JPH11193351A - Organic electroluminescent element, cyclic azine dye therefor, and production of cyclic azine dye - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an azine dye which fluoresces at a longer wavelength and has excellent durability by reacting a phenylenediamine derivative with a phenol derivative in the presence of an oxidizing agent in an alkaline atmosphere. SOLUTION: A cyclic azine dye of formula III is obtained by reacting a phenylenediamine of formula I (x<2> is O, S, or N-R<36> ; R<31> to R<35> and R<36> are each H or a substituent; and Y<1> to Y<4> are each H or a leaving group) with a phenol derivative of formula II (R<41> to R<43> are each H or a substituent) at -20 to 100 deg.C, desirably, 0-50 deg.C in the presence of 0.01-30 equivalents, desirably, 1-10 equivalents of an oxidizing agent of an inorganic or organic compound such as a metal oxide, a persulfate or a quinone derivative in an alcoholic, etheric, or like organic solvent, water, or a mixture thereof containing 0.01-30 equivalents, desirably, 1-10 equivalents, per equivalent of the phenylenediamine derivative, of an inorganic or organic base such as a metal hydroxide, a metal carbonate, a metal hydrogencarbonate, a metal alkoxide derivative, or an amine derivative.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a cyclic azine dye, an electroluminescence (EL) device using the same, and a method for producing a cyclic azine dye.

[0002]

2. Description of the Related Art At present, research and development on various display elements are active. Among them, an organic EL element is capable of obtaining high-luminance light emission at a low voltage, and is attracting attention as a promising display element. For example, an EL element that forms an organic thin film by vapor deposition of an organic compound is known (Applied Physics Letters, vol. 51, p. 913, 1987). The organic EL device described in the above document has a laminated structure of an electron transporting material and a hole transporting material, and its light emitting characteristics are greatly improved as compared with a conventional single-layer type device.

[0003] As a means for improving the luminous efficiency of the stacked EL device, a method of doping a fluorescent dye is known. For example, Journal of Applied Physics 6
The organic EL device doped with a coumarin dye described in Vol. 5, p. 3610, 1989 has significantly improved luminous efficiency as compared with a device not doped. Further, by doping a fluorescent dye, light having a desired wavelength can be extracted. In order to apply organic EL to full color displays and backlights, it emits light at an appropriate wavelength,
Development of a fluorescent dye having excellent durability is required, and development of a red fluorescent dye is particularly desired in terms of durability and luminous efficiency.

[0004] Nile red is known as a red fluorescent dye used in an organic electroluminescence device, but has problems such as short hue and poor durability.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electroluminescence device using a red fluorescent dye which emits light at an appropriate wavelength and has excellent durability. Another object of the present invention is to provide a red fluorescent dye which can be used for an organic electroluminescence device (EL device) and emits light at an appropriate wavelength and has excellent durability. Still another object of the present invention is to provide a method for producing such a red fluorescent dye.

[0006]

According to the present invention, an organic electroluminescent device according to the following [1] to [4],
A cyclic azine type dye and a method for producing a cyclic azine dye are provided, and the above object is achieved. [1] An organic electroluminescent device containing at least one organic thin film between electrodes, comprising at least one selected from the group consisting of cyclic azine dyes represented by the following general formula (1): Electroluminescence element.

[0007]

Embedded image

Wherein X ¹ is an oxygen atom, a sulfur atom or N
R ¹⁹ represents a group, and R ^{11 to} R ¹⁸ and R ¹⁹ are the same or different and each represent a hydrogen atom or a substituent. However, when X ¹ is an oxygen atom or a sulfur atom, R ¹⁶ and R
¹⁷ do not combine to form an aromatic ring. [2] A cyclic azine dye represented by the following general formula (2).

[0009]

Embedded image

In the formula, R ^{21 to} R ²⁹ and R _a and R _b are the same or different and each represent a hydrogen atom or a substituent. [3] A phenylenediamine derivative represented by the following general formula (3) is reacted with a phenol derivative represented by the following general formula (4) in the presence of an oxidizing agent in an alkaline atmosphere. A method for producing a cyclic azine dye represented by the general formula (5).

[0011]

Embedded image

In the formula, X ² represents an oxygen atom, a sulfur atom or an NR ³⁶ group; R ^{31 to} R ³⁵ and R ³⁶ are the same or different and each represent a hydrogen atom or a substituent;
R ^{41 to} R ⁴³ are the same or different and represent a hydrogen atom or a substituent, and Y ^{1 to} Y ⁴ are the same or different and represent a hydrogen atom or a leaving group, respectively. [4] A cyclic azine dye represented by the general formula (8), wherein the aniline derivative represented by the general formula (6) or (7) is oxidized with an oxidizing agent in an alkaline atmosphere. Manufacturing method.

[0013]

Embedded image

In the formula, X ³ represents an oxygen atom, a sulfur atom or an NR ⁶⁹ group, and R ^{61 to} R ⁶⁸ and R ⁶⁹ are the same or different and each represent a hydrogen atom or a substituent;
X ⁴ represents an oxygen atom, a sulfur atom or an NR ⁷⁹ group,
R ^{71 to} R ⁷⁸ and R ⁷⁹ are the same or different and each represent a hydrogen atom or a substituent, and Y ^{5 to} Y ¹⁰ are the same or different and represent a hydrogen atom or a leaving group, respectively.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below, which will clarify other objects, advantages and effects of the present invention. The general formula (1) will be described. X ¹ represents an oxygen atom, a sulfur atom or an NR ¹⁹ group. Particularly preferred are NR ¹⁹ groups. R ¹⁹ represents a hydrogen atom or a substituent. Examples of the substituent include the following. Alkyl group: preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methyl, ethyl, iso-propyl, ter
t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. Alkenyl group: preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like. Alkynyl group: preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, such as propargyl and 3-pentynyl. Aryl group: preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, and naphthyl.

