JPH06279323A - New styryl compound, production thereof and organic electroluminescence element therefrom - Google Patents

Abstract

PURPOSE:To provide a novel styryl compound excellent in thin-film formability, enabling high-luminance luminescence, useful as a luminescent material for organic electroluminescence elements. CONSTITUTION:The objective styryl compound of formula I [Ar is (substituted) 6-20C aryl; R<1> and R<2> are each H, (substituted) 6-20C aryl or 1-6C alkyl; R<3> is (substituted) 6-20C aryl or 4-18C heterocyclic group; R<2> and R<3> are respectively bound to substituted groups into (substituted) saturated five-membered ring or saturated six-membered ring; the above-mentioned substituent is 1-6C alkyl, 1-6C alkoxy, 6-18C aryloxy, phenyl, amino, CN, NO3, OH or halogen; X is H or of formula II], e.g. a compound of formula III. The compound of the formula I can be obtained by coupling of a phosphonic ester of formula IV (R is 1-4C alkyl or phenyl) in the presence of a base.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel styryl compound,
Regarding the manufacturing method thereof and an organic electroluminescence device (organic EL device) composed thereof, in detail, a novel styryl compound excellent in thin film property and capable of high-luminance emission,
The present invention relates to a method for producing the same and an organic EL device formed thereof.

[0002]

2. Description of the Related Art EL devices utilizing electroluminescence have the characteristics that they are self-luminous and therefore highly visible, and because they are completely solid-state devices, they are excellent in impact resistance. It is used for thin display devices, liquid crystal display backlights, flat light sources, and so on. The EL element currently put into practical use is a dispersion type EL element. This dispersion type EL device has several tens of volts and 10 kHz.
Since the above AC voltage is required, the drive circuit is complicated. On the other hand, since the organic thin film EL element can reduce the driving voltage to about 10 V and emits light with high brightness, research has been actively conducted in recent years, and many organic thin film EL elements have been developed (CWTang and SAVAN Slyke, Appl.Phys.L
ett., vol.51, pp.913-915 (1987); JP-A-63-264.
629 publication). These organic thin film EL devices are a laminated type of transparent electrode / hole injection layer / light emitting layer / back electrode, and holes can be efficiently injected into the light emitting layer by the hole injection layer. In the structure of the organic thin film EL device, an organic EL thin film device using a tetraphenylbutadiene compound derivative in the light emitting layer (Japanese Patent Laid-Open No. 59-194393, Japanese Patent Laid-Open No. 4-96990) and a styryl compound (European Patent Publication No. 1). No. 0388768, Japanese Patent Laid-Open No. 18489/1992
No. 2, JP-A-3-205478). Further, recently, an organic EL element containing a trifunctional compound derived from the styryl compound as a light emitting material has been disclosed, but there is a problem that the luminance and the light emitting efficiency are low. This problem is caused by crystallization of the light emitting material.

[0003]

Therefore, the present inventors have
As a result of diligent studies to solve the above problems, it was discovered that the presence of a large number of olefinic moieties in a styryl compound enables a wide variety of structures, thereby preventing rearrangement (crystallization) of molecules.

The present invention has been completed based on such findings. That is, the present invention has the general formula (I)

[0005]

[Chemical 4]

(In the formula, Ar represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, R ¹ and R ² are each a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or Indicates an alkyl group having 1 to 6 carbon atoms R ³
Is a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
Alternatively, it represents a heterocyclic group having 4 to 18 carbon atoms. Where R ¹
To R ³ may be the same or different from each other. Further, R ² and R ³ may be bonded to a substituent to form a substituted or unsubstituted saturated 5-membered ring or a substituted or unsubstituted saturated 6-membered ring. Here, as the substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a phenyl group, an amino group, a cyano group, a nitro group, a hydroxyl group or halogen. Indicates. These substituents may be single or multiple. X is hydrogen or

[0007]

[Chemical 5]

(Wherein R ^{1 to} R ³ are the same as above), and a novel styryl compound represented by the general formula (II)

[0009]

[Chemical 6]

(In the formula, R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ^{1 to} R ³ , X and Ar are the same as the above.) The present invention provides a method for producing the novel styryl compound which is coupled in the presence of the organic luminescent element, and an organic electroluminescent device which sandwiches the novel styryl compound.

