JPH06206865A - New anthracene compound and electroluminescent element using the compound - Google Patents

Abstract

PURPOSE:To provide a new compound useful as a luminous material for fluorescent coatings and electroluminescent elements, etc. CONSTITUTION:The compound of formula I (An is anthracene bonded to the 1, 2, or 9 position; n is 1, 2; Y is S, O, CH2, etc.; Y1 to Y8 are H, halogen, alkyl, etc.,), e.g. (9-anthracenyl)-methyl-9-carbazole. The compound of formula I is produced by condensing a releasable group-containing anthracene compound of formula: An-(CH2)n-X (X is halogen, releasable group) with an aromatic tertiary amine of formula II (Z is H, alkali metal salt) in a solvent (e.g. xylene) at room temperature to 200 deg.C. The compound of formula I is useful as a compound for EL elements capable of generating highly bright light at low voltage. The application of a direct current voltage to the element using the compound of formula I can give blue to greenish-blue light having a peak wavelength of 455-460nm and a light brightness of 450-500cd/m<2>.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel anthracene compound and a method for producing the same, and more particularly to a novel anthracene compound useful as a fluorescent paint, a light emitting material for an electroluminescence (EL) device and the like and a method for producing the same. It is a thing.

[0002]

2. Description of the Related Art Focusing on the high fluorescence efficiency of organic compounds, research on devices utilizing the EL performance of organic compounds has been conducted for a long time. For example, W. Helfris
h, Dresmer. Williams et al. Obtained blue emission using anthracene crystal (J. Chem. P.
hys. , 44, 2902 (1966)). Also Vin
Cett and Barlow et al. manufacture a light emitting device by a vacuum evaporation method of a condensed polycyclic compound (Thin.
Solid Films, 99, 171 (198
2)). However, in all cases, only low emission intensity and low emission efficiency are obtained. Therefore, the inventors of the present invention have conducted extensive studies to develop a novel anthracene compound, particularly a novel compound that effectively functions as an EL light emitting substance. As a result, the following general formula

[Chemical 7] [In the formula, An is anthracene bonded to the 1-position, 2-position, or 9-position, and substitutable positions other than the bond are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group, n is 1 or 2, Y is a bond, S, O, CH
₂ , or C = 0, or CH-R ¹ or NR
² (R ¹ and R ² are alkyl groups, alkoxy groups, allyl groups and aralkyl groups), and Y _{1 to} Y ₈ are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group and amino. Group, a cyano group, a hydroxycarbonyl group, an alkyl group, an alkoxy group, an allyl group, and an aralkyl group], and a novel anthracene compound in which an alkyl group is sandwiched at a tertiary amine moiety and an anthracene compound is effective I found out that The present invention has been completed based on such findings.

As is clear from the above description, the object of the present invention is to provide a novel anthracene compound which effectively functions as an EL light-emitting substance and has a high emission intensity and high emission efficiency as a device, a method for producing the same, and the use of the compound. The present invention is to provide an electroluminescent device.

[0004]

The present invention has the following configurations (1) to (4). (1) General formula

[Chemical 8] [In the formula, An is anthracene bonded to the 1-position, 2-position, or 9-position, and substitutable positions other than the bond are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group, n is 1 or 2, Y is a bond, S, O, CH
₂ , or C = 0, or CH-R ¹ or NR
² (R ¹ and R ² are alkyl groups, alkoxy groups, allyl groups and aralkyl groups), and Y _{1 to} Y ₈ are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group and amino. Group, a cyano group, a hydroxycarbonyl group, an alkyl group, an alkoxy group, an allyl group, and an aralkyl group.]. (2) General formula

[Chemical 9] [In the formula, An is anthracene bonded to the 1-position, 2-position, or 9-position, and substitutable positions other than the bond are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group, n is 1, 2 and X is fluorine, chlorine, bromine, iodine or tosyloxy group, mesyloxy group, trifluoromethoxy group, etc. Of an anthracene compound represented by

[Chemical 10] [Wherein Z is hydrogen or an alkali metal salt such as lithium, sodium or potassium, Y is a bond, S, O, CH ₂ ,
Or C = 0, or CH—R ¹ or NR ²
(R ¹ and R ² are an alkyl group, an alkoxy group, an allyl group,
Aralkyl group), and Y _{1 to} Y ₈ are each independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group. , Represents an aralkyl group] and is condensed with an aromatic tertiary amine

[Chemical 11] [In the formula, An is anthracene bonded to the 1-position, 2-position, or 9-position, and substitutable positions other than the bond are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group, n is 1 or 2, Y is a bond, S, O, CH
₂ , or C = 0, or CH-R ¹ or NR
² (R ¹ and R ² are alkyl groups, alkoxy groups, allyl groups and aralkyl groups), and Y _{1 to} Y ₈ are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group and amino. A group, a cyano group, a hydroxycarbonyl group, an alkyl group, an alkoxy group, an allyl group, and an aralkyl group]]. (3) General formula

[Chemical 12] [In the formula, An is anthracene bonded to the 1-position, 2-position, or 9-position, and substitutable positions other than the bond are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group, m is 0 to 5, Y is a bond, S, O, CH ₂ , or C = 0, or CH-R ¹ Or N-R ² (R
¹ , R ² is an alkyl group, an alkoxy group, an allyl group or an aralkyl group), and Y _{1 to} Y ₈ are each independently hydrogen,
Fluorine, chlorine, bromine, halogen such as iodine, nitro group,
Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group]
A general formula characterized by reducing the amide group of an anthracene compound represented by

[Chemical 13] [In the formula, An is anthracene bonded to the 1-position, 2-position, or 9-position, and substitutable positions other than the bond are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group, n is 1 to 6, Y is a bond, S, O, CH ₂ , or C = 0, or CH-R ¹ Or N-R ² (R
¹ , R ² is an alkyl group, an alkoxy group, an allyl group or an aralkyl group), and Y _{1 to} Y ₈ are each independently hydrogen,
Fluorine, chlorine, bromine, halogen such as iodine, nitro group,
Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group]
A method for producing an anthracene compound represented by (Method B). (4) An electroluminescent device using the compound described in the above item 1.

