JP3482719B2 - Carrier transportable polymer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is useful as a carrier transporting material or a light emitting material in an organic thin film EL (electroluminescence) device or an organic thin film photocell, or as a carrier transporting material in an electrophotographic photoreceptor. TECHNICAL FIELD The present invention relates to a polymer and a monomer compound for producing the polymer.

[0002]

2. Description of the Related Art Recently, as a light emitting display device, C.I. W. The direct current drive type organic thin film EL element developed by Tang et al. Is attracting attention because it can be thinned as a whole display device without requiring a peripheral device such as a voltage rising transformer. The basic structure of this device is a translucent insulating substrate, a translucent anode, a carrier transport layer (also referred to as an organic hole injection transport layer or a hole transport layer), an organic light emitting layer (also referred to as an organic electron transport light emitting layer). ) And a back cathode are sequentially laminated (JP-A-59-1).
94393, 63-295695, App
l.Phys.Lett., 51 (1987) 913, J.Appl.Phys., 65 (1989) 361
0 etc.). In this case, the work function of the carrier transport layer is set between the work function of the transparent anode and the work function of the organic light emitting layer.

Such an organic thin film EL device is specifically manufactured as follows.

First, a compound oxide of indium and tin (hereinafter abbreviated as ITO / work function 4.6 to 5.) on a translucent insulating substrate such as glass or resin film by a vapor deposition method or a sputtering method. A thin film of a light-transmissive conductor such as 0 eV) is formed and patterned to form an anode.

Next, a copper phthalocyanine having a work function in the range of 5.0 to 5.8 eV or a formula (C) or a formula (D) is formed thereon as a carrier transport layer.

[0006]

[Chemical 10] 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane represented by (melting point (mp) = 181.4 to
182.4 ° C) or N, N, N ', N'-tetra-p-
Triaryl-1,1′-biphenyl-4,4′-diamine (mp = 120 ° C.) and the like.
A thin layer having a thickness of about 1 μm or less is formed by vapor deposition.

Next, a thin layer of an organic phosphor such as an aluminum oxine complex having a work function of about 5.8 eV and having a thickness of about 0.1 μm or less is formed on the carrier transport layer by vapor deposition as an organic light emitting layer. .

Finally, Mg: Ag, Ag: Eu, Mg: Cu, Mg: I as a back cathode on the organic light emitting layer.
A thin film of an alloy material such as n, Mg: Sn, Al: Li is formed by a co-evaporation method. Thereby, an organic thin film EL element is obtained.

It has been proposed to form an organic electron injecting and transporting layer between the organic light emitting layer and the back electrode to improve electron transporting efficiency (Appl.Phys.Lett., 57 , 531).
(1990)). In this case, as a carrier transport layer on the anode made of ITO, the glass transition temperature is 67 ° C. and the melting point (mp) is 1.
N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-biphenyl-at 59-163 ° C
A thin film of 4,4′-diamine (hereinafter referred to as TPD) is formed, and 1- [4-N, N is formed on the thin film as an organic light emitting layer.
A thin film of -bis (p-methoxyphenyl) aminostyryl] naphthalene is formed, and 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4 is further used as an organic electron injecting and transporting layer. -Oxadiazole (hereinafter, B
A thin film (abbreviated as PBD) is formed. In this embodiment, the TPD layer may be omitted, and in that case, the organic light emitting layer is a carrier transport layer (organic hole injection transport light emitting layer).
Also works as.

[0010]

However, in the conventional organic thin film EL device, when the carrier transport layer is formed from copper phthalocyanine, the film formation cost is high because copper phthalocyanine is hardly soluble in the organic solvent. There is a problem in that a film cannot be formed by an evaporation method and a simple method such as a spin coating method cannot be used. Further, the copper phthalocyanine thin film formed by the vapor deposition method has high crystallinity, and since the surface thereof is likely to have irregularities, there is a problem that the possibility of short-circuiting the element cannot be denied. Furthermore, since the absorption of copper phthalocyanine in the visible light region is large, there is a problem that the emission intensity of the organic thin film EL element is reduced.

