KR20000033562A - Subphthalocyanine compound, its preparation method and display element using the same - Google Patents

Abstract

PURPOSE: A subphthalocyanine compound, a disc shaped liquid crystal compound, which shows liquid crystal property at room temperature and luminescence property, its preparation method and display element using the compound as a liquid crystal layer forming material or a color development material is provided. CONSTITUTION: The subphthalocyanine compound has a structure of formula I, wherein Ris alkyl group having 1-30 number of carbon, aliphatic cyclic hydrocarbons having a 5-20 number of carbon, or aromatic hydrocarbons having 6-30 number of carbon; X means halogen atom; and B means either boron(B) or aluminum(Al). Since the compound has liquid crystal at room temperature and luminescence property, it can be advantageously used for a display element such as a liquid crystal display element, an organic electroluminescence and the like. The preparation method for the compound includes reacting 1,2-dihalogen 4,5-dicyanobenzene with a thiol compound in the presence of a base to obtain 1,2-dialkylthio-4,5-dicyanobenzene, and conducting ring condensation step.

Description

Subphthalocyanine Compound, Manufacturing Method thereof and Display Device Using the Same

The present invention relates to a subphthalocyanine compound, a method for producing the same, and a display device employing the same, and more particularly, a subphthalocyanine compound having both liquid crystal properties and luminescent properties, a method for producing the compound, and the phthalocyanine A display element employing a compound as a liquid crystal layer forming material or a coloring material.

Liquid crystal display (LCD) is lighter and smaller in size compared to image display device using cathode ray tube (CRT), which is easy to carry, has low power consumption, and does not emit harmful electromagnetic waves. It has advantages Therefore, the liquid crystal display device is widely used from the small display unit of the electronic calculator to the large display unit of the notebook computer.

Among the liquid crystal display device methods, the STN (Super Twist Nematic) passive matrix method mainly uses a liquid crystal material and an external driving IC to perform a display function. Therefore, it is easy to manufacture and the manufacturing cost is low, so it has taken the mainstream of the liquid crystal display device.

Subsequently, the liquid crystal display device uses an AMTN (Active Matrix Twisted Nematic) method in which switching elements such as transistors and diodes are combined with liquid crystal materials. According to the AMTN method, a high quality image can be obtained, but there is a problem that the manufacturing method is complicated and the manufacturing cost is increased.

On the other hand, as the information display amount gradually increases, the demand for an image display device having high definition and excellent image quality is further increased. In response to this demand, ferroelectric display devices using ferroelectric liquid crysatl (FLC) have been developed.

The ferroelectric liquid crystal display device is driven in a passive matrix manner, and the response speed is about 100 times faster than that of the nematic liquid crystal. It also has a wide viewing angle and excellent optical memory characteristics. With the development of ferroelectric liquid crystal display devices, new technologies such as mass production technology of polysilicon thin film transistor (TFT) LCD using low temperature process, ultra-wide viewing angle technology of up, down, left and right 140 and reflective color LCD technology are being developed one after another. have.

On the other hand, the liquid crystal compound has a rod shape, a disc shape, and the like. Examples of the liquid crystal compound having a disc shape include disc-shaped ring compounds such as triphenylene, porphyrin, phthalocyanine, and the like. These ring compounds are stacked in a columnar form, as if coins are stacked in a shape to form a coin column, and the alkyl chains connected around the disk serve as a medium between the cylinders. Since the rigid disk-shaped aromatic substituents forming the cylinder are closely adjacent to each other in the column such as 3.5 to 4 Å, the overlap of the orbits can occur to a considerable extent, so that the cylindrical liquid crystal compound has a one-dimensional conductivity and molecular wire through proper doping process. wire).

In addition, the disc-shaped liquid crystal compound also forms a charge carrier through a photochemical method. Therefore, the photoconductivity of a Xerox copier and an organic light emitting layer active layer can also be usefully used as a new material.

The technical problem to be achieved by the present invention is to provide a sub-phthalocyanine compound and a manufacturing method thereof, which is a disc-shaped liquid crystal compound exhibiting liquid crystal properties at room temperature and at the same time exhibits luminescence properties.