In the general formula (I), n is 1 or 2, and Y may be any of the above-mentioned R ¹ in the formula,
R ² is a methyl group, an ethyl group, an i-propyl group, tert
-Alkyl group such as butyl group, phenyl group, naphthyl group,
An allyl group such as a pyridyl group or an aralkyl group such as a benzyl group or a phenethyl group is shown. The above-mentioned novel anthracene compound of the present invention can be produced by various methods, and can be efficiently synthesized by the method of the present invention. First, in the method A of the present invention, the anthracene compound represented by the general formula (II) and the aromatic amine compound represented by the general formula (III) are coupled to each other to form the desired general formula (I A) anthracene compound is produced. This reaction is based on a condensation reaction between an amino group and a leaving group such as halogen. The condensation reaction between the leaving group-containing anthracene compound of the general formula (II) and the tertiary amine compound of the general formula (III) is You can proceed under various conditions. Examples of X include fluorine, chlorine, bromine, iodine, tosyloxy group, mesyloxy group and trifluoromethoxy group. Z is hydrogen or an alkali metal salt such as lithium, sodium or potassium, but a lithium salt, a sodium salt or a potassium salt is preferable because of high reactivity. Hydrocarbons, ethers, and aprotic polar solvents are preferable as the reaction solvent used here. In particular,
Decane; tridecane; benzene; toluene; xylene;
1,4-dioxane; tetrahydrofuran; diethyl ether; N, N-dimethylformamide; dimethyl sulfoxide and the like. Of these, xylene and dimethyl sulfoxide are preferable. Also, 18-crown-6
The reaction can also be promoted by using a phase transfer catalyst such as. The reaction temperature varies depending on the type of raw materials used and other conditions and cannot be uniquely determined. Usually, it can be selected in a wide range from room temperature to about 200 ° C, but is preferably in the range of 50 to 150 ° C. Is.

The anthracene compound of the present invention can be efficiently produced by the above method A, and a specific one of the anthracene compounds can also be efficiently produced by the method B. In this method B, the general formula
The target anthracene compound of general formula (I) is produced by reducing the tertiary amide compound represented by (IV). This reaction is based on H. C. Braun, J .; Che
m. Educ. , 38, 173 (1961). In the general formula (IV), Y is the same as X in the general formula (I), and m corresponds to n having one carbon atom with a small number. The reduction reaction of the tertiary amide compound of the general formula (IV) can proceed under various conditions. The reaction solvent used here is preferably tetrahydrofuran; ethers such as dimethylglyoxal,
Of these, tetrahydrofuran is preferable. Also, the reaction temperature varies depending on the type of raw materials used and other conditions,
Although it cannot be unambiguously determined, it can be selected in a wide range from about -20 to about 100 ° C, but is preferably from 0 to 70 ° C.

Specific examples of the compound represented by the general formula (I) include those shown below.

[Chemical 14]

[Chemical 15]

[Chemical 16]

[Chemical 17]

[Chemical 18]

[Chemical 19]

[Chemical 20]

[Chemical 21]

[Chemical formula 22]

[Chemical formula 23]

[Chemical formula 24]

[Chemical 25]

[Chemical formula 26]

[Chemical 27]

[Chemical 28]

[Chemical 29]

[Chemical 30]

[Chemical 31]

[Chemical 32]

[Chemical 33]

[Chemical 34]

[Chemical 35]

[Chemical 36]

[Chemical 37]

[Chemical 38]

[Chemical Formula 39]

The thus-obtained anthracene compound of the present invention can be effectively used as a component of an EL device capable of emitting light with high brightness at a low voltage. The anthracene compound of the present invention has an electron injecting function, an electron transporting function, a hole injecting function, a hole transporting function and a light emitting function, which are indispensable as a light emitting layer of an EL device. As described above, the compound represented by the general formula (I) of the present invention is
It is effective as a light emitting layer in an EL element. The light emitting layer can be formed by thinning the compound of the general formula (I) by a known method such as a vapor deposition method, a spin coating method or a casting method, and in particular, a molecular deposition film can be formed. preferable. Here, the molecular deposition film is a thin film formed by depositing the compound in a gas phase state, or a film formed by solidifying from a solution state or a liquid phase state of the compound, for example, a vapor deposition film or the like. However, this molecular deposited film can be usually distinguished from a thin film (molecular heterogeneous film) formed by the LB method. Further, the light emitting layer is disclosed in
As disclosed in JP-A-194393, a binder such as a resin and the compound are dissolved in a solvent to form a solution, which can be formed into a thin film by a spin coating method or the like. The thickness of the thin film of the light emitting layer thus formed is not particularly limited and can be appropriately selected depending on the situation, but is usually 5 nm to 5000 n.
It is selected in the range of m. The light emitting layer in this EL device has (1) an injection function capable of injecting holes from the anode or the hole injection layer and injecting electrons from the cathode or the electron injection layer when an electric field is applied, (2 ) A transport function of moving the injected charges (electrons and holes) by the force of the electric field,
(3) Providing a field for recombination of electrons and holes inside the light emitting layer,
It has a light emitting function that connects this to light emission. It should be noted that there may be a difference between the ease with which holes are injected and the ease with which electrons are injected, and the transport capacity represented by the mobility of holes and electrons may be large or small. It is preferable to transfer the electric charges of.