On the other hand, when the carrier transport layer of the organic thin film EL device is formed from the compound of formula (C) or (D) or TPD by the vapor deposition method, an amorphous and smooth thin film can be obtained.
However, their glass transition temperature (Tg) and melting point (m
Since p) is relatively low, there is a problem that heat resistance is insufficient. Therefore, the carrier transport layer is an organic thin film EL.
When heated by the radiant heat of the vapor deposition source in the device manufacturing process, or when heated by Joule heat during driving of the organic thin film EL device, or in the summer (daytime)
When left in a high temperature atmosphere, such as when left in a high temperature automobile, the carrier transport layer is fused with other adjacent layers or crystallized to make its surface uneven,
As a result, the luminous efficiency may be significantly reduced, or the element may be short-circuited, and the device may not be driven. Therefore, it has been desired to set the Tg of the constituent compound of the carrier transport layer to 120 ° C. or higher.

Further, in order to stabilize the organic thin film EL device and to improve workability at the time of cathode patterning, it has been desired to further improve the mechanical strength of the above-mentioned conventional carrier transport layer.

The present invention is intended to solve the above-mentioned problems of the prior art and forms a carrier transport layer of an organic thin film EL element by a film forming method using a solvent such as a spin coating method or a casting method. Made possible, and T of the carrier transport layer
g is 120 ° C. or higher, and the mechanical strength is further improved.

[0014]

The present inventor has found that the organic thin film E
It was found that the above object can be achieved by using a specific polymer as the carrier transport layer of the L element,
The present invention has been completed.

That is, the present invention is based on the formula (A)

[0016]

[Chemical 11] (In the formula, m is a positive integer indicating the degree of polymerization, and G ¹ is absent or is an arylene group, an alkylene group, an alkylenedioxy group, or a formula (1) to a formula (9).

[0017]

[Chemical 12] G ² is a halogen-substituted or unsubstituted alkyl group, G ³ is a hydrogen atom or an alkyl group, and G ⁴ is a group represented by formulas (10) to (25)

[0018]

[Chemical 13]

[0019]

[Chemical 14] Is a linking group selected from among. Here, G ⁵ is a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms. ) The polymer represented by this is provided.

The present invention will be described in detail below.

In G ¹ of the formula (A), examples of the arylene group include phenylene group, biphenylene group, terphenylene group, anthrylene group and the like, and examples of alkylene group include methylene group, ethylene group, propylene group and the like. Examples of the alkylenedioxy group include a methylenedioxy group and an ethylenedioxy group. G
^{In 2} , the halogen-substituted alkyl group can be exemplified by a trifluoromethyl group and the like, and the terminally-substituted alkyl group can be exemplified by a methyl group, a t-butyl group and the like. G
Examples of the alkyl group in ³ include a methyl group and an ethyl group.

Among the polymers of the present invention of formula (A), those of formula (B)

[0023]

[Chemical 15] Those represented by are particularly preferable.
Among them, those in which G ¹ is p-phenylene are preferable.

The number average molecular weight (GPC method) of the polymer represented by the formula (A) or (B) is preferably 2,000 to 1,000,000, more preferably 5,000 to 1,000,000 from the viewpoint of film-forming property and mechanical strength. is there.

The polymer of the present invention specified as described above can be dissolved in general organic solvents such as chloroform and toluene. Therefore, a film can be formed by a method such as a spin coating method or a casting method using an organic solvent. Further, the polymer of the present invention can have a Tg of 120 ° C. or higher, and thus can improve heat resistance and mechanical strength of the film.

Further, since the polymer of the present invention contains a large number of aromatic tertiary amines such as triphenylamines, which are carrier transporting units, in the molecule, it is possible to remove holes or electrons in the carrier transporting layer. The carrier transport ability can be improved. Furthermore, in the polymer of the present invention, since double bonds are formed between the monomer units, the conjugated system in the molecule can be extended by combination with G ¹ .
Therefore, the carrier transport ability of the carrier transport layer formed from the polymer of the present invention can be further improved.

The polymer of the present invention has an emission (fluorescence) spectrum in the visible light region. Therefore, it can also be used as a constituent material of a carrier transporting light emitting layer, preferably an organic hole transporting light emitting layer.

When it is necessary to adjust the work function of the polymer of the present invention, the work function can be increased by using an electron-withdrawing group such as trifluoromethyl group, nitro group or cyano group as G ^2. It is also possible to reduce the work function by using an electron donating group such as a methyl group or a methoxy group.