Another object of the present invention is to provide a display device employing the subphthalocyanine compound as a liquid crystal layer forming material or a coloring material.

1a-b are diagrams showing the results of analysis using a differential scanning calorimeter (DSC) of subphthalocyanine prepared according to Synthesis Example 4,

2 is a diagram showing the results of X-ray diffraction analysis of subphthalocyanine prepared according to Synthesis Example 6.

In order to achieve the first object, the present invention provides a subphthalocyanine compound represented by the formula (1).

<Formula 1>

Wherein R is an alkyl group having 1 to 30 carbon atoms, an aliphatic ring hydrocarbon group having 5 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, X is a halogen atom, B is boron (B) or aluminum (Al) Indicates.

Preferably, R is an alkyl group having 8 to 18 carbon atoms, X is Cl and B is boron.

The second object of the present invention is to react 1,2-dihalogen 4,5-dicyanobenzene (A) and thiol compound (B) in the presence of a base to produce 1,2-dialkylthio-4,5-dicyanobenzene ( C) obtaining; And

It is made by the method for producing a subphthalocyanine represented by the formula (1) comprising the step of ring condensing the 1,2-dialkylthio-4,5-dicyanobenzene (C).

Wherein Q and X are halogen atoms, R is an alkyl group of 1 to 30 carbon atoms, an aliphatic ring hydrocarbon group of 5 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 30 carbon atoms, X is a halogen atom, and B is boron (B) or aluminum (Al) is shown.

Preferably, the said 1,2-alkylthio-4,5-dish ring condensation step of dicyano benzene (C) is the 1,2-di-alkylthio-4,5-dicyano benzene (C) BX ₃ (X is a halogen atom, and Cl, Br, I, etc. are possible).

A third object of the present invention is achieved by a display element, wherein the subphthalocyanine represented by the general formula (1) is employed as a liquid crystal material or a coloring material.

<Formula 1>

Wherein R is an alkyl group of 1 to 30 carbon atoms, an aliphatic ring hydrocarbon group of 5 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 30 carbon atoms, X is a halogen atom, B is boron (B) or aluminum ( Al).

The display device is not particularly limited, but is preferably a liquid crystal display device or an organic electro-luminescence device (EL).

The subphthalocyanine compound of formula 1 according to the present invention is a bidirectional liquid crystal which reversibly causes a phase change upon heating and cooling. Thus, the fact that the subphthalocyanine compound of Formula 1 has liquid crystal properties can be confirmed through thermal analysis using a differential scanning calorimeter and a thermal analyzer, polarization microscope and X-ray diffraction analysis.

Hereinafter, a method of preparing the subphthalocyanine compound of Chemical Formula 1 will be described with reference to Scheme 1.

First, the thiol compound (B) is dissolved in the first organic solvent, and then 1,2-dihalogen 4,5-dicyanobenzene (A) is added thereto and stirred for a predetermined time. Subsequently, a base is added to the reaction mixture for reaction. In this case, the organic solvent and the base are not particularly limited. Specific examples of the organic solvent include dimethyl sulfoxide and the like, and specific examples of the base include potassium carbonate and the like.

Upon completion of the reaction, a work-up process affords 1,2-dialkylthio-4,5-dicyanobenzene (C).

Thereafter, the 1,2-dialkylthio-4,5-dicyanobenzene (C) is dissolved in a second organic solvent, and then BX ₃ , particularly BCl ₃ or AlX _3, is added to carry out a ring condensation reaction. Thus, the subphthalocyanine compound of the formula (1) is prepared. The second solvent is not particularly limited, but 1-chloronaphthalene or the like is used.

Wherein Q and X are halogen atoms, R is an alkyl group of 1 to 30 carbon atoms, an aliphatic ring hydrocarbon group of 5 to 20 carbon atoms or an aromatic hydrocarbon group of 6 to 30 carbon atoms, and B is boron (B) or aluminum ( Al).

The subphthalocyanine compound prepared according to the above method can be used as a material for forming a liquid crystal layer of a display device, particularly a liquid crystal display device, or a material for forming a light emitting layer of an organic electroluminescent device. This will be described in detail below.

