JP2010222315A - Pyrrolopyridine compound and use thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new pyrrolopyridine compound and its use. <P>SOLUTION: There are provided the pyrrolopyridine compound expressed by formula 1, and a luminescent agent for organic electroluminescent devices containing the pyrrolopyridine compound expressed by formula 1. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel pyrrolopyridine compound and its use.

  In recent years, the use of organic dye compounds in the fields of information display and light absorbers has attracted attention.

  Applications of the organic dye compound in the field of information display include applications to organic electroluminescent elements (hereinafter abbreviated as “organic EL elements”). Organic EL elements are attracting attention as next-generation display elements, and currently, cathode ray tubes are mainly used in relatively large information display devices such as computer terminals and television receivers. However, a cathode ray tube is large in both volume and weight and has a high operating voltage, so it is not suitable for a device that places importance on portability. Small devices are required to be thinner and lighter, have a low operating voltage and low power consumption. At present, liquid crystal elements are frequently used in various fields because they are bought with low operating voltage and relatively low power consumption. However, since the information display device using a liquid crystal element changes in contrast depending on the viewing angle, a clear display cannot be obtained unless it is read within a certain angle range, and a backlight is usually required. There is a problem that it is not so small. An organic EL element has emerged as a display element that solves these problems.

  An organic EL element is usually formed by interposing a light-emitting layer containing a light-emitting compound between an anode and a cathode, and applying a DC voltage between the anode and the cathode to generate holes and electrons in the light-emitting layer. A light emitting element that emits light such as fluorescence or phosphorescence that is emitted when the excited state of the luminescent compound is created by injecting each other and bonding them together to return the ground state to the excited state. The organic EL device is capable of appropriately changing the color tone of light emission by using an appropriate organic compound as a host compound and changing a guest compound (dopant) combined with the host compound in forming a light emitting layer. There is. Further, depending on the combination of the host compound and the guest compound, there is a possibility that the luminance and lifetime of light emission can be significantly improved. In the first place, since an organic EL element emits light by itself, it has an advantage of reducing power consumption, and is said to be an excellent light emitting element in principle (see, for example, Non-Patent Documents 1 and 2).

  Among the luminescent compounds that have been proposed so far, for example, those having a coumarin skeleton have the advantage of being highly safe and easy to handle even in organic EL devices since coumarin is a naturally occurring substance. . However, many coumarin derivatives, for example, can bring about the expected electroluminescence only when combined with a host compound such as a quinolinol metal complex, and the light emitting layer is formed by using it alone or in combination with a guest compound. As a result, there is a problem that it is difficult to produce an organic EL element that has no practical problem (see, for example, Patent Documents 4 to 10). On the other hand, Patent Document 1 proposes an organic EL element using an organic light-emitting substance that can emit light with high luminance even at a low driving voltage, but the characteristics required for the organic EL element are still insufficient. Met.

  On the other hand, as an application of the organic dye compound in the field of the light absorber, a chemical means for shielding light by absorbing light with a light absorbent as a light shielding means in various articles has attracted attention. As a chemical means using an organic dye compound as a light absorber, for example, in the field of clothing, as shown in Patent Documents 2 and 3, an organic dye compound having ultraviolet absorbing ability such as a benzotriazole derivative or a benzophenone derivative is used as a fiber. There are known methods for imparting ultraviolet absorption capability to clothing by kneading into fabric and methods for imparting infrared absorption capability to clothing by dyeing fibers using an organic dye compound having infrared absorption capability such as an aminium derivative. It was done. However, when fibers are dyed using the organic dye compounds described in Patent Documents 2 and 3, it is difficult to adjust the desired color, tone, and texture depending on the clothing.