The peak wavelength of the fluorescence spectrum is G
^{When 1} or G ² is a non-conjugated or low-conjugated group (for example, a group such as m-xylylene that is connected at the meta position of an aromatic ring), the wavelength can be shortened, and a conjugated linking group can be used. When used, the wavelength can be made longer. Thus, the polymer of the present invention can set the work function and the emission (fluorescence) spectrum with a high degree of freedom, and is an excellent organic hole injecting and transporting layer material or organic hole transporting and emitting layer material.

The inventive polymers of formula (A) can be prepared as shown in the reaction schemes below. here,
M, G ¹ , G ² , G ³ and G ⁴ in the reaction scheme are as defined in formula (A), and X is a halogen atom such as chloro or bromo.

[0031]

[Chemical 16]

[0032]

[Chemical 17] Reaction Scheme 1 First, in the presence of potassium carbonate and CuI, a diamine compound of formula (i) is reacted with iodobenzene in tetralin to introduce a phenyl group into an amino group, and N, N ′ of formula (ii) is introduced.
Produce a diphenyldiamine compound.

Further, a compound of formula (ii) is reacted with a G ² -substituted iodobenzene of formula (iii) under similar reaction conditions to obtain a compound of formula
The compound of (iv) is prepared.

The compound of the formula (iv) can be obtained by another method.
It can also be produced by reacting G ² -substituted aminobenzene of (V) with iodobenzene to form a compound of formula (vi) and further reacting with a diiodo compound of formula (vii).

Next, the compound of formula (iv)
The reaction or Friedel-Crafts reaction is performed to produce a compound of formula (a) in which a formyl group (G ³ = H) or an acyl group (G ³ = alkyl group) is introduced.

Reaction Scheme 2 Separately from this, a compound of formula (viii) is reacted with triphenylphosphine to form a bisphosphonium salt of formula (ix), and then the bisphosphonium salt of formula (viii) is added with butyl. A phosphorus ylide of the formula (x) is produced by reacting a base such as lithium or sodium methoxide.

Reaction Scheme 3 Next, the phosphorus ylide of formula (x) and the compound of formula (a) are subjected to Witt.
The polymer of formula (A) can be produced by the ig reaction. This Wittig reaction is based on the experimental chemistry course (4th
Edition, Vol. 19 (1), page 57, published by Maruzen Publishing Co., Ltd.).

As described above, the compound of the formula (a) used for producing the polymer of the present invention is a novel compound and is useful as a raw material for producing the compound of the formula (A). Therefore,
This compound also forms part of the present invention.

Among the polymers of the present invention represented by the formula (A), the compound of the formula (B) is represented by the following formula (b) in the formula (a).

[0040]

[Chemical 18] It can be produced from a dicarbonyl compound represented by the formula (wherein n is 1 or 2).

The polymer of the present invention of the formula (A) can be preferably applied to the hole injecting and transporting layer of a general organic thin film EL device. For example, when the polymer of the present invention of the formula (A) is formed on the ITO anode by the spin coating method, the aluminum oxine complex is used as the organic light emitting layer, and the AlLi alloy is used as the cathode to form the EL device, 1000 cd / m ²
Yellow-green light emission having the above light intensity can be obtained. Also,
The hole injecting and transporting layer made of the polymer of the present invention can also function as a light emitting layer.

Further, the organic thin film EL device using the polymer of the present invention as the carrier transport layer can generate a photovoltaic voltage of 1 V or more by irradiating with light having the absorption wavelength, so that it is applied to a photovoltaic cell. You can also do it. For example, an organic thin film EL element using the polymer of the present invention can be used as a solar cell by providing a phthalocyanine-based or perylene-based organic dye layer suitable for absorbing solar rays as its organic light emitting layer.

The polymer of the present invention can be applied to the carrier transport layer of a function-separated photoreceptor in electrophotography. In that case, carrier generation containing organic dyes such as perylene-based, polycyclic quinone-based, phthalocyanine-based, and azo-based carrier-generating materials and inorganic materials such as Se, Se-Te, CdS, and amorphous Si A carrier transport layer made of the polymer of the present invention may be formed on the layer (“Basics and Applications of Electrophotographic Technology”, page 441 (1988), edited by The Institute of Electrophotography, published by Corona Publishing Co., Ltd.).