The structure of an EL device using the compound of the present invention has various modes. Basically, the light emitting layer is sandwiched between a pair of electrodes (anode and cathode). A hole injection layer or an electron injection layer may be interposed if necessary. Specifically, (1) anode / light emitting layer / cathode, (2) anode / hole injection layer / light emitting layer / cathode, (3) anode / light emitting layer /
Electron injection layer / cathode, (4) anode / hole injection layer / light emitting layer /
Examples of the structure include an electron injection layer / cathode. The hole injection layer and the electron injection layer are not always necessary,
The presence of these layers further improves the light emission performance. Also,
It is preferable that all of the elements having the above-mentioned constitution are supported by a substrate, and there is no particular limitation on the substrate, and those elements conventionally used for EL elements, for example, glass, transparent plastic, quartz, etc. are used. Any thing can be used. As the anode in this EL element, a material having a high work function (4 eV or more) metal, alloy, electrically conductive compound or a mixture thereof as an electrode substance is preferably used. Specific examples of such an electrode material include a metal such as Au and a dielectric transparent material such as CuI, ITO, SnO ₂ and ZnO. The anode can be prepared by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering. When the emitted light is taken out from this electrode, it is desirable that the transmittance is higher than 10%, and the sheet resistance as the electrode is preferably several hundred Ω / mm or less. Further, the film thickness depends on the material, but is usually 10 nm to 1 μm, preferably 1
It is selected in the range of 0 to 200 nm. On the other hand, as the cathode, one having a metal, an alloy, an electrically conductive compound having a low work function (4 eV or less), or a mixture thereof as an electrode substance is used. Specific examples of such an electrode material include:
Sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, Al / AlO
₂ , indium and the like. The cathode can be produced by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering. The sheet resistance as an electrode is preferably several hundreds Ω / mm or less, and the film thickness is usually 10 nm to 1 μm, preferably 5
It is selected in the range of 0 to 200 nm. In this EL element, it is convenient that either the anode or the cathode is transparent or semi-transparent to allow the emitted light to pass therethrough, so that the emission efficiency of the emitted light is good. E using the compounds of the invention
The L element has various configurations as described above,
The hole injecting layer (hole injecting and transporting layer) in the EL device having the configuration (2) or (4) is a layer made of a hole transporting compound, and the holes injected from the anode serve as a light emitting layer. By having this hole injection layer interposed between the anode and the light emitting layer, a large number of holes are injected into the light emitting layer at a lower electric field, and furthermore, the hole injecting layer has a function of transmitting, and a cathode or an electron is added to the light emitting layer. Electrons injected from the injection layer are accumulated near the interface in the light-emitting layer and the hole-injection layer due to the barrier of the electrons existing at the interface, and the luminous efficiency is improved. Become. The hole transfer compound used in the hole injection layer is
A compound which is arranged between two electrodes to which an electric field is applied and which can appropriately transfer the holes to the light emitting layer when the holes are injected from the anode, for example, 10 ⁴ to 10 ⁶ V / Those having a hole mobility of at least 10 ⁻⁶ cm ² / V · sec when an electric field of cm is applied are preferable. The hole transporting compound is not particularly limited as long as it has the above-mentioned preferable properties, and is conventionally used as a charge transporting material for holes in photoconductive materials and holes for EL elements. Any known material used for the injection layer can be selected and used.

Examples of the charge transport material include triazole derivatives (described in US Pat. No. 3,112,197) and oxadiazole derivatives (US Pat. No. 3,189,447). Described), imidazole derivatives (described in Japanese Patent Publication No. 37-16096, etc.), polyarylalkane derivatives (US Pat. Nos. 3,615,402 and 3,820,98).
No. 9, No. 3,542,544, Japanese Patent Publication No. 4
No. 5-555, No. 51-10983, No. 51-93224, No. 55-17105.
56-4148, 55-108667, 55-156953, 56-36656.
Those described in Japanese Patent Publication No.), pyrazoline derivatives and pyrazolone derivatives (US Pat. Nos. 3,180,729, 4,278,746 and JP-A-55-88).
064, 55-88065, 49-1.
05537, 55-51086, 56.
-80051 gazette, the same 56-88141 gazette, the same 5
No. 7-45545, No. 54-112637,
55-74546), phenylenediamine derivatives (U.S. Pat. No. 3,615,404, Japanese Patent Publication No. 51-10105, 46-37).
12, JP-A-47-25336, JP-A-54-
No. 53435, No. 54-110536, No. 5
Nos. 4,119,925 and the like), arylamine derivatives (US Pat. Nos. 3,567,450, 3,180,703, and 3,240,5).
No. 97, No. 3,658,520, No. 4,
No. 232,103, No. 4,175,961, No. 4,012,376, Japanese Patent Publication No. 49-35.
702, 39-27577 and JP-A-55.
No. 144250, No. 56-119132,
No. 56-22437, West German Patent No. 1,110,5
No. 18, etc.), amino-substituted chalcone derivatives (such as those described in US Pat. No. 3,526,501), oxazole derivatives (US Pat. No. 3,2).
57,203) and the like, styrylanthracene derivatives (as described in JP-A-56-46234), fluorenone derivatives (JP-A-54-1).
10837) and hydrazone derivatives (U.S. Pat. No. 3,717,462, Japanese Patent Laid-Open No. Sho 5).
No. 4-59143, No. 55-52063, No. 55-52064, No. 55-46760,
No. 55-85495, No. 57-11350, No. 57-148749, etc.) and stilbene derivatives (JP-A-61-210363).
No. 61-228451 and No. 61-146.
42 publication, 61-72255 publication, 62-47.
No. 646, No. 62-36674, No. 62-1
No. 0652, No. 62-30255, No. 60-
No. 93445, No. 60-94462, No. 60
Nos. -174749 and 60-175052).

