JPH05135878A - Organic electroluminescence element - Google Patents

Abstract

PURPOSE:To obtain elements of high luminance in spite of low voltage and emit bluish light, by using polycarbonates containing styryl amine skeletons having electroluminescence functions as a repeating unit for luminous materials and/or positive hole injection materials. CONSTITUTION:As for polycarbonates containing styryl amine skeletons having electric charge injecting and transfering functions and luminous functions, polycarbonates containing repeating units denoted with general formula I, II and III can be used desirably. Where, Ar<1>-Ar<4> and Ar<7> denote allylene radicals of 6-20 in carbon number independently substituted or not, Ar<5> and Ar<6> denote similar aryle radicals, and R<1> and R<2> denote independently hydrogen atom, alkyl radicals of 1-6 in carbon number, or aryle radicals of 6-20 in carbon number. These are made to films with usual spin-coating methods.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence device (organic EL device), and more specifically, it has a high luminance and a high luminous efficiency and is capable of emitting light in a blue to green region, while maintaining an excellent thin film. The present invention relates to an organic EL device using a polycarbonate having a function.

[0002]

PRIOR ART AND PROBLEMS TO BE SOLVED BY THE INVENTION Recently, Friend R. H. Et al. Disclosed an organic EL device having a light emitting layer using polyphenylene vinylene (PPV) as a light emitting material (International Publication WO90 / 1314).
8). This organic EL device is a fully conjugated polymer (con
By injecting electric charges from a suitable injection electrode into a Jugated polymer, an electroluminescence effect is exhibited. As a feature of this organic EL device, they are stable against oxygen and moisture and do not deteriorate even at high temperatures. The light emitting layer has adhesiveness to the lower electrode etc. In contrast, it is resistant, prevents recrystallization, and prevents migration of ions and atoms due to high crystallinity or high melting point. However, this organic EL element has a drawback that it is difficult to emit blue light and the luminous efficiency is low due to the extended conjugate property of PPV. This drawback is due to the low fluorescence of PPV, as described by Friend R. H. By J. Phys. D20, 1367 (1987) and J. Mol. Electronics; 5, 19, (1
989). The fluorescence yield of the PPV is 1% or less. If the fluorescence yield is low as described above, the electroluminescence efficiency (EL efficiency) is lower than the fluorescence yield, so that it is impossible to obtain high brightness. Furthermore, the production of the polyphenylene vinylene thin film is
It can be easily obtained by spin-coating the soluble precursor and then heat-treating it. However, the heat-treatment conditions are not easily found, and defects easily enter the main chain conjugation and
This will reduce efficiency. Therefore, it is practically impossible or difficult to use a thin film of an all-conjugated polymer such as polyphenylene vinylene as a light emitting layer.

In addition, D. Braun et al. Disclosed a device in which a soluble derivative in which a long-chain alkoxy group was introduced into PPV was formed into a light emitting layer by spin coating (A).
PPl. Phys. Lett. 58, 1982 (199
1)). However, since the fluorescence yield (quantum yield) of this PPV is small, the EL quantum yield is as small as 5 × 10 ⁻⁴ when using the In cathode and 10 ⁻² when using the Ca cathode. Yes, the emission color was limited to orange. Also, Hosokawa et al. Discloses an organic EL device having a light emitting layer of a low molecule having an arylene vinylene structure (EP 037).
3582, EP No. 0388768, etc.). This organic E
The L element can realize greenish blue light emission with a high luminance of 300 cd / m ² by applying only 5 V. At this time, the luminous efficiency was 2.9 lumen / W. In addition, they used a compound of similar structure as a light emitting layer at 1000c.
High-brightness blue light emission of d / m ² or more is also realized,
It is possible to produce various emission colors over the green region with high brightness and high efficiency. However, it is necessary to use a vapor deposition method to form the light emitting layer, and this method takes more time than the spin coating method and is inferior in productivity. In addition, the vapor-deposited film of an organic low molecule has a problem that it tends to be recrystallized due to a change with time or heat generation during operation, and thus does not function as a light emitting layer or a hole injecting layer, that is, it has no ability to maintain a thin film.

[0004]

Therefore, the present inventors have solved the above-mentioned drawbacks of the prior art and made it possible to easily thin the light emitting layer by a spin coating method. By using this light emitting layer,
The inventors have earnestly studied to develop an organic EL device which emits light in the blue to green region with high brightness despite a low voltage. As a result, by using a polymer composed of polycarbonate having a styrylamine skeleton as a repeating unit and having an excellent thin film-maintaining ability as compared with an organic low molecule, all conjugated polymers such as PPV, which is a conventional technique, can be obtained. It was found that the luminous efficiency can be remarkably improved and the above objects can be sufficiently achieved as compared with the device used. It was also found at the same time that the polycarbonate of the present invention can also be used as a hole injection layer having a thin film maintaining ability. The present invention has been completed based on such findings.

That is, the present invention relates to a light emitting material and / or a polycarbonate containing a styrylamine skeleton having an electroluminescence function as a repeating unit.
Alternatively, the present invention provides an organic electroluminescence device characterized by being used as a hole injection material.
In particular, polycarbonate has the general formula (I)

[0006]

[Chemical 7]

(In the formula, Ar ^{1 to} Ar ⁴ each independently represent a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. Ar ⁵ and Ar ⁶ each independently represent a substituted or unsubstituted carbon number. And an aryl group having 6 to 20. R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted 6 carbon atom.
~ 20 aryl groups are shown. Here, the substituent is an alkyl group or an alkoxy group having 1 to 10 carbon atoms. P represents an integer of 0 or 1. ) The above organic electroluminescent device having a repeating unit represented by

[0008]

[Chemical 8]

(In the formula, Ar ^{1 to} Ar ⁶ , R ¹ , R ² and P are as defined above. R ⁷ is independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. .) And the general formula (II)
I)

[0010]

[Chemical 9]

(In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
Y is a single bond,

[0012]

[Chemical 10]

(Where x is an integer of 2 to 10 and R is
⁵ and R ⁶ are each independently a hydrogen atom and a carbon number of 1 to
It is an alkyl group having 6 or an aryl group having 6 to 10 carbon atoms. ) Is shown. The present invention provides the above organic electroluminescence device having a repeating unit (β) represented by Further, in the present invention, polycarbonate has the general formula (IV)

[0014]

[Chemical 11]

(Wherein R ¹ , R ² , P and Ar ^{1 to} A
r ⁶ is the same as above. Ar ^7's each independently represent a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. Here, the substituent is an alkyl group or an alkoxy group having 1 to 10 carbon atoms. The dotted line indicates that they may be connected by a single bond. ) The organic electroluminescent device having a repeating unit represented by

[0016]

[Chemical 12]

(Wherein Ar ^{1 to} Ar ⁷ , R ¹ , R ² and P have the same meanings as described above. The dotted line indicates that they may be linked by a single bond.) The present invention also provides the above organic electroluminescence device having a unit (γ) and a repeating unit (β) represented by the general formula (III).

In the present invention, a polycarbonate containing a styrylamine skeleton having an electroluminescence function is used as a light emitting material and / or a hole injecting material. Here, the electroluminescence function means a charge injecting and transporting function and a light emitting function. That is, having an electroluminescence function means, for example, a compound deposition method, spin coating method, casting method, LB
When a thin film is formed by a known method such as a method and used as a light emitting layer, holes can be injected from the anode or the hole injecting and transporting layer when an electric field is applied, and electrons can be injected from the cathode or the electron injecting and transporting layer. It has an injection function that can inject, a transport function that moves injected charges (electrons and holes) by the force of an electric field, and a light emission function that provides a field for recombination of electrons and holes and connects them to light emission. Is what you are doing.

In the present invention, the portion having the electroluminescence function is the styrylamine skeleton contained in the general formula (I). In the polycarbonate having a styrylamine skeleton used in the present invention, a specific styrylamine skeleton cuts the conjugated system.