First, the liquid crystal display device generally has the following structure.

That is, transparent electrode layers are formed on upper and lower substrates spaced apart from each other by a predetermined interval, and an alignment layer for alignment of liquid crystals is formed on the transparent electrode layers. A liquid crystal layer is formed between the alignment films on the upper and lower substrates. In this case, the subphthalocyanine compound represented by Chemical Formula 1 may be used as the liquid crystal layer forming material.

On the other hand, an organic electroluminescent device typically has a structure in which an anode, a light emitting layer and a cathode are sequentially formed on the substrate. In this case, if the hole transport layer is further formed between the anode and the light emitting layer or the electron transport layer is further formed between the light emitting layer and the cathode, the luminous efficiency and luminance of the organic EL device can be improved.

The hole transporting layer, the light emitting layer, and the electron transporting layer are all organic thin films made of organic compounds, and among them, a subphthalocyanine compound represented by Chemical Formula 1 according to the present invention may be used as a light emitting layer forming material. Here, only the subphthalocyanine compound of Formula 1 may be used when forming the light emitting layer, but a composition mixed with a matrix polymer such as polyvinylcarbazole and the like at a predetermined mixing ratio may be used. In this way, when the matrix polymer is added to the light emitting compound to form the light emitting layer, the intermolecular (chain-to-chain) interaction of the excitons is reduced by the dilution effect, thereby increasing the quantum efficiency and the organic electrons by the energy transfer. The effect of increasing the brightness of the light emitting device can be obtained.

Hereinafter, the present invention will be described in detail with reference to the following Synthesis Examples and Examples, but the present invention is not limited to the following Examples.

Synthesis Example 1. Preparation of 1,2-didodecylthio-4,5-dicyanobenzene

Under argon gas atmosphere, 7 ml of dodecane thiol was dissolved in 40 ml of dimethyl sulfoxide, and then 2.85 g of 4,5-dicyanobenzene was added thereto and stirred for 20 minutes.

7.27 g of potassium carbonate was added little by little over 1 hour to the reaction mixture, followed by stirring at 40 ° C. for 12 hours.

When the reaction was completed, 100 ml of water was added to the reaction mixture, which was then extracted with chloroform. The combined chloroform layers were washed with an aqueous sodium carbonate solution and then dried over anhydrous sodium sulfate (Na ₂ SO ₄ ). The resultant was then filtered and chloroform was removed from the filtrate. Thereafter, the mixture was recrystallized from ethanol to obtain 6.23 g of 1,2-didodecylthio-4,5-dicyanobenzene (yield: 81%).

¹ H NMR (CDCl ₃ , 300 MHz): δ 0.87 (t, 6H), 1.48 (m, 28H), 1.76 (m, 4H), 3.01 (t, 4H), 7.38 (s, 1H).

¹³ C NMR (CDCl ₃ , 300 MHz): δ 14.51, 23.07, 28.45, 29.29, 29.49, 29.68, 29.82, 29.90, 32.27, 33.12, 111.43, 116.09, 128.52, 144.63

Synthesis Example 2. Chloro [2,3,9,10,16,17-hexakis (dodecylthio) -7,12,14,19-diimino-21,5-nitrilo-5H-tribenzo [chm ] [1,6,11] Triazacyclopentadecinenate- (2-)-N ²² , N ²³ , N ²⁴ ]-(T-4) -Boron Preparation

Under argon gas atmosphere, 1,2-didodecyl-4,5-dicyano-thio dissolved in benzene 2.89g of 1-chloronaphthalene 4㎖ Next, here BCl ₃ solution (1M solution in n-heptane) adding 1.0㎖ And stirred at 100 ℃ for 4 hours.

Upon completion of the reaction, the reaction mixture was cooled to room temperature. Then ethanol was added to the reaction mixture to form a precipitate. The precipitate obtained was filtered and then purified by silica gel column chromatography (developing solvent: dichloromethane) to give chloro [2,3,9,10,16,17-hexakis (dodecylthio) -7,12,14, 19-Diimino-21,5-nitrilo-5H-tribenzo [chm] [1,6,11] triazacyclopentadedecyneto- (2-)-N ²² , N ²³ , N ²⁴ ]-( T-4) 0.18 g was obtained (yield: 11%).

