JPH11149982A - Manufacture of electroluminescent element and cyclic azine pigment - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an element emitting light to a wavelength of a blue, green color part and containing a fluorescent pigment with its superior durability by containing at least one kind of pigment selected from a cyclic azine pigment group of specific structure. SOLUTION: A compound is expressed by the formula, wherein R<1> represents a hydrogen atom or substituent; X<1> represents an oxygen atom, a sulfur atom, or a >NR<2> group; R<2> represents a hydrogen atom or substituent, Z<1> represents a -NR<3> R<4> or -OG<1> ; R<3> and R<4> each represent a same or different hydrogen atom or substituent, G<1> represents a hydrogen atom, a counter-cation, or substituent; R<5> represents a substituent, and n<1> represents an integer of 0 to 3. When n<1> is 2 or 3, a plurality of above R<5> may be identical or different. In the formula, Z<1> is preferably-NR<3> R<4> . Thereby blue, green color light is emitted at a desired wavelength, and manufacture of a fluorescent pigment with its superior durability is obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art At present, research and development on various display elements are active, and 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 device which forms an organic thin film by vapor deposition of an organic compound is known (see Applied Physics Letters, vol. 51, paragraph 913, 1987). The organic EL device described in the 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.

In an organic EL device, the required emission color differs depending on the application, but light of a desired wavelength can be extracted by changing the type of fluorescent dye used. However, in particular, the number of fluorescent dyes that emit light in the blue-green portion is small, and it has been desired to develop a fluorescent dye that emits light in the wavelength of the blue-green portion and has excellent durability.

[0005]

SUMMARY OF THE INVENTION An object of the present invention is to provide an organic electroluminescent device containing a fluorescent dye which emits light in a blue-green wavelength and has excellent durability. It is another object of the present invention to provide a method for producing a fluorescent dye that emits blue-green light at a desired wavelength and has excellent durability.

[0006]

According to the present invention, the following object of the present invention is achieved by providing the following organic electroluminescent device and fluorescent dye. [1] An organic electroluminescent device having at least one organic thin film between electrodes, comprising at least one dye selected from the group of cyclic azine dyes represented by the following general formula (1): .

[0007]

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In the general formula (1), R¹Is a hydrogen atom or
Represents a substituent. X¹Represents an oxygen atom, a sulfur atom, or>
NR^TwoRepresents a group. Where R^TwoIs a hydrogen atom or a substituent
Represents Z¹Is -NR^ThreeR^FourOr -OG¹Represents here
And R^ThreeAnd R^FourAre the same or different, and
Or a substituent;¹Is a hydrogen atom, counter cation,
Represents a substituent. R^FiveRepresents a substituent. n¹Is 0-3
Represents an integer. Where n¹Is 2 or 3
R above ^FiveMay be the same or different. [2] Z in the general formula (1)¹Is -NR^ThreeR^FourThat is
The organic electroluminescent device according to the above [1]
Sense element. [3] At least one organic thin film between electrodes
In the electroluminescent element, the following general formula
A small number selected from the group of cyclic azine dyes represented by (2)
An organic element containing at least one dye.
Castroluminescence element.

[0009]

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In the above general formula (2), R⁶Is a hydrogen atom
Or a substituent. X^TwoIs an oxygen atom, a sulfur atom,
Is> NR⁷Represents a group. Where R⁷Is a hydrogen atom or
Represents a substituent. R⁸And R⁹Are the same or different, water
Represents an atom or a substituent. R^TenRepresents a substituent. n
^TwoRepresents an integer of 0 to 3. Where n^TwoIs 2 or 3
Is a plurality of R ^TenAre the same but different
Is also good. [4] A carbonyl compound represented by the following general formula (3)
A derivative and an aniline compound represented by the following general formula (4)
Derivative or its salt with an oxidizing agent in an alkaline atmosphere
Wherein the reaction is carried out in the presence of
A method for producing the cyclic azine dye represented by (1).