These compounds can be used as a hole transfer compound, and the following porphyrin compounds (described in JP-A-63-295695)
And aromatic tertiary amine compounds and styrylamine compounds (US Pat. No. 4,127,412;
No. 3-27033, No. 54-58445, No. 54-149634, No. 54-64299, No. 55-79450, No. 55-144250.
No. 56-119132, No. 61-295.
No. 558, No. 61-98353, No. 63-2.
Those described in JP-A-95695), and particularly preferably the aromatic tertiary amine compound. Typical examples of the porphyrin compound include porphyrin; 5,1
0,15,20-tetraphenyl-21H, 23H-porphyrin copper (II); 5,10,15,20-tetraphenyl-21H, 23H-porphyrin zinc (II);
5,10,15,20-Tetrakis (pentafluorophenyl) -21H, 23H-porphyrin; Silicon phthalocyanine oxide; Aluminum phthalocyanine chloride; Phthalocyanine (metal free); Dilithium phthalocyanine; Copper tetramethylphthalocyanine; Copper phthalocyanine; Chromium phthalocyanine; Zinc phthalocyanine;
Lead phthalocyanine; titanium phthalocyanine oxide; magnesium phthalocyanine; copper octamethylphthalocyanine; and the like. Further, as typical examples of the aromatic tertiary compound and the styrylamine compound, N,
N, N ', N',-tetraphenyl-4,4'-diaminobiphenyl; N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminobiphenyl (TPD) 2,2-bis (4-di-p-tolylaminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ',
N ',-tetra-p-tolyl-4,4'-diaminobiphenyl; 1,1-bis (4-di-p-tolylaminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methyl) Phenyl) phenylmethane;
N, N'-diphenyl-N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl; N, N'-
Tetraphenyl-4,4'-diaminobiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4-
(Di-p-tolylamine) -4 '-[4 (di-p-tolylamine) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-
Methoxy-4′-N, N-diphenylaminostilbene; N-phenylcarbazole and the like.

The hole injecting layer in the above EL device may be composed of a single layer containing one or more of these hole transporting compounds, or a hole injecting layer containing a compound different from the above layer. It may be a stack of layers.
On the other hand, the electron injecting layer (electron injecting and transporting layer) in the EL device having the above configuration (3) or (4) is made of an electron transfer compound, and has a function of transferring electrons injected from the cathode to the light emitting layer. have. There is no particular limitation on such an electron transfer compound, and any compound can be selected and used from conventionally known compounds.

Preferred examples of the electron transfer compound include:

[Chemical 40]

[Chemical 41] Nitro-substituted fluorenone derivatives, such as

[Chemical 42] Thiopyran oxide derivatives such as

[Chemical 43] And other diphenylquinone derivatives ["Polymer Preprints, Japan", Volume 37, No. 9, page 681 (1988)
Year)] etc., or

[Chemical 44]

[Chemical formula 45] Such as "[Journal of Applied Physics]", Vol. 27,
Those described on page 269 (1988), etc.,
Anthraquinodimethane derivative (JP-A-57-14925)
No. 9, JP 58-55450, JP 61-225.
No. 151, No. 61-233750, No. 63-
No. 104061), fluorenylidene methane derivatives (the ones described in JP-A-60-69657, JP-A-61-143764, JP-A-61-148159, etc.), and anthrone derivatives (JP-A- Sho 61
No. 225151, No. 61-233750, etc.) and the like.