Acyl group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 carbon atom
To 12, for example, acetyl, benzoyl, formyl, pivaloyl and the like. Alkoxycarbonyl group: preferably having 2 to 20 carbon atoms
More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl. Aryloxycarbonyl group: preferably having 7 to 2 carbon atoms
It has 0, more preferably 7 to 16 carbon atoms, and particularly preferably 7 to 10 carbon atoms, such as phenyloxycarbonyl. Alkylaminocarbonyl group: preferably having 1 to 4 carbon atoms
It has 0, more preferably 1 to 30 carbon atoms, particularly preferably 1 to 25 carbon atoms, and examples thereof include an ethylaminocarbonyl group and a dimethylaminocarbonyl group. Arylaminocarbonyl group: preferably having 7 to 4 carbon atoms
0, more preferably 7 to 30 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenylaminocarbonyl. Sulfonyl group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl. Heterocyclic group: a heterocyclic group having 3 to 30 carbon atoms (preferably a heteroatom such as oxygen, nitrogen, sulfur) having a 5- or 6-membered monocyclic or condensed ring structure, for example, imidazolyl, pyridyl, furyl , Piperidyl, morpholino and the like. These substituents may be further substituted.

R ¹⁹ can combine with R ¹³ or R ¹⁸ to form a 5- or 6-membered nitrogen-containing heterocyclic ring having 3 to 20 carbon atoms. R ¹⁹ is preferably a hydrogen atom,
A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted carbonyl group having 1 to 20 carbon atoms, and a substituted sulfonyl group having 1 to 20 carbon atoms are exemplified. Examples of the substituted carbonyl group include an aliphatic group and an aryl group. Represents a group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an unsubstituted or substituted amino group, a hydroxyl group, and the substituent of the substituted sulfonyl group is an aliphatic group, an aryl group, an alkoxy group, a substituted or It represents an unsubstituted amino group or hydroxyl group. The substituted amino group represents an alkylamino group, an arylamino group, a sulfonamide group, a carbonamide group, a ureido group, a urethane group, a carbamoylamino group, or a sulfamoylamino group. Particularly preferably, a hydrogen atom,
It is an alkyl group having 1 to 10 carbon atoms.

R ^{11 to} R ¹⁸ are the same or different and each represents a hydrogen atom or a substituent. Examples of the substituent for R ¹¹ and R ¹² include the substituents described for R ¹⁹ above. R ¹³ ~R
Examples of the substituent of ¹⁸ include the following. Alkyl group: preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methyl, ethyl, iso-propyl, ter
t-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. Alkenyl group: preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like. Alkynyl group: preferably having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and particularly preferably 2 to 8 carbon atoms, such as propargyl and 3-pentynyl. Aryl group: preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenyl, p-methylphenyl, and naphthyl.

Amino group: preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 carbon atoms
To 6, for example, amino, methylamino, dimethylamino, diethylamino, dibenzylamino and the like. Alkoxy group: preferably 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, such as methoxy, ethoxy and butoxy. Aryloxy group: preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 1 carbon atoms
2, for example, phenyloxy, 2-naphthyloxy and the like. Acyl group: preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, acetyl, benzoyl, formyl, pivaloyl and the like. Alkoxycarbonyl group: preferably having 2 to 20 carbon atoms
More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonyl and ethoxycarbonyl.

Aryloxycarbonyl group: preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 10 carbon atoms, such as phenyloxycarbonyl. Alkylaminocarbonyl group: preferably having 1 to 4 carbon atoms
It has 0, more preferably 1 to 30 carbon atoms, and particularly preferably 1 to 25 carbon atoms, and examples thereof include an ethylaminocarbonyl group and a dimethylaminocarbonyl group. Arylaminocarbonyl group: preferably having 7 to 4 carbon atoms
0, more preferably 7 to 30 carbon atoms, particularly preferably 7 to 10 carbon atoms, such as phenylaminocarbonyl. Acyloxy group: preferably 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms
And examples thereof include acetoxy and benzoyloxy.

Acylamino group: preferably having 2 to 2 carbon atoms
It has 0, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, and includes, for example, acetylamino, benzoylamino and the like. Alkoxycarbonylamino group: preferably having 2 to 2 carbon atoms
20, more preferably 2 to 16 carbon atoms, particularly preferably 2 to 12 carbon atoms, such as methoxycarbonylamino. Aryloxycarbonylamino group: preferably having 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino. Sulfonylamino group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms
12, for example, methanesulfonylamino, benzenesulfonylamino and the like. Sulfamoyl group: preferably 0 to 20 carbon atoms, more preferably 0 to 16 carbon atoms, particularly preferably 0 to 1 carbon atoms.
2, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like.

Carbamoyl group: preferably having 1 to 2 carbon atoms
It has 0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl. Alkylthio group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms
And examples thereof include methylthio, ethylthio and the like. Arylthio group: preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms
And for example, phenylthio and the like. Sulfonyl group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl. Sulfinyl group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms
And examples thereof include methanesulfinyl and benzenesulfinyl. Ureido group: preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, and particularly preferably 1 to 12 carbon atoms, such as ureido, methylureide, and phenylureide. Phosphate amide group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms
And examples thereof include diethylphosphoramide and phenylphosphoramide. Other groups: hydroxyl group, mercapto group, halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), cyano group, sulfo group, carboxyl group, nitro group, hydroxamic acid group, sulfino group, hydrazino group, Examples include an imino group and a heterocyclic group (eg, imidazolyl, benzimidazolyl, benzoxazolyl, thiazolyl, benzthiazolyl, pyridyl, furyl, piperidyl, morpholino, and the like). These substituents may be further substituted.

R¹³~ R¹⁸Each substituent of
To form a 5- to 6-membered alicyclic, heterocyclic or aromatic ring
With the proviso that X¹Is an oxygen atom or sulfur
For an atom, R¹⁶, R¹⁷Are not linked to form an aromatic ring.
No. For example, the substituent R¹²And R ¹⁴, R¹¹And R¹³Are combined
A 5- or 6-membered alicyclic ring may be formed;¹⁶And R¹⁷Is
May form an aromatic ring,¹Is an oxygen atom
Or when it is a sulfur atom, R¹⁶, R¹⁷Is linked to an aromatic ring
Does not form.