[0044]

The polymer of the present invention contains a large number of aromatic tertiary amines such as triphenylamines, which serve as carrier transport units, in the molecule. Therefore, by forming a carrier transport layer from the polymer of the present invention, it becomes possible to improve the carrier transport ability of holes or electrons of the carrier transport layer. Furthermore, since a double bond is formed between the monomer units, the conjugated system in the molecule can be extended. Therefore, the carrier transport ability of the carrier transport layer formed from the polymer of the present invention can be further improved.

Since the polymer of the present invention is soluble in a general organic solvent, it can be formed into a film by a film forming method using a solvent. Moreover, the polymer of the present invention has high heat resistance due to its high molecular weight. Therefore, it exhibits sufficient heat resistance against heating by Joule heat generated during the manufacturing process of the organic thin film EL element or during element driving.

..

EXAMPLES The present invention will be specifically described below with reference to examples.

Example 1 (Compound of the formula (b) with n = 1 [N, N'-bis (4-pho
Rumilphenyl) -N, N'-di (p-tolyl) -p-
Synthesis of [phenylenediamine] 107 g (1 mol ) of p-toluidine, 61.2 g (0.3 mol) of iodobenzene, and 44.9 g of potassium carbonate.
(0.33 mol) and CuI 5.7 g (0.03 mo)
1) was charged into a reaction vessel, and the Ullmann reaction was carried out while stirring at 200 ° C. for 20 hours. After the reaction was completed, toluene was added and the produced salt was filtered off. After removing toluene, p-toluidine and iodobenzene from the filtrate by vacuum distillation, the residue was purified by a silica gel column using a 1: 1 eluent of toluene-hexane and recrystallized from ethanol. As a result, N-phenyl-p-toluidine (yield 65%, melting point 90 ° C.) was obtained as white crystals.

Obtained N-phenyl-p-toluidine 2
2 g (120 mmol), p-diiodobenzene 10.
3 g (31 mmol), 16 g potassium carbonate (116 m
mol), 3 g (16 mmol) of CuI and 100 ml of tetralin were charged in a reaction vessel, and Ullmann reaction was carried out while stirring at 200 ° C. for 20 hours. After the reaction was completed, toluene was added and the produced salt was filtered off. After distilling off toluene and tetralin from the filtrate, the residue was purified on an alumina gel column using toluene as an eluent. as a result,
N, N′-diphenyl-N, N′-di (p-tolyl) -p-phenylenediamine (yield 40
%, Melting point 192.5-197 ° C. (hot plate method),
A glass transition point of 66 ° C. (DTA 10 ° C./min) was obtained.

Next, 12.27 g of phosphoryl chloride (80
mmol) was added dropwise to 21.05 g (266 mmol) of ice-cooled N, N'-dimethylformamide (DMF) to generate a methyleneiminium compound.

After the exothermic heat of the reaction solution has subsided, the previously prepared N, N'-diphenyl-N, N'-di (p-tolyl) -p- was added to the reaction mixture containing the methyleneiminium compound. Phenylenediamine 4.4 g (10 mmo
l) was added to a solution of 20 ml of DMF,
The reaction was carried out at 0 ° C for 5 hours. Then, the reaction mixture was put into ice water, neutralized with an aqueous solution of sodium hydroxide and hydrolyzed. In that state, the mixture was left in the refrigerator overnight to mature the precipitate, which was then filtered, washed with water, and vacuum dried to give 4.9 g of a brown powder.
(Yield 99%) of the target compound (N, N′-bis (4-
Formylphenyl) -N, N'-di (p-tolyl) -p
-Phenylenediamine) was obtained. Identification data for this compound are shown below.

Mp: 227 ° C. (DTA 10 ° C./mi
n) IR (KBr method): FIG. 1 [1692 cm ⁻¹ (CO expansion / contraction), 825 cm ⁻¹ (p-substituted benzene out-of-plane bending angle)] UV-visible absorption spectrum (1.7 × 10 ⁻⁵ M THF)
Solution): FIG. 2 ¹³ C-NMR (CDCl ₃ ): FIG. 3 [190.1 pp
m (CHO), 20.9 ppm (CH3 ₎ ].

