JPH1131584A - Organic thin-film el element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic thin-film EL element having no aging effect, and excellent heat resistance and durability by containing aromatic polycarbonate resin made of specific repeating units in at least one layer of an organic compound thin film. SOLUTION: A specific repeating unit is expressed by Formula I, where R1 , R2 each represent an acyl group, an alkyl group, an aromatic hydrocarbon group, or a heterocyclic group, Ar1 , Ar2 , Ar3 each represents bivalent groups of aromatic hydrocarbon, (p) represents an integer of one to five, and (n) represents an integer of five to 5000. X are aliphatic, cyclic aliphatic, or a bivalent group of Formula II, where R3 , R4 are each alkyl group, aromatic hydrocarbon group, or halogen, (l), (m) are an integer of zero to four, Y is a single bonding, alkylene group of the number of carbon atoms of one to 12, -O-, -S-, -CO-, -CO-O-Z-O-CO-, or the like (Z expresses an aliphatic hydrocarbon two valences group), or a bivalent group of Formula III. R5 , R6 each represents alkyl group, aromatic hydrocarbon group, (a) in an integer of zero to 20, and (b) represents an integer of one to 2000.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a novel organic thin film EL.
More specifically, the present invention relates to an organic thin-film EL device made of an aromatic polycarbonate resin having excellent heat resistance, mechanical strength, and durability without change over time.

[0002]

2. Description of the Related Art In recent years, organic thin-film EL elements are self-luminous and have a high viewing angle dependency and high visibility. Further, since they are thin-film type solid-state elements, they are attracting attention from the viewpoint of space saving and the like. It has been started for practical research. However, there are many problems to be solved, such as further improvement of energy conversion efficiency and emission quantum efficiency, and provision of stability of the organic thin film over time.

Heretofore, there have been reported organic thin film EL devices using low molecules and those using polymers.
In the case of low molecular weight systems, it has been reported that high efficiency can be achieved by employing various laminated structures, and that durability can be improved by properly controlling the doping method. However, it has been reported that in the case of a low-molecular assembly, a change in the film state occurs over time over a long period of time, and there is an essential problem with respect to the stability of the film. On the other hand, in the case of polymer materials, PPV (poly-p-
phenylenevinylene) series and poly
-Thiophene and the like have been energetically studied. However, it is difficult to increase the purity of these materials, and the fluorescence quantum yield is essentially low. Therefore, at present, a high-performance EL device has not been obtained. In the case of a polymer material, considering that the glass state is essentially stable, if high fluorescence quantum efficiency can be imparted, an excellent EL device can be constructed.

[0004]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art, and particularly has a charge transporting property and is excellent in heat resistance as a component constituting an organic thin film layer of a light emitting layer. It is an object of the present invention to provide an organic thin film EL element containing an aromatic polycarbonate resin, which does not change with time and has excellent durability.

[0005]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that an EL element having an organic layer containing a specific aromatic polycarbonate resin has excellent light emitting characteristics, and completed the present invention. I came to.

That is, according to the present invention, in an organic thin-film EL device having a light-emitting layer composed of a single layer or a plurality of organic compound thin films between an anode and a cathode facing each other, at least one layer of the organic compound thin film is provided. Is a layer containing an aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (I):
An element is provided.

Embedded image [Wherein, R ₁ , R ₂ , Ar ₁ , Ar ₂ , Ar ₃ , n and X are the same as defined above, respectively. ]

Further, according to the present invention, at least one layer of the organic compound thin film of the light emitting layer contains an aromatic polycarbonate resin represented by the above general formula and an electron transporting substance, or a layer containing a light emitting substance. Wherein the organic thin film EL device is provided. According to the present invention, there is provided an organic thin-film EL device including a light-emitting layer composed of a plurality of organic compound thin films having at least one hole injection / transport layer between an anode and a cathode facing each other.
An organic thin film EL device is provided, wherein at least one of the hole injecting and transporting layers is a layer containing the aromatic polycarbonate resin represented by the general formula (I). According to the present invention, in an organic thin-film EL device including a light-emitting layer composed of a plurality of organic compound thin films between an anode and a cathode facing each other, the light-emitting layer is represented by the general formula (I). A layer containing an aromatic polycarbonate resin, at least one hole injection transport layer, and / or
Alternatively, there is provided an organic thin-film EL device comprising at least one electron injection / transport layer, or at least one hole and electron injection / transport layer.

Further, according to the present invention, the aromatic polycarbonate resin comprises a repeating unit represented by the following general formulas (2) and (3), and the composition ratio of the repeating unit is 0 <k / (k + j) ≦ 1 is an aromatic polycarbonate resin.

Embedded image

Embedded image [Wherein, R ₁ , R ₂ , Ar ₁ , Ar ₂ , Ar ₃ , p, k, j
And X are the same as defined above. ]

According to the present invention, there is provided each of the organic thin film EL devices, wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (4). Is done.

Embedded image [Wherein R ₁ , R ₂ , n and X are the same as defined above, respectively. ]

Further, according to the present invention, the aromatic polycarbonate resin comprises a repeating unit represented by the following general formulas (5) and (3), and the composition ratio of the repeating unit is 0 <k / (k + j) ≦ 1 is an aromatic polycarbonate resin.