R ¹¹ and R ¹² are preferably a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² are
Each of R ¹³ and R ¹⁴ may be combined with each other to form a 5- to 6-membered alicyclic ring, for example, an indoline ring, a tetrahydroquinoline ring, or a julolidine ring. Also, R ¹¹ and R
^The ring may be linked by ¹² to form a ring, for example, a pyrrolidine ring, a piperidine ring, a morpholine ring and the like. R
¹³ , R ¹⁴ , and R ¹⁵ are preferably a hydrogen atom, and have 1 to 2 carbon atoms.
0 substituted or unsubstituted alkyl group, halogen atom, hydroxy group, substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, unsubstituted amino group, substituted amino group having 1 to 20 carbon atoms, The group represents an alkylamino group, an arylamino group, an aromatic heterocyclic amino group, a sulfonamide group, a carbonamide group, a ureido group, a urethane group, a carbamoylamino group, or a sulfamoylamino group.
Particularly preferred are a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, and a substituted amino group having 1 to 10 carbon atoms. The group represents an alkylamino group, an arylamino group, an aromatic heterocyclic amino group, a sulfonamide group, a carbonamide group, a ureido group, a urethane group, a carbamoylamino group, or a sulfamoylamino group.

R ¹⁶ and R ¹⁷ are preferably a hydrogen atom,
Halogen atom, substituted sulfonamide group having 0 to 30 carbon atoms, carbonamide group having 1 to 30 carbon atoms, 1-2 carbon atoms
When X ¹ is an NR ¹⁹ group, R ¹⁶ and R ¹⁷ may combine to form an aromatic ring, and a benzo-condensed ring is preferred. R ¹⁸ is preferably a hydrogen atom, a halogen atom, a cyano group, a carbon number of 1 to 30.
An alkyl group, an aryl group having 6 to 30 carbon atoms, and 2 carbon atoms
To 30 heterocyclic groups, substituted carbonyl groups having 1 to 30 carbon atoms, sulfamoyl groups having 0 to 30 carbon atoms, and 1 to 3 carbon atoms
A sulfonamide group having 0, a carbonamide group having 1 to 30 carbon atoms, and a ureido group having 1 to 30 carbon atoms. Particularly preferably, a hydrogen atom, a halogen atom, a carbon number of 1 to 30 is preferable.
And an amide group having 1 to 30 carbon atoms.

Hereinafter, preferred combinations of the substituents represented by the general formula (1) will be described. In a preferred combination of the general formula (1), X ¹ is an NR ¹⁹ group, R ¹⁹ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and 1 carbon atom.
A substituted carbonyl group having from 20 to 20 carbon atoms; and a substituted sulfonyl group having from 0 to 20 carbon atoms. Examples of the substituent of the substituted carbonyl group include an aliphatic group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an unsubstituted or substituted amino group, and a hydroxyl group. Represents an aliphatic group, an aryl group, an alkoxy group, a substituted or unsubstituted amino group, or a hydroxyl group. The substituted amino group is an alkylamino group, an arylamino group, an aromatic heterocyclic amino group, a sulfonamide group, a carbonamide group, a ureido group, a urethane group, a carbamoylamino group, or a sulfamoylamino group. R ¹¹ , R ¹²
Is an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and may be combined with R ¹³ or R ¹⁴ to form a ring (preferably a 5- to 6-membered alicyclic ring); It may form a tetrahydroquinoline ring or a julolidine ring. Further, R ¹¹ and R ¹² may be linked to form a ring, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring. R ¹³ , R ¹⁴ and R ^{15 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a halogen atom, a hydroxy group, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, an unsubstituted amino group. Group, carbon number 1-2
0 is a substituted amino group, wherein the substituted amino group is an alkylamino group, an arylamino group, an aromatic heterocyclic amino group, a sulfonamide group, a carbonamide group, a ureido group, a urethane group, a carbamoylamino group, a sulfamoylamino group Represents R ¹⁶ and R ¹⁷ are a hydrogen atom, a halogen atom, a sulfonylamino group having 1 to 30 carbon atoms, an acylamino group having 2 to 30 carbon atoms, and a ureido group having 1 to 30 carbon atoms;
R ¹⁶ and R ¹⁷ may combine to form an aromatic ring. R ¹⁸ is a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms,
30 heterocyclic groups, a substituted carbonyl group having 1 to 30 carbon atoms, a sulfamoyl group having 0 to 30 carbon atoms, 1 to 3 carbon atoms
A sulfonamide group having 0, a carbonamide group having 1 to 30 carbon atoms, and a ureido group having 1 to 30 carbon atoms.

More preferably, X ¹ is an NR ¹⁹ group, R ¹⁹ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, and a substituted carbonyl group having 1 to 20 carbon atoms. Examples of the substituent of the substituted carbonyl group include an aliphatic group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, an unsubstituted or substituted amino group, and a hydroxyl group. The substituted amino group represents an alkylamino group, an arylamino group, a sulfonamide group, a carbonamide group, a ureido group, a urethane group, a carbamoylamino group, or a sulfamoylamino group. R
¹¹ and R ¹² are an unsubstituted or substituted alkyl group having 1 to 20 carbon atoms, and may be combined with R ¹³ or R ¹⁴ to form a ring (preferably a 5- to 6-membered alicyclic ring); For example, an indoline ring, a tetrahydroquinoline ring, or a julolidine ring may be formed. Further, R ¹¹ and R ¹² may be linked to form a ring, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring. R ¹³ , R ¹⁴ and R ^{15 each} represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms, or a substituted amino group having 1 to 20 carbon atoms. There, a substituted amino group is an alkylamino group, an arylamino group, a sulfonamide group, a carbonamide group, a ureido group, a urethane group,
Represents a carbamoylamino group or a sulfamoylamino group. R ^16, R ¹⁷ forms a aromatic ring bonded, R ¹⁸
Is a hydrogen atom, a cyano group, a substituted carbonyl group having 1 to 20 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms,
A sulfonamide group of 20; a carbonamide group of 2 to 20 carbon atoms; and a ureido group of 1 to 20 carbon atoms.

