DPN).
2.5 g (55% yield) were obtained. m. p. 207.4 ~
208.2 ° C (literature value 207-208 ° C)

Production Example 2 (Synthesis of DSA) (1) Synthesis of Wittig reagent (Wittig)

Embedded image Benzyl chloride 10 in a 200 ml four-necked flask
g (79.0 mmol) and triethyl phosphite 13.1
g (79.0 mmol) was added and the mixture was distilled for 24 hours. The obtained Wittig reagent was used as it was in the next step.

(2) Synthesis of DSA

Embedded image Witti obtained earlier in a 500 ml four-necked flask
g reagent 20 g (68.3 mmol) and 9,10-anthracene-dicarboxaldehyde 12.3 g (34.1 g).
mmol). 150 ml of well-dried tetrahydrofuran (THF) is added thereto, and the mixture is stirred at room temperature under a nitrogen stream. 9.2 g of potassium t-butoxide (1
(22.4 mmol). The reaction solution turned red at the same time as the introduction, and heat was generated. After the addition, the mixture is stirred at room temperature for 24 hours. After the reaction, pour into 500 ml of methanol in a 1 liter beaker. The obtained crystals are filtered, collected and dried. This crystal is n
3.3 g (8.5 mmol)
1) is obtained. m. p. 201.0-202.3 ° C (literature value 200-201 ° C)

Example 1 (Laminated multicolor element, FIG. 3
0.04 g of polyvinyl carbazole (PVK), formula

Embedded image A green coating of 1.6 mg (4 wt%) of 5,12-diphenylnaphthacene (DPN) in 1,2-dichloroethane (4.0 mL) was spin-coated on a 25 mm × 25 mm ITO glass substrate by spin coating (1700 rpm).
m, 3 sec) to form a film of 500 ° (PVK layer)
This was used as a hole transporting light emitting layer. 250W here
Interference filter with high pressure mercury lamp [Japan Vacuum Engineering Co., Ltd.
Co., Ltd.) and a photomask (black underlay) was irradiated with 365 nm light at 2700 mJ / cm ² to partially oxidize DPN. Next, bis [(2-benzoxazoyl) phenolato] is used as an electron transporting light emitting layer.
Zinc (II) complex (ZnBOX) was deposited by vacuum evaporation
A film was formed at 0 °, and then a Mg: Ag electrode was formed at 2000 ° to produce an organic EL device. The partially irradiated part emits blue light derived from ZnBOX, and the unirradiated part is D
Light was emitted in a bluish green color that was a mixture of green derived from PN and blue of ZnBOX.

Example 2 (Single-layer type multicolor element, FIG.
Reference) polyvinyl carbazole (PVK) 0.0525 g, oxadiazole derivative (PBD) 0.0225 g, 1,
4-tetraphenyl-1,3-butadiene (TPB)
3.7 mg (3 mol%), formula

Embedded image Of the green fluorescent dye 9,10-distyrylanthracene (DSA) 0.7 mg (0.5 mol%)
-25 mm x from dichloroethane solution (3.75 mL)
Spin coating method (18) on a 25 mm ITO glass substrate
00 rpm, 3 sec) to form a film at 1000 ° (P
VK layer). This film was irradiated with 4050 mJ / cm ^{2 of} 365 nm light using a 250 W high-pressure mercury lamp using an interference filter [manufactured by Nippon Vacuum Engineering Co., Ltd.] and a photomask (with a black underlay cut), and partially exposed to DSA. Photooxidized. The light irradiation amount was controlled by the irradiation time. Thereafter, an Mg: Ag electrode was formed to a film thickness of 2000 ° by a vacuum evaporation method to produce an organic EL device. In the part where light was partially irradiated, green light emission derived from DSA was remarkably reduced and light was emitted in blue light derived from TPB, and in the non-irradiated part, light was emitted in blue-green mixed with green light derived from DSA and blue light derived from TPB.

[0052]

According to the present invention, a novel photo-modifiable luminescent organic dye useful for producing a multicolor organic EL device by the photobleaching method can be provided.

[Brief description of the drawings]

FIG. 1 is a schematic view of a single-layer type multicolor organic EL device of the present invention.

FIG. 2 is a schematic view showing one example of a method for manufacturing a multicolor organic EL device of the present invention.