Embedded image

Embedded image [Wherein R ₁ , R ₂ , k, j and X are the same as defined above, respectively. ]

The aromatic polycarbonate resin contained in the light emitting layer of the organic thin film EL device of the present invention is represented by the following general formula (I), the following general formula (2) or the following general formulas (2) and (3): (4) It comprises a repeating unit represented by the following general formula (5) or the following general formulas (5) and (3), has a tertiary amino group in a side chain, and has both hole transportability and fluorescence characteristics. Therefore, the organic thin film EL device can be used as a charge transporting polymer material or a fluorescent material.

Embedded image

Embedded image

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Embedded image [Wherein R ₁ , R ₂ , Ar ₁ , Ar ₂ , Ar ₃ , p,
n, k, j and X are each the same as defined above. ]

The aromatic polycarbonate resin to be contained in the light emitting layer of the organic thin film EL device of the present invention can be produced by the same method as the polymerization of bisphenol and a carbonic acid derivative, which is conventionally known as a method for producing a polycarbonate resin. That is, the aromatic polycarbonate resin comprising a repeating unit represented by the general formula (2) or (5) of the present invention is a third resin represented by the following general formula (6) or (7). Method of transesterifying diol compound having a primary amino group with bisaryl carbonate, phosgene method by solution or interfacial polymerization with phosgene, or chloroformate method using monochloroformate or bischloroformate derived from diol And so on. At this time, by using a diol represented by the following general formula (8) in combination, an aromatic resin comprising a repeating unit represented by the general formula (2) and a repeating unit represented by the general formula (3) is used. Carbonate resin or an aromatic polycarbonate resin comprising a repeating unit represented by the general formula (5) and a repeating unit represented by the general formula (3), whereby desired properties can be obtained. Is obtained. The ratio of the repeating unit having a tertiary amino group represented by the general formula (2) to the repeating unit represented by the general formula (3), and the tertiary group represented by the general formula (5) The ratio of the repeating unit having an amino group to the repeating unit represented by the general formula (3) can be selected from a wide range depending on desired characteristics. The aromatic polycarbonate resin comprising the repeating unit represented by the general formula (1) or (4) is a tertiary amino acid represented by the following general formula (6) or (7). It can be obtained by interfacial polymerization or solution polymerization of a diol compound having a group or the like and a bischloroformate derived from the general formula (8). Further, bischloroformate derived from a diol compound having a tertiary amino group represented by the general formula (6) or (7) and a general formula (8)
Can also be obtained by polymerization with a diol represented by the formula:

[0013]

Embedded image

Embedded image

Embedded image HO—X—OH (8) [In each of the formulas (6) to (8), R ₁ , R ₂ , Ar ₁ , Ar ₂ , A
r ₃ , p and X are each the same as defined above. ]

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. As described above, the present invention provides an aromatic polycarbonate resin comprising the repeating unit represented by the general formula (I), the general formula (2), or the general formula (2) and the general formula (3), particularly A light emitting layer comprising an organic thin film containing an aromatic polycarbonate resin comprising a repeating unit represented by the general formula (4), the general formula (5), or the general formula (5) and the general formula (3) The present invention relates to an organic thin-film EL device provided with:

The aromatic polycarbonate resin used in the present invention may be a homopolymer comprising a repeating unit represented by the general formula (2) or (5), or a homopolymer represented by the general formula (1) or (4). And a random or block copolymer having a repeating unit represented by formulas (2) and (3) or a repeating unit represented by formulas (5) and (3) as a structural unit. Any of polymers may be used. The molecular weight of the aromatic polycarbonate resin of the present invention is 1 in terms of polystyrene-equivalent number average molecular weight.
000 to 1,000,000, preferably 2000 to 500
000.

The aromatic polycarbonate resin used in the present invention comprises the above-mentioned general formulas (1), (2),
(3) of the raw material giving each repeating unit represented by (4) and (5),
In a diol compound having a secondary amino group, R ₁ ,
Specific examples of the alkyl group as a residue of the acyl group when R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are a substituted or unsubstituted alkyl group and R ₁ and R ₂ are an acyl group are as follows. Things can be mentioned. C1 to C5 straight-chain or branched-chain alkyl groups, and these alkyl groups may further be a fluorine atom, a cyano group, a phenyl group or a halogen atom or a C1 to C5 alkyl group.
It may contain a phenyl group substituted with 5 alkyl groups. Specifically, methyl, ethyl, n-propyl, i-propyl, t-butyl, s-butyl, n
-Butyl group, i-butyl group, trifluoromethyl group, 2
-Cyanoethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group and the like.

In the tertiary amino group-containing diol compounds represented by the general formulas (6) and (7),
Specific examples in which ₁ , R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ are substituted or unsubstituted aromatic hydrocarbon groups include the following. Phenyl, naphthyl, biphenylyl, terphenylyl, pyrenyl, fluorenyl, 9,9-dimethyl-2-fluorenyl, azulenyl, anthryl, triphenylenyl, chrysenyl, fluorenylidenephenyl, 5H-dibenzo [A, d] cycloheptenylidenephenyl group and the like, which may have a lower alkyl group, a lower alkoxy group and a halogen atom as substituents. Further, groups represented by the following general formula can be mentioned.