[0020]

[Chemical 13]

The compound is bound by a divalent group containing ## STR1 ## so that extension of the conjugation of the styrylamine skeleton is suppressed and green to blue light is emitted. Further, the molecule having a specific styrylamine skeleton used in the present invention has excellent EL performance and excellent thin film property. There are various styrylamine skeletons, but one preferable form includes one aromatic tertiary amine,
1 formed by removing a hydrogen atom from a compound in which at least one aromatic ring of this aromatic tertiary amine is substituted with at least one arylvinylene group having 8 to 22 carbon atoms.
It is a valent or divalent group. Here, the aromatic tertiary amine is a compound containing a trivalent nitrogen atom, and a compound in which at least one atom of the three carbon atoms substituted by the nitrogen atom forms an aromatic ring having 4 to 20 carbon atoms. Is. The arylvinylene group has the formula

[0022]

[Chemical 14]

(In the formula, R ¹ and R ² are the same as above.) A group containing a carbon-carbon double bond (vinylene group) and an aryl group having 6 to 20 carbon atoms are bonded. It is a monovalent group. Another preferred form is two or three
Including two of the above aromatic tertiary amines, the two or three
It is a divalent group formed by removing a hydrogen atom from a compound formed by bonding two aromatic tertiary amines with the above vinylene group or vinylenearylenevinylene group. Preferred examples of the styrylamine skeleton are those in which a divalent group consisting of an aromatic tertiary amine and an arylene vinylene group are sequentially bonded, or a divalent group consisting of an aromatic tertiary amine, a vinylene group and an aromatic group 3. Examples thereof include those in which divalent groups composed of a primary amine are sequentially bound. Particularly preferred styrylamine skeletons include those represented by the above general formulas (I) and (IV).

The polycarbonate in the present invention may have various structures, but the preferred one is represented by the repeating unit (α) represented by the general formula (II) and the general formula (III). Those having a repeating unit (β) (polycarbonate A), and those having a repeating unit (γ) represented by the general formula (V) and a repeating unit (β) represented by the general formula (III) (polycarbonate B) Is mentioned. Particularly preferred are polycarbonates A and B having a weight average molecular weight of 4000 or more. A in the above general formulas (I), (II), (IV) and (V)
r ^{1 to} Ar ⁴ and Ar ⁷ are each independently a substituted or unsubstituted arylene group having 6 to 20 carbon atoms (for example,
Phenylene group, biphenylene group, naphthylene group, terphenylene group, anthranylene group, etc.). Examples of the substituent include alkyl groups such as methyl group, ethyl group, isopropyl group and t-butyl group, and alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group. Ar ⁵ and Ar ⁶ are each independently a substituted or unsubstituted aryl group having 6 to 20 carbon atoms (eg, phenyl group, biphenyl group, naphthyl group, terphenyl group, etc.). Examples of the substituent include an alkyl group such as a methyl group, an ethyl group, an isopropyl group, and a t-butyl group, a methoxy group, an ethoxy group, a propoxy group,
Examples thereof include alkoxy groups such as butoxy group.

R ¹ and R ² are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 carbon atoms (eg, phenyl group, biphenyl group, naphthyl group). Group). Examples of the substituent include an alkyl group such as a methyl group, an ethyl group, an isopropyl group and a t-butyl group, an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. The polycarbonate used in the present invention may have a styrylamine skeleton in the side chain in addition to the repeating unit (β).

The method for producing this polycarbonate is not particularly limited and can be produced by various methods according to known methods. As a preferred method, the general formula (VI)

[0027]

[Chemical 15]

(Wherein Ar ^{1 to} Ar ⁶ , R ¹ , R ² and P are the same as above), or a bisphenol compound having a styrylamine skeleton or this bisphenol compound and the general formula (VII).

[0029]

[Chemical 16]

It is carried out by reacting the dihydroxy compound represented by the formula (wherein R ³ , R ⁴ and Y are the same as described above) with a carbonic acid ester forming compound.
Specific examples of the bisphenol compound having this styrylamine skeleton include:

[0031]

[Chemical 17]

[0032]

[Chemical 18]

[0033]

[Chemical 19]

[0034]

[Chemical 20]

And the like. Further, as the dihydroxy compound,

[0036]

[Chemical 21]

[0037]

[Chemical formula 22]

[0038]

[Chemical formula 23]

And the like. Similarly, the general formula (VI
II)

[0040]

[Chemical formula 24]

(Wherein Ar ^{1 to} Ar ⁶ , R ¹ , R ² and P are the same as above), or a bisphenol compound having a styrylamine skeleton or this bisphenol compound and the general formula (VII). It is carried out by reacting the dihydroxy compound represented by with a carbonic acid ester forming compound. Specific examples of the bisphenol compound having this styrylamine skeleton include:

[0042]

[Chemical 25]

[0043]

[Chemical formula 26]

[0044]

[Chemical 27]

And the like. Here, as the carbonic acid ester-forming compound, various compounds used in the general field of polycarbonate production can be used. Examples thereof include carbonyl dihalides such as phosgene, haloformates such as chloroformates, and carbonate compounds. Of these, phosgene is particularly preferred.

In the present invention, one or more of the bisphenol compounds are reacted with at least one of the carbonic acid ester-forming compounds, or one or more of the dihydroxy compounds and the bisphenol compounds are reacted. The polycarbonate used in the present invention can be produced by reacting one kind or two or more kinds with at least one kind of the carbonic acid ester forming compound. Here, the ratio (molar ratio) of the repeating units (α) and (β) or (γ) and (β) can be adjusted by appropriately selecting the ratio of the bisphenol compound and the dihydroxy compound used. In the polycarbonate used in the present invention, the repeating unit (α) or (γ) having a styrylamine skeleton is essential, and the repeating unit (β) is optional and may be 0. The reaction conditions are not particularly limited, and for example, when a carbonyl dihalide such as phosgene or a halogenate such as chloroformate is used as a carbonate forming compound, the reaction is carried out in a suitable solvent with an acid acceptor (for example, alkali metal water). It can be carried out in the presence of a water-soluble alkali metal compound such as an oxide or an alkali metal carbonate or an organic base). Various kinds of alkali metal hydroxides and alkali metal carbonates can be used, but from the economical aspect, usually, sodium hydroxide aqueous solution, potassium hydroxide aqueous solution, sodium carbonate aqueous solution, potassium carbonate aqueous solution and the like are used. It is preferably used. Further, the use ratio of the carbonic acid ester forming compound may be appropriately adjusted in consideration of the stoichiometric ratio of the reaction. When using a gaseous carbonic acid ester forming compound such as phosgene,
A method of blowing this into the reaction system is suitable. Similarly, the ratio of the acid acceptor used may be appropriately adjusted in consideration of the stoichiometric ratio of the reaction. Specifically, it is preferable to use 2 equivalents or a slight excess of the acid acceptor with respect to the total number of moles of the bisphenol compound and the dihydroxy compound.

As the solvent, various solvents used in the production of known polycarbonates may be used alone or as a mixed solvent. As typical examples, a halogen compound hydrocarbon such as methylene chloride and a solvent such as tetrahydrofuran (THF) are preferable. further,
When carrying out this reaction, a molecular weight modifier (such as a cross-linking agent such as monophenols) or a reaction accelerator (such as an alkylamine) may be added to adjust the molecular weight and the reaction rate, if desired. The reaction temperature in this reaction is usually 0 to
It is 150 ° C, preferably 0 to 40 ° C. The reaction pressure is
Any of reduced pressure, normal pressure, and increased pressure is possible, but normally, normal pressure or self pressure of the reaction system is preferable. Reaction time is usually
It is 0.5 minutes to 10 hours, preferably about 1 minute to 2 hours. The reaction system may be a continuous method, a semi-continuous method or a batch method.

In the polycarbonate thus obtained, the styrylamine skeleton is bound by a divalent group that cuts the conjugated system, and as a result, it is possible to prevent the EL light emission from becoming longer and to have a high brightness in the blue to green region. It enables the emission of light. If this blue light emission is possible, various light emission of red, orange, green, yellow, white, etc. can be achieved by known conventional techniques such as a fluorescent dye doping method or a fluorescent conversion method using a fluorescent film. It also has the advantage that it can be easily synthesized or purified. Further, an ultrathin film having a film thickness of 10 to 200 nm can be formed from the solution by a known method such as a spin coating method, a dip coating method, a casting method, and an LB method. This ultra-thin film does not have pinholes and there is no fear of electrical short circuit. Further, polycarbonate is extremely soluble in the above solvent, and a 0.01 to 10 wt% solution preferable for film formation can be prepared.