[0011]

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In the above general formulas (3) and (4), X
³ represents an oxygen atom, a sulfur atom or,> NR ¹² group.
Here, R ¹² represents a hydrogen atom or a substituent. R
¹¹ represents a hydrogen atom or a substituent. Y ¹ and Y ² are
The same or different, and represents a hydrogen atom or a leaving group. Z
² represents a -NR ¹³ R ¹⁴ or -OG ^2. Where R ¹³
And R ¹⁴ are the same or different and represent a hydrogen atom or a substituent. R ¹⁵ represents a substituent. n ³ represents an integer of 0 to 3. However, when n ³ is 2 or 3, a plurality of R
¹⁵ may be the same or different.

[0013]

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. R ¹ represents a hydrogen atom or a substituent. Examples of the above substituents are described below, but are not limited thereto. 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. Substituted carbonyl group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms
2, for example, acetyl, benzoyl, methoxycarbonyl, phenyloxycarbonyl, dimethylaminocarbonyl, phenylaminocarbonyl and the like. Substituted amino group: preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as dimethylamino, methylcarbamoyl, ethylsulfonylamino, dimethylaminocarbonylamino, phthalimide and the like Is mentioned. 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: preferably having 1 to 20 carbon atoms
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and as the hetero atom, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino, Examples include benzoxazolyl and triazolyl. Alkoxy group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methoxy and benzyloxy. Aryloxy group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms
2, for example, phenoxy, naphthyloxy and the like. Halogen atom: preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. 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 a methylthio group. Arylthio 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 a phenylthio group. Other sulfo groups, carboxyl groups, hydroxyl groups, thiol groups, cyano groups, etc. These substituents may be further substituted.

Preferred R ¹ is a cyano group, a substituted or unsubstituted aryl group, an aromatic heterocyclic group (for example, a substituted or unsubstituted benzazole group (such as a benzoxazolyl group) or a triazolyl group), or a substituted carbonyl group. (For example, phenylaminocarbonyl group, methoxycarbonyl group, t
-Butylcarbonyl group), and a substituted sulfonyl group (for example, a methanesulfonyl group). Particularly preferred are a cyano group, a substituted or unsubstituted benzazole group (such as a benzoxazolyl group), and a substituted carbonyl group. More preferred are a substituted or unsubstituted benzazole (such as a benzoxazolyl group) and a substituted carbonyl group.

X ¹ is an oxygen atom, a sulfur atom or> NR ²
And preferably a> NR ² group or a sulfur atom, particularly preferably a> NR ² group. Here, the R ² group represents a hydrogen atom or a substituent. Examples of the above substituents are described below, but are not limited thereto. 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. Substituted carbonyl group: preferably 1 to 40 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 1 carbon atoms
2, for example, acetyl, benzoyl, methoxycarbonyl, dimethylaminocarbonyl, phenylaminocarbonyl and the like. Substituted sulfonyl group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms
2, for example, mesyl and tosyl. Heterocyclic group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms. Examples of the hetero atom include a nitrogen atom, an oxygen atom,
Sulfur atom, specifically, for example, imidazolyl, pyridyl,
Frills, piperidyl and the like. The above substituents may be further substituted.

R ^{2 in the} NR ² group is preferably a hydrogen atom, a substituted or unsubstituted alkyl group, an aryl group, a substituted carbonyl group, a substituted sulfonyl group, or a heterocyclic group, and particularly preferably a hydrogen atom, It is a substituted or unsubstituted alkyl group.

Z ¹ represents —NR ³ R ⁴ or —OG ¹ ,
Preferably from -NR ³ R ^4. G ¹ represents a hydrogen atom, a substituent, or a counter cation. Examples of the substituent include the substituents described above for R ² . The counter cation is not particularly limited. For example, metal cations (such as lithium ion, sodium ion, aluminum ion, and europium ion) and quaternary ammonium ion (preferably having 1 to 30 carbon atoms, particularly preferably having 1 to 20 carbon atoms) And more preferably C1-10, for example, tetrabutylammonium ion). The metal cation may have a ligand. Preferred G ¹ is a hydrogen atom; a substituted or unsubstituted alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, for example, methyl, isopropyl, methoxy An ethoxymethyl group or the like); a substituted or unsubstituted aryl group (preferably having 1 to 30 carbon atoms, particularly preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 10 carbon atoms, such as phenyl and p-methoxyphenyl groups); alkali metal ions; alkaline earth metal ions; aluminum ions; zinc ions; europium ions; boron ions; is there. More desirable G
¹ is a hydrogen atom, a substituted or unsubstituted alkyl group, an alkali metal ion, or a quaternary ammonium ion. G ¹ is particularly preferably a hydrogen atom, a substituted or unsubstituted alkyl group.