Embedded image Wherein, B is -O -, - S -, - SO -, - SO 2 -,
—CO— or the following divalent group.

Embedded image

Embedded image (Where R ₇ is the same as a hydrogen atom or a substituent of the aromatic hydrocarbon group, and R ₈ is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon. Represents a group, c is an integer of 1 to 12, d is 1 to
Represents an integer of 3. )]

[0018] Specific examples of the divalent aromatic hydrocarbon group R ₈ in the specific example is an alkyl group and a substituted or unsubstituted substituted or unsubstituted B in the general formula wherein R _1,
The definition is the same as that of R ₂ , R ₃ , R ₄ , R ₅ , and R ₆ .

Further, when R ₁ and R ₂ are a substituted or unsubstituted heterocyclic group, specific examples of the heterocyclic group include:
Thienyl group, benzothienyl group, furyl group, benzofuranyl group, carbazolyl group and the like, these heterocycles, wherein R ₁ to R have been substituted or unsubstituted defined in ₆ alkyl group, a substituted or unsubstituted aromatic It may have an aromatic group as a substituent.

When R ₃ and R ₄ are halogen atoms,
Specific examples of the halogen atom include fluorine, chlorine and bromine.

Further, in the general formulas (6) and (7), 2
Specific examples of Ar ₁ , Ar ₂ and Ar ₃ representing a monovalent aromatic hydrocarbon group include divalent groups derived from the aromatic hydrocarbon groups represented by R _{1 to} R ₆ described above. .

These aromatic hydrocarbon groups or heterocyclic groups may have a substituent as described above, and specific examples of the substituent are shown below. Specific examples of R _{7 in} the general formula are also the same as these specific examples. (1) Halogen atom, trifluoromethyl group, cyano group, nitro group. (2) alkyl group; preferably C ₁ -C _12, especially C ₁
To C ₈ , more preferably a C _{1 to} C ₄ linear or branched alkyl group, and these alkyl groups are furthermore a fluorine atom, a hydroxyl group, a cyano group, a C _{1 to} C ₄ alkoxy group,
It may contain a phenyl group or a phenyl group substituted with a halogen atom, a C ₁ -C ₄ alkyl group or a C ₁ -C ₄ alkoxy group. Specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group,
s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-hydroxyethyl group, 2-cyanoethyl group, 2-ethoxyethyl group, 2-methoxyethyl group, benzyl group, 4-chlorobenzyl Group, 4-methylbenzyl group, 4-methoxybenzyl group and the like. (3) alkoxy group (—OR ₉ ); R ₉ represents an alkyl group defined in (2). Specifically, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, n-butoxy, s-butoxy, i-butoxy, 2-hydroxyethoxy, 2-cyano Examples include an ethoxy group, a benzyloxy group, a 4-methylbenzyloxy group, and a trifluoromethoxy group.

(4) Aryloxy group: Examples of the aryl group include a phenyl group and a naphthyl group. This is C ₁
It may contain a C ₄ to C ₄ alkoxy group, a C _{1 to} C ₄ alkyl group or a halogen atom as a substituent. Specifically, a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 4-methylphenoxy group, a 4-methoxyphenoxy group, a 4-chlorophenoxy group, a 6-methyl-2
-Naphthyloxy group and the like. (5) a substituted mercapto group or an arylmercapto group;
Specific examples include a methylthio group, an ethylthio group, a phenylthio group, and a p-methylphenylthio group. (6) ; Wherein R ₁₀ and R ₁₁ represent each independently an alkyl group or an aryl group as defined in (2) is a phenyl group as the aryl group or naphthyl group, and these alkoxy C ₁ -C ₄ group may contain an alkyl group or a halogen atom C ₁ -C ₄ as a substituent. Further, a ring may be formed together with a carbon atom on the aryl group. Specifically, a diethylamino group, an N-methyl-N-phenylamino group, an N, N-diphenylamino group, an N, N-di (p-tolyl) amino group, a dibenzylamino group, a piperidyl group, a morpholino group, And a euroridyl group. (7) An alkylenedioxy group or an alkylenedithio group such as a methylenedioxy group or a methylenedithio group.

Next, specific examples of the diol represented by the general formula (8) are shown below. 1,3-propanediol,
1,4-butanediol, 1,5-pentanediol,
1,6-hexanediol, 1,8-octanediol, 1,10-decanediol, 2-methyl-1,3-
Propanediol, 2,2-dimethyl-1,3-propanediol, 2-ethyl-1,3-propanediol,
Aliphatic diols such as diethylene glycol, triethylene glycol, polyethylene glycol, and polytetramethylene ether glycol, and cyclic aliphatic diols such as 1,4-cyclohexanediol, 1,3-cyclohexanediol, and cyclohexane-1,4-dimethanol are used. No.