A particularly preferable film forming method is a known spin coating method. This is because the thin film can be formed uniformly without pinholes, and is a very easy film forming method. At this time, the solvent used for the solution is preferably a low boiling point solvent such as benzene, toluene, dichloromethane, chloroform, and the concentration is preferably 0.5 to 3% by weight. Moreover, the rotation speed of the spin coater is preferably 2000 to 10000 rpm, and in the case of forming a film with a thickness of 200 nm or less, 5000 to
7000 rpm is preferred. Further, since the dust in the solution is connected to the pinhole after film formation, it is preferable to remove it with a filter in advance. The polycarbonate thin-filmed as described above has an excellent EL-function and is improved in thin-film property and thermal stability by being polymerized by binding a styrylamine skeleton having an EL-function and a dihydroxy compound. ing. That is, the thin film is not destroyed by crystallization or the like, and the change with time is extremely small.

Polycarbonate having such a thin film maintaining ability can be used as a light emitting layer and / or a hole injecting layer in an organic EL device. Here, when polycarbonate is used as the hole injection layer, EL emission does not occur from the polycarbonate layer. On the other hand, when used as a light emitting layer, EL light is emitted from the polycarbonate layer. This is due to the following circumstances. When a compound having a hole barrier property that does not allow holes that are transported from the anode side to pass through is used as the electron injection layer by inserting it between the polycarbonate layer and the cathode, holes are accumulated in the light emitting layer made of the above polycarbonate. Then, the EL emission is generated by combining with the electrons supplied from the electron injection layer. on the other hand,
When a compound having fluorescence and not having a hole barrier property and having an electron transporting property is laminated on the polycarbonate, the polycarbonate serves as a hole injection layer and the laminated compound serves as a light emitting layer. Therefore, the polycarbonate of the present invention can be appropriately used for both the light emitting layer and the hole injection layer. That is, it can be used both as a light emitting material having an electroluminescence function and as a hole injection material (hole transfer compound).

The compound preferably used as the electron injecting layer having the hole blocking property is represented by the general formula (IX) or (X).

[0052]

[Chemical 28]

(In the formula, Ar ^{8 to} Ar ¹⁰ and Ar ¹² each independently represent a substituted or unsubstituted aryl group;
r ¹¹ represents a substituted or unsubstituted arylene group. ) And an electron transfer compound. 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 (IX) or (X) is preferably a thin film-forming compound.

Specific examples of the compound represented by the general formula (IX) or (X) include

[0055]

[Chemical 29]

[0056]

[Chemical 30]

[0057]

[Chemical 31]

And the like.

Although the EL device of the present invention has various modes, it is basically configured such that a light emitting layer is sandwiched between a pair of electrodes (anode and cathode), and if necessary, a positive electrode is used. A hole injection / transport layer (hole injection layer) or an electron injection / transport layer (electron injection layer) may be interposed. 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 / transport layer / cathode. , (4) Anode / light emitting layer / electron injecting / transporting layer / cathode. The hole injecting and transporting layer and the electron injecting and transporting layer are not always necessary, but the presence of these layers further improves the light emission performance. In addition, in the element having the above-mentioned structure, it is preferable that all are supported by a substrate, and there is no particular limitation on the substrate, and those which are conventionally used in organic EL elements such as glass, transparent plastic, quartz and the like can be used. Can be used.

As the anode in the organic EL device of the present invention, those having a high work function (4 eV or more) metal, alloy, electrically conductive compound or a mixture thereof as an electrode substance are preferably used. Specific examples of such an electrode material include metals such as Au, Cu, I, ITO, and SnO.
₂ , conductive transparent materials such as ZnO. The anode can be produced by forming a film thickness 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 / □ or less. Further, the film thickness depends on the material, but is usually 10 nm to 1 μm, especially 5
The range of 0 to 150 nm is preferable.

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, a magnesium / copper mixture, Al / AlO ₂ , indium, and a rare earth metal. The cathode can be produced by forming a film thickness of these electrode substances by a method such as vapor deposition or sputtering. The sheet resistance as an electrode is preferably several hundreds Ω / □ or less, and the film thickness is usually 10 nm to 1 μm, particularly preferably 50 to 200 nm. In the device of the present invention, although not particularly specified, it is preferable that either the anode or the cathode is transparent or semi-transparent, because the emission is transmitted and the extraction efficiency is good.

The hole transporting compound used in the hole injecting and transporting layer is disposed between two electrodes to which an electric field is applied, and when holes are injected from the anode, the holes are appropriately emitted. A compound that can be transferred to, for example, 10 ⁴ to 10 ⁶ V
A material having a hole mobility of at least 10 ^-6 cm ² / V · sec when an electric field of / cm is applied is preferable. The hole transporting compound is not particularly limited as long as it has the above-mentioned preferable properties, and in addition to the polycarbonate used in the present invention, conventionally, it is conventionally used as a hole charge transporting material in a photoconductive material. Any known material used for the hole injecting and transporting layer of the EL element can be selected and used.

Examples of the charge transport material include triazole derivatives (see US Pat. No. 3,112,197 etc.), oxadiazole derivatives (see US Pat. No. 3,189,447 etc.), imidazole derivatives (JP-B-37-1609).
No. 6, etc.), polyarylalkane derivatives (US Pat. Nos. 3,615,402 and 3,820,989, and
3,542,544, 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. No. 3,180,
729, 4,278,746, JP-A-55-8
No. 8064, No. 55-88065, No. 49-
No. 105537, No. 55-51086, No. 5
6-80051, 56-88141, 57-54545, 54-112637, 55-74546, etc.), phenylenediamine derivatives (US Pat. No. 3,615,404, patent) JP-A-51-10105, JP-A-46-3712, JP-A-47-25336, JP-A-54-53435, JP-A-54-1510536, and JP-A-54-11992.
No. 5, etc.), arylamine derivatives (US Patent No.
3,567,450, 3,180,703, 3,240,
No. 597, No. 3,658,520, No. 4,232,103, No. 4,175,961, No. 4,012,376, No. Sho 49-35702, No. 39-2757.
No. 7, JP-A-55-144250, No. 56-
119132, 56-22437, West German Patent 1,110,518, etc.), amino-substituted chalcone derivatives (US Pat. No. 3,526,501, etc.), oxazole derivatives (US Pat. No. 3,257,203, etc.) Those described), styrylanthracene derivatives (see JP-A-56-46234, etc.), fluorenone derivatives (see JP-A-54-110837, etc.), hydrazone derivatives (US Pat. No. 3,717,462, JP-A-SHO). 54
-59143, 55-52063, 5
No. 5-52064, No. 55-46760, No. 55-85495, No. 57-11350.
No. 57-148749, etc.), stilbene derivatives (Japanese Patent Laid-Open No. 61-210363, 61-228).
No. 451, No. 61-14642, No. 61-7.
No. 2255, No. 62-47646, No. 62-
36674, 62-10652, 62.
-30255, 60-93445, and 6
0-94462, 60-174749,
No. 60-175052, etc.) and the like.

In the present invention, these compounds can be used as the hole transfer compound, and the following porphyrin compounds (described in JP-A-63-295965 and the like) and aromatic tertiary Amine compounds and styrylamine compounds (U.S. Pat. No. 4,127,412, JP-A-53-27033, JP-A-54-584)
No. 45, No. 54-149634, No. 54-6.
No. 4299, No. 55-79450, No. 55-
144250, 56-119132, 61-295558, 61-98353, 63-295695 and the like), and it is particularly preferable to use the aromatic tertiary amine compound.

As a typical example of the porphyrin compound,
Porphine, 1,10,15,20-tetraphenyl-
21H, 23H-porphin copper (II), 1,10,1
5,20-tetraphenyl 21H, 23H-porphine cuprous (II), 5,10,15,20-tetrakis (pentafluorophenyl) -21H, 23H-porphine,
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 octamethyl phthalocyanine and the like can be mentioned.

Representative examples of the aromatic tertiary amine compound and styrylamine compound include N, N, N ',
N'-tetraphenyl-4,4'-diaminophenyl,
N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminobiphenyl, 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-methylphenyl) phenylmethane, bis (4-di) -P-tolylaminophenyl) phenylmethane, N, N'-diphenyl-
N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'
-Bis (diphenylamino) quadriphenyl, N,
N, N-tri (P-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4 (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenylamino-
(2-diphenylvinyl) benzene, 3-methoxy-
4'-N, N-diphenylaminostilbenzene, N-
Examples include phenylcarbazole.