¹ H NMR (CDCl ₃ , 300 MHz): δ 0.88 (t, 18H), 1.59 (m, 84H), 1.89 (m, 12H), 3.31 (m, 12H), 8.51 (s, 6H).

¹³ C NMR (CDCl ₃ , 300 MHz): δ 14.52, 23.09, 28.86, 29.56, 29.72, 29.74, 29.96, 30.01, 32.31, 34.08, 119.91, 128.69, 141.23, 149.53

IR (KBr): ν 2955, 2924, 2853, 2360, 2342, 1597, 1462, 1419, 1368, 1080, 979

UV (CHCl ₃ ): λ _max (lg ε) 602 (5.00), 306 (4.85), 415 (4.53), 389 (4.52)

Fluorescence spectrometer (excitation wavelength: 360 nm, CHCl ₃ ) λ _max 613, 504 nm

Mass spectrometer: m / e 1463.8

Synthesis Example 3. Preparation of 1,2-dihexadecylthio-4,5-dicyanobenzene

The same method as in Synthesis Example 1, except that 5 ml of hexadecyl thiol and 1.59 g of 1,2-dichloro-4,5-dicyanobenzene were used instead of 4 ml of dodecane thiol and 1.88 g of 4,5-dicyanobenzene. It carried out according to the above, to obtain 4.74 g of 1,2-dihexadecylthio-4,5-dicyanobenzene (yield: 92%).

¹ H NMR (CDCl ₃ , 300 MHz): δ 0.87 (t, 6H), 1.48 (m, 52H), 1.77 (m, 4H), 3.01 (t, 4H), 7.38 (s, 1H).

¹³ C NMR (CDCl ₃ , 300 MHz): δ 14.53, 23.10, 28.46, 29.50, 29.77, 29.84, 29.96, 30.04, 30.07, 30.10, 32.33, 33.12, 111.43, 116.08, 128.45, 128.51, 144.63

Synthesis Example 4. Chloro [2,3,9,10,16,17-hexakis (hexadecylthio) -7,12,14,19-diimino-21,5-nitrilo-5H-tribenzo [chm ] [1,6,11] triazocyclopentadecineto- (2-)-N ²² , N ²³ , N ²⁴ ]-(T-4) -preparation of boron

The same method as in Synthesis Example 2 was used except that 2.89 g of 1,2-dihexadecylthio-4,5-dicyanobenzene was used instead of 2.89 g of 1,2-didodecylthio-4,5-dicyanobenzene. Chloro [2,3,9,10,16,17-hexakis (hexadecylthio) -7,12,14,19-diimino-21,5-nitrilo-5H-tribenzo [chm] 0.68 g of [1,6,11] triacyclopentadedecineito- (2-)-N ²² , N ²³ , N ²⁴ ]-(T-4) -boron was obtained (yield: 23%).

¹ H NMR (CDCl ₃ , 300 MHz): δ 0.88 (t, 18H), 1.66 (m, 156H), 1.90 (m, 12H), 3.31 (t, 4H), 8.52 (s, 6H).

¹³ C NMR (CDCl ₃ , 300 MHz): δ 14.54, 23.11, 28.87, 29.58, 29.75, 29.79, 29.99, 30.09, 30.13, 32.34, 34.08, 119.90, 128.70, 141.25, 149.53

IR (KBr): ν 2955, 2923, 1732, 1598, 1463, 1369, 1240, 1185, 1081, 979

UV (CHCl ₃ ): λ _max (lg ε) 602 (5.19), 304 (5.08), 559 (4.92), 421 (4.86)

Fluorescence spectrometer (excitation wavelength: 360 nm, CHCl ₃ ) λ _max 612,506 nm

Mass spectrometer: m / e 1969.65 (Calcd for C ₁₂₀ H ₂₄₀ BClN ₆ S ₆ : 1969.65):

Synthesis Example 5. Preparation of 1,2-dioctadecylthio-4,5-dicyanobenzene

The same method as in Synthesis Example 1, except that 7.03 g of octadecyl thiol and 1.93 g of 1,2-dichloro-4,5-dicyanobenzene were used instead of 4 ml of dodecane thiol and 1.88 g of 4,5-dicyanobenzene. According to the above procedure, 6.51 g of 1,2-dioctadecylthio-4,5-dicyanobenzene was obtained (yield: 95%).