The diol having an aromatic ring includes
4,4′-dihydroxydiphenyl, bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2 -Bis (4-hydroxyphenyl) propane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-
Bis (4-hydroxyphenyl) cyclopentane, 2,
2-bis (3-phenyl-4-hydroxyphenyl) propane, 2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, 4,4′-dihydroxydiphenylsulfone, 4,
4'-dihydroxydiphenylsulfoxide, 4,4 '
-Dihydroxydiphenyl sulfide, 3,3'-dimethyl-4,4'-dihydroxydiphenyl sulfide,
4,4'-dihydroxydiphenyl oxide, 2,2-
Bis (4-hydroxyphenyl) hexafluoropropane, 9,9-bis (4-hydroxyphenyl) fluorene, 9,9-bis (4-hydroxyphenyl) xanthene, ethylene glycol-bis (4-hydroxybenzoate), diethylene glycol- Bis (4-hydroxybenzoate), triethylene glycol-bis (4
-Hydroxybenzoate), 1,3-bis (4-hydroxyphenyl) -tetramethyldisiloxane, phenol-modified silicone oil and the like.

The aromatic polycarbonate resin used in the present invention comprises, as described above, the diol compound having a tertiary amino group represented by the general formula (6) or (7), and A diol represented by the formula (8) is transesterified or a phosgene method, or a diol compound having an amino group represented by the general formula (6) or (7) and the diol compound represented by the general formula It can be produced by a method of reacting bischloroformate derived from the diol represented by (8) in the presence of a solvent and a deoxidizing agent.

Hereinafter, the production method will be described in more detail. In the transesterification method, a diol compound and a bisaryl carbonate are mixed in the presence of an inert gas, and the reaction is usually performed at 120 to 350 ° C. under reduced pressure. The degree of pressure reduction is changed stepwise, and finally, the pressure is reduced to 1 mmHg or less, and phenols produced are distilled out of the system. The reaction time is usually 1 to
It is about 4 hours. Moreover, you may add a molecular weight modifier and an antioxidant as needed. As the bisaryl carbonate, diphenyl carbonate, di-p-tolyl carbonate, phenyl-p-tolyl carbonate, di-p
-Chlorophenyl carbonate, dinaphthyl carbonate and the like.

In the phosgene method, the reaction is usually carried out in the presence of a deoxidizing agent and a solvent. As the deoxidizing agent, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, pyridine and the like are used. As the solvent, for example, a halogenated hydrocarbon such as dichloromethane or chlorobenzene is used. In order to promote the reaction, for example, a tertiary amine,
A catalyst such as a quaternary ammonium salt can be used,
Phenol, p-tert as a molecular weight regulator
It is desirable to use a terminal terminator such as -butylphenol. The reaction temperature is usually 0 to 40 ° C, and the reaction time is several minutes to
It is preferably 5 hours and the pH during the reaction is usually maintained at 10 or more.

When bischloroformate is used, it can be obtained by dissolving a diol compound in a solvent, adding a deoxidizing agent, and adding bischloroformate thereto. As the deoxidizing agent, trimethylamine, triethylamine,
Tertiary amines such as tripropylamine and pyridine are used. As the solvent used in the reaction, for example, halogenated hydrocarbons such as dichloromethane, dichloroethane, trichloroethane, tetrachloroethane, trichloroethylene and chloroform, and cyclic ether solvents such as tetrahydrofuran and dioxane are preferable. Further, it is desirable to use a terminal terminator such as phenol or p-tert-butylphenol as the molecular weight regulator. Reaction temperature is usually 0 to 40 ° C,
The reaction time is a few minutes to 5 hours.

If necessary, additives such as an antioxidant, a light stabilizer, a heat stabilizer, a lubricant, and a plasticizer may be added to the aromatic polycarbonate resin produced according to the above method.

Next, the organic thin film EL device of the present invention will be described. The layer containing the above-mentioned aromatic polycarbonate resin among the organic compound thin film layers in the organic thin film EL device of the present invention can be thinned by a known method such as a spin coating method or a casting method. The aromatic polycarbonate resin is easily dissolved in an organic solvent such as dichloromethane and tetrahydrofuran. Accordingly, a thin film can be prepared by preparing a solution having an appropriate concentration with an appropriate solvent capable of dissolving the aromatic polycarbonate resin, and applying the solution by the above method or the like. When a film containing an electron transporting substance or a luminescent substance is produced, they can be produced by dissolving them together in the above aromatic polycarbonate resin solution and applying them. In addition, by utilizing the property that different polymers are hardly compatible with each other, it is also possible to prepare a film that forms another kind of polymer micro-dispersed phase in one kind of polymer medium. In this case, a mixed solution in which the combination and the mixing ratio of the resins are changed is prepared, and the mixed solution may be applied by a similar wet film forming method. In such a film, the aromatic polycarbonate resin may be used as a polymer medium or as a finely dispersed phase.

Since these films are usually as thin as 20 μm or less, it is preferable to use the solution before filtration by filtering the solution with a filter having a pore size of 0.45 μm or less, more preferably 0.1 μm or less. In the case where the organic layer in the organic thin film EL device is composed of a plurality of organic compound thin film layers and has a low molecular compound layer, a dry film forming method such as vacuum evaporation or sputtering can be used other than the wet film forming method. .

The light emitting layer constituting the organic thin film EL device of the present invention may be composed of a single layer or a plurality of organic compound thin films. When the light-emitting layer is composed of a single layer, the layer may be composed of a polycarbonate resin alone, and in some cases, a dispersion of a low-molecular compound having an electron-transport property, a blend with a polymer, or another charge. Blending with a transportable polymer and doping a trace amount of a fluorescent molecule with extremely high fluorescence quantum efficiency are also effective in increasing the efficiency.