[0019] R ³ and R ⁴ of the -NR ³ R ^4, identical or different, represent a hydrogen atom or a substituent. Examples of the substituent include the substituents described above for R ² . Preferred R ³ and R ⁴ are a substituted or unsubstituted alkyl group, aryl group, substituted carbonyl group, substituted sulfonyl group or heterocyclic group, and more preferred R ³ and R ⁴
Is a substituted or unsubstituted alkyl group.

R ^{5 in the} general formula (1) represents a substituent. Examples of the substituent include the substituents described above for R ¹ . Preferred R ⁵ is a substituted or unsubstituted alkyl group,
An alkoxy group or a halogen atom, more preferably R
⁵ is a substituted or unsubstituted alkyl group. n ¹ 0-3
And when n ¹ is 2, 3, each R ⁵ may be the same or different.

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). X ^{2 in the} general formula (2) represents an oxygen atom, a sulfur atom, and a> NR ⁷ group, preferably a sulfur atom, a> NR ⁷ group, and more preferably a> NR ⁷ group. R ⁷ has the same meaning as R ² , and the preferred range is also the same.

R ^{6 in the} general formula (1) represents a substituent. Examples of the substituent are described below, but are not limited thereto. 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. Substituted amino 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 dimethylamino and phenylamino groups. Heterocyclic group: preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms. Examples of the hetero atom include a nitrogen atom, an oxygen atom,
Sulfur atom, specifically, for example, imidazolyl, pyridyl,
Examples include furyl, morpholino, and triazolyl groups. Alkoxy 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 a methoxy group and a benzyloxy group. Aryloxy group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms
2, and examples thereof include a phenoxy group and a naphthyloxy group. 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 a methylthio group. Arylthio group: preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as a phenylthio group. Others, such as a hydroxyl group. These substituents may be further substituted.

Preferred R ⁶ is a substituted or unsubstituted alkyl group (eg, t-butyl), an aryl group (eg, phenyl, p-methoxyphenyl), an amino group (eg, dimethylamino, phenylamino), and an alkoxy group (eg, dimethylamino, phenylamino). Methoxy). Particularly preferred are a substituted or unsubstituted alkyl group, amino group and alkoxy group.

R⁸And R⁹Is the R^Three, R^FourSynonymous with
The preferred range is also the same. R^TenIs the R^Five
And its preferred range is also the same. n
^TwoIs n¹Is synonymous with Also, R⁸And R⁹Are the same
May be different. R ^TenWhen there are multiple
Is a multiple R^TenMay be the same or different
No.

The compound represented by the general formula (1) or (2) is a high molecular weight compound having the skeleton represented by the general formula (1) or (2) bonded to the polymer main chain, or the compound represented by the general formula (1) Alternatively, a high molecular weight compound having a skeleton represented by (2) in the main chain may be used. In the case of a high molecular weight compound, it may be a homopolymer or a copolymer.

Examples of the compounds represented by formulas (1) and (2) are shown below, but the present invention is not limited thereto.

[0027]

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Next, a method for synthesizing the cyclic azine dye of the present invention represented by the general formula (1) will be described. The cyclic azine dye represented by the general formula (1) can be synthesized by various methods. For example, a carbonyl compound derivative represented by the general formula (3) and a carbonyl compound derivative represented by the general formula (3) can be synthesized by a method represented by the following reaction formula (1). It can be synthesized by reacting the aniline compound derivative represented by the formula (4) or a salt thereof with an oxidizing agent in an alkaline atmosphere to cause a reaction.