Example 2 (N = N'-bis (4-pho) -compound of formula (b) with n = 2
Rumilphenyl) -N, N'-di (p-tolyl) -ben
Synthesis of dizine ] 35 g (104 mmo ) of N, N′-diphenylbenzidine
l), 91 g (416 mmol) of p-iodotoluene,
35 g (253 mmol) of potassium carbonate, CuI1.4
7 g (7.7 mmol) and 100 ml of tetralin were charged into a reaction vessel and stirred at 200 ° C. for 20 hours while distilling off the produced water to carry out an Ullmann reaction.

After completion of the reaction, toluene was added and the produced salt was filtered off. After toluene was distilled off from the filtrate, iodobenzene was extracted and removed with hexane, the residue was purified by a silica gel column using toluene as an eluent, and recrystallized from toluene-acetone. As a result, N, N′-biphenyl-N, N′-di (p-tolyl) -benzidine (yield 57%, melting point 153-164.
5 ° C. (hot plate method) was obtained.

Next, 12.27 ml of phosphoryl chloride (8
0 mmol) was added dropwise to 21.05 g (266 mmol) of ice-cooled N, N′-dimethylformamide (DMF) to give a methyleneiminium compound (Vilsmeier complex).
Was generated.

The reaction mixture containing the methyleneiminium compound was added to the previously synthesized N, N'-diphenyl-
5.16 g of N, N'-di (p-tolyl) -benzidine
A solution prepared by dissolving (10 mmol) in 30 ml of DMF was added, and the mixture was reacted at 80 ° C. for 5 hours. Then, the reaction mixture was put into ice water, neutralized with an aqueous solution of sodium hydroxide and hydrolyzed. In that state, the mixture was left overnight in the refrigerator to mature the precipitate, which was then filtered, washed with water, and vacuum dried to give 5.7 g (yield 99%) of the target compound (N, N ′) as an ocher amorphous powder. -Bis (4-formylphenyl) -N, N '
-Di (p-tolyl) -benzidine) was obtained. Identification data for this compound are shown below.

IR spectrum (KBr method): FIG.
689 cm ^-1 (CO expansion and contraction), 819 cm ^-1 (out-of-plane bending angle of p-substituted benzene)] UV-visible absorption spectrum (1 x 10 ^-5 M THF solution): Fig. 5 ¹³ C-NMR (CDCl ₃ ): FIG. 6 [190.2 pp
m (CHO), 20.1ppm (CH 3)].

Example 3 (Polymerization of Formula (B) of n = 1 and G ¹ = m-xylylene Group)
Synthesis of body) N, N'-bis (4-formylphenyl) -N, N'-di (p-tolyl) -p-phenylenediamine obtained in Example 1, 1.2415 g (2.5 mmol) and m -Xylyl-bis (triphenylphosphonium chloride)
1.7491 g (2.5 mmol) was dissolved in 76 ml of chloroform / ethanol (1/1), sodium ethoxide (6 mmol) was added to the solution, and the mixture was stirred at room temperature for 3 times.
It was stirred for a day.

Then, the reaction solution was added with a 2% hydrochloric acid aqueous solution 2.5 m.
l was added to form a precipitate, and the precipitate was centrifuged and then reprecipitated with chloroform / methanol. The precipitate was filtered off and dried to obtain 0.42 g (yield 29.6%) of the target compound as a yellow powder. Identification data for this compound are shown below.

Tg: 153.5 ° C. (20 ° C. by DSC /
Number average molecular weight (polystyrene conversion): 90,000 (GP)
Weight average molecular weight (converted to polystyrene): 25,000 (G)
Work function: 5.5 eV (cast film on a quartz plate was measured with AC-1 manufactured by Riken Keiki Co., Ltd. with a light amount of 1.0 nW) IR spectrum (KBr method): FIG. 7 UV-visible absorption spectrum ( 8.8 mg / I THF solution): Fig. 8 Fluorescence spectrum: Fig. 9 (cast film on quartz plate measured with Shimadzu RF-5000 Fluorometer).