The present invention provides a tetrafunctional styryl compound represented by the general formula (I). Here, in the general formula (I), Ar is i) when X is hydrogen.

[0012]

[Chemical 7]

[0013]

[Chemical 8]

Phenanthrene; perylene; 1,2-benzanthracene; naphthacene; chrysene; quarter phenylene and the like, which is a trivalent aromatic hydrocarbon having an arbitrary bonding position, and may be mono-substituted or plural-substituted.

[0015]

[Chemical 9]

A tetravalent aromatic hydrocarbon having an arbitrary bonding position such as phenanthrene; perylene; 1,2-benzanthracene; naphthacene; chrysene; quarterphenylene and the like, which may be mono-substituted or plural-substituted. R ¹ and R ² are, for example, an aryl group having 6 to 20 carbon atoms represented by a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, an anthrylyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a methyl group, or an ethyl group. Group, n-propyl group, i-propyl group, n-butyl group,
i-butyl group, sec-butyl group, t-butyl group, i-
1 to 6 carbon atoms represented by pentyl group, t-pentyl group, neopentyl group, n-hexyl group, i-hexyl group, etc.
Of alkyl groups, which may be the same or different. These aryl groups or alkyl groups may be substituted or unsubstituted, and may be mono-substituted or plural-substituted. R
³ is, for example, an aryl group having 6 to 20 carbon atoms represented by a phenyl group, a naphthyl group, a biphenyl group, a terphenyl group, an anthryl group, a phenanthryl group, a pyrenyl group, a perylenyl group or a pyrazyl group, a pyridyl group, a quinolyl group. A heterocyclic group having 4 to 18 carbon atoms represented by a group, a carbazolyl group, a quinoxalyl group, or the like. These aryl groups or heterocyclic groups may be substituted or unsubstituted, and may be mono-substituted or plural-substituted. further,
R ² and R ³ may combine with a substituent to form a substituted or unsubstituted saturated five-membered ring or a substituted or unsubstituted saturated six-membered ring. Here, as the substituent, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, i-pentyl group, t A pentyl group,
C1-C6 alkyl groups such as neopentyl group, n-hexyl group, i-hexyl group, methoxy group, ethoxy group, propoxy group, i-propoxy group, butyloxy group, i-butyloxy group, sec-butyloxy group, i
An alkoxy group having 1 to 6 carbon atoms such as -pentyloxy group, t-pentyloxy group and n-hexyloxy group, an aryloxy group having 6 to 18 carbon atoms such as phenoxy group and naphthyloxy group, a phenyl group, an amino group, Examples thereof include a cyano group, a nitro group, a hydroxyl group and halogen. Specifically, as an amino group

[0017]

[Chemical 10]

(Wherein R ⁴ and R ⁵ represent an alkyl group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. R ⁴ and R ⁵ may be the same or different. Good)).

The novel styryl compound represented by the general formula (I) can be synthesized by subjecting the phosphonate ester represented by the general formula (II) to a coupling reaction. This reaction is usually carried out in the presence of a base in a polar solvent in the temperature range from room temperature to the boiling point of the solvent used. Specifically, a phosphonate ester of the general formula (II),
Equivalent or more bases and polar solvents are mixed at the same time and reacted at a predetermined temperature. Further, after dissolving the phosphonate ester in a polar solvent, a base is added and the reaction is carried out at a predetermined temperature. After completion of the reaction, the mixture is poured into a large amount of water or a saturated aqueous solution in which a salt is dissolved, and the obtained solid is collected, or the obtained solid is dissolved in any organic solvent and fractionated to remove the organic solvent. The novel styryl compound can be obtained. Here, R in the general formula (II) represents an alkyl group having 1 to 4 carbon atoms as a lower alkyl group and a phenyl group, and is preferably a methyl group or an ethyl group.
The phosphonate ester represented by the general formula (II) is represented by the general formula (III) or (IV)

[0020]

[Chemical 11]

(Wherein R ¹ and Ar are the same as those described above, and Y is a halogen, and may be the same or different from each other) and P (OR) ₃ (in the formula, R is the same as above.) And can be obtained. In addition, the phosphonate ester represented by the general formula (II) is represented by the general formula (V) or (VI).