[0029]

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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, potassium carbonate,
The use of sodium bicarbonate, triethylamine, sodium alkoxide and the like is preferred. The amount of the base is not particularly limited, but is preferably 0.01 to 30 equivalents, more preferably 1 to 30 equivalents to the carbonyl compound derivative.
Equivalent to 10 equivalents are used. The minimum amount of the base required to dissociate the acidic hydrogen of the carbonyl compound derivative used in the reaction is defined as 1 equivalent. When the aniline compound derivative is basic, it may not be necessary to use a base.

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. In addition,
Oxygen may be able to be used as an oxidizing agent.
The amount of the oxidizing agent is not particularly limited, but is preferably 0.01 to 30 equivalents, more preferably 1 to 10 equivalents, based on the aniline compound derivative. The minimum amount of the oxidizing agent required for two-electron oxidation of the aniline compound derivative used in the reaction is defined as one equivalent.

The above reaction is preferably carried out using a solvent. Various solvents can be used, and examples thereof include organic solvents such as alcohols, ethers, and esters, water, and mixed solvents thereof. Above all,
It is preferable to use methanol, an ethyl acetate-ethanol-water mixed solvent, tetrahydrofuran, or the like. The reaction temperature is not particularly limited, but is preferably from -20 ° C to 100 ° C,
C. to 50.degree. C. is more preferred.

Next, general formulas (3) and (4) will be described. R ¹¹ has the same meaning as R ¹ , and the preferred range is also the same. X ³ is an oxygen atom, a sulfur atom,>
It represents NR ¹² group, a sulfur atom,> NR ¹² group is preferred. Particularly preferred are> NR ¹² group. Here, R ¹² has the same meaning as R ² , and the preferred range is also the same.
Z ² is, -NR ¹³ R ^14, or represents -OG ^2, preferably a -NR ¹³ R ^14. Here, G ² has the same meaning as G ¹ , and R ¹³ and R ¹⁴ have the same meanings as R ³ and R ⁴ , respectively, and their preferred ranges are also the same. R ¹⁵ is
It has the same meaning as R ⁵ , and its preferred range is also the same. n ³ has the same meaning as n ¹ .

Y ¹ and Y ² are the same or different and each represent a hydrogen atom or a group capable of leaving by coupling. The leaving group is not particularly limited, and examples thereof include the following. Halogen atom: for example, fluorine atom, chlorine atom, bromine atom. Alkylsulfonyl group: preferably having 1 to 20 carbon atoms, for example, a methanesulfonyl group and a butanesulfonyl group. Arylsulfonyl group: preferably having 1 to 20 carbon atoms, for example, a benzenesulfonyl group and a paratoluenesulfonyl group. Alkoxy group: preferably having 1 to 20 carbon atoms, for example, a methoxycarbonylmethyleneoxy group. Aryloxy group: preferably having 1 to 20 carbon atoms;
For example, a phenoxy group and a cyanophenoxy group. Nitrogen-containing heterocyclic group: preferably having 1 to 20 carbon atoms, examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom,
Specifically, for example, a phthalimide group, a dimethylhydantoin group, a urazolyl group, a pyrazolyl group, and a dimethyloxazolidinedione group. Acyloxy group: preferably having 1 to 20 carbon atoms, for example, an acetoxy group. Alkoxycarbonyloxy group: preferably 1 to 1 carbon atoms
20, for example, a methoxycarbonyloxy group. Aminocarbonyloxy group: preferably having 1 to 20 carbon atoms
And examples thereof include a dimethylaminocarbonyloxy group and a morpholinocarbonyloxy group. Arylthio group: preferably having 1 to 20 carbon atoms, such as a phenylthio group. Alkylthio group: preferably having 1 to 20 carbon atoms, for example, butoxycarbonylmethylenethio group.

Preferred Y ¹ is a hydrogen atom, a halogen atom, an aryloxy group, or a substituted or unsubstituted nitrogen-containing heterocyclic group. Particularly preferred Y ¹ is a hydrogen atom, a chlorine atom, a bromine atom, a substituted or unsubstituted hydantoin, or an oxazolidinedione group. Desirable Y ² is a substituted or unsubstituted alkoxy or aryloxy group. Particularly preferred Y ² is a substituted or unsubstituted aryloxy group.