FIG. 3 is a schematic diagram of a multi-color laminated organic EL device of the present invention.

[Explanation of symbols]

 REFERENCE SIGNS LIST 1 glass substrate 2 ITO 5 cathode 6 hole transporting luminescent layer 7 electron transporting luminescent layer 9 photomask 21 glass substrate 22 ITO 23 luminescent layer 24 cathode

Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat II (Reference) C09K 11/06 635 C09K 11/06 635 640 640 655 655 H05B 33/14 H05B 33/14 (72) Inventor Takayuki Suzuki Nagano 1-7-43 Jouire, Ueda-shi, Etoile 1008 Ueda 1008 F-term (reference) 3K007 AB04 CA01 CB01 DA00 DB03 EB00 FA00 FA01 4H056 CA02 CA05 CB03 CC02 CC05 CD01 CE02 CE03 CE06 CE07 DD04 DD09 DD12 DD15 EA05 EA06 EA13 EA14 FA05

Claims (4)

[Claims] [Claim 1] The following general formula (1) (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 2 carbon atoms, and Ar ¹ and Ar ² are aromatic groups. An anthracene derivative represented by the following general formula (2): (Wherein, Ar ¹ and Ar ² are each independently selected from the group consisting of an aromatic ring and a heterocyclic ring), a naphthacene derivative represented by the following general formula (3): (Wherein R ¹ , R ² , R ³ and R ⁴ are each independently selected from the group consisting of hydrogen and an alkyl group having 1 to 2 carbon atoms, and Ar ¹ and Ar ² are aromatic groups. R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently selected from the group consisting of hydrogen, fluorine, a cyano group, and a linear or branched group having 1 to 20 carbon atoms. Alkyl group, linear or branched alkoxy group having 1 to 20 carbon atoms, saturated aliphatic ring having 3 to 6 carbon atoms, aryl group which may have a substituent, linear or branched Mono- or dialkylamino groups, linear or branched mono-, di- or tri-alkylsilyl groups having 1 to 10 carbon atoms, each independently selected from the group consisting of the same or the same ring Two or more bonds in different groups And a condensed ring may be formed between two adjacent carbon atoms), and a spiro anthracene derivative represented by the following general formula (4): (Wherein, Ar ¹ and Ar ² are each independently selected from the group consisting of an aromatic ring and a heterocyclic ring,
R ¹¹ , R ¹² , R ¹³ and R ^{14 each} represent hydrogen, fluorine, a cyano group, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, A saturated aliphatic ring having 3-6, an aryl group which may have a substituent, a linear or branched mono- or dialkylamino group having 1-8 carbon atoms, a linear or branched mono-alkyl group having 1-10 carbon atoms, Groups independently selected from the group consisting of di- or tri-alkylsilyl groups, which may be bonded to one ring in the form of the same or different groups, and two or more A spiro-based naphthacene derivative represented by the following formula (1), which may form a condensed ring between two matching carbon atoms; 2. The method of claim 2, wherein the Ar¹And Ar²IsEmbedded imageC₆₀And C₇₀ Independently selected from the group consisting of
The radical¹¹, R¹², R¹³, R¹⁴, R
^Fifteen, R¹⁶, R¹⁷And R¹⁸Is hydrogen, fluorine,
Cyano group, linear or branched alkyl having 1 to 20 carbon atoms
Group, a linear or branched alkoxy group having 1 to 20 carbon atoms,
It may have a saturated aliphatic ring having 3 to 6 carbon atoms and a substituent.
An aryl group, a linear or branched mono- or C1-C8 mono- or
Is a dialkylamino group, a straight or branched chain having 1 to 10 carbon atoms.
Group consisting of various mono-, di- or tri-alkylsilyl groups
Are each independently selected from
Two or more rings in the same or different groups
And condensation between two adjacent carbon atoms
May form a ring,²¹Is hydrogen, fluorine, silicon
An ano group and a linear or branched alkyl having 1 to 20 carbon atoms
A group selected from the group consisting of
Or two or more different groups may be bonded,
R²³Is hydrogen and a straight or branched chain having 1 to 20 carbon atoms
R is a group selected from the group consisting of²⁵
Is hydrogen, linear or branched alkyl having 1 to 20 carbons
, Cyano and alkyl groups having 1 to 2 carbon atoms
A group selected from the group consisting of anoalkyl groups;
³¹And R³²Is hydrogen, halogen, cyano group, carbon