[0022]

[Chemical 12]

(Wherein R, R ¹ and Ar are the same as above) and the phosphonate represented by the general formula (VI
I)

[0024]

[Chemical 13]

It can be obtained by controlling the molar ratio of the carbonyl compound represented by the formula (wherein R ² and R ³ are the same as above) to react. In particular,
Two times the molar amount of the general formula (VII) carbonyl compound is used for the phosphonic acid ester of the general formula (V), and three times the molar amount of the general formula (VII) carbonyl compound is used for the phosphonic acid ester of the general formula (VI). By reacting, the phosphonate ester of the general formula (II) can be obtained. However, depending on the reaction temperature, it is possible to directly obtain the novel styryl compound of the general formula (I) without going through the phosphonate ester of the general formula (II) by this reaction. Examples of the base used in the synthesis of the novel styryl compound include sodium hydroxide, potassium hydroxide, sodium methylate, sodium ethylate, potassium t-butoxide, sodium amide, sodium hydride, potassium hydride,
Examples thereof include lithium diisopropylamide. As the reaction solvent, polar solvents such as hydrocarbons, alcohols and ethers are preferable. Specifically, methanol; ethanol; isopropanol; butanol; 2
-Methoxyethanol; alcohol solvent such as 1,2-dimethoxyethanol, ether solvent such as diethyl ether, ethylene glycol, dimethyl ether, diethylene glycol dimethyl ether, bis (2-methoxyethyl) ether, dioxane and tetrahydrofuran, benzene, toluene, xylene Aromatic solvents such as; dimethyl sulfoxide; N, N-dimethylformamide; N-methylpyrrolidone; 1,3-dimethyl-2
-Imidazolidinone and the like. Particularly, tetrahydrofuran and dimethyl sulfoxide are preferable.

Specific examples (1) to (20) of the novel styryl compound used in the present invention (hereinafter referred to as compound (1)
May be abbreviated to (20). ), But the present invention is not limited thereto.

[0027]

[Chemical 14]

[0028]

[Chemical 15]

[0029]

[Chemical 16]

[0030]

[Chemical 17]

[0031]

[Chemical 18]

[0032]

[Chemical 19]

[0033]

[Chemical 20]

[0034]

[Chemical 21]

[0035]

[Chemical formula 22]

The novel styryl compound represented by the general formula (I) of the present invention thus obtained is effective as a light emitting material or a hole injecting and transporting material in an organic EL device. When the novel styryl compound is used as a light emitting layer, it can be formed by thinning the novel styryl compound of the general formula (I) by a known method such as a vapor deposition method, a spin coating method, or a casting method. It is particularly preferable to use a molecular deposition film. Here, the molecular deposition film is a thin film formed by depositing the compound from 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. Show,
Usually, this molecular deposition film can be distinguished from a thin film (molecular cumulative film) formed by the LB method. Further, as disclosed in JP-A-59-194393, etc., the light-emitting layer is prepared by dissolving a binder such as a resin and the compound in a solvent to form a solution, which is then spin-coated. For example, it can be formed into a thin film. The thickness of the light emitting layer thus formed is not particularly limited and may be appropriately selected depending on the circumstances, but is usually selected in the range of 5 nm to 5 μm.

The light emitting layer in this organic EL device is
(1) An injection function capable of injecting holes from the anode or the hole injecting and transporting layer when an electric field is applied, and injecting electrons from the cathode or the electron injecting layer, (2) injected charge (electron Transport function that moves (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. Since the compound represented by the general formula (I) used for the light emitting layer generally has an ionization energy smaller than about 6.0 eV, holes can be relatively easily injected by selecting an appropriate anode metal or anode compound. Further, since the electron affinity is larger than about 2.8 eV, if an appropriate cathode metal or cathode compound is selected, it is relatively easy to inject electrons and the electron and hole transporting ability is excellent. Furthermore, since the solid-state fluorescence is strong, it has a large ability to convert the excited state formed at the time of recrystallization of electrons and holes of the compound or its associated body or crystal into light.