Next, the EL device containing the cyclic azine type 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 are 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. 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, etc., and may be made of a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof. 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 thereof, copper iodide, inorganic conductive substances such as copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates thereof with ITO, and the like. It is a metal oxide, and especially in terms of productivity, high conductivity, transparency, etc.
O is preferred. 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 be cleaned or otherwise treated to lower the device's drive voltage,
It is also possible to increase the luminous efficiency. For example, in the case of ITO, UV-ozone treatment, plasma treatment and the like are effective.

The cathode supplies electrons to the electron injection layer, the electron transport layer, the light emitting layer, and the like. The cathode has good adhesion and ionization potential between the negative electrode and the adjacent layers such as the electron injection layer, the electron transport layer, and the light emitting layer. , Stability and so on. 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. Specifically, alkali metals (eg, Li, Na, K, etc.) and their fluorides; alkaline earth metals (eg, Mg, Ca, etc.) and their fluorides; gold, silver, lead, aluminum, sodium-potassium alloy or Lithium-aluminum alloy or mixed metal thereof; magnesium-silver alloy or mixed metal thereof; rare earth metal such as indium and ytterbium; and the like. A preferred material is a material having a work function of 4 eV or less. More preferred materials include aluminum, a lithium-aluminum alloy or a mixed metal thereof; a magnesium-silver alloy or a mixed metal thereof, and the like. The cathode can have not only a single-layer structure of the above materials but also a stacked structure including the above materials. The thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm,
It is more preferably 50 nm to 1 μm, and still more preferably 100 nm to 1 μm.

The cathode is manufactured by a method such as an electron beam method, a sputtering method, a resistance heating evaporation method, and a coating method. The metal can be evaporated alone or two or more components can be evaporated simultaneously. Furthermore, it is also possible to form an alloy electrode by simultaneously depositing a plurality of metals,
Alternatively, a previously adjusted alloy may be deposited. The sheet resistance of the anode and the cathode is preferably low, and several hundred Ω /
□ The following is preferred.

The material of the light emitting layer is capable of injecting holes from an anode or a hole injection layer or a hole transport layer when applying an electric field, and also capable of injecting electrons from a cathode or an electron injection layer or an electron transport layer. 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. A preferred light-emitting layer contains the above-mentioned cyclic azine compound, 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, polyphenylene vinylene, etc. And the like.
Although the thickness of the light emitting layer is not particularly limited, it is usually 1
It is preferably in the range of nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 5 μm.
00 nm. The method for forming the light emitting layer is not particularly limited, but includes resistance heating evaporation, electron beam, sputtering, molecular lamination, coating (spin coating, casting, dip coating, etc.), LB, etc. The method is preferably a resistance heating evaporation or coating method.

The material of the hole injection layer and the hole transport layer has a function of injecting holes from the anode, a function of transporting holes, or 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, conductive polymer oligomers such as polythiophene, and the cyclic azine dye of the present invention. 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 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.

The hole injecting layer and the hole transporting layer may be formed by a vacuum evaporation method, an LB method, or a method in which the hole injecting and transporting agent is dissolved or dispersed in a solvent and coated (spin coating, casting, Dip coating method) is 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, polyamides,
Examples include 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, or 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, and naphthaleneperylene;
Examples include metal complexes of phthalocyanine derivatives, 8-quinolinol derivatives, various metal complexes represented by metal phthalocyanines, metal complexes having benzoxazole or benzothiazole as ligands, and the cyclic azine dyes of the present invention.

The thickness of the electron injection layer and the electron transport layer is not particularly limited, but is preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm.
More preferably, it is 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.

The electron injecting layer and the electron transporting layer may be formed by vacuum evaporation, LB, or by dissolving or dispersing the electron injecting and transporting agent in a solvent and coating (spin coating, casting, dip coating, etc.). Etc.) are used. In the case of the coating method, it can be dissolved or dispersed together with the resin component.
What was illustrated in the case of the hole injection transport layer can be applied.