Next, an example of a suitable method for producing an EL device using the compound of the present invention will be described for each device of each constitution. Explaining the method for producing the EL element consisting of the above anode / light emitting layer / cathode, first, on an appropriate substrate,
A thin film of the desired electrode material, eg, anode material,
After forming an anode by a method such as vapor deposition or sputtering so as to have a film thickness of m or less, preferably in the range of 10 to 200 nm, it is represented by the general formula (I) which is a light emitting material. A thin film of the compound is formed and a light emitting layer is provided. Examples of methods for thinning the light emitting material include spin coating, casting, vapor deposition, and the like. However, vapor deposition is preferred because a uniform film is easily obtained and pinholes are not easily generated. preferable. When this vapor deposition method is used for thinning the light emitting material, the vapor deposition conditions generally differ depending on the type of organic compound used in the light emitting layer used, the target crystal structure of the molecular cumulative film, the association structure, etc. Boat heating temperature 50-400 ℃, vacuum 10
-5 to 10-3 Pa, vapor deposition rate 0.01 to 50 nm / s
ec, substrate temperature −50 to + 300 ° C., and film thickness 5 nm to 5 μm. Next, after forming this light-emitting layer, a thin film of a cathode material is formed thereon to a thickness of 1 μm.
Hereinafter, a desired EL element can be obtained by forming it by a method such as vapor deposition or sputtering and providing a cathode. In the production of this EL element, the production order may be reversed and the cathode, the light emitting layer and the anode may be produced in this order. Next, a method of manufacturing an EL element composed of anode / hole injection layer / light emitting layer / cathode will be described. First, an anode is formed in the same manner as in the case of the EL element described above, and then the hole transfer layer is formed thereon. A thin film made of a compound is formed by a vapor deposition method or the like to provide a hole method entry layer. The vapor deposition conditions at this time are
The vapor deposition conditions for forming the thin film of the light emitting material may be applied. Next, a desired EL element is obtained by sequentially providing a light emitting layer and a cathode on the hole injecting layer in the same manner as in the case of manufacturing the EL element. Also in the production of this EL element, the production order is reversed and the cathode, the light emitting layer,
It is also possible to fabricate the hole injection layer and the anode in this order. A method of manufacturing an EL element composed of anode / light emitting layer / electron injection layer / cathode will be described.
After forming in the same manner as in the case of the device, a thin film made of a light emitting material is formed thereon according to the above vapor deposition conditions to provide a light emitting layer. Next, a thin film made of an electron transfer compound is formed on the light emitting layer by a vapor deposition method or the like, an electron injection layer is provided, and then a cathode is provided thereon in the same manner as in the case of manufacturing the EL element. Thus, a desired EL element can be obtained. Also in the production of this EL element, the production order may be reversed, and the cathode, the electron injection layer, the light emitting layer and the anode may be produced in this order. Furthermore, anode / hole injection layer /
A method for manufacturing an EL device composed of a light emitting layer / electron injection layer / cathode will be described below.
A desired EL device can be obtained by sequentially providing an anode, a hole injection layer, a light emitting layer, an electron injection layer and a cathode. Also in the fabrication of this EL element, the fabrication order can be reversed and the cathode, the electron injection layer, the light emitting layer, the hole injection layer, and the anode can be fabricated in this order. When a direct current voltage is applied to the EL device thus obtained, a voltage of about 5 to 40 V is applied with the positive polarity of the anode and the negative polarity of the cathode, and the light emission is observed from the transparent or semitransparent electrode side. it can. Moreover, even if a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the − state. The waveform of the alternating current applied may be arbitrary.

Next, the light emitting mechanism of the EL device will be described by taking the case of the structure of anode / hole injecting / transporting layer / light emitting layer / cathode as an example. When a voltage is applied with the anode having a positive polarity and the cathode having a negative polarity, holes are injected from the anode into the hole injection layer by an electric field. The injected holes are transported in the hole injecting and transporting layer toward the interface with the light emitting layer,
From this interface, it is injected or transported to a region where a light emitting function is exhibited (for example, a light emitting layer). On the other hand, the electrons are injected from the cathode into the light emitting layer by an electric field, further transported, and recombined with the holes in the region where the holes are present, that is, the region where the light emitting function is exhibited (in this sense, the region is It may be called a recombination region). When this recombination occurs, an excited state of a molecule, its associated body, a crystal, or the like is formed, and this is converted into light. The recombination region may be at the interface between the hole injecting and transporting layer and the light emitting layer, at the interface between the light emitting layer and the cathode, or at the center of the light emitting layer distant from both interfaces. This depends on the type of compound used, its association and crystal structure.

[0016]

EXAMPLES Next, the present invention will be described in more detail based on examples and application examples. Example 1 Preparation of (9-anthracenyl) -methyl-9-carbazole (AMCZ) 9.67 g (0.025) of 9-chloromethylanthracene
and 6.16 g (0.10 mol) of carbazole potassium salt.
(03 mol) was suspended in 50 ml of xylene and heated under reflux for 5 hours. The reaction solution was cooled to 70 ° C. and the precipitate was filtered off. The filtrate was evaporated and washed with acetone,
Column chromatography (silica gel, solvent toluene)
And purified to obtain 4.16 g of yellowish white crystals (yield 47%). The melting point of this product was 279.6 to 281.3 ° C. The ¹ H-NMR analysis is as follows. ¹ H-NMR (CDCl ₃ ) δ = 8.54 ppm (1H, s), 8.31 ppm (2
H, d), 8.07ppm (4H, m), 7.44pp
m (4H, m), 7.12-7.2 ppm (6H,
m), 6.36 ppm (2H, s)

Example 2 Preparation of 2- (9-anthracenyl) -ethane-9-carbazolide (AECZD) 11.81 g (0.05 mol) 9-anthracene acetic acid
Was suspended in 100 ml of toluene, and thionyl chloride 11.
9 g (0.1 mol) was added, and the mixture was heated and dissolved at 70 ° C., and the heating was continued for 1 hour. After removing excess thionyl chloride and reduced pressure, it was dissolved in toluene. This solution was added dropwise to a solution prepared by suspending 10.27 g (0.05 mol) of carbazole potassium salt in 100 ml of toluene. The reaction solution was refluxed for 1 hour, allowed to cool, and the precipitate was collected by filtration. The precipitate was washed with water and recrystallized from ethyl acetate to give yellowish white crystals 1.
6.5 g (yield 85.6%) was obtained. The melting point of this product was 273.6 to 274.8 ° C. Also, ¹ H-N
The MR analysis is as follows. ¹ H-NMR (CDCl ₃ ) δ = 8.53 ppm (lH, s), 8.40 ppm (2
H, d), 8.05 to 8.13 ppm (6H, m),
7.45 to 7.54 ppm (8H, m), 5.50 pp
Production of m (2H, s) 2- (9-anthracenyl) -ethyl-9-carbazole (AECZ) AECZD 11.56 g (0.03 mol) was suspended in tetrahydrofuran (THF) 500 ml and cooled under ice-cooling 1.
100 ml (0.1 mol) of M borane-THF solution was added dropwise. The mixture was stirred under ice cooling for 1 hour and then refluxed for 1 hour. After allowing to cool, 20 ml of 6N hydrochloric acid was added dropwise to decompose borane, and then THF was distilled off. Sodium hydroxide was added to the residue to make it strongly alkaline, and then toluene was added for extraction. The toluene layer was washed with water, dehydrated with magnesium sulfate, and concentrated with an evaporator. After purified by column chromatography (silica gel, hexane-toluene = 1: 1), it was recrystallized from toluene to give 1.42 g of yellowish white crystals,
(Yield 12.8%) was obtained. The melting point of this product is 297.
It was 4-298.0 degreeC. The ¹ H-NMR analysis is as follows. ¹ H-NMR (CDCl ₃ ) δ = 8.42 ppm (lH, s), 8.35 ppm (2
H, d), 8.12 ppm (2H, d), 8.04 pp
m (2H, d), 7.46 to 7.59 ppm (8H,
m), 7.25 ppm (2H, d), 4.70 ppm
(2H, t), 4.15ppm (2H, t)