The constitution of the organic EL device using the novel styryl compound of the present invention has various modes, but basically,
The light emitting layer may be sandwiched between a pair of electrodes (anode and cathode), and a hole injecting and transporting layer and an electron injecting layer may be interposed therebetween as necessary. The intervening method includes mixing into the polymer and simultaneous adsorption. Specifically, (1) anode / light emitting layer / cathode, (2) anode / hole injection / transport layer / light emitting layer / cathode, (3) anode / hole injection / transport layer / light emitting layer / electron injection layer / cathode, (4) Anode / light emitting layer / electron injection layer / cathode and the like can be mentioned. The hole injecting and transporting layer and the electron injecting layer are not always necessary, but the presence of these layers further improves the light emitting performance. Further, 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 the elements conventionally used for EL elements such as glass, transparent plastic, quartz and the like are used. Any thing can be used.

As the anode in this organic EL device,
A material having a high work function (4 eV or more), an alloy, an electrically conductive compound, or a mixture thereof as an electrode material is preferably used. Specific examples of such an electrode material include metals such as Au, CuI, ITO, SnO ₂ , and ZnO.
Dielectric transparent materials such as The anode is prepared by subjecting these electrode materials to a method such as vapor deposition or sputtering.
It can be produced by forming a thin film. 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 an electrode is preferably several hundred Ω / □ or less. Further, although this film thickness depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.

On the other hand, as the cathode, a material having a low work function (4 eV or less), an alloy, an electrically conductive compound 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. Further, the sheet resistance as an electrode is preferably several hundred Ω / □ or less, and the film thickness is usually 10 nm.
To 1 μm, preferably 50 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.

The structure of the organic EL device of the present invention has various modes as described above, and the hole injecting and transporting layer in the EL device having the structure of (2) or (3) is made of a hole transporting compound. Layer having a function of transmitting holes injected from the anode to the light emitting layer, and by interposing this hole injecting and transporting layer between the anode and the light emitting layer, many layers can be generated at a lower electric field. Holes are injected into the light emitting layer. In addition, the electrons injected from the cathode or the electron injection layer into the light emitting layer are accumulated near the interface in the light emitting layer due to the electron barrier existing at the interface between the light emitting layer and the hole injecting and transporting layer, and the EL element emits light. An EL element with improved efficiency and excellent light emission performance.

The hole transport compound used in the hole injecting and transporting layer is disposed between two electrodes to which an electric field is applied, and when the hole is injected from the anode, the hole is appropriately emitted. A compound which can be transmitted to, for example, 10 ⁴ to 10 ⁶ V
At least 10 ^-6 cm ² / (V
A hole mobility of (sec) is 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 or a positive electrode of an organic EL device. Any known material used for the hole injecting and transporting layer can be selected and used.

Examples of the charge transport material include triazole derivatives (described in US Pat. No. 3,112,197), oxadiazole derivatives (US Pat. No. 3,1).
89,447, etc.), imidazole derivatives (described in Japanese Patent Publication No. 37-16096, etc.), polyarylalkane derivatives (US Pat. No. 3,61).
5,402, 3,820,989, 3,5
42,544, Japanese Patent Publication No. 45-555, 5
1-10983, JP-A-51-93224, JP-A-55-17105, JP-A-56-4148, JP-A-55-108667, and JP-A-55-15695.
No. 3, JP-A-56-36656, etc.), pyrazoline derivatives and pyrazolone derivatives (US Pat. Nos. 3,180,729, 4,278,746 and JP-A-55-55). No. 88064, 55-8806.
5 gazette, the same 49-105537 gazette, the same 55-51.
086, 56-80051, 56-8
No. 8141, No. 57-45545, No. 54-
No. 112637, No. 55-74546, etc.), phenylenediamine derivatives (U.S. Pat. No. 3,615,044, Japanese Patent Publication Nos. 51-10105, 46-3712, 47). No. 25336, JP-A No. 54-53435, and No. 54-1105.
No. 36, No. 54-119925, etc.), arylamine derivatives (US Pat. No. 3,567,4).
No. 50, No. 3,180,703, No. 3,24
No. 0,597, No. 3,658,520, No. 4,2
32,103, 4,175,961, 4,012,376, JP-B-49-35702, 39-27577, and JP-A-55-1442.
No. 50, No. 56-119132, No. 56-2
2437 gazette, those described in West German Patent No. 1,110,518 etc.), amino-substituted chalcone derivatives (described in US Pat. No. 3,526,501 etc.), oxazole derivatives (US patent Nos. 3,257,203), styrylanthracene derivatives (described in JP-A-56-46234), fluorenone derivatives (described in JP-A-54-110837). ), Hydrazone derivatives (US Pat. No. 3,71
7,462, JP-A-54-59143, JP-A-55-52063, JP-A-55-52064,
55-46760, 55-85495, 57-11350 and 57-148749.
Those described in JP-A-62-110363 and JP-A-61-2284.
No. 51, No. 61-14642, No. 61-72.
255, 62-47646, 62-3.
6674, 62-10652, and 62-
No. 30255, No. 60-93445, No. 60
-94462, 60-174749, 60-175052, etc.) and the like.