The light-emitting layer constituting the organic thin-film EL device of the present invention may further comprise a plurality of layers, if necessary. In this case, an electron injection / transport layer, another light emitting layer, and the like can be further laminated on the polycarbonate resin-containing layer by a spin coating method or a vacuum evaporation method. Forming a hole injecting and transporting layer before forming a polycarbonate resin-containing layer may also be effective in improving performance.

As the electron transporting substance, an existing material having the ability to transport electrons can be used. For example, it has been reported that fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone and the like and derivatives thereof and have excellent electron transportability so far. It is possible to use the oxadiazole derivative or the triazole derivative that is used.

As the fluorescent molecule having extremely high fluorescence quantum efficiency, a laser dye or the like which exhibits strong fluorescence in a solution state or an existing low molecular fluorescent material which has been used as a light emitting material in an organic EL device is used. It is possible to For example, anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, Bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazole quinolated oxinoid compound, quinacridone, rubrene And their derivatives.

Further, as the material constituting the hole injecting and transporting layer, phthalocyanine compounds, porphyrin compounds, oxadiazole, triazole, triphenylamine compounds which have been reported to function in organic EL devices have been reported. It is possible to use an existing material such as polysilane.

The thickness of the organic compound thin film layer formed in this manner is not particularly limited, and is usually from 5 nm to 20 nm.
It is selected in the range of μm. More preferably, from 5 nm to 0.1 nm.
The range is 2 μm. The film thickness is adjusted in consideration of the occurrence of film defects such as pinholes, light interference within the device at the emission wavelength, and an increase in applied voltage due to an increase in film thickness.

As the anode of the organic thin film EL device in the present invention, a metal, an alloy, a metal oxide, or the like having a work function of 4 eV, preferably greater than 4.8 eV is used. Specific examples of such an electrode material include gold, platinum, palladium, silver, tank stainless steel, nickel, cobalt, ITO,
Use of a transparent electrode such as CuI, SnO2, or ZnO may be used. Particularly preferably, an ITO substrate is suitable. ITO
In the case of a substrate, a substrate having a smooth surface is preferable, and dirt on the surface is thoroughly washed before use. As a cleaning method, a known method may be used, but a method in which ultraviolet irradiation in an ozone atmosphere or plasma treatment in an oxygen atmosphere is performed is preferable.

On the other hand, as the cathode, a metal, an alloy or the like having a work function smaller than 4 eV is used. Specific examples of such a substance include sodium, calcium, magnesium, lithium, aluminum, samarium, and alloys thereof.

When the organic thin-film EL device of the present invention is used as a surface-emitting device, at least one of these electrodes is sufficiently transparent in the emission wavelength region of the device, and the other side has a sufficient reflectance in the emission wavelength region. It is desirable to be large. In the case of edge emission, it is not necessary to be transparent. As the transparent electrode, the above-mentioned ITO is preferable, and a transparent glass plate or a plastic plate is also used for the substrate.

In order to improve the stability of the obtained organic thin-film EL device against the temperature, humidity and atmosphere of the environment, it is effective to provide a protective layer on the surface of the device, or to protect the entire device by enclosing silicon oil or the like. It is.

Using the organic thin film EL device of the present invention obtained in this way, by connecting a positive electrode to a positive electrode and a negative electrode to a cathode and applying a voltage, EL emission can be observed. Normally, in an organic thin film EL device, Joule heat is generated by energization, and the heat causes recrystallization of the organic compound thin film layer, progress of aggregation, and diffusion of a low molecular material, all of which reduce the durability of the device. Have the problem to say. In the organic thin film EL device of the present invention, since a stable aromatic polycarbonate resin having a high melting point and an amorphous state is used for the organic compound thin film layer, device deterioration due to crystallization or aggregation and device deterioration due to diffusion can be suppressed, An element having good durability can be obtained.

[0044]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

Production Example 1 1,1-bis (4-hydroxyphenyl) under a nitrogen stream
3.80 g (7.4 mmol) of 4- [4- (di-p-tolylamino) phenyl] butane and 2.25 g (22.2 mmol) of triethylamine were dissolved in 30 ml of dry tetrahydrofuran (hereinafter referred to as THF). 1.71 of diethylene glycol bis (chloroformate)
g (7.4 mmol) in 6 ml of dry THF was added dropwise at 19.0-21.0 ° C. over 30 minutes. After the dropwise addition, the mixture was stirred at room temperature for 30 minutes, then a solution of 0.03 g (0.3 mmol) of phenol dissolved in 0.7 ml of THF was added, and the mixture was stirred for 10 minutes. Next, the precipitated triethylamine hydrochloride was removed by filtration, the THF solution was added dropwise to methanol, and the precipitated resin was separated by filtration. Then TH
The reprecipitation purification with F-methanol was repeated twice, and the resultant was dried by heating under reduced pressure.
2.6%). Its glass transition temperature Tg is 8
2.2 ° C., and the results of elemental analysis were as follows. _{(C 42 H 41 NO 7)} n C% H% N% Found 75.15 6.18 2.38 Calculated 75.08 6.16 2.09

Embedded image When the molecular weight of this product was measured by gel permeation chromatography, the molecular weight in terms of polystyrene was as follows. Number average molecular weight 14,000 Weight average molecular weight 31000 Also, in the infrared absorption spectrum of this product, 1760 cm ⁻¹
In addition, absorption based on C = 0 stretching vibration of carbonate was observed.