The hole injecting and transporting layer in the EL device of the present invention may be composed of a single layer consisting of one or more of these hole transporting compounds, or a compound different from the above layer. It may be a stack of hole injecting and transporting layers consisting of. On the other hand, the electron injecting and transporting layer in the EL device having the above configuration (3) is made of an electron transporting compound, and has a function of transmitting the electrons injected from the cathode to the light emitting layer. 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:

[0068]

[Chemical 32]

Thiopyran dioxide derivatives such as

[0070]

[Chemical 33]

Diphenylquinone derivatives such as [“Polymer Preprints, Japan”
37, No. 3, 681 (1988), etc.], or

[0072]

[Chemical 34]

Compounds such as [“Japanese Journal of Applied Physics (JJAppl.Phy
s.) ", Volume 27, L269 (1988), etc.],
Anthraquinodimethane derivative (JP-A-57-14925)
9 gazette, the same 58-55450 gazette, the same 61-225.
No. 151, No. 61-233750, No. 63-
104061 and the like), fluorenylidene methane derivatives (JP-A-60-69657 and JP-A 61-14).
3764, 61-148159, etc.), anthrone derivative (see JP-A-61-225151, 61-233750, etc.)

[0074]

[Chemical 35]

"Appl. Phys. Lett." Volume 55, 148
Examples thereof include oxadiasol derivatives disclosed on page 9 (1989). A particularly preferable example is the compound of the general formula (IX) or the general formula (X), which is the compound for the electron injection layer having the hole blocking property. 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 manufacturing method of the EL element consisting of the above anode / light emitting layer / cathode, first, on a suitable substrate, the desired electrode material,
For example, a thin film made of a material for an anode is formed by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably in the range of 10 to 200 nm, and an anode is prepared. A thin film of a compound is formed and a light emitting layer is provided. Examples of methods for thinning the light emitting material include spin coating, casting, and LB.
Although a spin coating method, a vapor deposition method, and the like are available, the spin coating method is preferable because a uniform film is easily obtained and pinholes are not easily generated. Next, after forming this light emitting layer, a thin film made of a substance for the cathode is formed thereon with a thickness of 1 μm or less, preferably 50
A desired organic EL device can be obtained by forming the film so as to have a film thickness in the range of up to 200 nm 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 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 it 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. Also in the fabrication of this EL element, it is possible to reverse the fabrication order and fabricate the cathode, the light emitting layer, the hole injecting and transporting layer, and the anode in this order. Furthermore, anode / hole injecting / transporting layer /
A method of manufacturing an EL device composed of a light emitting layer / electron injecting / transporting layer / cathode will be described. First, an anode, a hole injecting / transporting layer, and a light emitting layer are sequentially provided in the same manner as in the case of manufacturing the EL device. 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 injecting and transporting layer, and then a cathode is provided thereon in the same manner as in the case of manufacturing the EL element. The desired E
An L element is obtained. Also in the production of this EL element, the order of production may be reversed to produce the anode, the electron injecting and transporting layer, the light emitting layer, the hole injecting and transporting layer, and the anode in this order.

The organic EL device of the present invention thus obtained
When a direct current voltage is applied to the device, by applying a voltage of about 1 to 30 V with the anode having a positive polarity and the cathode having a negative polarity, light emission can be observed from the transparent or semitransparent electrode side. Also,
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.

[0078]

EXAMPLES The present invention will be described in more detail with reference to Reference Examples, Synthesis Examples, Examples and Comparative Examples.

Synthesis Example 1 In 600 ml of a 3N aqueous sodium hydroxide solution, the structural formula was added.

[0080]

[Chemical 36]

Bisphenol compound having styrylamine skeleton represented by 66.5 g (0.125 mol) and 1,1
-Bis (4-hydroxyphenyl) cyclohexane 33.
A solution in which 5 g (0.125 mol) was dissolved and 250 ml of methylene chloride were placed in a 1-liter flask. The reaction liquid was vigorously stirred while maintaining the liquid temperature around 10 ° C. by external cooling, and phosgene was blown thereinto at a rate of 340 ml / min for 30 minutes. Then, stirring was continued for 1 hour to complete the polymerization. After completion of the reaction, 500 ml of methylene chloride was added to the organic layer to dilute it, and water, diluted hydrochloric acid,
After washing with water in that order, it was poured into methanol to obtain a polycarbonate. This polycarbonate had a concentration of 0.5 g / dl in methylene chloride as a solvent and a reduced viscosity [η _sp / c] at 20 ° C. of 0.85 dl / g. The average molecular weight (Mw) measured by gel permeation chromatography (GPC) was 35,000. The structure and composition of this polymer was determined by proton nuclear magnetic resonance ( ¹ H-NM
R), infrared absorption (IR), mass spectrometry (MS) spectrum analysis revealed that the polycarbonate copolymer was composed of the following repeating units and compositions.

[0082]

[Chemical 37]

Synthesis Example 2 Structural formula

[0084]

[Chemical 38]

A bisphenol compound having a styrylamine skeleton represented by 75.8 g (0.2 mol) and 2,2-bis (3-methyl-4) instead of 1,1-bis (4-hydroxyphenyl) cyclohexane -Hydroxyphenyl) propane, except that 12.8 g (0.05 mol) was used.
A polycarbonate was obtained in the same manner as in Synthesis Example 1. This polycarbonate has a concentration of 0.5 in methylene chloride.
g / dl solution, [η _sp / c] at 20 ° C is 0.92
It was dl / g. Mw is 380 by GPC measurement
It was 00. The structure and composition of this polymer is ¹ H-
From a NMR, IR, and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0086]

[Chemical Formula 39]

Synthesis Example 3 Structural formula

[0088]

[Chemical 40]

A bisphenol compound having a styrylamine skeleton represented by 20.4 g (0.05 mol) and 1,1-
1,1-bis (4-hydroxyphenyl) -1,1 instead of bis (4-hydroxyphenyl) cyclohexane
A polycarbonate was obtained in the same manner as in Synthesis Example 1, except that 70.4 g (0.20 mol) of diphenylmethane was used.
This polycarbonate has a concentration of 0.5 g / dl in methylene chloride as a solvent and [η _sp / c] at 20 ° C.
It was 0.78 dl / g. Mw is measured by GPC
It was 30,000. The structure and composition of this polymer is
It was a polycarbonate copolymer having the following repeating units and compositions by ¹ H-NMR, IR and MS spectrum analysis.

[0090]

[Chemical 41]

Synthesis Example 4 Structural formula

[0092]

[Chemical 42]

71.75 g (0.125 mol) of a bisphenol compound having a styrylamine skeleton represented by
A polycarbonate was obtained in the same manner as in Synthesis Example 1 except that 28.5 g (0.125 mol) of 2,2-bis (4-hydroxyphenyl) propane was used instead of 1-bis (4-hydroxyphenyl) cyclohexane. It was This polycarbonate has a concentration of 0.5 g / d in methylene chloride.
1 solution, [η _sp / c] at 20 ° C. is 0.77 dl /
It was g. The Mw was 32000 as measured by GPC. The structure and composition of this polymer is ¹ H-NM
From R, IR, and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0094]

[Chemical 43]

Synthesis Example 5 Structural formula

[0096]

[Chemical 44]

139.6 g (0.20 mol) of a bisphenol compound having a styrylamine skeleton represented by
-Bis (4-hydroxyphenyl) cyclohexane 13.
A polycarbonate was obtained in the same manner as in Synthesis Example 1 except that 4 g (0.05 mol) was used. This polycarbonate had a concentration of 0.5 g / dl in methylene chloride as a solvent, and [η _sp / c] at 20 ° C. of 0.61 dl / g. Mw was 25,000 as measured by GPC. The structure and composition of this polymer are ¹ H-NMR, I
From the R and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0098]

[Chemical 45]

Synthesis Example 6 Structural formula

[0100]

[Chemical 46]

A bisphenol compound having a styrylamine skeleton represented by 27.3 g (0.05 mol) and 1,1-
1,1-bis (4-hydroxyphenyl) -1,1 instead of bis (4-hydroxyphenyl) cyclohexane
A polycarbonate was obtained in the same manner as in Synthesis Example 1, except that 70.4 g (0.20 mol) of diphenylmethane was used.
This polycarbonate has a concentration of 0.5 g / dl in methylene chloride as a solvent and [η _sp / c] at 20 ° C.
It was 0.57 dl / g. Mw is measured by GPC
It was 24,000. The structure and composition of this polymer is
It was a polycarbonate copolymer having the following repeating units and compositions by ¹ H-NMR, IR and MS spectrum analysis.