Example 3 Preparation of (9-anthracenyl) -ethyl-9-phenoxazine (AEPO) 3.66 g (0.02 mol) of phenoxazine and 2.24 g (0.02 mol) of potassium t-butoxide in 50 ml of toluene. , 9-bromoethylanthracene 2.41 g (0.01 mol) was added, and the mixture was heated under reflux for 5 hours. After the reaction solution was cooled to room temperature, the precipitate was filtered off.
The filtrate was evaporated and then purified by column chromatography (silica gel, solvent toluene-hexane) to obtain 1.20 g (31%) of AEPO.

Example 4 Preparation of (9-anthracenyl) -ethyl-9-phenothiazine (AEPT) 3.99 g (0.02 mol) of phenothiazine and 2.24 g (0.02 mol) of potassium t-butoxide were dissolved in 50 ml of toluene. Then, 2.41 g (0.01 mol) of 9-bromoethylanthracene was added, and the mixture was heated under reflux for 5 hours. After the reaction solution was cooled to room temperature, the precipitate was filtered off.
The filtrate was evaporated and then purified by column chromatography (silica gel, solvent toluene-hexane) to obtain 2.01 g (50%) of AEPT.

Application Example 1 IT on a 25 mm × 75 mm × 1.1 mm glass substrate
A transparent support substrate was prepared by forming a film of O to a thickness of 50 nm (manufactured by Tokyo Sanyo Vacuum Co., Ltd.). This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition device (manufactured by Vacuum Kiko Co., Ltd.), TPD was placed in a quartz crucible, and another crucible was obtained in Example 1 (9-anthracenyl).
-Methyl-9-carbazole (AMCZ) was added and the pressure in the vacuum chamber was reduced to 1 x 10 ^-4 Pa. Then, the crucible containing TPD is heated to deposit TPD at a deposition rate of 0.1 to 0.2.
A hole injection layer having a film thickness of 50 nm was formed by vapor deposition on the transparent supporting substrate at a rate of nm / sec. Next, without removing this from the vacuum chamber, AMCZ was vapor-deposited as a light emitting layer from another crucible to a thickness of 50 nm on the hole injection layer. The vapor deposition rate was 0.1 to 0.2 nm / sec. This was taken out of the vacuum chamber, a mask made of aluminum was placed on the light emitting layer, and again fixed to the substrate holder. Next, magnesium was placed in a graphite crucible, and silver was placed in another crucible. After that, the vacuum chamber was decompressed to 2 × 10 ⁻⁴ Pa, and magnesium was evaporated at a deposition rate of 1.2 to 2.4 nm / sec.
Deposition was performed at a deposition rate of ~ 0.2 nm / sec. Under the above conditions, a mixed metal electrode of magnesium and silver is formed on the light-emitting layer to 200n
An element was formed by evaporating m layers to form a counter electrode. ITO
When a DC voltage of 28 V was applied to the obtained device with an electrode serving as an anode and a mixed electrode of magnesium and silver as a cathode, a current of about 100 mA / cm ² flowed, and blue light emission was obtained in chromaticity coordinates. The peak wavelength is 455 nm and the emission brightness is 500.
It was cd / m ² .

Application Example 2 IT on a glass substrate of 25 mm × 75 mm × 1.1 mm
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm (manufactured by Tokyo Sanyo Vacuum Co., Ltd.). This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Vacuum Kiko Co., Ltd.), TPD was placed in a quartz crucible, and another crucible was obtained in Example 2 (9-anthracenyl). -Ethyl-9-carbazole (AECZ) was added and the vacuum chamber was decompressed to 1 x 10 ^-4 Pa. After that, the TPD-containing crucible is heated to deposit TPD at a deposition rate of 0.1 to 10.
A film thickness of 50 is obtained by vapor deposition on a transparent support substrate at 0.2 nm / sec.
A hole injection layer having a thickness of nm was formed. Then, without taking this out from the vacuum chamber, AECZ was vapor-deposited as a light emitting layer from another crucible to a thickness of 50 nm on the hole injecting layer. The vapor deposition rate was 0.1 to 0.2 nm / sec. Remove this from the vacuum chamber, made of aluminum on the light emitting layer,
The mask was set and fixed again on the substrate holder. next,
Magnesium was placed in a graphite crucible and silver was placed in another crucible. After that, set the vacuum chamber to 2 × 10 ^-4 P
After decompressing to a, magnesium of 1.2-2.4n
Silver was vapor-deposited from the other crucible at a vapor deposition rate of 0.1 to 0.2 nm / sec at the same time with a vapor deposition rate of m / sec. Under the above conditions, a mixed metal electrode of magnesium and silver is placed on the light emitting layer.
A device having a thickness of 00 nm was vapor-deposited to form a counter electrode.
When a DC voltage of 32 V is applied to the obtained device with an ITO electrode as an anode and a mixed electrode of magnesium and silver as a cathode, a current of about 100 mA / cm ² flows, and Gre is expressed in chromaticity coordinates.
An emission of blue light was obtained. Peak wavelength 460n
At m, the emission luminance was 450 cd / m ² .