These compounds can be used as hole transfer compounds, and the porphyrin compounds shown below (those described in JP-A-63-295695)
And aromatic tertiary amine compounds and styrylamine compounds (U.S. Pat. No. 4,127,412, JP-A-53-53)
27033, 54-58445, 54.
No. 149634, No. 54-64299, No. 55-79450, No. 55-144250, No. 56-119132, No. 61-29555.
8 gazette, the same 61-98353 gazette, the same 63-295.
No. 695, etc.), particularly the aromatic tertiary amine compound is preferably used as the hole transfer compound.

Typical examples of the porphyrin compound include:
Porphyrin; 5,10,15,20-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 tetramethyl phthalocyanine; copper phthalocyanine; chromium phthalocyanine; zinc phthalocyanine; lead phthalocyanine; titanium phthalocyanine oxide; magnesium phthalocyanine; copper octamethyl phthalocyanine.
Further, as typical examples of the aromatic tertiary compound and the styrylamine compound, N, N, N ′, N′-tetraphenyl- (1,1′-biphenyl) -4,4′-diamine;
N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1'-biphenyl] -4,4'-diamine; 2,2-bis (4-di-p-tolylamino) Phenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ', N'-tetra-p-tolyl- (1,1'-biphenyl) -4,
4'-diamine; 1,1-bis (4-di-p-tolylaminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl) phenylmethane; bis (4-di-p- Tolylaminophenyl) phenylmethane; N, N′-diphenyl-N, N′-di (4-methoxyphenyl)-(1,1′-biphenyl)
-4,4'-diamine; N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl 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-diphenylamino Stilbene; N-
Examples include phenylcarbazole.

The hole injecting and transporting layer in the above organic EL device may be composed of a single layer composed of one or more of these hole transporting compounds, or a positive layer composed of a compound different from the layer. It may be a laminate of hole injecting and transporting layers. On the other hand, the electron injecting layer (electron injecting and transporting layer) in the EL device having the above-mentioned configuration (3) is made of an electron transfer compound and has a function of transferring the electrons injected from the cathode to the light emitting layer. There is. 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:

[0047]

[Chemical formula 23]

Nitro-substituted fluorenone derivatives such as

[0049]

[Chemical formula 24]

Thiopyran dioxide derivatives such as

[0051]

[Chemical 25]

Diphenylquinone derivatives such as those described in "Polymer Preprints, Japan", Vol. 37, No. 3, page 681 (1988), or the like.

[0053]

[Chemical formula 26]

Compounds such as [Journal of Applied Physics, Vol. 27,
Those described on page 269 (1988), etc., and anthraquinodimethane derivatives (JP-A-57-149259, JP-A-58-55450, JP-A-61-22515).
No. 1, gazette 61-233750, gazette 63-10.
4061) and fluorenylidene methane derivatives (JP-A-60-69657 and 61).
Those described in JP-A-143764, JP-A-61-148159, etc.) and anthrone derivatives (JP-A-61-2).
No. 25151, No. 61-233750, etc.) Further, the following general formula (A) or (B)

[0055]

[Chemical 27]

(In the formula, Ar ^{1 to} Ar ³ and Ar ⁵ each independently represent a substituted or unsubstituted aryl group, and Ar ⁴
Represents a substituted or unsubstituted arylene group. ) And an electron transfer compound represented by. Here, examples of the aryl group include a phenyl group, naphthyl group, biphenyl group, anthranyl group, perylenyl group, and pyrenyl group, and examples of the arylene group include a phenylene group, a naphthylene group, a biphenylene group, an anthracenylene group, a perylenylene group, and a pyrenylene group. Etc. Moreover, as a substituent, a C1-C10 alkyl group, a C1-C10 alkoxy group, a cyano group, etc. are mentioned. The compound represented by formula (A) or (B) is preferably a thin film-forming compound. Specific examples of the compound represented by formula (A) or (B) include:

[0057]

[Chemical 28]

[0058]

[Chemical 29]

[0059]

[Chemical 30]

And the like.