Production Examples 2 to 10 In the same manner as in Production Example 1, aromatic polycarbonate resins (Compound Nos. 2 to 10) shown in Table 1 were obtained.

[0047]

[Table 1- (1)]

[0048]

[Table 1- (2)]

[0049]

[Table 1- (3)]

Example 1 An ITO substrate etched into a 2 mm stripe was washed with boiling alcohol, and the surface was treated with oxygen plasma. Compound No. A 1.0 wt% dichloromethane solution of the aromatic polycarbonate resin of No. 2 was prepared, and filtered with a membrane filter having a pore size of 0.1 μm. Using this solution, an organic light emitting layer having a thickness of 100 nm was formed on the ITO substrate by spin coating.
After sufficient drying, the substrate was set inside the vapor deposition apparatus, and a 200 nm MgAg alloy layer was formed at a degree of vacuum of 10 ⁻⁴ Pa through a mask to produce an organic thin film EL device. The size of the light emitting surface was 2 mm × 2 mm. Using the EL element thus produced, ITO was used as an anode, and M
When gAg was connected to the cathode, blue light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.

Example 2 An organic thin film EL device was produced in the same manner as in Example 1. However, in this case, 2- (4-biphenyly) represented by the following structural formula is further contained in a dichloromethane solution.
l) -5- (4-t-butylphenyl) -1,
3,4-oxadiazole (PBD) (A) was dissolved to a solid content of 30 wt% to form an organic light emitting layer. Using the EL element manufactured in this way, IT
When O was connected to the anode and MgAg was connected to the cathode, blue light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.

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Example 3 An organic thin film EL device was manufactured in the same manner as in Example 1. However, in the dichloromethane solution, 2- (4-Bip
(Henylyl) -5- (4-t-butylphenyl)
yl) -1,3,4-oxadiazole (PBD)
Was dissolved in a solid content of 30 wt% and a trace amount of a perylene derivative (B) represented by the following structural formula at 3 wt% to form an organic light emitting layer. Using the EL device manufactured in this manner, when ITO was connected to the anode and MgAg was connected to the cathode, orange light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.

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Example 4 A 50 nm film similar to that of Example 1 was formed on an ITO substrate treated in the same manner as in Example 1 by the dipping method using the same dichloromethane solution as in Example 1. After performing sufficient drying, the substrate is set inside the vapor deposition apparatus, and 10 ^-4
An Alq molecule deposited film of the compound (C) represented by the following structural formula of 50 nm was formed at a degree of vacuum of Pa, and an MgAg alloy layer of 200 nm was further formed through a mask to produce an organic thin film EL device. The size of the light emitting surface is 2mm x 2m
m. Using the EL device thus manufactured,
When ITO was connected to the anode and MgAg was connected to the cathode, green light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.

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Example 5 An organic thin film EL device was manufactured in the same manner as in Example 2. However, compound N is used as a polycarbonate resin component.
o. 3 was used. Using the EL element manufactured in this manner, when ITO was connected to the anode and MgAg was connected to the cathode, blue light emission was observed at an applied voltage of 10 V. Also,
This organic layer did not undergo any alteration such as crystallization.

Example 6 An organic thin film EL device was produced in the same manner as in Example 2. However, compound N is used as a polycarbonate resin component.
o. 4 was used. Using the EL element manufactured in this manner, when ITO was connected to the anode and MgAg was connected to the cathode, blue light emission was observed at an applied voltage of 10 V. Also,
This organic layer did not undergo any alteration such as crystallization.

Example 7 An organic thin film EL device was manufactured in the same manner as in Example 2. However, compound N is used as a polycarbonate resin component.
o. 6 was used. Using the EL element manufactured in this manner, when ITO was connected to the anode and MgAg was connected to the cathode, blue light emission was observed at an applied voltage of 10 V. Also,
This organic layer did not undergo any alteration such as crystallization.

Example 8 An organic thin film EL device was manufactured in the same manner as in Example 2. However, compound N is used as a polycarbonate resin component.
o. 7 was used. Using the EL element manufactured in this manner, when ITO was connected to the anode and MgAg was connected to the cathode, blue light emission was observed at an applied voltage of 10 V. Also,
This organic layer did not undergo any alteration such as crystallization.

Example 9 An organic thin film EL device was produced in the same manner as in Example 2. However, compound N is used as a polycarbonate resin component.
o. 9 was used. Using the EL element manufactured in this manner, when ITO was connected to the anode and MgAg was connected to the cathode, blue light emission was observed at an applied voltage of 10 V. Also,
This organic layer did not undergo any alteration such as crystallization.

Example 10 An organic thin film EL device was produced in the same manner as in Example 4. However, compound N is used as a polycarbonate resin component.
o. 1 was used. Using the EL device manufactured in this manner, when ITO was connected to the anode and MgAg was connected to the cathode, green light emission was observed at an applied voltage of 10 V. Also,
This organic layer did not undergo any alteration such as crystallization.