In a particularly preferred combination, X ¹ is an NR ¹⁹ group, R ¹⁹ is a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, and R ¹¹ and R ¹² are each a group having 1 carbon atom.
An unsubstituted or substituted alkyl group of 12, each bound with R ¹³ or R ¹⁴ ring (preferably a cycloaliphatic 5- or 6-membered) may be formed, for example indoline ring, tetrahydroquinoline ring, A julolidine ring may be formed.
Further, R ¹¹ and R ¹² may be linked to form a ring, and examples thereof include a pyrrolidine ring, a piperidine ring, and a morpholine ring. R ¹³ , R ¹⁴ , and R ^{15 each} represent a hydrogen atom, and have 1 to 1 carbon atoms.
A substituted or unsubstituted alkyl group of 2 or a substituted or unsubstituted alkoxy group having 1 to 12 carbon atoms, R ¹⁶ and R ¹⁷ are bonded to form a benzene ring, R ¹⁸ is a hydrogen atom,
A cyano group, a substituted carbonyl group having 1 to 20 carbon atoms, a sulfamoyl group having 0 to 20 carbon atoms, a sulfonamide group having 1 to 20 carbon atoms, a carbonamide group having 2 to 20 carbon atoms, and a ureido group having 1 to 20 carbon atoms It is.

Next, the general formula (2) will be described. The cyclic azine dye represented by the general formula (2) is included in the cyclic azine dye represented by the general formula (1). R ²¹ ,
R ²² represents a hydrogen atom or a substituent, and examples of the substituent and preferred ranges thereof are the same as those of R ¹¹ and R ¹² .
R ²³ , R ²⁴ , and R ²⁵ each represent a hydrogen atom or a substituent.
¹³ is the same as R ^14, R ^15.

R ^{26 to} R ^{29 each} represent a hydrogen atom or a substituent, and examples of the substituent are the same as those of the substituents described above for R ^{13 to} R ¹⁸ . R ²⁶ is preferably a hydrogen atom, a halogen atom, a substituted or unsubstituted carbonylamino group having 1 to 30 carbon atoms (eg, perfluorobenzoylamino group, methoxycarbonylamino group), or a sulfonamide group having 1 to 20 carbon atoms. No. Above all, hydrogen atom,
A substituted or unsubstituted carbonylamino group having 1 to 20 carbon atoms and a sulfonamide group having 1 to 20 carbon atoms are particularly preferred. R ^{27 to} R ²⁹ are preferably a hydrogen atom, having 1 to 2 carbon atoms.
It is a substituted or unsubstituted alkyl group of 0 or a halogen atom, and a hydrogen atom is particularly preferred.

R _a represents a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted amino group having 1 to 30 carbon atoms, a hydroxyl group, or an alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms and a substituted or unsubstituted amino group having 1 to 30 carbon atoms are preferable. R _b has the same meaning as R ¹⁹ above

The compound represented by the general formula (1) or (2) may be a low molecular weight compound, or a compound represented by the general formula (1) or (2) is connected to the polymer main chain. High molecular weight compound (preferably a weight average molecular weight of 1,000 to
5,000,000, particularly preferably 5000 to 20,000
00, more preferably 10,000 to 1,000,000)
Alternatively, a high molecular weight compound having a skeleton of the general formula (1) or (2) in the main chain (preferably a weight average molecular weight of 1000
-5,000,000, particularly preferably 5,000-2,000
000, more preferably 10,000 to 1,000,000)
It may be. In the case of a high molecular weight compound, it may be a homopolymer or a copolymer with another monomer. The compound represented by the general formula (1) or (2) is preferably a low molecular weight compound. Also,
The general formula (1) or (2) is represented by a limiting structural formula for convenience, but may be a tautomer thereof.

Next, specific examples of the cyclic azine dyes represented by the general formulas (1) and (2) are shown, but the present invention is not limited thereto.

[0034]

Embedded image

[0035]

Embedded image

[0036]

Embedded image

[0037]

Embedded image

[0038]

Embedded image

[0039]

Embedded image

Next, a method for synthesizing the cyclic azine dye of the present invention will be described. The cyclic azine dye of the present invention can be synthesized according to the following reaction formulas (1) and (2).

[0041]

Embedded image

First, a synthesis method according to the reaction formula (1) will be described. The cyclic azine dye represented by the general formula (5) is obtained by adding a phenylenediamine derivative represented by the general formula (3) or a salt thereof and a phenol derivative represented by the general formula (4) to an oxidizing agent in an alkaline atmosphere. It can be obtained by reacting. In order to carry out the reaction in an alkaline atmosphere, a base is usually added. However, if the above-mentioned reaction raw materials are sufficiently basic, it is not necessary to add a base. As the base, various inorganic or organic bases can be used,
For example, metal hydroxides, metal carbonates, metal bicarbonates, metal alkoxide derivatives, amine derivatives and the like can be used. Specifically, it is preferable to use potassium carbonate, sodium hydrogen carbonate, triethylamine, sodium alkoxide and the like. The amount of the base is not particularly limited, but is preferably from 0.01 equivalent to 3 equivalents to the reaction substrate.
It is preferable to use 0 equivalent, particularly preferably 1 to 10 equivalent. (Here, the reaction substrate refers to a phenol derivative, and the amount of the base used is defined as the equivalent. The minimum amount of the base required to dissociate all the phenolic hydroxyl groups of the phenol derivative used in the reaction is defined as 1 equivalent.)

The oxidizing agent is not particularly limited, but an oxidizing agent of an inorganic or organic compound can be used, and examples thereof include metal oxides, persulfates, and quinone derivatives. Specifically, it is preferable to use ammonium persulfate, silver oxide, manganese dioxide, chloranil, or the like. The amount of the oxidizing agent is not particularly limited, but preferably 0.01 to 30 equivalents, particularly preferably 1 to 10 equivalents, to the reaction substrate. (Here, the reaction substrate is a phenylenediamine derivative, and the amount of the oxidizing agent used is defined as an equivalent. The minimum amount of the oxidizing agent required for two-electron oxidation of the phenylenediamine derivative used in the reaction is defined as one equivalent.)