Example 4 (Polymerization of Formula (B) with n = 1 and G ¹ = p-xylylene Group)
Synthesis of body] 1.7490 g (2.5 mmo) of p-xylyl-bis (triphenylphosphonium chloride) in place of m-xylyl-bis (triphenylphosphonium chloride)
l) By the same operation as in Example 3 except that the compound was used, 0.273 g (yield 19.3%) of the target compound was obtained as a yellow powder. Identification data for this compound are shown below.

Glass transition temperature: 149.4 ° C. (DSC
20 ° C./min temperature increase) Number average molecular weight (polystyrene conversion): 90,000 (GP
Measured by C) Weight average molecular weight (polystyrene conversion): 23,000 (G
Work function: 5.2 eV (measurement of cast film on quartz plate with AC-1 manufactured by Riken Keiki Co., Ltd., light intensity 749 nW) IR spectrum (KBr method): FIG. 10 UV-visible absorption spectrum (5 mg / I THF solution): Fig. 11 Fluorescence spectrum: Fig. 12 (measured by a Shimadzu RF-5000 fluorometer on a cast film on a quartz plate).

Example 5 (A polymer of the formula (B) having n = 2 and G ¹ = m-xylylene group)
Synthesis of N, N'-bis (4-formylphenyl) -N, N'-di (p-tolyl) -benzidine obtained in Example 2.
4320 g (2.5 mmol) and m-xylyl-bis (triphenylphosphonium chloride) 1.7491
g (2.5 mmol) was dissolved in 76 ml of chloroform / ethanol (1/1), sodium ethoxide (6 mmol) was added to the solution, and the mixture was stirred at room temperature for 3 days.

Then, 2.5m of a 2% hydrochloric acid aqueous solution was added to the reaction solution.
l was added to form a precipitate, and the precipitate was centrifuged and then reprecipitated with chloroform / methanol. The precipitate was filtered off and dried to give a yellow powder, 0.6
70 g (41.7% yield) of the desired compound was obtained. Identification data for this compound are shown below.

Tg: 180.6 ° C. (20 ° C. by DSC /
Temperature rise of min) Number average molecular weight (polystyrene conversion): 16,000 (GP
Weight average molecular weight (converted to polystyrene): 36,000 (G)
Work function: 5.3 eV (cast film on a quartz plate was measured with a light intensity of 749 nW by AC-1 manufactured by Riken Keiki Co., Ltd.) IR spectrum (KBr method): FIG. 13 UV-visible absorption spectrum (5 mg / I THF solution): Fig. 14 Fluorescence spectrum: Fig. 15 (cast film on quartz plate measured by Shimadzu RF-5000 fluorometer).

Example 6 (Polymerization of Formula (B) with n = 2 and G ¹ = p-xylylene Group)
Synthesis of body] 1.7492 g (2.5 mmo) of p-xylyl-bis (triphenylphosphonium chloride) in place of m-xylyl-bis (triphenylphosphonium chloride)
l) By the same operation as in Example 5 except that used, 0.762 g (yield 47.4%) of the target compound was obtained as a yellow powder. Identification data for this compound are shown below.

N, N'-bis (4-formylphenyl)
-N, N'-di (p-tolyl) -benzidine 1.431
7 g (2.5 mmol) and p-xylyl-bis (triphenylphosphonium chloride) 1.7492 g (2.
5 mmol) in chloroform / ethanol (1/1) 7
It was dissolved in 6 ml, 6 mmol of sodium ethoxide was added, and the mixture was stirred at room temperature for 2 to 3 days.

Thereafter, 2.5 ml of a 2% hydrochloric acid aqueous solution was added, the resulting precipitate was centrifuged, and then chloroform / methano-
Re-precipitation and drying to obtain 0.762 g of yellow powder (yield 4
7.4%). Identification data for this compound are shown below.

Tg: 193.6 ° C. (20 ° C. by DSC /
Temperature rise of min) Number average molecular weight (polystyrene conversion): 23,000 (GP
Weight average molecular weight (converted to polystyrene): 50,000 (G)
Work function: 5.5 eV (cast film on a quartz plate was measured with AC-1 manufactured by Riken Keiki Co., Ltd., with a light amount of 1.3 nW) IR spectrum (KBr method): FIG. 16 UV-visible absorption spectrum ( 5 mg / I THF solution): FIG. 17 Fluorescence spectrum: FIG. 18 (measured by a Shimadzu RF-5000 fluorometer on a cast film on a quartz plate).