¹ H NMR (CDCl ₃ , 300 MHz): δ 0.87 (t, 6H), 1.48 (m, 60H), 1.77 (m, 4H), 3.01 (t, 4H), 7.38 (s, 1H).

¹³ C NMR (CDCl ₃ , 300 MHz): δ 14.53, 23.10, 28.46, 28.95, 29.31, 29.51, 29.66, 29.78, 29.84, 29.97, 30.05, 30.08, 30.12, 32.34, 33.13, 111.43, 116.08, 128.51, 144.63

Synthesis Example 6. Chloro [2,3,9,10,16,17-hexakis (octadecylthio) -7,12,14,19-diimino-21,5-nitrilo-5H-tribenzo [chm ] [1,6,11] Triazacyclopentadecinenate- (2-)-N ²² , N ²³ , N ²⁴ ]-(T-4) -Boron Preparation

Didodecyl 1,2-thio-4,5-dicyano benzene and 2.89g BCl ₃ solution 1.5㎖ instead of 1,2-di-octadecyl-thio-4,5-dicyano benzene with 1.46g and BCl ₃ solution 0.7㎖ Except that, chloro [2,3,9,10,16,17-hexakis (octadecylthio) -7,12,14,19-diimino-21, 5-nitrilo-5H-tribenzo [chm] [1,6,11] triacyclopentadedecineito- (2-)-N ²² , N ²³ , N ²⁴ ]-(T-4) -boron 0.11 g was obtained (yield: 7%).

¹ H NMR (CDCl ₃ , 300 MHz): δ 0.87 (t, 18H), 1.22 (m, 180H), 1.90 (m, 12H), 3.30 (m, 12H), 8.60 (s, 6H).

¹³ C NMR (CDCl ₃ , 300 MHz): δ 14.50, 23.09, 28.89, 29.56, 29.76, 29.98, 30.11, 32.33, 34.12, 120.03, 128.77, 141.33, 149.55.

IR (KBr): ν 2955, 2923, 1732, 1598, 1463, 1369, 1240, 1185, 1081, 979

UV (CHCl ₃ ): λ _max (lg ε) 602 (4.70), 307 (4.56), 415 (4.24)

Fluorescence spectrometer (excitation wavelength: 360 nm, CHCl ₃ ) λ _max 610, 505 nm

Mass spectrometer: m / e 2138

DSC (Perkin elmer Model: Pyris), Polarization Microscope (Zeiss Company, Model: JENALAB-pol) Thermogravimetric Analyzer (Perkin elmer Model: TGA 7) and X-ray Diffractometer (Pohang Radiation Accelerator, Model: Rigaku Denki generator ) Was used to investigate the liquid crystal properties of the subphthalocyanine compounds prepared according to Synthesis Examples 2, 4 and 6. When DSC is used here, the phase transition temperature of a subphthalocyanine compound and the enthalpy change according to a phase transition are measured. The polarizing microscope examines the characteristic optical structure of the liquid crystal, the thermogravimetric analyzer examines the thermal stability, and the X-ray diffraction analysis using the X-ray diffractometer examines the three-dimensional structure of the subphthalocyanine compound.

First, the analysis results through DSC are as follows.

In the subphthalocyanine compound prepared according to Synthesis Example 2, no transition between crystal and liquid crystal was observed during heating and cooling. The transition between the liquid crystal and the isotropic liquid was observed at 86 ° C. on heating and at 70 ° C. on cooling, respectively.

Referring to FIGS. 1A-B, the subphthalocyanine compound prepared according to Synthesis Example 4 transitions from crystal to liquid crystal at 27 ° C. and isotropic liquid at 75 ° C. when heated. And upon cooling, it transitions from an isotropic liquid to liquid crystal at 68 ° C. and from crystal to liquid crystal at 21 ° C.