In this reaction, it is preferable to use a solvent.
As the solvent, various organic solvents such as alcohols and ethers, water and a mixed solvent thereof can be used.
Of these, use of methanol, a mixed solvent of ethanol and water, tetrahydrofuran, or the like is preferable. The reaction temperature is not particularly limited, but is preferably from -20 ° C to 100 ° C,
To 50 ° C is particularly preferred.

The general formulas (3) and (4) will be described.
X ² represents an oxygen atom, a sulfur atom, or an NR ³⁶ group, and the preferred range is the same as that of X ¹ . R ³¹ ,
R ³² , R ³³ , R ³⁴ , R ³⁵ , and R ³⁶ are the same as R ¹¹ , R ¹² , R
^{13, R 14, R 15,} R 19 and have the same meanings, examples of the substituents, and preferred ranges thereof are also the same. R ⁴¹ ,
R ^42, R ^43, said R ^18, R ^17, R ¹⁶ and have the same meanings and preferred embodiments the same.

Y ^{1 to} Y ^{4 each} represent a hydrogen atom or a group capable of coupling and leaving. The leaving group is not particularly limited, and examples thereof include a halogen atom (for example, a fluorine atom, a chlorine atom, and a bromine atom), an alkylsulfonyl group (preferably having 1 to 20 carbon atoms, for example, a methanesulfonyl group and a butanesulfonyl group), and an arylsulfonyl group. Groups (preferably having 1 to 20 carbon atoms, such as a benzenesulfonyl group,
A paratoluenesulfonyl group), an alkoxy group (preferably having 1 to 20 carbon atoms, for example, methoxycarbonylmethyleneoxy group), an aryloxy group (preferably having 1 carbon atom).
-20, for example, a phenoxy group, a cyanophenoxy group),
A nitrogen-containing heterocyclic group (preferably having 1 to 20 carbon atoms, for example, a phthalimide group, a dimethylhydantoin group, a urazolyl group, a pyrazolyl group, a dimethyloxazolidinedione group), an acyloxy group (preferably having 1 to 20 carbon atoms, for example, an acetoxy group), Alkoxycarbonyloxy group (preferably having 1 to 20 carbon atoms, for example, methoxycarbonyloxy group), aminocarbonyloxy group (preferably having 1 to 20 carbon atoms, for example, dimethylaminocarbonyloxy group, morpholinocarbonyloxy group), arylthio group (Preferably having 6 to 20 carbon atoms, for example, a phenylthio group), an alkylthio group (preferably having 6 to 20 carbon atoms,
For example, butoxycarbonylmethylenethio group) and the like. Y ¹ and Y ² are preferably hydrogen atoms, and Y ³ and Y ²
Y ⁴ is preferably a hydrogen atom, a chlorine atom, or a bromine atom.

Next, the synthesis method represented by the reaction formula (2) will be described. The cyclic azine compound of the present invention represented by the general formula (8) is prepared by reacting the phenol derivative represented by the general formula (6) or (7) with an oxidizing agent in an alkaline atmosphere to form an intramolecular cup. It can be obtained by ringing. The base, oxidizing agent and reaction conditions that can be used to make the atmosphere alkaline are the same as those in the above-mentioned reaction formula (1).

In the general formula (6), X ³ represents an oxygen atom, a sulfur atom or an NR ⁶⁹ group, and the preferred range is the same as that of X ¹ . R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ ,
R ⁶⁵ , R ⁶⁶ , R ⁶⁷ , R ⁶⁸ , and R ⁶⁹ are the same as R ¹¹ , R ¹² , R
¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and R ¹⁹ have the same meanings, and the examples of the substituents and the preferred ranges thereof are also the same. Y ^{5 to} Y ⁷ represent a hydrogen atom or a group capable of coupling and leaving. The leaving group includes, for example, the leaving groups described above for Y ¹ . Y ⁷ is preferably a hydrogen atom, and Y ⁵ and Y ⁶ are preferably a hydrogen atom, an alkylsulfonyl group having 1 to 30 carbon atoms or an arylsulfonyl group having 6 to 30 carbon atoms.

In the general formula (7), X ⁴ is NR ⁷⁹
And the preferred range is the same as that of X ¹ described above.
R ⁷¹ , R ⁷² , R ⁷³ , R ⁷⁴ , R ⁷⁵ , R ⁷⁶ , R ⁷⁷ , R ⁷⁸ , R
⁷⁹ represents R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ ,
R ¹⁷ , R ¹⁸ , and R ¹⁹ have the same meanings, and examples of the substituent include
The preferred ranges are also the same. Y ⁸
To Y ¹⁰ represents a group that splits off in a hydrogen atom or a coupling. The leaving group includes, for example, the leaving groups described above for Y ¹ . Y ⁸ is preferably a hydrogen atom.
Y ⁹ and Y ¹⁰ are preferably a hydrogen atom, an alkylsulfonyl group having 1 to 30 carbon atoms, or an arylsulfonyl group having 6 to 30 carbon atoms.

Next, the EL device containing the cyclic azine dye of the present invention will be described. The method for forming the organic layer of the EL device containing the cyclic azine type dye of the present invention is not particularly limited, and a method such as resistance heating evaporation, electron beam, sputtering, molecular lamination, or coating is used. From the viewpoint of characteristics and production, resistance heating evaporation and coating are preferred.

The light emitting device of the present invention is a device in which a light emitting layer or a plurality of organic compound thin films including the light emitting layer is formed between a pair of anode and cathode electrodes. It may have a transport layer, an electron injection layer, an electron transport layer, a protective layer, and the like, and each of these layers may have another function. Various materials can be used for forming each layer.