[0102]

[Chemical 47]

Synthesis Example 7 Structural formula

[0104]

[Chemical 48]

Bisphenol compound having a styrylamine skeleton represented by 109.2 g (0.20 mol) and 1,1
In the same manner as in Synthesis Example 1 except that 12.8 g (0.05 mol) of 2,2-bis (3-methyl-4-hydroxyphenyl) propane was used instead of -bis (4-hydroxyphenyl) cyclohexane. A polycarbonate was obtained. This polycarbonate has a concentration of methylene chloride as a solvent.
0.5 g / dl solution, [η _sp / c] at 20 ° C is 0.
It was 68 dl / g. Mw is 2 by GPC measurement
It was 9000. The structure and composition of this polymer is ¹
From a 1 H-NMR, IR, and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0106]

[Chemical 49]

Example 1 A glass substrate of 25 mm × 75 mm × 1.1 mm, on which ITO was formed into a film having a thickness of 100 nm by a vapor deposition method (HOYA
As a transparent support substrate. This substrate was ultrasonically cleaned with isopropyl alcohol, then blown with nitrogen to dry, and then UV ozone cleaned (Samco International UV
300) was performed for 8 minutes. On this transparent supporting substrate, a 0.9 wt% solution obtained by dissolving 200 mg of the polycarbonate obtained in Synthesis Example 7 in 20 g of dichloromethane was spin-coated to form a light emitting layer. The spin coating at this time was performed at 7,000 rPm for 50 seconds, and the obtained film thickness was 600 ± 100Å ^{* 1} (surface shape measuring instrument: DEKTAK3030 manufactured by Sloan). Next, this transparent supporting substrate was fixed to a substrate holder of a commercially available vacuum vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.).
Three kinds of resistance heating boats were attached to the vacuum vapor deposition device, one of which was PBD 200 mg which was an electron injection material,
Magnesium (2 g) was added to one and silver (200 mg) to the other one, and the pressure in the vacuum chamber was reduced to 2 × 10 ⁻³ Pa. Then, the boat containing PBD is heated to deposit PBD on the transparent support substrate at a deposition rate of 0.3 to 0.5 nm / sec.
An electron injection layer having a film thickness of 20 nm was formed. The substrate temperature at this time was room temperature. Next, a magnesium-containing boat and a silver-containing boat are simultaneously energized so that the magnesium: silver electrode is deposited in a thickness of 120 nm so that the vapor deposition rate ratio (magnesium: silver) is 1: 7 to 1:10. Was sensed by a crystal oscillator type film thickness sensor) to form a counter electrode and an element was formed. Next, when a DC voltage of 6 V is applied, a current of about 136 mA / cm ² flows, and the emission color is Purp in chromaticity coordinates.
I got lish Blue. Peak wavelength from spectroscopic measurement is 460
nm, and the emission luminance was 120 cd / m ² . * 1: This thin film maintained the thin film even after 6 months without crystallization observable by an optical microscope. In FIG. 1, up to 0Å on the vertical axis indicates that there is no polycarbonate layer. In addition, the size of the rise around 220 μm on the horizontal axis indicates the thickness of the polycarbonate,
The deviation from Å of ± 100 Å indicates that the ultrathin film has excellent flatness.

Reference Example 1 Dimethyl sulfoxide (DMSO) under argon atmosphere
20 ml, structural formula

[0109]

[Chemical 50]

The phosphonate ester represented by
1.0 g of potassium-t-butoxide (t-BuOK) was added. Then the structural formula

[0111]

[Chemical 51]

The compound represented by the above was added and stirred for 5 hours.
As a result of adding 100 ml of methanol to the obtained reaction product, a pale yellow powder was deposited. A benzene solution containing iodine was added to this powder and recrystallized to obtain 0.8 g of a pale yellow powder. As a result of analyzing the structure and composition of the obtained pale yellow powder by a proton nuclear magnetic resonance ( ¹ H-NMR) spectrum, it was confirmed to be the following styrylamine compound.

[0113]

[Chemical 52]

On the transparent supporting substrate, in the same manner as in Example 1, 200 mg of this compound was added to 20 g of dichloromethane.
The solution of 0.9% by weight obtained by dissolving in was spin coated. Spin coating at this time is 7000rP
m for 50 seconds. The obtained film thickness is the same as DEKTAK
When measured at 3030, the obtained film thickness is 600 ± 5
It was confirmed that the film was in a thin film state of 00 Å with severe irregularities.

[0115] The organic low-molecular weight compound having such a large unevenness cannot usually be used to form a thin film by the spin coating method, and cannot be used as a light emitting layer or a hole injecting layer.

Comparative Example 1 Structural formula

[0117]

[Chemical 53]

In the same manner as in Reference Example 1, except that the phosphonate ester represented by

[0119]

[Chemical 54]

A styrylamine compound represented by: was synthesized. Further, an organic EL device was prepared in the same manner as in Example 1 except that the above styrylamine compound (film thickness 50 nm) was used as the light emitting layer. Using the ITO electrode as the anode and the mixed metal electrode of magnesium and silver as the cathode, the EL element was short-circuited and no light emission occurred even when a DC voltage of 10 V was applied to the obtained element.

Example 2 Polycarbonate 200 obtained in the same manner as in Example 1
A 0.9 wt% solution obtained by dissolving millig in 20 g of dichloromethane was spin-coated to form a hole injection layer.
The spin coating at this time was 7,000 rPm and 5
After 0 seconds, the obtained film thickness was 600 ± 100Å (surface shape measuring instrument: DEKTAK3030). Then
This transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.). Three kinds of resistance heating boats were attached to the vacuum vapor deposition apparatus, one of which was 200 mg of an aluminum complex (Alq) in which 8-hydroxyquinoline, which is a light emitting material, was three-coordinated, and one of which was 2 g of magnesium, 200 mg of silver was added to the other one, and the pressure in the vacuum chamber was reduced to 10 ⁻³ Pa. After that, the boat containing Alq is heated to 250 to 270 ° C.
q was vapor-deposited on the transparent support substrate at a vapor deposition rate of 0.1 to 0.3 nm / sec to form an electron-transmitting light-emitting layer having a film thickness of 50 nm. The substrate temperature at this time was room temperature. Next, a magnesium-containing boat and a silver-containing boat are simultaneously energized to make a vapor deposition rate ratio (magnesium: silver) of 1: 7 to 1:10 so that a magnesium: silver electrode is laminated by 120 nm (film thickness). Was confirmed by a crystal oscillator type film thickness sensor) to form a counter electrode and an element was formed. When a DC voltage of 12 V was applied to the obtained device with the ITO electrode as the anode and the mixed metal electrode of magnesium and silver as the cathode, the current was 168 m.
The flow rate was about A / cm ² , and the emission color was Green on the chromaticity coordinate. According to spectroscopic measurement, the peak wavelength was 513 nm, and the emission luminance was 800 cd / m ² .

Comparative Example 2 Except that the polycarbonate layer used as the hole injection layer was removed,
An EL device was prepared in the same manner as in Example 2. When a DC voltage of 17 V is applied to the obtained device with an ITO electrode as an anode and a mixed metal electrode of magnesium and silver as a cathode, a current of about 20 mA / cm ² flows and the emission color is Gr in chromaticity coordinates.
got een. According to the spectroscopic measurement, the peak wavelength was 513 nm, and the emission luminance was 20 cd / m ² . The applied voltage is remarkably increased and the emission brightness is also small. Therefore, in Example 2, the polycarbonate layer sufficiently functioned as a hole injection layer.

Examples 3 to 8 EL elements were prepared in the same manner as in Example 1 using the polycarbonates listed in Table 1 as the light emitting layer. The results obtained are shown in Table 1. High brightness and high emission efficiency are obtained in the blue region where the EL emission layer is difficult.

[0124]

[Table 1]

[0125]

[Table 2]

Reference Example 2

[0127]

[Chemical 55]

[0128]

[Chemical 56]

Under ice cooling, 6.0 g (0.08 mol) of DMF was added dropwise to 4 g (0.026 mol) of phosphorus oxychloride to obtain a transparent solution. Next, 6.6 g (0.024 mol) of 4-methoxytriphenylamine was added to give a yellow suspension, which was stirred at 4 ° C for 1 hour and then heated at 80 ° C for 1 hour with stirring to obtain a reddish brown solution. Was given. After cooling, the obtained reaction solution was poured into 100 ml of water, and 2 g of sodium acetate was added to neutralize the reaction solution. The yellow precipitate formed here was filtered, washed with 100 ml of water three times, and then distilled under reduced pressure. The obtained yellow powder 6.1 g (yield 83
%) Was the target compound as a result of proton nuclear magnetic resonance ( ¹ H-NMR) measurement.