Example 11 An organic thin film EL device was manufactured in the same manner as in Example 4. However, compound N is used as a polycarbonate resin component.
o. 5 was used. When the ITO element was connected to the anode and the MgAg was connected to the cathode using the EL device thus manufactured, multicolor green light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.

Example 12 An organic thin film EL device was manufactured in the same manner as in Example 4. However, compound N is used as a polycarbonate resin component.
o. 6 was used. Using the EL device manufactured in this manner, when ITO was connected to the anode and MgAg was connected to the cathode, green light emission was observed at an applied voltage of 10 V. Also,
This organic layer did not undergo any alteration such as crystallization.

Example 13 An organic thin film EL device was manufactured in the same manner as in Example 4. However, compound N is used as a polycarbonate resin component.
o. 8 was used. Using the EL device manufactured in this manner, when ITO was connected to the anode and MgAg was connected to the cathode, green light emission was observed at an applied voltage of 10 V. Also,
This organic layer did not undergo any alteration such as crystallization.

Example 14 An organic thin film EL device was manufactured in the same manner as in Example 4. However, compound N is used as a polycarbonate resin component.
o. 9 was used. Using the EL device manufactured in this manner, when ITO was connected to the anode and MgAg was connected to the cathode, green light emission was observed at an applied voltage of 10 V. Also,
This organic layer did not undergo any alteration such as crystallization.

Example 15 An ITO substrate etched into a 2 mm stripe was washed with boiling alcohol, and the surface was further treated with oxygen plasma. A 10 nm-thick film of copper phthalocyanine was formed thereon as a hole injection / transport layer by vacuum evaporation. On top of this, the compound No. used in Example 1 was used. 2
The organic light-emitting layer having a thickness of 90 nm was formed by a spin coating method using the aromatic polycarbonate resin solution of (1). After performing sufficient drying, set the substrate inside the evaporation device,
200 nm Mg through a mask at a degree of vacuum of 10 ^-4 Pa
An Ag alloy layer was formed to produce an organic thin film EL device. The size of the light emitting surface was 2 mm × 2 mm. Using the EL element thus produced, ITO was used as an anode, and MgAg was used.
Was connected to the cathode, blue light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.

Example 16 In the same manner as in Example 15, a copper phthalocyanine layer and a compound no. A second aromatic polycarbonate layer was prepared. A 50 nm Alq molecule deposited film was formed thereon by a vacuum evaporation method in the same manner as in Example 4, and a 200 nm MgAg alloy layer was further formed via a mask, to produce an organic thin film EL device. The size of the light emitting surface is 2mm x 2m
m. Using the EL device thus manufactured,
When ITO was connected to the anode and MgAg was connected to the cathode, green light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.

Example 17 A copper phthalocyanine layer was formed on an ITO substrate in the same manner as in Example 15. On top of this, the compound N used in Example 3
o. An organic light emitting layer was prepared by a spin coating method using a mixed solution of the aromatic polycarbonate resin of No. 2, PBD, and a perylene derivative (B). Further, a 30 nm electron injection / transport layer of an oxadiazole compound of the compound (D) represented by the following structural formula was prepared by a vacuum evaporation method. Further, an MgAg alloy layer having a thickness of 200 nm was formed through a mask, thereby producing an organic thin film EL device. The size of the light emitting surface is 2mm x 2m
m. Using the EL device thus manufactured,
When ITO was connected to the anode and MgAg was connected to the cathode, orange light emission was observed at an applied voltage of 10 V. This organic layer did not undergo any alteration such as crystallization.

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[0067]

According to the organic thin film EL device of the present invention, the organic compound thin film layer constituting the light emitting layer has the general formula (I) or the general formula (2) having a tertiary amine structure in a side chain.
Alternatively, an aromatic polycarbonate resin comprising a repeating unit represented by the general formula (2) and the general formula (3) is used, and the aromatic polycarbonate resin has a charge transporting ability and a high mechanical strength. Since it has a high melting point and a stable amorphous state, it is an organic thin film EL device having excellent durability without causing deterioration of the device due to crystallization, aggregation or diffusion. Further, in the organic thin film EL device of the present invention, the aromatic polycarbonate resin is preferably represented by the general formula (4), the general formula (5), or the general formula (5) and the general formula (3). A device using an aromatic polycarbonate resin composed of the repeating unit represented is an organic thin film EL device having more excellent performance.

Claims (8)