As a material for the protective layer, a material such as moisture or oxygen is used.
A device that prevents elements that promote element degradation from entering the element
What is necessary is just to have a function. As a specific example
Is In, Sn, Pb, Au, Cu, Ag, Al, T
i, metals such as Ni, MgO, SiO, SiO_Two, Al_Two
O_Three, GeO, NiO, CaO, BaO, Fe_TwoO_Three, Y_Two
O _Three, TiO_TwoMetal oxides such as MgF_Two, LiF, A
IF_Three, CaF_TwoMetal fluorides such as polyethylene, polyethylene
Polypropylene, polymethyl methacrylate, polyimi
, Polyurea, polytetrafluoroethylene, polyc
Lorotrifluoroethylene, polydichlorodifluoroe
Tylene, chlorotrifluoroethylene and dichlorodifur
Copolymer with oroethylene, tetrafluoroethylene and
A monomer mixture comprising at least one comonomer
Copolymer obtained by copolymerization, cyclic structure in copolymer main chain
Fluorine-containing copolymer, water-absorbing substance having a water absorption of 1% or more
And moisture-absorbing substances with a water absorption of 0.1% or less.
You.

The method for forming the protective layer is not particularly limited. For example, a vacuum deposition method, a sputtering method, a reactive sputtering method, an MBE (molecular beam epitaxy) method, a cluster ion beam method, an ion plating method, a plasma polymerization method ( High frequency excitation ion plating), plasma CVD, laser CVD, thermal CVD, and gas source CVD.

[0050]

EXAMPLES Specific examples of the present invention will be described below, but the embodiments of the present invention are not limited to these examples. [Synthesis of Cyclic Azine Dye (1-1)] The synthesis scheme is described below.

[0051]

Embedded image

1 g of phenyl ester (a-1) and 0.88 g of phenylenediamine derivative (a-2) were dissolved in a mixed solvent consisting of 8 ml of ethyl acetate, 2 ml of ethanol and 10 ml of water, and 0.82 g of potassium carbonate was added thereto. 0.8 g of ammonium persulfate was added and stirred at room temperature for 30 minutes. The reaction solution was diluted with 30 ml of ethyl acetate and 10 ml of water, and the separated organic layer was washed with aqueous hydrochloric acid and further washed with water. After drying the organic layer over sodium sulfate, the organic solution was concentrated to obtain crude crystals. The crude crystals were purified by column chromatography (hexane / ethyl acetate system) to obtain 0.6 g of the cyclic azine dye (1-1). The optical properties of this dye were as follows. λmax = 442
(Nm) (in ethyl acetate), ε = 29900

[Production and Evaluation of EL Element] (Comparative Example) Polyvinylcarbazole 40 mg, PBD
12 mg of (pt-butylphenylbiphenyloxadiazole) and 1 mg of tetraphenylbutadiene were dissolved in 3 ml of dichloroethane, and spin-coated on a washed ITO substrate. The thickness of the formed organic thin film is about 120
nm. A mask patterned on an organic thin film is installed, and magnesium: silver = 10: 1 is added in a vapor deposition apparatus.
After co-evaporation of 50 nm, 300 nm of silver was evaporated thereon. 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 luminance is measured by a luminance meter BM-8 manufactured by Topcon, and the emission wavelength is measured by a spectrum analyzer PMA-11 manufactured by Hamamatsu Photonics.
It measured using. As a result, the maximum luminance is 280 at 12V.
cd / m ² . Λmax of light emission was 450 nm. After emitting the fabricated device for 5 hours,
Dark spots were visible on the light emitting surface. The occurrence of a dark spot on the light emitting surface means that the element has deteriorated.

(Example 1) Instead of the tetraphenylbutadiene of the comparative example, the cyclic azine dye (1)
-1), an EL element was similarly fabricated and evaluated. As a result, emission of λmax = 480 nm was obtained, and 520 at 14 V was obtained.
Light emission of cd / m ² was obtained. No dark spots were visible on the light emitting surface.

(Example 2) An EL device was prepared and evaluated in the same manner as in Comparative Example, except that the above-mentioned cyclic azine dye (1-5) was used instead of tetraphenylbutadiene.
= 485 nm, and 435 cd / m ^{2 at} 15 V. No dark spots were visible on the light emitting surface.