[0130]

[Chemical 57]

Synthesis of

[0132]

[Chemical 58]

5.0 g of a phosphonate represented by
011 mol) and potassium t-butoxide 22.5 g (0.
022 moles) and aldehyde (6.7 g) synthesized in Reference Example 2
(0.022 mol) was suspended in 100 ml of anhydrous dimethyl sulfoxide and stirred at room temperature under an argon gas atmosphere. After stirring the resulting red suspension for 5 hours,
When 50 ml of methanol and 50 ml of water were added, a yellow oily substance was obtained. This was purified by silica gel chromatography to obtain 4.0 g (yield 48%) of a yellow amorphous compound. The compound obtained is ¹ H
As a result of NMR measurement, it was the target compound.

[0134]

[Chemical 59]

Synthesis of compound (3.0 g, 0.0039 mol) obtained in Reference Example 2
Was placed in a 200 ml flask having a nitrogen introduction tube, and dissolved with 50 ml of methylene chloride while cooling. 0.7 ml (0.0075 mol) of boron tribromide was slowly added dropwise. After completion of the dropping, the reaction solution was stirred at room temperature for 3 hours, and then 50 ml of water was added little by little while cooling again. The organic layer was washed 3 times with 50 ml of water and dried over sodium sulfate. After filtration of sodium sulfate, the solvent was distilled off to obtain 2.2 g of the target compound (yield 77%). The obtained compound was analyzed by ¹ H-NMR.
As a result of the measurement, it was the target compound.

Synthesis Example 8 In 600 ml of 3N aqueous sodium hydroxide solution, 88.8 g (0.125 mol) of the bisphenol compound having a styrylamine skeleton synthesized in Reference Example 2 and 1,1-bis (4-hydroxyphenyl) ) A solution in which 33.5 g (0.125 mol) of cyclohexane and 250 ml of methylene chloride were placed in a 1-liter flask. The reaction liquid was vigorously stirred while maintaining the liquid temperature around 10 ° C. by external cooling, and phosgene was blown thereinto at a rate of 340 ml / min for 30 minutes. Then, stirring was continued for 1 hour to complete the polymerization. After completion of the reaction, 500 ml of methylene chloride was added to the organic layer to dilute it, and the organic layer was washed with water, diluted hydrochloric acid and water in this order, and then poured into methanol to obtain a polycarbonate. This polycarbonate is a solution of methylene chloride at a concentration of 0.5 g / dl at 20 ° C.
The reduced viscosity [η _sp / c] was 0.70 dl / g. The average molecular weight (Mw) as measured by gel permeation chromatography (GPC) was 28,000. Also,
The results of ¹ H-NMR and IR spectrum of this polymer are shown below. ¹ H-NMR (solvent: CD ₂ Cl ₂ ) δ (ppm) = 1.55 (6 H, s), 2.3 (4 H,
s), 6.8 to 7.5 (144H, m) IR (KBr tablet method) 981 cm ^-1 (δ _CH trans) The structure and composition of this polymer are determined from the above repeating units and compositions by the above spectrum analysis. It was a polycarbonate copolymer.

[0137]

[Chemical 60]

Synthesis Example 9 As phosphonate ester

[0139]

[Chemical formula 61]

The following bisphenol compound was obtained in the same manner as in Reference Example 2 except that was used. Structural formula

[0141]

[Chemical formula 62]

136.4 g (0.2 mol) of this bisphenol compound having a styrylamine skeleton and 2,2-bis (3-methyl-4-hydroxyphenyl) instead of 1,1-bis (4-hydroxyphenyl) cyclohexane )
A polycarbonate was obtained in the same manner as in Synthesis Example 8 except that 12.8 g (0.05 mol) of propane was used. This polycarbonate has a concentration of 0.5 g / methylene chloride as the solvent.
dl solution, [η _sp / c] at 20 ° C is 0.53 dl
/ G. Mw is 28,000 as measured by GPC
Met. The structure and composition of this polymer is ¹ H-NM
From R, IR, and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0143]

[Chemical 63]

Synthesis Example 10 As phosphonate ester

[0145]

[Chemical 64]

The following bisphenol compound was obtained in the same manner as in Reference Example 2 except that was used. Structural formula

[0147]

[Chemical 65]

23.35 g (0.05 mol) of this bisphenol compound having a styrylamine skeleton and 1,1-bis (4-hydroxyphenyl) -1, in place of 1,1-bis (4-hydroxyphenyl) cyclohexane, A polycarbonate was obtained in the same manner as in Synthesis Example 8 except that 70.4 g (0.20 mol) of 1-diphenylmethane was used. This polycarbonate has a concentration of methylene chloride as a solvent.
0.5 g / dl solution, [η _sp / c] at 20 ° C is 0.
It was 74 dl / g. Mw is 3 by GPC measurement
It was 0000. The structure and composition of this polymer is ¹
From a 1 H-NMR, IR, and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0149]

[Chemical 66]

Synthesis Example 11 As phosphonate ester

[0151]

[Chemical 67]

As an aldehyde derivative

[0153]

[Chemical 68]

The following bisphenol compound was obtained in the same manner as in Reference Example 2 except that was used. Structural formula

[0155]

[Chemical 69]

Bisphenol compound having a styrylamine skeleton represented by 113.5 g (0.125 mol) and 1,
A polycarbonate was obtained in the same manner as in Synthesis Example 8 except that 28.5 g (0.125 mol) of 2,2-bis (4-hydroxyphenyl) propane was used instead of 1-bis (4-hydroxyphenyl) cyclohexane. It was This polycarbonate has a concentration of 0.5 g / d in methylene chloride.
1 solution, [η _sp / c] at 20 ° C. is 0.68 dl /
It was g. The Mw was 24000 as measured by GPC. The structure and composition of this polymer is ¹ H-NM
From R, IR, and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0157]

[Chemical 70]

Synthesis Example 12 As phosphonate ester

[0159]

[Chemical 71]

As an aldehyde derivative

[0161]

[Chemical 72]

The following bisphenol compound was obtained in the same manner as in Reference Example 2, except that was used. Structural formula

[0163]

[Chemical formula 73]

158 g (0.20 mol) of a bisphenol compound having a styrylamine skeleton and 1,1-
Bis (4-hydroxyphenyl) cyclohexane 13.4
A polycarbonate was obtained in the same manner as in Synthesis Example 8 except that g (0.05 mol) was used. This polycarbonate is
0.5 g / dl solution with methylene chloride as solvent, 2
[Η _sp / c] at 0 ° C was 0.52 dl / g.
The Mw was 21,000 as measured by GPC. The structure and composition of this polymer are as follows: ¹ H-NMR, IR, MS
From the spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0165]

[Chemical 74]

Synthesis Example 13 As phosphonate ester

[0167]

[Chemical 75]

The following bisphenol compound was obtained in the same manner as in Reference Example 2, except that was used. Structural formula

[0169]

[Chemical 76]

Bisphenol compound having a styrylamine skeleton represented by 34.1 g (0.05 mol) and 1,1-
1,1-bis (4-hydroxyphenyl) -1,1 instead of bis (4-hydroxyphenyl) cyclohexane
A polycarbonate was obtained in the same manner as in Synthesis Example 8 except that 70.4 g (0.20 mol) of diphenylmethane was used.
This polycarbonate has a concentration of 0.5 g / dl in methylene chloride as a solvent and [η _sp / c] at 20 ° C.
It was 0.62 dl / g. Mw is measured by GPC
It was 27,000. The structure and composition of this polymer is
It was a polycarbonate copolymer having the following repeating units and compositions by ¹ H-NMR, IR and MS spectrum analysis.