"Appl. Phys. Lett." Vol. 55, 148
Oxadiazole derivatives disclosed on page 9 (1989) can be mentioned. Note that the hole injecting and transporting layer and the electron injecting layer are layers having any of an injecting property, a transporting property, and a barrier property for electrification, and in addition to the above-mentioned organic materials, crystallinity of Si-based, SiC-based, CdS-based, etc. It is also possible to use an inorganic material such as an amorphous material. The hole injecting and transporting layer and the electron injecting layer using the organic material can be formed in the same manner as the light emitting layer, and the hole injecting and transporting layer and the electron injecting layer using the inorganic material are formed by the vacuum deposition method or the sputtering. However, it is preferable to use the vacuum vapor deposition method for the same reason as in the case of the light emitting layer regardless of whether organic or inorganic materials are used.

Next, an example of a suitable method for producing the organic EL element of the present invention will be described for each element of each constitution. Explaining the method for manufacturing the EL device consisting of the above-mentioned anode / light-emitting layer / cathode, first, on a suitable substrate, a thin film of a desired electrode substance, for example, a substance for anode, is 1 μm or less, preferably in the range of 10 to 200 nm. To form a thin film of a tetrafunctional styryl compound compound represented by the general formula (I), which is a light emitting material, after forming an anode by a method such as vapor deposition or sputtering to form a thin film. Providing a light emitting layer. As a method for thinning the light emitting material, there are, for example, a spin coating method, a casting method, a vapor deposition method and the like, but the vapor deposition method is preferable from the viewpoint that a uniform film is easily obtained and pinholes are not easily generated. .
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 deposited film, the association structure, etc. Boat heating temperature 50-400 ℃,
Vacuum degree 10 ^-5 to 10 ^-3 Pa, vapor deposition rate 0.01 to 50 nm
/ Sec, substrate temperature −50 to + 300 ° C., and film thickness 5 nm to 5 μm. Next, after forming this light emitting layer, a thin film made of a substance for the cathode is formed thereon.
A desired EL is formed by forming a film having a film thickness of 1 μm or less, preferably in the range of 50 to 200 nm by a method such as vapor deposition or sputtering and providing a cathode.
The device is obtained. In the production of this EL element, it is possible to reverse the production order and produce the cathode, the light emitting layer and the anode in this order.

A hole injecting and transporting material is provided between the pair of electrodes.
In the case of an element composed of an anode / a light emitting layer / a cathode, which is sandwiched between electrodes in a form of a mixture of a light emitting material and an electron injecting material, a manufacturing method is, for example, a suitable substrate and an anode material. A thin film made of, and applied with a solution containing a hole injecting and transporting material, a light emitting material, an electron injecting material, a binder such as polyvinylcarbazole, or a thin film is formed from this solution by a dip coating method to form a light emitting layer. And a thin film made of a cathode material is formed thereon. Here, an element material which is a material of the light emitting layer may be further vacuum-deposited on the produced light emitting layer, and a thin film made of a substance for a cathode may be formed thereon. Alternatively, a hole injecting and transporting material, an electron injecting material and a light emitting material are simultaneously vapor deposited to form a light emitting layer,
You may form a thin film which consists of materials for cathodes on it.

Next, a method of manufacturing an EL element composed of anode / hole injecting / transporting 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, and then the anode is formed thereon. A thin film made of a hole transfer compound is formed by a spin coating method or the like to provide a hole injecting and transporting layer.
The conditions at this time may be the same as the conditions for forming the thin film of the light emitting material. Next, a desired EL element is obtained by sequentially providing a light emitting layer and a cathode on the hole injecting and transporting layer in the same manner as in the case of manufacturing the EL element. In addition,
Also in the fabrication of this EL element, the fabrication order is reversed,
It is also possible to fabricate the cathode, the light emitting layer, the hole injecting and transporting layer, and the anode in this order. Further, a method of manufacturing an EL element composed of anode / hole injecting / transporting layer / light emitting layer / electron injecting layer / cathode will be described. First, in the same manner as in the case of manufacturing the EL element, an anode and a hole injecting / transporting layer are formed. After sequentially providing a layer and a light emitting layer, a thin film made of an electron transfer compound is formed on the light emitting layer by a spin coating method or the like to provide an electron injection layer, and then a cathode is provided on the light emitting layer of the EL device. A desired EL element can be obtained by providing the EL element in the same manner as in the case of manufacturing. Also in the production of this EL element, the order of production may be reversed, and the anode, the electron injection layer, the light emitting layer, the hole injection transport layer, and the anode may be produced in this order.