Example 3 Instead of the tetraphenylbutadiene of the comparative example, the cyclic azine dye (1-13) was used.
The EL device was similarly fabricated and evaluated using
x = 465 nm emission, 290 cd / m ^{2 at} 16 V
Was obtained. No dark spots were visible on the light emitting surface. From the results of the above examples, using the cyclic azine dye specified in the present invention makes it possible to manufacture a blue-green light-emitting EL element that emits light at the wavelength of the blue-green portion, and this cyclic azine dye has improved durability. It is clear that it is excellent.

[0057]

The cyclic azine dye specified in the present invention is
Since it emits light at the wavelength of the blue-green portion and has excellent durability, the electroluminescent element using the same emits light at the wavelength of the blue-green portion and has excellent durability.

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[Procedure amendment]

[Submission date] January 21, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0014

[Correction method] Change

[Correction contents]

Heterocyclic group: preferably having 1 to 20 carbon atoms
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and as the hetero atom, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino, Examples include benzoxazolyl and triazolyl. Alkoxy group: preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as methoxy and benzyloxy. 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, phenoxy, naphthyloxy and the like. Halogen atom: preferably a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like. 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 a methylthio group. Arylthio group: preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, and particularly preferably having 6 to 12 carbon atoms.
And examples thereof include a phenylthio group. Other sulfo groups, carboxyl groups, hydroxyl groups, thiol groups, cyano groups, etc. These substituents may be further substituted.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0018

[Correction method] Change

[Correction contents]

Z ¹ represents —NR ³ R ⁴ or —OG ¹ ,
Preferably from -NR ³ R ^4. G ¹ represents a hydrogen atom, a substituent, or a counter cation. Examples of the substituent include the substituents described above for R ² . The counter cation is not particularly limited. For example, metal cations (such as lithium ion, sodium ion, aluminum ion, and europium ion) and quaternary ammonium ion (preferably having 1 to 30 carbon atoms, particularly preferably having 1 to 20 carbon atoms) And more preferably C1-10, for example, tetrabutylammonium ion). The metal cation may have a ligand. Preferred G ¹ is a hydrogen atom; a substituted or unsubstituted alkyl group (preferably having 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, particularly preferably 1 to 10 carbon atoms, for example, methyl, isopropyl, methoxy An ethoxymethyl group or the like); a substituted or unsubstituted aryl group (preferably having 6 to 30 carbon atoms, particularly preferably having 6 to 20 carbon atoms,
More preferably, it has 6 to 10 carbon atoms, such as phenyl and p-methoxyphenyl groups); alkali metal ions; alkaline earth metal ions; aluminum ions; zinc ions; europium ions; boron ions; is there. Furthermore preferred correct G ¹ is,
A hydrogen atom, a substituted or unsubstituted alkyl group, an alkali metal ion and a quaternary ammonium ion, and particularly preferred G ¹ is a hydrogen atom, a substituted or unsubstituted alkyl group.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0022

[Correction method] Change

[Correction contents]

R ^{6 in the} general formula (1) represents a substituent. Examples of the substituent are described below, but are not limited thereto. 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. A substituted amino group: preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example dimethylamino, and the like phenylamino group. Heterocyclic group: preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms. Examples of the hetero atom include a nitrogen atom, an oxygen atom,
Sulfur atom, specifically, for example, imidazolyl, pyridyl,
Examples include furyl, morpholino, and triazolyl groups. Alkoxy 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 a methoxy group and a benzyloxy group. Aryloxy group: preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 1 carbon atoms.
2, and examples thereof include a phenoxy group and a naphthyloxy group. Alkylthio group: preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms.
And examples thereof include a methylthio group. Arylthio group: preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, and particularly preferably having 6 to 12 carbon atoms.
And examples thereof include a phenylthio group. Others, such as a hydroxyl group. These substituents may be further substituted.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction contents]