The anode supplies holes to the hole injection layer, the hole transport layer, the light emitting layer, and the like. A metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof is used. It is possible to use a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), or metals such as gold, silver, chromium, and nickel, and furthermore, these metals and conductive metal oxides. Mixtures or laminates, inorganic conductive substances such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, and the like. Oxides,
In particular, ITO is preferable in terms of productivity, high conductivity, transparency, and the like. The thickness of the anode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 500 nm.

As the anode, a layer formed on a soda lime glass, an alkali-free glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass in order to reduce ions eluted from the glass. Further, when soda lime glass is used, it is preferable to use a glass coated with a barrier coat such as silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength. When glass is used, the thickness is usually 0.2 mm or more, preferably 0.7 mm or more. Various methods are used for producing the anode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating evaporation method, a chemical reaction method (such as a sol-gel method), and a coating of a dispersion of indium tin oxide are used. The film is formed by the method described above. The anode can reduce the driving voltage of the element or increase the luminous efficiency by washing or other treatment. For example, ITO
In this case, UV-ozone treatment, plasma treatment and the like are effective.

The cathode supplies electrons to the electron injecting layer, the electron transporting layer, the light emitting layer, etc., and provides the adhesion between the negative electrode such as the electron injecting layer, the electron transporting layer, the light emitting layer, and the ionization potential. , Stability and the like. As a material for the cathode, a metal, an alloy, a metal halide, a metal oxide, an electrically conductive compound, or a mixture thereof can be used. Specific examples thereof include an alkali metal (for example, L
i, Na, K, etc.) and their fluorides, alkaline earth metals (eg, Mg, Ca, etc.) and their fluorides, gold,
Silver, lead, aluminum, sodium-potassium alloy or a mixed metal thereof, lithium-aluminum alloy or a mixed metal thereof, magnesium-silver alloy or a mixed metal thereof, indium, rare earth metals such as ytterbium and the like, preferably It is a material having a work function of 4 eV or less, more preferably aluminum, lithium-
An aluminum alloy or a mixed metal thereof, a magnesium-silver alloy or a mixed metal thereof, or the like is used. The cathode is
Not only a single-layer structure of the compound and the mixture but also a stacked structure including the compound and the mixture can be employed.
The thickness of the cathode can be appropriately selected depending on the material.
It is preferably in the range of 0 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm.
m to 1 μm. A method such as an electron beam method, a sputtering method, a resistance heating evaporation method, or a coating method is used for manufacturing the cathode, and a metal can be evaporated alone or two or more components can be simultaneously evaporated. Further, an alloy electrode can be formed by depositing a plurality of metals at the same time, or an alloy prepared in advance may be deposited.
The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

The material of the light emitting layer is capable of injecting holes from an anode, a hole injection layer, or a hole transport layer and applying electrons from a cathode, an electron injection layer, or an electron transport layer when an electric field is applied. Any material can be used as long as it can form a layer having a function, a function of transferring injected charges, and a function of providing a field of recombination of holes and electrons to emit light. Preferably, the light emitting layer contains the cyclic azine compound of the present invention, but other light emitting materials can also be used. For example, benzoxazole derivatives, benzimidazole derivatives, benzothiazole derivatives, styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazine derivatives , Metal complexes and rare earth complexes of pyrrolidine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, 8-quinolinol derivatives Polymer compounds such as polythiophene, polyphenylene, polyphenylenevinylene, etc. And the like. Although the thickness of the light emitting layer is not particularly limited, it is usually 1 nm to
It is preferably in the range of 5 μm, more preferably 5 nm
１1 μm, more preferably 10 nm to 500 n
m. The method for forming the light-emitting layer is not particularly limited, but a method such as resistance heating evaporation, electron beam, sputtering, molecular lamination, coating (spin coating, casting, dip coating, etc.), and LB method And preferably a resistance heating evaporation and coating method.

The material of the hole injection layer and the hole transport layer has any of a function of injecting holes from the anode, a function of transporting holes, and a function of blocking electrons injected from the cathode. Should be fine. Specific examples thereof include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, and styryl anthracene derivatives , Fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidin compound, porphyrin compound, polysilane compound,
Examples thereof include poly (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, and conductive polymer oligomers such as polythiophene. The thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 1 μm.
500 nm. The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the hole injection layer and the hole transport layer include a vacuum deposition method, an LB method, and a method in which the hole injection / transport agent is dissolved or dispersed in a solvent and coated (spin coating method, casting method, dip coating method). Etc.) are used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinyl carbazole), hydrocarbon resins, ketone resins, phenoxy resins,
Examples include polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane, melamine resin, unsaturated polyester resin, alkyd resin, epoxy resin, and silicone resin.

The material of the electron injecting layer and the electron transporting layer is not limited as long as it has a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. Good. Specific examples thereof include triazole derivatives, oxazole derivatives, oxadiazole derivatives,
Heterocyclic tetracarboxylic anhydrides such as fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbidiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthaleneperylene, and phthalocyanines And various metal complexes represented by metal complexes of derivatives, 8-quinolinol derivatives, metal phthalocyanines, and metal complexes having benzoxazole or benzothiazole as ligands. The thickness of the electron injection layer and the electron transport layer is not particularly limited, but is usually 1 nm to 5 μm.
m, more preferably 5 nm to 1
μm, and more preferably 10 nm to 500 nm. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-mentioned materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. As a method of forming the electron injection layer and the electron transport layer,
A vacuum deposition method, an LB method, a method of dissolving or dispersing the electron injecting / transporting agent in a solvent and coating (eg, a spin coating method, a casting method, a dip coating method) and the like are used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection transport layer can be applied.