The organic EL of the present invention thus obtained
When a DC voltage is applied to the device, a voltage of about 1 to 30 V is applied with the positive polarity of the anode and the negative polarity of the cathode, and light emission can be observed from the transparent or semitransparent electrode side. 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. In addition,
The waveform of the alternating current applied may be arbitrary.

[0066]

Next, the present invention will be described in more detail with reference to synthetic examples and device preparation examples. Synthesis Example 1

[0067]

[Chemical 31]

Compound A (1.0 g, 0.0012 mol) and potassium t-butoxide (0.22 g, 0.002 mol) were suspended in 30 ml of dimethyl sulfoxide (DMSO), and the suspension was allowed to stand at room temperature (20 to 25 ° C.) for 20 minutes. Reacted for hours. The obtained reaction product was allowed to stand overnight, 50 ml of methanol was added thereto, and the precipitated white powder was filtered to obtain a filter cake, which was purified with a silica gel column (developing solvent: methylene chloride). The resulting white powder was reprecipitated with methylene chloride-methanol to give 0.4 g of white crystals (yield 23.8).
%)Obtained. The melting point of this crystal was 170 to 170.5 ° C. As a result of mass spectrometry (FD-MS), M ⁺ (m / Z = 1
400) and M ²⁺ (m / Z = 700). Further Elemental analysis (() calculated value), as _{C 110 H 80 C: 94.28%} (94.25%) H: was 5.72% (5.75%). From the above, it was confirmed that the target compound (13) was synthesized.

Example of device preparation 1 A 25 mm × 75 mm × 1.1 mm glass substrate was formed by vapor deposition.
An ITO film (corresponding to the anode) with a thickness of 100 nm is provided
Was used as the transparent support substrate. This transparent support substrate is
Ultrasonically clean with pure alcohol for 5 minutes and then in pure water for 5 minutes.
After ultrasonic cleaning for a minute, UV ion cleaner (Samcoin
20 minutes at a substrate temperature of 150 ° C
Washed. Dry this transparent support substrate with dry nitrogen gas
Substrate holder for commercially available vapor deposition equipment (Nippon Vacuum Technology Co., Ltd.)
Fixed on the surface of the molybdenum, and Cu is coordinated to the resistance heating boat made of molybdenum.
Phthalocyanine (hereinafter abbreviated as CuPc) of 200
For adding mg, or for resistance heating of another molybden boat
N, N'-bis (3-methylphenyl) -N, N'-di
Phenyl- [1,1'-biphenyl] -4,4'-dia
Add 200 mg of min (hereinafter abbreviated as TPD), and add
To another resistance heating boat made of molybdenum in Example 1
Represented by the obtained compound (13) (DPV)₆BiV
200 mg was added. Then vacuum layer 4 × 10^-FourPa
After decompressing to the above, pass through the heating boat containing CuPc.
And heat up to 350 ° C, vapor deposition rate 0.1-0.3nm /
CuPc with a film thickness of 20 nm deposited on a transparent support substrate in seconds
Layers were provided. The substrate temperature at this time was room temperature. That
215 ℃ by energizing the heating boat containing TPD
The above CuP is heated at a deposition rate of 0.1 to 0.3 nm / sec.
Evaporating TPD on the c layer to form a 40 nm thick TPD layer.
Provided. The substrate temperature at this time was also room temperature. like this
The two layers, the CuPc layer and the TPD layer provided in
It corresponds to the transport layer. Then (DPV)₆BiV in
The heating boat is energized to heat up to 300 ° C and vapor deposition
Deposition on the TPD layer at a speed of 0.1-0.3 nm / sec.
A light emitting layer having a film thickness of 40 nm was provided. Next, these three layers of organic
The transparent support substrate on which the product layers are stacked is removed from the vacuum chamber and
Place a stainless steel mask over the light chamber and
And fixed to the substrate holder. Next, the molybdenum
Tris (8-quinolinol) aluminium in anti-heat boat
(Hereinafter, Alq₃Abbreviated. ) 200mg is true
It was vapor-deposited in an empty tank. In addition, 1g magnesium ribbon
Molybdenum resistance heating boat and silver wire 500
Attach the tungsten basket containing mg to the vacuum chamber.
I wore it. Then, the vacuum chamber is set to 1 x 10^-FourDecompress to Pa
It was After depressurization, Alq₃Add a boat containing 270 ℃ to 270 ℃
Heated and deposited Alq on the light-emitting layer at a deposition rate of 0.1-0.3 nm / sec.
₃Vapor deposition of Alq₃Layer (on electron injection layer
Equivalent). Next, a basket with silver wire
When silver is vapor-deposited at a deposition rate of 0.1 nm / sec by energizing
Sometimes a boat with a magnesium ribbon is energized to speed up vapor deposition.
Magnesium was vapor-deposited at a rate of 1.4 to 2.0 nm / sec. this
By dual source simultaneous vapor deposition, Alq₃A 20 nm thick film is formed on the layer.
A gnesium-silver layer (corresponding to the cathode) was formed. This element
The ITO electrode of the child serves as an anode, and the magnesium-silver layer serves as a cathode.
As a result, when a direct current of 10 V is applied, the current density becomes 14
Milliampere / cm²Current flows, peak wavelength 470
Blue emission of nm was obtained. The brightness at this time is 180
cd / m ²And the luminous efficiency is 0.41 lumen / W.
It was. The emission obtained is (DPV)₆BiV solid state fluorescence
It is almost the same as (DPV)₆Light emission from BiV
Was confirmed. A uniform thin film is formed on the obtained device.
It did not crystallize for more than a month. This is the departure
Used as an optical material (DPV)₆BiV is 7 in one molecule
It has a variety of olefin moieties,
This is because it is possible to obtain the formation. Therefore, the luminescent material
Used for (DPV)₆BiV prevents the rearrangement of molecules.
And can easily become amorphous.
It Furthermore, because this amorphous state is uniform, crystallization
Since it will not be damaged, a stable thin film as a whole element
It is formed.