Application Example 3 IT on a glass substrate of 25 mm × 75 mm × 1.1 mm
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm (manufactured by Tokyo Sanyo Vacuum Co., Ltd.). This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Vacuum Kiko Co., Ltd.), TPD was placed in a quartz crucible, and another crucible was obtained in Example 3 (9-anthracenyl). -Ethyl-9-phenoxazine (AEPO) was added and the pressure in the vacuum chamber was reduced to 1 x 10 ^-4 Pa. Then TPD
The crucible containing the above is heated to deposit TPD at a deposition rate of 0.1 to 10.
50 nm film thickness by vapor deposition on a transparent support substrate at 0.2 nm / sec.
A hole injection layer of m was formed. Then, without taking this out from the vacuum chamber, AECZ was vapor-deposited as a light emitting layer from another crucible to a thickness of 50 nm on the hole injecting layer. The vapor deposition rate was 0.1 to 0.2 nm / sec. This was taken out of the vacuum chamber, an aluminum mask was placed on the above light emitting layer, and again fixed to the substrate holder. Next, magnesium was placed in a graphite crucible, and silver was placed in another crucible. After that, the vacuum chamber was decompressed to 2 × 10 ⁻⁴ Pa, and magnesium was added at 1.2 to 2.4 nm /
With a vapor deposition rate of 0.2 seconds, silver from the other crucible was simultaneously added to 0.2.
Deposition was performed at a deposition rate of 1 to 0.2 nm / sec. Under the above conditions, a mixed metal electrode of magnesium and silver is placed on the light emitting layer to form 200
A layer having a thickness of 10 nm was vapor-deposited to form a counter electrode to form a device. IT
Using a O electrode as an anode and a mixed electrode of magnesium and silver as a cathode, a DC voltage was applied to the obtained device to obtain Blue light emission.

Application Example 4 IT on a glass substrate of 25 mm × 75 mm × 1.1 mm
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm (manufactured by Tokyo Sanyo Vacuum Co., Ltd.). This transparent support substrate was fixed to a substrate holder of a commercially available vapor deposition apparatus (manufactured by Vacuum Kiko Co., Ltd.), TPD was placed in a quartz crucible, and another crucible was obtained in Example 3 (9-anthracenyl). -Ethyl-9-phenothiazine (AEPT) was added and the pressure in the vacuum chamber was reduced to 1 x 10 ^-4 Pa. Then TPD
The crucible containing the above is heated to deposit TPD at a deposition rate of 0.1 to 10.
A film thickness of 50 is obtained by vapor deposition on a transparent support substrate at 0.2 nm / sec.
A hole injection layer having a thickness of nm was formed. Then, without taking this out from the vacuum chamber, AECZ was vapor-deposited as a light emitting layer from another crucible to a thickness of 50 nm on the hole injecting layer. The vapor deposition rate was 0.1 to 0.2 nm / sec. This was taken out of the vacuum chamber, an aluminum mask was placed on the above light emitting layer, and again fixed to the substrate holder. Next, magnesium was placed in a graphite crucible, and silver was placed in another crucible. After that, the vacuum chamber is set to 2 × 10 ⁻⁴ Pa
After reducing the pressure down to 1.2-2.4 nm
Silver was vapor-deposited from the other crucible at a vapor deposition rate of 0.1 to 0.2 nm / sec at the same time with a vapor deposition rate of / sec. Under the above conditions, a mixed metal electrode of magnesium and silver is placed on the light emitting layer.
A device having a thickness of 00 nm was vapor-deposited to form a counter electrode.
When an ITO electrode is used as an anode and a mixed electrode of magnesium and silver is used as a cathode, a DC voltage is applied to the obtained device to produce Blu.
ish Violet emission was obtained.

Application Example 5 IT on a glass substrate of 25 mm × 75 mm × 1.1 mm
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm (manufactured by Tokyo Sanyo Vacuum Co., Ltd.). On this transparent support substrate, 0.5 part by weight of poly (N-vinylcarbazole) as a hole injecting and transporting material and 2- (4′-tert-butylphenyl) -5 as an electron injecting and transporting material.
From a 1,2-dichloroethane solution containing 0.5 part by weight of-(4 "-biphenyl) -1,3,4-oxadiazole and 0.01 part by weight of AECZ as a light emitting material, 1000
rpm, 10 sec and 6000 rpm, 15 sec
The light-emitting layer was spin-coated at two successive rotation speeds, to form a thin film. Then, the vacuum layer was fixed to a substrate holder of a vapor deposition apparatus (manufactured by Vacuum Kiko Co., Ltd.) and the vacuum layer was depressurized to 1 × 10 ⁻⁴ Pa,
Tris (8-hydroxyquinolino) aluminum contained in a quartz crucible was vapor-deposited at 20 nm as an electron injecting and transporting layer. Further, magnesium was put into a graphite crucible, and then the vacuum layer was depressurized to 2 × 10 ⁻⁴ Pa, and then magnesium electrode was laminated on the light emitting layer to a thickness of 200 nm at a deposition rate of 5 to 50 nm / sec. Then, a counter electrode was formed and an element was formed. When a direct current voltage is applied to the obtained device using the ITO electrode as the anode and the magnesium electrode as the cathode, the emission luminance is 160 cd / m ² at the current density of 100 mA / cm ² , and the Purlis is in the chromaticity coordinate.
h Blue was obtained.