[Claims] 1. An organic thin-film EL device comprising a light-emitting layer comprising a single layer or a plurality of organic compound thin films between an anode and a cathode facing each other, wherein at least one of the organic compound thin films has the following general formula ( An organic thin film EL device comprising a layer containing an aromatic polycarbonate resin comprising a repeating unit represented by I). Embedded image [In the formula, R ₁ and R ₂ represent an acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. Is also good. Ar ₁ , Ar ₂ and Ar ₃ represent a substituted or unsubstituted aromatic hydrocarbon divalent group, which may be the same or different. p represents an integer of 1 to 5, and n represents an integer of 5 to 5000. X is an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula: In the formula, R ₃ and R ₄ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a halogen atom l, m: each independently represent an integer of 0 to 4 Y: a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-,
_{-SO 2 -, - CO -,} - CO-O-Z-O-CO-
(Where Z represents a divalent group of an aliphatic hydrocarbon) or a divalent group represented by the following general formula: (Wherein, R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a is an integer of 0 to 20, and b is an integer of 1 to 2000. Represents.) Represents｝. ] 2. The method according to claim 1, wherein at least one layer of the organic compound thin film of the light emitting layer comprises a layer containing an aromatic polycarbonate resin represented by the following general formula (I) and an electron transporting substance. 2. The organic thin film EL device according to 1. Embedded image [Wherein, R ₁ , R ₂ , Ar ₁ , Ar ₂ , Ar ₃ , p, n, and X are the same as defined above, respectively. ] 3. The organic light-emitting device according to claim 1, wherein at least one layer of the organic compound thin film of the light-emitting layer comprises a layer containing an aromatic polycarbonate resin represented by the following general formula (I), an electron-transporting substance, and a light-emitting substance. The organic thin film EL device according to claim 1, wherein Embedded image [Wherein, R ₁ , R ₂ , Ar ₁ , Ar ₂ , Ar ₃ , p, n, and X are the same as defined above, respectively. ] 4. An organic thin-film EL device comprising a light emitting layer composed of a plurality of organic compound thin films having at least one hole injection / transport layer between an anode and a cathode facing each other, wherein at least one of the hole injection / transport layers is provided. An organic thin film EL device, wherein one layer is a layer containing an aromatic polycarbonate resin represented by the following general formula (I). Embedded image [Wherein, R ₁ , R ₂ , Ar ₁ , Ar ₂ , Ar ₃ , p, n, and X are the same as defined above, respectively. ] 5. An organic thin film EL having a light emitting layer composed of a plurality of organic compound thin films between an anode and a cathode facing each other.
In the device, the light emitting layer comprises a layer containing an aromatic polycarbonate resin represented by the following general formula (I), at least one hole injection transport layer and / or at least one layer.
An organic thin-film EL device comprising: an electron injection / transport layer; or at least one hole and an electron injection / transport layer. Embedded image [Wherein, R ₁ , R ₂ , Ar ₁ , Ar ₂ , Ar ₃ , p, n, and X are the same as defined above, respectively. ] 6. The aromatic polycarbonate resin comprises repeating units represented by the following general formulas (2) and (3), and the composition ratio of the repeating units is 0 <k / (k + j).
The organic thin film E according to claim 1, 2, 3, 4, or 5, which is an aromatic polycarbonate resin satisfying ≦ 1.
L element. Embedded image Embedded image [In the formula, R ₁ and R ₂ represent an acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. Is also good. Ar ₁ , Ar ₂ and Ar ₃ represent a substituted or unsubstituted aromatic hydrocarbon divalent group, which may be the same or different. p represents an integer of 1 to 5, and X is an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula: In the formula, R ₃ and R ₄ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a halogen atom l, m: each independently represent an integer of 0 to 4 Y: a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-,
_{-SO 2 -, - CO -,} - CO-O-Z-O-CO-
(Where Z represents a divalent group of an aliphatic hydrocarbon) or a divalent group represented by the following general formula: (Wherein, R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a is an integer of 0 to 20, and b is an integer of 1 to 2000. Represents.) Represents｝. k is an integer of 5-5000, j is 0
Represents an integer of 5000. ] 7. The organic compound according to claim 1, wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin comprising a repeating unit represented by the following general formula (4). Thin film EL element. Embedded image [In the formula, R ₁ and R ₂ represent an acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. Is also good. n represents an integer of 5 to 5000. X is an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula: In the formula, R ₃ and R ₄ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a halogen atom l, m: each independently represent an integer of 0 to 4 Y: a single bond, a linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-,
_{-SO 2 -, - CO -,} - CO-O-Z-O-CO-
(Where Z represents a divalent group of an aliphatic hydrocarbon) or a divalent group represented by the following general formula: (Wherein, R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a is an integer of 0 to 20, and b is an integer of 1 to 2000. Represents.) Represents｝. ] 8. The aromatic polycarbonate resin comprises repeating units represented by the following general formulas (5) and (3), and the composition ratio of the repeating units is 0 <k / (k + j).
6. The organic thin-film EL device according to 1, 2, 3, 4 or 5, wherein the organic thin-film EL device is an aromatic polycarbonate resin satisfying ≦ 1. Embedded image Embedded image [In the formula, R ₁ and R ₂ represent an acyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a substituted or unsubstituted heterocyclic group. Is also good. X is an aliphatic divalent group, a cycloaliphatic divalent group, or a divalent group represented by the following general formula: {Wherein, R ₃ and R ₄ each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, or a halogen atom l, m: an integer of 0 to 4 Y: a single bond A linear, branched or cyclic alkylene group having 1 to 12 carbon atoms, -O-, -S-, -SO-,
_{-SO 2 -, - CO -,} - CO-O-Z-O-CO-
(Where Z represents a divalent group of an aliphatic hydrocarbon) or a divalent group represented by the following general formula: (Wherein, R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aromatic hydrocarbon group, a is an integer of 0 to 20, and b is an integer of 1 to 2000. Represents.) Represents｝. k is an integer of 5-5000, j is 0
Represents an integer of 5000. ]