[0171]

[Chemical 77]

Synthesis Example 14 As phosphonate ester

[0173]

[Chemical 78]

As an aldehyde derivative

[0175]

[Chemical 79]

The following bisphenol compound was obtained in the same manner as in Reference Example 2, except that was used. Structural formula

[0177]

[Chemical 80]

Bisphenol compound having a styrylamine skeleton represented by 132.4 g (0.20 mol) and 1,1
In the same manner as in Synthesis Example 8 except that 12.8 g (0.05 mol) of 2,2-bis (3-methyl-4-hydroxyphenyl) propane was used instead of -bis (4-hydroxyphenyl) cyclohexane. A polycarbonate was obtained. This polycarbonate has a concentration of methylene chloride as a solvent.
0.5 g / dl solution, [η _sp / c] at 20 ° C is 0.
It was 68 dl / g. Mw is 2 by GPC measurement
It was 9000. The structure and composition of this polymer is ¹
From a 1 H-NMR, IR, and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0179]

[Chemical 81]

Synthesis Example 15 Structural formula

[0181]

[Chemical formula 82]

Bisphenol compound having a styrylamine skeleton represented by 144.8 g (0.2 mol) and 1,1-
20.2 g of 4,4'-hydroxybiphenyl ether instead of bis (4-hydroxyphenyl) cyclohexane
A polycarbonate was obtained in the same manner as in Reference Example 2 and Synthesis Example 8 except that (0.2 mol) was used. This polycarbonate had a concentration of 0.5 g / dl in methylene chloride as a solvent, and [η _sp / c] at 20 ° C. was 0.71 dl / g. The Mw measured by GPC was 30,000. The structure and composition of this polymer are ¹ H-NMR, I
From the R and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0183]

[Chemical 83]

Synthesis Example 16 Structural formula

[0185]

[Chemical 84]

Bi having a styrylamine skeleton represented by
Sphenol compound 72.4g (0.1mol) and 1,1-bi
Substitute for (4-hydroxyphenyl) cyclohexane
2,4'-hydroxybiphenyl sulfone 21.8g
Same as Reference Example 2 and Synthesis Example 8 except that (0.1 mol) was used.
Thus, a polycarbonate was obtained. This polycarbonate
Is a methylene chloride solvent at a concentration of 0.5 g / dl.
Solution at 20 ° C [η _sp/ C] is 0.5 dl / g
It was. Mw was 19000 as measured by GPC.
It was The structure and composition of this polymer is¹H-NMR, I
From R and MS spectrum analysis, the following repeating units and
It was a polycarbonate copolymer having a composition.

[0187]

[Chemical 85]

Synthesis Example 17 Structural formula

[0189]

[Chemical formula 86]

Bisphenol compound having a styrylamine skeleton represented by 72.4 g (0.1 mol) and 25 g of 4,4'-hydroxybiphenyl sulfide instead of 1,1-bis (4-hydroxyphenyl) cyclohexane
A polycarbonate was obtained in the same manner as in Reference Example 2 and Synthesis Example 8 except that (0.1 mol) was used. This polycarbonate had a concentration of 0.5 g / dl in methylene chloride as a solvent, and [η _sp / c] at 20 ° C. of 0.62 dl / g. The Mw was 24000 as measured by GPC. The structure and composition of this polymer are ¹ H-NMR, I
From the R and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0191]

[Chemical 87]

Synthesis Example 18 Structural formula

[0193]

[Chemical 88]

Bisphenol compound having a styrylamine skeleton represented by 72.4 g (0.1 mol) and 1,4-bis (4-hydroxyphenyl) instead of 1,1-bis (4-hydroxyphenyl) cyclohexane Butane 19
Polycarbonate was obtained in the same manner as in Reference Example 2 and Synthesis Example 8 except that g (0.1 mol) was used. This polycarbonate had a concentration of 0.5 g / dl in methylene chloride as a solvent, and [η _sp / c] at 20 ° C. was 0.71 dl / g. The Mw measured by GPC was 31,000. The structure and composition of this polymer are ¹ H-NMR, I
From the R and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0195]

[Chemical 89]

Synthesis Example 19 Structural formula

[0197]

[Chemical 90]

72.4 g (0.1 mol) of a bisphenol compound having a styrylamine skeleton and 34.4 g of 1,1-bis (4-hydroxyphenyl) cyclohexane
A polycarbonate was obtained in the same manner as in Reference Example 2 and Synthesis Example 8 except that (0.1 mol) was used. This polycarbonate had a concentration of 0.5 g / dl in methylene chloride as a solvent and [η _sp / c] at 20 ° C. of 0.65 dl / g. Mw was 25,000 as measured by GPC. The structure and composition of this polymer are ¹ H-NMR, I
From the R and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0199]

[Chemical Formula 91]

Synthesis Example 20 Structural formula

[0201]

[Chemical Formula 92]

A bisphenol compound having a styrylamine skeleton represented by 72.4 g (0.1 mol) and 4,4'-biphenyl (18.6 g (0 mol) instead of 1,1-bis (4-hydroxyphenyl) cyclohexane) Polycarbonate was obtained in the same manner as in Reference Example 2 and Synthesis Example 8 except that 0.1 mol) was used. This polycarbonate had a concentration of 0.5 g / dl in methylene chloride as a solvent and [η _sp / c] at 20 ° C. of 0.68 dl / g. The Mw measured by GPC was 29000. The structure and composition of this polymer were found to be a polycarbonate copolymer composed of the following repeating units and compositions by ¹ H-NMR, IR, and MS spectrum analysis.

[0203]

[Chemical formula 93]

Synthesis Example 21 Structural formula

[0205]

[Chemical 94]

Bisphenol compound having a styrylamine skeleton represented by 75.2 g (0.2 mol) and 2,2-bis (4-hydroxyphenyl) instead of 1,1-bis (4-hydroxyphenyl) cyclohexane Propane 2
A polycarbonate was obtained in the same manner as in Reference Example 2 and Synthesis Example 8 except that 1.6 g (0.1 mol) was used. This polycarbonate has a concentration of 0.5 g / d in methylene chloride.
1 solution, [η _sp / c] at 20 ° C. is 0.68 dl /
It was g. Mw was 25,000 as measured by GPC. The structure and composition of this polymer is ¹ H-NM
From R, IR, and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0207]

[Chemical 95]

Synthesis Example 22 Structural formula

[0209]

[Chemical 96]

61.8 g (0.1 mol) of a bisphenol compound having a styrylamine skeleton and 2,2-bis (4-hydroxyphenyl) instead of 1,1-bis (4-hydroxyphenyl) cyclohexane Propane 2
A polycarbonate was obtained in the same manner as in Reference Example 2 and Synthesis Example 8 except that 1.6 g (0.1 mol) was used. This polycarbonate has a concentration of 0.5 g / d in methylene chloride.
1 solution, [η _sp / c] at 20 ° C. is 0.85 dl /
It was g. The Mw was 34000 as measured by GPC. The structure and composition of this polymer is ¹ H-NM
From R, IR, and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0211]

[Chemical 97]

Synthesis Example 23 Structural formula

[0213]

[Chemical 98]

Bisphenol compound having a styrylamine skeleton represented by 78.4 g (0.1 mol) and 2,2-bis (4-hydroxyphenyl) instead of 1,1-bis (4-hydroxyphenyl) cyclohexane Propane 4.
Reference Example 2 and Synthesis Example 8 except that 6 g (0.1 mol) was used.
A polycarbonate was obtained in the same manner as in. This polycarbonate has a concentration of 0.5 g / dl in methylene chloride.
Solution of [η _sp / c] at 20 ° C is 0.59 dl / g
Met. The Mw measured by GPC was 20,000. The structure and composition of this polymer are ¹ H-NMR,
From the IR and MS spectrum analysis, it was a polycarbonate copolymer having the following repeating unit and composition.