Application Example 6 IT on a glass substrate of 25 mm × 75 mm × 1.1 mm
A transparent support substrate was prepared by forming a film of O to a thickness of 100 nm (manufactured by Tokyo Sanyo Vacuum Co., Ltd.). On this transparent support substrate, 0.5 part by weight of poly (N-vinylcarbazole) as a hole injecting and transporting material and 2- (4′-tert-butylphenyl) -5 as an electron injecting and transporting material.
From a 1,2-dichloroethane solution containing 0.5 part by weight of-(4 "-biphenyl) -1,3,4-oxadiazole and 0.01 part by weight of AMCZ as a light emitting material, 1000
rpm, 10 sec and 6000 rpm, 15 sec
The light-emitting layer was spin-coated at two successive rotation speeds, to form a thin film. Then, the vacuum layer was fixed to a substrate holder of a vapor deposition apparatus (manufactured by Vacuum Kiko Co., Ltd.) and the vacuum layer was depressurized to 1 × 10 ⁻⁴ Pa,
Tris (8-hydroxyquinolino) aluminum contained in a quartz crucible was vapor-deposited at 20 nm as an electron injecting and transporting layer. Further, magnesium was put into a graphite crucible, and then the vacuum layer was depressurized to 2 × 10 ⁻⁴ Pa, and then magnesium electrode was laminated on the light emitting layer to a thickness of 200 nm at a deposition rate of 5 to 50 nm / sec. Then, a counter electrode was formed and an element was formed. When a direct current voltage is applied to the obtained device using the ITO electrode as an anode and the magnesium electrode as a cathode, when the current density is 100 mA / cm ² , the emission brightness is 60 cd / m ² , and the chromaticity coordinates are Purplish.
Blue light emission was obtained.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display location C07D 241/52 8615-4C 265/38 279/22 C09K 11/06 Z 9159-4H // G03G 5 / 06 314 B 9221-2H 315 D 9221-2H 319 9221-2H

Claims (4)

[Claims] 1. A general formula: [In the formula, An is anthracene bonded to the 1-position, 2-position, or 9-position, and substitutable positions other than the bond are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group, n is 1 or 2, Y is a bond, S, O, CH
₂ , or C = 0, or CH-R ¹ or NR
² (R ¹ and R ² are alkyl groups, alkoxy groups, allyl groups and aralkyl groups), and Y _{1 to} Y ₈ are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group and amino. Group, a cyano group, a hydroxycarbonyl group, an alkyl group, an alkoxy group, an allyl group, and an aralkyl group.]. 2. A general formula: [In the formula, An is anthracene bonded to the 1-position, 2-position, or 9-position, and substitutable positions other than the bond are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group, n is 1, 2 and X is fluorine, chlorine, bromine, iodine or tosyloxy group, mesyloxy group, trifluoromethoxy group, etc. A leaving group] and an anthracene compound represented by the general formula: [Wherein Z is hydrogen or an alkali metal salt such as lithium, sodium or potassium, Y is a bond, S, O, CH ₂ ,
Or C = 0, or CH—R ¹ or NR ²
(R ¹ and R ² are an alkyl group, an alkoxy group, an allyl group,
Aralkyl group), and Y _{1 to} Y ₈ are each independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group. , Represents an aralkyl group] and is condensed with an aromatic tertiary amine represented by the general formula: [In the formula, An is anthracene bonded to the 1-position, 2-position, or 9-position, and substitutable positions other than the bond are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group, n is 1 or 2, Y is a bond, S, O, CH
₂ , or C = 0, or CH-R ¹ or NR
² (R ¹ and R ² are alkyl groups, alkoxy groups, allyl groups and aralkyl groups), and Y _{1 to} Y ₈ are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group and amino. Group, a cyano group, a hydroxycarbonyl group, an alkyl group, an alkoxy group, an allyl group, and an aralkyl group.]. 3. A general formula: [In the formula, An is anthracene bonded to the 1-position, 2-position, or 9-position, and substitutable positions other than the bond are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group, m is 0 to 5, Y is a bond, S, O, CH ₂ , or C = 0, or CH-R ¹ Or N-R ² (R
¹ , R ² is an alkyl group, an alkoxy group, an allyl group or an aralkyl group), and Y _{1 to} Y ₈ are each independently hydrogen,
Fluorine, chlorine, bromine, halogen such as iodine, nitro group,
Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group]
A general formula characterized by reducing the amide group of an anthracene compound represented by: [In the formula, An is anthracene bonded to the 1-position, 2-position, or 9-position, and substitutable positions other than the bond are independently hydrogen, fluorine, chlorine, bromine, halogen such as iodine, nitro group, Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group, n is 1 to 6, Y is a bond, S, O, CH ₂ , or C = 0, or CH-R ¹ Or N-R ² (R
¹ , R ² is an alkyl group, an alkoxy group, an allyl group or an aralkyl group), and Y _{1 to} Y ₈ are each independently hydrogen,
Fluorine, chlorine, bromine, halogen such as iodine, nitro group,
Amino group, cyano group, hydroxycarbonyl group, alkyl group, alkoxy group, allyl group, aralkyl group]
The manufacturing method of the anthracene compound represented by. 4. An electroluminescent device comprising the compound according to claim 1.