[0070]

As described above, the EL device using the novel styryl compound of the present invention has excellent luminous efficiency and enables high brightness light emission. Therefore, the novel styryl compound of the present invention can be effectively used for fluorescent whitening dyes, electrophotographic photoreceptors, and the like, and the organic EL device of the present invention can be effectively used for various light emitting materials and the like. .

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C07C 25/24 9280-4H 41/30 43/166 7419-4H 209/68 211/44 9280-4H 211/54 9280-4H 253/30 255/32 9357-4H C07D 521/00 C09K 11/06 Z 9159-4H H05B 33/14

Claims (4)

[Claims] 1. A compound represented by the general formula (I): (In the formula, Ar represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, and R ¹ and R ² are each a hydrogen atom, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or 1 carbon atom. .R ³ showing the 6 alkyl group represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a heterocyclic group having 4 to 18 carbon atoms. wherein, R ¹ to R ³ are also the same, And R ² and R ³ may be different from each other.
May each combine with a substituent to form a substituted or unsubstituted saturated five-membered ring or a substituted or unsubstituted saturated six-membered ring. Here, the substituent has 1 to 1 carbon atoms.
An alkyl group having 6 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryloxy group having 6 to 18 carbon atoms, a phenyl group, an amino group,
Indicates a cyano group, nitro group, hydroxyl group or halogen.
These substituents may be single or multiple.
In addition, X is hydrogen or (In the formula, R ^{1 to} R ³ are the same as described above.)). 2. A compound represented by the general formula (II): (In the formula, R represents an alkyl group having 1 to 4 carbon atoms or a phenyl group, and R ^{1 to} R ³ and Ar are the same as the above.) Coupling the phosphonate ester in the presence of a base. The method for producing the novel styryl compound according to claim 1, wherein 3. An organic electroluminescence device, comprising the novel styryl compound according to claim 1 sandwiched between an anode and a cathode. 4. An organic electroluminescence device comprising the novel styryl compound according to claim 1 as a light emitting material of the light emitting layer in the organic electroluminescence device.