A linear or branched alkyl group having 1 to 20 carbon atoms;
20 straight-chain or branched alkoxy groups having 3 to 6 carbon atoms
Saturated aliphatic ring, aryl group which may have a substituent, charcoal
A linear or branched mono- or di-alkyl group having a prime number of 1 to 8;
Amino groups, straight-chain or branched mono- and di-C 1-10
Or a trialkylsilyl group, each independently.
A group selected from the group consisting of R³¹And R³²Is one
May form a condensed ring with
⁴¹Is hydrogen, fluorine, cyano group, hydroxyl group, carbon number 1
20 linear or branched alkyl groups having 1 to 20 carbon atoms
A straight or branched alkoxy group, a straight chain having 1 to 4 carbon atoms,
Or a branched aralkyl group, a saturated aliphatic ring having 3 to 6 carbon atoms,
An aryl group which may have a substituent, having 1 to 8 carbon atoms
Linear or branched mono- or dialkylamino group, carbon
Linear or branched mono-, di- or tri-a
A group selected from the group consisting of
These may be two or more in the same or different groups in one ring
May be bonded to each other, or between two adjacent carbon atoms.
2. A condensed ring may be formed between them.
Light-modifiable luminescent organic dye described above. 3. The method according to claim 1, wherein the light-modifiable luminescent organic dye is: Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image (Wherein, R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R
¹⁶ , R ¹⁷ and R ¹⁸ are hydrogen, fluorine, a cyano group, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms, A saturated aliphatic ring, an aryl group which may have a substituent, a linear or branched mono- or dialkylamino group having 1 to 8 carbon atoms, a linear or branched mono-, di- or tri-alkyl group having 1 to 10 carbon atoms. Groups independently selected from the group consisting of alkylsilyl groups, which may be bonded to one ring in the form of the same or different groups, and two or more A condensed ring may be formed between atoms, and R ²¹ and R ²² are hydrogen, fluorine,
A group selected from the group consisting of a cyano group and a linear or branched alkyl group having 1 to 20 carbon atoms, and two or more of the same or different groups may be bonded to one ring; ²³ is a group selected from the group consisting of hydrogen and a linear or branched alkyl group having 1 to 20 carbon atoms;
²⁵ and R ²⁶ are each independently selected from the group consisting of hydrogen, a linear or branched alkyl group having 1 to 20 carbon atoms, a cyano group, and a dicyanoalkyl group having 1 to 2 carbon atoms in the alkyl group. R ³¹ , R ³² , R ³³ and R ^{34 each} represent hydrogen, a halogen, a cyano group, a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms , Carbon number 3 ~
6, a saturated aliphatic ring, an aryl group which may have a substituent, a linear or branched mono- or dialkylamino group having 1 to 8 carbon atoms, a linear or branched mono-, di- or tri-alkyl group having 1 to 10 carbon atoms. A group independently selected from the group consisting of alkylsilyl groups, wherein R ³¹ and R ³² may be combined to form a condensed ring,
R ⁴¹ and R ⁴² represent hydrogen, fluorine, a cyano group, a hydroxyl group,
A linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkoxy group having 1 to 20 carbon atoms,
A straight-chain or branched aralkyl group having 4 to 6 carbon atoms, a saturated aliphatic ring having 3 to 6 carbon atoms, an aryl group which may have a substituent, a straight-chain or branched mono- or dialkylamino group having 1 to 8 carbon atoms, Groups independently selected from the group consisting of straight-chain or branched mono-, di- or tri-alkylsilyl groups of the formulas 1 to 10, which are the same or different in the form of the same or different groups in one ring; Or two or more adjacent carbon atoms, and a condensed ring may be formed between two adjacent carbon atoms). Organic dyes. 4. An organic dye serving as a luminescence center is at least 2
2. A multicolor organic EL device having a light emitting layer containing at least one kind of organic dye, wherein at least one of the organic dyes is used.
4. A multicolor organic EL device, wherein the light-emitting organic dye according to any one of (1) to (3) is light-modified to change the color of light emitted from the device.