Then, the subphthalocyanine compound prepared according to Synthesis Example 6 is transferred from crystal to liquid crystal at 43 ° C. and isotropic liquid at 78 ° C. upon heating. And upon cooling, it is transferred from the isotropic liquid to the liquid crystal at 68 ° C, from the liquid crystal to the crystal at 36 ° C, and from crystal to another crystal at 33 ° C.

Table 1 below shows optical and thermal data obtained using DSC of the subphthalocyanine compounds according to Synthesis Examples 2, 4, and 6.

division heating Cooling Synthesis Example 2 D 86.1 ^a (0.68 ^b ) I I 70.5 ^a (1.31 ^b ) D Synthesis Example 4 K 27.2 ^a (13.42 ^b ) D 75.3 ^a (0.35 ^b ) I I 67.6 ^a (0.61 ^b ) D 20.9 ^a (10.36 ^b ) K Synthesis Example 6 K 43.4 ^a (21.80 ^b ) D 70 ^c I I 65 ^c D 36.6 ^a (0.53 ^b ) K 33.6 ^a (9.56 ^b ) K ¹

a: The transition temperature (degreeC) measured using DSC, and the measurement rate is 10 degrees C / min.

b: Enthalpy (J / g) measured using DSC, measuring rate is 10 ° C / min.

c: transition temperature (degreeC) observed with the polarization microscope.

K, K 'is a crystalline phase, D is a cylindrical phase, I is an isotropic liquid phase, respectively.

Observing the optical structure of the subphthalocyanine compounds of Synthesis Examples 2, 4 and 6 using a polarization microscope, it was confirmed that the subphthalocyanine compounds are liquid crystals having a typical disc shape as a semiconical focusing structure.

In addition, when the thermal stability of the subphthalocyanine compounds of Synthesis Examples 2, 4 and 6 was examined using a thermogravimetric analyzer, it was found to be stable up to 250 ° C.

2 shows the results of X-ray diffraction analysis of the subphthalocyanine compound according to Synthesis Example 6.

Referring to FIG. 2, three peaks were observed near the incineration of the subphthalincyanine compound in which the octadecyl group was substituted, and the long distance ratios corresponding to (100), (110), and (200) Breg diffraction, respectively The lattice constant of 1: √3: 2 was 33.02Å, and it was found to be a regular hexagonal arrangement of the cylinders. The peak of the disordered liquid nature of the alkyl chain period appeared at a wide angle around 2θ = 20 ° C.

Meanwhile, X-ray diffraction analysis data of the subphthalocyanine compounds according to Synthesis Examples 2, 4, and 6 are shown in Table 2 below.

division Mesophase Lattice constant Peak Miller indexes Synthesis Example 2 D at 60 ℃ 29.74 25.7414.92 (100) (110) Synthesis Example 4 D at room temperature 33.02 28.616.514.34.43 (100) (110) (200) halo Synthesis Example 6 D at 50 ℃ 33.22 30.5017.65 (100) (110) K at room temperature 37.40 32.39 (100)

In Table 2, K means a crystal phase and D means a cylinder shape, respectively.

On the other hand, the emission spectra of the subphthalincyanine compound of Synthesis Example 2 were at 613 nm and 513 nm, and the emission spectra of the subphthalincyanine compound of Synthesis Example 4 were at 612 nm and 506 nm, and in Synthesis Example 6 The emission spectrum of the subphthalin cyanine compound showed absorption wavelength at 610 nm and 505 nm, respectively. From these results, the subphthalincyanine compounds according to Synthesis Examples 2, 4, and 6 may implement a red-based color.

The following examples relate to a liquid crystal display device and an organic electroluminescent device using the subphthalocyanine compounds prepared according to Synthesis Examples 2, 4 and 6.

Example 1 Fabrication of Liquid Crystal Display Device

After the thin film transistor was formed on the glass substrate, spacers were injected therein.