As the material of the protective layer, any material may be used as long as it has a function of preventing a substance that promotes element deterioration such as moisture and oxygen from entering the element. As a specific example,
In, Sn, Pb, Au, Cu, Ag, Al, Ti, N
metal such as i, MgO, SiO, SiO ₂ , Al ₂ O ₃ , G
eO, NiO, CaO, BaO, Fe 2 O 3, Y 2 O 3, T
metal oxides such as iO ₂ , MgF ₂ , LiF, AlF ₃ , C
aF ₂ metal fluorides such as, polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, poly-dichloro-difluoroethylene, a copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, At least one with tetrafluoroethylene
A copolymer obtained by copolymerizing a monomer mixture containing a kind of comonomer, a fluorinated copolymer having a cyclic structure in the copolymer main chain, a water-absorbing substance having a water absorption of 1% or more, a water absorption of 0.1% The following moisture-proof substances are listed. There is no particular limitation on the method of forming the protective layer, for example, a vacuum evaporation method,
Sputtering method, reactive sputtering method, MBE
(Molecular beam epitaxy) method, cluster ion beam method,
An ion plating method, a plasma polymerization method (high-frequency excitation ion plating method), a plasma CVD method, a laser CVD method, a thermal CVD method, a gas source CVD method, a coating method, and the like can be applied.

The compounds represented by the general formula (2) of the present invention can be used for organic EL, photographic dyes, ink jet dyes, printing dyes, thermal transfer recording dyes, color filter dyes, and color conversion filters. It can be used for pigments for medical use and medical applications.

[0060]

EXAMPLES The present invention will now be described in detail with reference to examples, but the scope of the present invention is not limited to the examples. (Synthesis Example) <Synthesis of Compound (1-1)> The compound (1-1) was synthesized by the method shown below.

[0061]

Embedded image

Specifically, 1.1 g of the amine derivative (b) and 1.0 g of the phenol derivative (a) were added to 5 g of ethanol.
1 and 1 ml of water were added, followed by stirring at room temperature. To this, 1.05 g of potassium carbonate and 1.0 g of ammonium persulfate were added and stirred at room temperature for 1 hour. After completion of the reaction, ethyl acetate,
Water was added, and the separated organic layer was washed with 1N hydrochloric acid. The organic layer was dried over sodium sulfate and concentrated to obtain a crude crystal of compound (1-1). The compound (1-1) was purified by column chromatography (hexane / ethyl acetate system).
0.4 g of crystals were obtained. When the absorption spectrum of (1-1) in ethyl acetate was measured, λmax = 548 n
m, ε = 57000. <Synthesis of Compound (1-11)>
The compound (1-11) was synthesized.

[0063]

Embedded image

That is, the phenol derivative (c) 0.5
5 ml of ethanol and 1 ml of water were added to the resulting mixture, and the mixture was stirred at room temperature. 0.5 g of potassium carbonate and 0.5 g of ammonium persulfate were added thereto, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, ethyl acetate and water were added, and the separated organic layer was washed with water. The compound (1-1) was crystallized from ethyl acetate / hexane.
0.17 g of the crystal of 1) was obtained. When the absorption spectrum in ethyl acetate was measured, it was λmax = 596 nm.

<Synthesis of Compound (1-19)> According to the synthesis scheme shown below, 2.9 g of the compound (1-19) was prepared in the same manner as in the synthesis of the compound (1-1) described above.
Synthesized. When the absorption spectrum in dichloroethane was measured, it was λmax = 542 nm.

[0066]

Embedded image

<Synthesis of Compound (1-20)> According to the synthesis scheme shown below, 0.5 g of the compound (1-20) was prepared in the same manner as in the synthesis of the compound (1-1) described above.
Synthesized. When the absorption spectrum in dichloroethane was measured, it was λmax = 555 nm.

[0068]

Embedded image

<Synthesis of Compound (1-24)> According to the synthesis scheme shown below, 3.1 g of the compound (1-24) was prepared in the same manner as in the synthesis of the compound (1-1) described above.
Synthesized. When the absorption spectrum in dichloroethane was measured, it was λmax = 548 nm.

[0070]

Embedded image

<Synthesis of Compound (1-36)> According to the synthesis scheme shown below, 2.7 g of the compound (1-36) was prepared in the same manner as in the synthesis of the compound (1-1) described above.
Synthesized. When the absorption spectrum in dichloroethane was measured, it was λmax = 546 nm.

[0072]

Embedded image

(Production and Evaluation of EL Element) Example 1 An IT was placed on a 25 mm × 25 mm × 0.7 mm glass substrate.
A film formed of O with a thickness of 150 nm (manufactured by Tokyo Sanyo Vacuum Co., Ltd.) was used as a transparent support substrate. After etching and washing this transparent support substrate, poly (N-vinylcarbazole)
40 mg, PBD (2- (4-biphenylyl) -5-
(4-tert-butylphenyl) -1,3,4-oxadiazole) 12 mg, the compound described in Table 1 1.0 mg
Was dissolved in 3 ml of 1,2-dichloroethane and washed I
It was spin-coated on a TO substrate. The thickness of the generated organic thin film was about 120 nm. After a patterned mask was placed on the organic thin film, magnesium: silver = 10: 1 was co-deposited at 250 nm in a vapor deposition apparatus, and then 300 nm of silver was vapor-deposited on the cathode. Using a source measure unit 2400 manufactured by Toyo Technica, a DC constant voltage is applied to the EL element to emit light, and the brightness is measured by a luminance meter BM-8 manufactured by Topcon Corporation, and the emission wavelength is measured by a spectrum analyzer P manufactured by Hamamatsu Photonics.
It was measured using MA-11. Table 1 shows the results.

[0074]

[Table 1]

[0075]

[0076]

Embedded image

Nile Red of Comparative Compound B showed a maximum luminance of 110 cd / m ² at 16 V. Λmax of light emission is 59
0 nm, and a dark spot was visually observed on the light emitting surface. As is clear from the results in Table 1, in the device using the compound of the present invention, low-voltage driving and high-luminance light emission are possible even in a coating method in which the normal light-emitting luminance is lower than the comparative compound.
Red light emission with high color purity was exhibited. In addition, the results in Table 1 show that the device using the compound of the present invention has excellent durability.

Embodiment 2 After etching and cleaning the ITO substrate in the same manner as in Embodiment 1,
PD (N, N'-bis (3-methylphenyl) -N,
N'-diphenylbenzidine) about 40 nm, the compound shown in Table 2 about 20 nm, 2,5-bis (1-naphthyl)-
About 40 nm of 1,3,4-oxadiazole is sequentially added to 10 ^−5.
Vapor deposition was performed at a substrate temperature of room temperature in a vacuum of -10 ^-6 Torr. Next, a cathode was deposited and evaluated in the same manner as in Example 1. Table 2 shows the results.