Y ¹ and Y ² are the same or different and each represent a hydrogen atom or a group capable of leaving by coupling. The leaving group is not particularly limited, and examples thereof include the following. Halogen atom: for example, fluorine atom, chlorine atom, bromine atom. Alkylsulfonyl group: preferably having 1 to 20 carbon atoms, for example, a methanesulfonyl group and a butanesulfonyl group. Arylsulfonyl group: preferably having 6 to 20 carbon atoms, for example, a benzenesulfonyl group and a paratoluenesulfonyl group. Alkoxy group: preferably having 1 to 20 carbon atoms, for example, a methoxycarbonylmethyleneoxy group. Aryloxy group: preferably having 6 to 20 carbon atoms;
For example, a phenoxy group and a cyanophenoxy group. Nitrogen-containing heterocyclic group: preferably having 1 to 20 carbon atoms, examples of the hetero atom include a nitrogen atom, an oxygen atom, a sulfur atom,
Specifically, for example, a phthalimide group, a dimethylhydantoin group, a urazolyl group, a pyrazolyl group, and a dimethyloxazolidinedione group. Acyloxy group: preferably having 1 to 20 carbon atoms, for example, an acetoxy group. Alkoxycarbonyloxy group: preferably 1 to 1 carbon atoms
20, for example, a methoxycarbonyloxy group. Aminocarbonyloxy group: preferably having 1 to 20 carbon atoms
And examples thereof include a dimethylaminocarbonyloxy group and a morpholinocarbonyloxy group. Arylthio group: preferably having 6 to 20 carbon atoms, such as a phenylthio group. Alkylthio group: preferably having 1 to 20 carbon atoms, for example, butoxycarbonylmethylenethio group.

Claims (4)

[Claims] At least one organic thin film is provided between electrodes.
In the organic electroluminescent element to
Selected from the group of cyclic azine dyes represented by the general formula (1)
Organic electroluminescence containing at least one dye
Essence element. Embedded imageIn the general formula (1), R¹Represents a hydrogen atom or a substituent
You. X¹Is an oxygen atom, a sulfur atom, or> NR^TwoTable
You. Where R^TwoRepresents a hydrogen atom or a substituent. Z¹
Is -NR^ThreeR^FourOr -OG¹Represents Where R^ThreeAnd
And R^FourAre the same or different and each represents a hydrogen atom or a substituent
And G¹Represents a hydrogen atom, counter cation, or substituent
Represent. R^FiveRepresents a substituent. n¹Represents an integer of 0 to 3
You. Where n¹Is 2 or 3, a plurality of R ^Five
May be the same or different. 2. The organic electroluminescent device according to claim 1, wherein Z ^{1 in the} general formula (1) is —NR ³ R ⁴ . 3. An electrode having at least one organic thin film between electrodes.
In the organic electroluminescent element to
Selected from the group of cyclic azine dyes represented by the general formula (2)
Characterized in that it contains at least one dye
Electroluminescent element. Embedded imageIn the above general formula (2), R⁶Represents a hydrogen atom or a substituent
Represent. X^TwoIs an oxygen atom, a sulfur atom, or> NR⁷Base
Represent. Where R⁷Represents a hydrogen atom or a substituent.
R⁸And R⁹Are the same or different and each represents a hydrogen atom or
Represents a substituent. R^TenRepresents a substituent. n^TwoIs 0-3
Represents an integer. Where n^TwoIs 2 or 3
R above ^TenMay be the same or different. 4. A carbonyl compound derivative represented by the following general formula (3) is reacted with an aniline compound derivative represented by the following general formula (4) or a salt thereof in an alkaline atmosphere in the presence of an oxidizing agent. A method for producing a cyclic azine dye represented by the above general formula (1). Embedded image In the above general formulas (3) and (4), X ³ is an oxygen atom,
It represents a sulfur atom or,> NR ¹² group. Where R ¹² is
Represents a hydrogen atom or a substituent. R ¹¹ represents a hydrogen atom or a substituent. Y ¹ and Y ² are the same or different,
Represents a hydrogen atom or a leaving group. Z ² represents an -NR ¹³ R ¹⁴ or -OG ^2. Here, R ¹³ and R ¹⁴ are the same or different and represent a hydrogen atom or a substituent. R ¹⁵ represents a substituent. n ³ represents an integer of 0 to 3. However, when n ³ is 2 or 3, a plurality of R ¹⁵ may be the same or different.