An ITO electrode layer, a black matrix, and a color filter are formed on another glass substrate, and a sealant is applied thereon. At this time, a sealant was used as a UV curable or thermosetting material.

After aligning and arranging fine pixels on the glass substrate on which the thin film transistor was formed and the glass substrate on which the electrode layer, the black matrix and the color filter were formed, the two substrates were bonded to each other to prepare a blank cell having a predetermined thickness. . After injecting the subphthalocyanine according to Synthesis Example 2 into the empty cell thus prepared, the liquid crystal display device was completed by irradiating ultraviolet rays.

Example 2-3. Manufacture of liquid crystal display device

A liquid crystal display device was completed in the same manner as in Example 1 except that the subphthalocyanine compounds of Synthesis Examples 4 and 6 were used instead of the subphthalocyanines of Synthesis Example 2.

Example 4 Fabrication of Organic Electroluminescent Device

After the ITO electrode was formed on the glass substrate, the light emitting layer was formed to a thickness of 500 kV using the phthalocyanine compound of Synthesis Example 2 and polyvinylcarbazole.

Thereafter, Al: Li was vacuum-deposited on the emission layer to form an aluminum lithium electrode having a thickness of 1200 Å, thereby manufacturing an organic EL device.

Example 5-6. Fabrication of Organic Electroluminescent Device

An organic electroluminescent device was manufactured according to the same method as Example 4 except that the subphthalocyanine compounds of Synthesis Examples 4 and 6 were used instead of the subphthalocyanines of Synthesis Example 2.

The performance of the liquid crystal display device manufactured according to Example 1-3 was evaluated.

As a result of evaluation, the response speed, driving voltage, viewing angle, and optical memory characteristics of the liquid crystal display device according to Example 1-3 were excellent.

On the other hand, the driving voltage of the organic electroluminescent device manufactured according to Example 4-6 was almost the same or lower level than the conventional organic electroluminescent device, it was possible to implement a red-based color with good luminous efficiency.

The subphthalocyanine compound of Formula 1 according to the present invention has liquid crystal properties at room temperature and has luminescent properties. Therefore, such a subphthalocyanine compound is very usefully applicable to display devices such as liquid crystal display devices, organic electroluminescent devices, and the like.

Claims (8)

Subphthalocyanine compounds represented by Formula 1: <Formula 1> In the above formula, R is an alkyl group having 1 to 30 carbon atoms, an aliphatic ring hydrocarbon group having 5 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, X is a halogen atom, B represents boron (B) or aluminum (Al). The subphthalocyanine compound of claim 1, wherein R is an alkyl group having 8 to 18 carbon atoms, X is chlorine, and B is boron. Reacting 1,2-dihalogen 4,5-dicyanobenzene (A) and thiol compound (B) in the presence of a base to obtain 1,2-dialkylthio-4,5-dicyanobenzene (C); And Method for producing a subphthalocyanine represented by the formula (1) comprising the step of ring condensing the 1,2-dialkylthio-4,5-dicyanobenzene (C): Wherein X and Q are halogen atoms, R is an alkyl group having 1 to 30 carbon atoms, an aliphatic ring hydrocarbon group having 5 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, B represents boron (B) or aluminum (Al). 4. The ring condensation step according to claim 3, wherein the ring condensation step is performed by reacting the 1,2-dialkylthio-4,5-dicyanobenzene (C) with BX ₃ (X is a halogen atom). Method for producing a subphthalocyanine compound represented by the formula (1). The method of claim 3, wherein R is an alkyl group having 8 to 18 carbon atoms, X is chlorine, and B is boron (B). The method for producing a subphthalocyanine compound according to claim 3, wherein the base is potassium carbonate. A display element comprising subphthalocyanine represented by the formula (1) as a liquid crystal material or a coloring material. <Formula 1> In the above formula, R is an alkyl group having 1 to 30 carbon atoms, an aliphatic ring hydrocarbon group having 5 to 20 carbon atoms or an aromatic hydrocarbon group having 6 to 30 carbon atoms, X is a halogen atom, B represents boron (B) or aluminum (Al). The display device according to claim 7, wherein the display device is a liquid crystal display device or an organic electroluminescent device.