[0215]

[Chemical 99]

Example 9 ITO was formed into a film with a thickness of 100 nm on a 25 mm × 75 mm × 1.1 mm glass substrate by a vapor deposition method (HOYA
As a transparent support substrate. This substrate was ultrasonically cleaned with isopropyl alcohol, then blown with nitrogen to dry, and then UV ozone cleaned (Samco International UV
300) was performed for 8 minutes. On this transparent support substrate, 200 m of the polycarbonate obtained in Synthesis Example 10
0.9 g obtained by dissolving 20 g of 1,2-dichloroethane
A weight% solution was spin-coated to form a light emitting layer.
The spin coating at this time was 7,000 rPm and 5
After 0 second, the obtained film thickness was 600 ± 50Å ^{* 1} (surface shape measuring instrument: DEKTAK3030 manufactured by Sloan). This is a light emitting layer with an extremely thin film,
It was possible to realize an organic EL device sufficiently. Next, this transparent supporting substrate was fixed to a substrate holder of a commercially available vacuum vapor deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.). Three kinds of resistance heating boats were attached to the vacuum evaporation system. One was 200 mg of PBD, which is an electron injection material, one was 2 g of magnesium, and the other one was 200 mg of silver. Was reduced to 2 × 10 ⁻³ Pa. After that, the boat containing PBD is heated to deposit PBD at a deposition rate of 0.3 to 0.5.
An electron injection layer having a film thickness of 20 nm was formed by vapor deposition on the transparent supporting substrate at a rate of nm / sec. The substrate temperature at this time was room temperature. Next, the magnesium-containing boat and the silver-containing boat were energized at the same time, and the deposition rate ratio (magnesium: silver)
Was formed into a counter electrode by laminating a 120 nm magnesium: silver electrode in a laminated manner (the film thickness was sensed by a crystal oscillator type film thickness sensor) so that the ratio was 1: 7 to 1:10. Next, when a DC voltage of 6 V is applied, the current becomes 70 mA / cm.
² flow, emission color obtained blue green in chromaticity coordinates. The peak wavelength is 483 nm according to the spectroscopic measurement, and the emission brightness is 1
It was 200 cd / m ² . * 1: This thin film remained a thin film without disturbance and crystallization that could be detected by an optical microscope even after 3 months.

Reference Example 3 Dimethyl sulfoxide (DMSO) under argon atmosphere
20 ml, structural formula

[0218]

[Chemical 100]

The phosphonate ester represented by
1.0 g of potassium-t-butoxide (t-BuOK) was added. Then the structural formula

[0220]

[Chemical 101]

The compound represented by the above was added and stirred for 5 hours.
As a result of adding 100 ml of methanol to the obtained reaction product, a pale yellow powder was deposited. A benzene solution containing iodine was added to this powder and recrystallized to obtain 0.9 g of a pale yellow powder. As a result of analyzing the structure and composition of the obtained pale yellow powder by a proton nuclear magnetic resonance ( ¹ H-NMR) spectrum, it was confirmed to be the following styrylamine compound.

[0222]

[Chemical 102]

On the transparent supporting substrate, in the same manner as in Example 9, 200 mg of this compound was added to 20 g of dichloromethane.
The solution of 0.9% by weight obtained by dissolving in was spin coated. Spin coating at this time is 7000rP
m for 50 seconds. The obtained film thickness is the same as DEKTAK
When measured at 3030, the obtained film thickness is 600 ± 4
It was confirmed that the film was in a thin film state of 00 Å with severe irregularities.

[0224] With such an organic low-molecular-weight compound having severe irregularities, it is usually impossible to form a thin film by the spin coating method, and it is impossible to use it as a light emitting layer or a hole injecting layer.

Comparative Example 3 An organic EL device was prepared in the same manner as in Example except that the styrylamine compound obtained in Reference Example 3 was used as the light emitting layer (film thickness 60 nm). Using the ITO electrode as the anode and the mixed metal electrode of magnesium and silver as the cathode, the EL element was short-circuited and no light emission occurred even when a DC voltage of 7 V was applied to the obtained element.

Example 10 Polycarbonate 200 obtained in the same manner as in Example 9
A 0.9 wt% solution obtained by dissolving millig in 20 g of dichloromethane was spin-coated to form a hole injection layer.
The spin coating at this time was 7,000 rPm and 5
After 0 seconds, the obtained film thickness was 600 ± 100Å (surface shape measuring instrument: DEKTAK3030). Then
This transparent support substrate was fixed to a substrate holder of a commercially available vacuum deposition device (manufactured by Nippon Vacuum Technology Co., Ltd.). Three kinds of resistance heating boats were attached to the vacuum vapor deposition apparatus, one of which was 200 mg of an aluminum complex (Alq) in which 8-hydroxyquinoline, which is a light emitting material, was three-coordinated, and one of which was 2 g of magnesium, 200 mg of silver was added to the other one, and the pressure in the vacuum chamber was reduced to 10 ⁻³ Pa. After that, the boat containing Alq is heated to 250 to 270 ° C.
q was vapor-deposited on the transparent support substrate at a vapor deposition rate of 0.1 to 0.3 nm / sec to form an electron-transmitting light-emitting layer having a film thickness of 50 nm. The substrate temperature at this time was room temperature. Next, a magnesium-containing boat and a silver-containing boat were simultaneously energized, and a magnesium: silver electrode was deposited to a thickness of 120 nm so that the deposition rate ratio (magnesium: silver) was adjusted to 1: 7 to 1:10. Sub-type film thickness sensor) as an opposite electrode,
The device was formed. When a DC voltage of 7 V was applied to the obtained device using the ITO electrode as an anode and the mixed metal electrode of magnesium and silver as a cathode, a current flowed at about 50 mA / cm ² and the emission color was Green on the chromaticity coordinate. The peak wavelength is 513 nm from the spectroscopic measurement, and the emission brightness is 1000 cd.
/ M ² .

Comparative Example 4 Except that the polycarbonate layer used as the hole injection layer was removed,
An EL device was prepared in the same manner as in Example 10. When a DC voltage of 17 V is applied to the obtained device with an ITO electrode as an anode and a mixed metal electrode of magnesium and silver as a cathode, a current of about 20 mA / cm ² flows and the emission color is Gr in chromaticity coordinates.
got een. According to the spectroscopic measurement, the peak wavelength was 513 nm, and the emission luminance was 20 cd / m ² . The applied voltage is remarkably increased and the emission brightness is also small. Therefore, in Example 2, the polycarbonate layer worked well as a hole injection layer.

Examples 11 to 25 Using the polycarbonates shown in Table 2 as the light emitting layer, EL devices were prepared in the same manner as in Example 9. The results obtained are shown in Table 2. High brightness and high luminous efficiency are obtained in the blue to green region where the EL light emitting layer is difficult.

[0229]

[Table 3]

[0230]

[Table 4]

[0231]

As described above, the organic EL device of the present invention is
The light emitting layer and / or the hole injecting layer of the device could be easily formed by the spin coating method, and the thin film maintaining ability was provided to the light emitting layer and / or the hole injecting layer. Furthermore, the organic EL of the present invention
When the polycarbonate of the present invention was used as a light emitting layer, the device was capable of emitting light in the blue to green region, achieving high luminance and high light emitting efficiency at a low voltage, and achieving a long life. Therefore, the organic EL device of the present invention is expected to be effectively used in various fields as having high practical value.

[Brief description of drawings]

FIG. 1 is a graph showing the results of measuring the film thickness of a thin film obtained in Example 1.

Claims (5)

[Claims] 1. An organic electroluminescence device comprising a polycarbonate containing a styrylamine skeleton having an electroluminescence function as a repeating unit, as a light emitting material and / or a hole injection material. 2. Polycarbonate has the general formula (I): (In the formula, Ar ^{1 to} Ar ⁴ each independently represent a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. Ar
⁵ and Ar ⁶ each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms. Here, the substituent is an alkyl group or an alkoxy group having 1 to 10 carbon atoms. P represents an integer of 0 or 1. The organic electroluminescent element of Claim 1 which has a repeating unit represented by these. 3. Polycarbonate has the general formula (II): (In the formula, Ar ^{1 to} Ar ⁶ , R ¹ , R ² and P are as defined above.) And the repeating unit (α) represented by the general formula (III): (In the formula, R ³ and R ⁴ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Y is a single bond, and (Here, x represents an integer of 2 to 10, and R ⁵ and R ⁶
Are each independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aryl group having 6 to 10 carbon atoms. ) Is shown. ) Having a repeating unit (β) represented by
The organic electroluminescence device described. 4. The polycarbonate has the general formula (IV): (Wherein, R ^1, R ^2, P and Ar ¹ to Ar ⁶ are .Ar ⁷ is the same as defined above each independently represent a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. Where The substituent is an alkyl group or an alkoxy group having 1 to 10 carbon atoms, and the dotted line indicates that they may be linked by a single bond.). Electroluminescent device. 5. The polycarbonate has the general formula (V): (In the formula, Ar ^{1 to} Ar ⁷ , R ¹ , R ² and P are as defined above. The dotted line indicates that they may be linked by a single bond.) (Γ) ) And the repeating unit (β) represented by the general formula (III), the organic electroluminescence device according to claim 1.