[0079]

[Table 2]

As is clear from the results shown in Table 2, the device using the compound of the present invention was capable of emitting light of higher luminance and emitting red light of higher color purity than the comparative compound even in the vapor deposition method.

Embodiment 3 After etching and cleaning the ITO substrate in the same manner as in Embodiment 1,
After vapor deposition of about 40 nm of PD, the compounds shown in Table 3 and A
1q (tris (8-hydroxyquinolinato) aluminum) was co-deposited at a deposition rate of 0.04 ° / sec and 4 ° / sec to a film thickness of about 60 nm. Next, Example 1
A cathode was deposited and evaluated in the same manner as described above. Table 3 shows the results.

[0082]

[Table 3]

[0083]

As is evident from the results in Table 3, the device using the compound of the present invention can emit light with higher luminance than the comparative compound even in the case of the doping system of the vapor deposition method, and has high color purity and planarity. Excellent red emission was exhibited. In addition, it can be seen that the device using the compound of the present invention has excellent durability.

Embodiment 4 After etching and cleaning the ITO substrate in the same manner as in Embodiment 1,
After depositing about 40 nm of PD, Exemplified Compound (1-20) was deposited to about 60 nm. Next, a cathode was deposited in the same manner as in Example 1. As a result of evaluating the prepared device, the luminance was 1 at 12 V.
10 cd / m ² was shown. λmax = 625 nm, CIE
Red light emission with high color purity of chromaticity (x, y) = (0.66, 0.32) was observed, indicating that the compound of the present invention is effective as an electron injecting / transporting agent and a luminescent agent.

Example 5 40 mg of poly (N-vinylcarbazole) was placed on an ITO glass substrate etched and washed in the same manner as in Example 1.
2,5-bis (1-naphthyl) -1,3,4-oxadiazole 12 mg, tetraphenylbutadiene 10 m
g, DCM 0.5 mg and Exemplified Compound 1 of the present invention
A solution obtained by dissolving 0.1 mg in 3 ml of 1,2-dichloroethane was spin-coated. Next, a cathode was deposited in the same manner as in Example 1. This element has an ITO electrode as an anode, and Mg: Ag.
When a DC voltage was applied using the electrode as a cathode and the light emission characteristics were examined, (x, y) = (0.3 on the CIE chromaticity diagram at 16 V)
6, 0.35) was obtained, which was effective for white light emission (luminance: 1280 cd / m ² ).

[0087]

The organic EL device containing the cyclic azine compound of the present invention enables emission of red EL having higher luminance and higher color purity than conventional ones, and provides a device having excellent surface properties and excellent durability. In particular, good light-emitting characteristics can be obtained even in a coating method with low light emission luminance, and an element can be manufactured which is advantageous in terms of manufacturing cost and the like. Further, the compound of the present invention also functions as a light emitting material and an electron injecting and transporting agent, which allows simple device fabrication.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] March 3, 1999

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] Claim 3

[Correction method] Change

[Correction contents]

Embedded image Wherein, X ² represents an oxygen atom, a sulfur atom or N-R ³⁶ group, R ³¹ to R ³⁵ and the R ³⁶ are the same or different, each represents a hydrogen atom or a substituent, R ⁴¹ to R ⁴³
Are the same or different and represent a hydrogen atom or a substituent, and Y ^{1 to} Y ⁴ are the same or different and represent a hydrogen atom or a leaving group, respectively.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

[0011]

Embedded image

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0041

[Correction method] Change

[Correction contents]

[0041]

Embedded image

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI // C07D 265/38 C07D 265/38 279/20 279/20 471/06 471/06 471/16 471/16

Claims (4)

[Claims] 1. An organic electroluminescent device containing at least one organic thin film between electrodes, comprising at least one member selected from the group consisting of cyclic azine dyes represented by the following general formula (1). Organic electroluminescent element. Embedded image In the formula, X ¹ represents an oxygen atom, a sulfur atom or an NR ¹⁹ group, and R ^{11 to} R ¹⁸ and R ¹⁹ are the same or different,
Each represents a hydrogen atom or a substituent. However, when X ¹ is an oxygen atom or a sulfur atom, R ¹⁶ and R ¹⁷ are not linked to form an aromatic ring. 2. A cyclic azine dye represented by the following general formula (2). Embedded image In the formula, R ^{21 to} R ²⁹ and R _a and R _b are the same or different and each represent a hydrogen atom or a substituent. 3. A reaction between a phenylenediamine derivative represented by the following general formula (3) and a phenol derivative represented by the following general formula (4) in the presence of an oxidizing agent in an alkaline atmosphere. A method for producing a cyclic azine dye represented by the following general formula (5): Embedded image Wherein, X ² represents an oxygen atom, a sulfur atom or N-R ³⁶ group, R ³¹ to R ³⁵ and the R ³⁶ are the same or different, each represents a hydrogen atom or a substituent, R ⁴¹ to R ⁴³
Are the same or different and represent a hydrogen atom or a substituent, and Y ^{1 to} Y ⁴ are the same or different and represent a hydrogen atom or a leaving group, respectively. 4. A cyclic compound represented by the general formula (8), wherein the aniline derivative represented by the general formula (6) or (7) is oxidized with an oxidizing agent in an alkaline atmosphere. A method for producing an azine dye. Embedded image Wherein, X ³ represents an oxygen atom, a sulfur atom or N-R ⁶⁹ group, R ⁶¹ to R ⁶⁸ and the R ⁶⁹ are the same or different, each represents a hydrogen atom or a substituent, X ⁴ is Represents an oxygen atom, a sulfur atom or an NR ⁷⁹ group, and R ^{71 to} R ⁷⁸
And R ⁷⁹ is the same or different and represents a hydrogen atom or a substituent, respectively, and Y ^{5 to} Y ¹⁰ are the same or different and represent a hydrogen atom or a leaving group, respectively.