Example 7 A 120 nm IT film was formed on a 1.1 mm thick glass substrate.
O was sputtered to form a transparent anode. A hole injection layer was formed by vacuum-depositing copper phthalocyanine to a thickness of 15 nm on this anode.

Then, a toluene solution of the polymer synthesized in Example 4 was spin-coated on the hole injection layer to give a thickness of 4
A 0 nm hole transport layer was formed.

Next, an aluminum oxine complex was vapor-deposited to a thickness of 50 nm as an organic electron-transporting light-emitting layer on the hole-transporting layer, and an alloy of Al and Li was vapor-deposited to a thickness of 20 nm as a cathode. An organic thin film EL device was produced by vapor deposition with a large thickness.

The obtained organic thin-film EL device had a DC voltage of 1
It emitted light at a luminance of 1300 cd / m ^{2 at} 6V.

[0073]

By using the novel polymer of the present invention, it is possible to form a carrier transport layer exhibiting high carrier transport ability and high heat resistance in organic thin film EL devices, electrophotographic photoreceptors and the like. it can.

[Brief description of drawings]

FIG. 1 is an infrared absorption spectrum diagram of a dicarbonyl compound of the present invention.

FIG. 2 is an ultraviolet-visible absorption spectrum diagram of the dicarbonyl compound of the present invention.

FIG. 3 is a ¹³ C-NMR spectrum diagram of the dicarbonyl compound of the present invention.

FIG. 4 is an infrared absorption spectrum diagram of the dicarbonyl compound of the present invention.

FIG. 5 is an ultraviolet-visible absorption spectrum diagram of the dicarbonyl compound of the present invention.

FIG. 6 is a ¹³ C-NMR spectrum diagram of the dicarbonyl compound of the present invention.

FIG. 7 is an infrared absorption spectrum diagram of the polymer of the present invention.

FIG. 8 is an ultraviolet-visible absorption spectrum diagram of the polymer of the present invention.

FIG. 9 is a fluorescence spectrum chart of the polymer of the present invention.

FIG. 10 is an infrared absorption spectrum diagram of the polymer of the present invention.

FIG. 11 is an ultraviolet-visible absorption spectrum diagram of the polymer of the present invention.

FIG. 12 is a fluorescence spectrum chart of the polymer of the present invention.

FIG. 13 is an infrared absorption spectrum diagram of the polymer of the present invention.

FIG. 14 is an ultraviolet-visible absorption spectrum diagram of the polymer of the present invention.

FIG. 15 is a fluorescence spectrum chart of the polymer of the present invention.

FIG. 16 is an infrared absorption spectrum diagram of the polymer of the present invention.

FIG. 17 is an ultraviolet-visible absorption spectrum diagram of the polymer of the present invention.

FIG. 18 is a fluorescence spectrum chart of the polymer of the present invention.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C09K 11/06 690 C09K 11/06 690 (56) References JP-A-2-154269 (JP, A) JP-A-55-94351 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 61/00-61/12 CA (STN) REGISTRY (STN)

Claims (5)

(57) [Claims] 1. Formula (A): (In the formula, m is a positive integer indicating the degree of polymerization, and G ¹ is absent or is an arylene group, an alkylene group, an alkylenedioxy group or a formula (1) to a formula (9). G ² is a halogen-substituted or unsubstituted alkyl group, G ³ is a hydrogen atom or an alkyl group, and G ⁴ is a group represented by formulas (10) to (25): [Chemical 4] Is a linking group selected from among. Here, G ⁵ is a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms. ) The polymer represented by. 2. Formula (B): The polymer according to claim 1, which is represented by the formula (n is 1 or 2). 3. The number average molecular weight measured by GPC is 20.
The polymer according to claim 1 or 2, which is from 0 to 1,000,000. 4. Formula (a): (In the formula, G ² is a halogen-substituted or unsubstituted alkyl group, G ³ is a hydrogen atom or an alkyl group, and G ⁴ is represented by the formulas ( 11 ) to (25). [Chemical 8] Is a linking group selected from among. Here, G ⁵ is a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms. ) The dicarbonyl compound represented by. 5. The formula (b): The dicarbonyl compound according to claim 4, which is represented by the formula (n is 2 ).