JP-A-3-37293 JP-A-7-189018 JP-A-9-255890 JP 2001-76875 A JP 2001-76876 A JP 2001-329257 A JP 2002-226484 A JP 2003-249371 A JP 2003-249372 A JP 2004-6222 A

Edited by Hiroyuki Sparrow, "Organic Photonics", Agne Jofusha Co., Ltd., published on March 20, 1995, 1st edition, pages 136-160 Yoshinori Saito, “Journal of the Institute of Electronics, Information and Communication Engineers”, Vol. 84, No. 11, pp. 767 to 774 (2001)

  In view of such a situation, an object of the present invention is to provide an organic compound that sufficiently exhibits characteristics required for an organic EL element and a light absorber, and an application thereof.

  In view of such a situation, the present inventors diligently researched and searched. As a result, when the pyrrolopyridine compound represented by the general formula 1 is applied to an organic EL device as a light emitting layer material such as a host compound and a guest compound, It emits visible light with brightness, and the light emission is found to be stable for a long time at room temperature. The pyrrolopyridine compound represented by the general formula 1 efficiently emits light from the ultraviolet region to the visible region. It has been found that it is extremely useful as a light absorber capable of shielding light.

General formula 1:

(In general formula 1, X is a methylene group, an ethylene group, a propylene group, a phenylene group or biphenylene group, R ₁ is the .R ₂ to R ₅ represents a hydrogen atom or a substituent, each independently, a hydrogen atom Alternatively, it represents a substituent, and the bonding position of these substituents may be any of the ortho, meta, and para positions in each phenyl group to which they are bonded, and the ortho, meta, and para positions in each phenyl group. The substituents may be the same or different, and the adjacent groups are bonded to each other, including the carbon atom to which they are bonded, A cyclic structure may be formed, n represents 1 or 2. However, when n is 1, X represents a phenylene group, and when n is 2, a pyrrolopyridine compound represented by the general formula 1 Is 2 through X Embody, _{R 1} is absent.)

  Moreover, this invention solves the said subject by providing the light-emitting agent for organic EL elements using the pyrrolopyridine compound represented by General formula 1.

General formula 1:

(In General Formula 1, X represents a methylene group, ethylene group, propylene group, phenylene group or biphenylene group, R ₁ represents a hydrogen atom or a substituent. R _{2 to} R ₅ each independently represents a hydrogen atom. Alternatively, it represents a substituent, and the bonding position of these substituents may be any of the ortho, meta, and para positions in each phenyl group to which they are bonded, and the ortho, meta, and para positions in each phenyl group. The substituents may be the same or different, and the adjacent groups are bonded to each other, including the carbon atom to which they are bonded, A cyclic structure may be formed, n represents 1 or 2. However, when n is 1, X represents a phenylene group, and when n is 2, a pyrrolopyridine compound represented by the general formula 1 Is 2 through X Embody, _{R 1} is absent.)

  Furthermore, this invention solves the said subject by providing the organic EL element using the pyrrolopyridine compound represented by General formula 1.

General formula 1:

(In General Formula 1, X represents a methylene group, ethylene group, propylene group, phenylene group or biphenylene group, R ₁ represents a hydrogen atom or a substituent. R _{2 to} R ₅ each independently represents a hydrogen atom. Alternatively, it represents a substituent, and the bonding position of these substituents may be any of the ortho, meta, and para positions in each phenyl group to which they are bonded, and the ortho, meta, and para positions in each phenyl group. The substituents may be the same or different, and the adjacent groups are bonded to each other, including the carbon atom to which they are bonded, A cyclic structure may be formed, n represents 1 or 2. However, when n is 1, X represents a phenylene group, and when n is 2, a pyrrolopyridine compound represented by the general formula 1 Is 2 through X Embody, _{R 1} is absent.)

  Moreover, this invention is an organic electroluminescent element provided with an organic electroluminescent element provided with an anode, a positive hole transport layer, a light emitting layer, an electron carrying layer, and a cathode, Comprising: The said light emitting layer is represented by General formula 1. The object is achieved by providing an organic electroluminescent device in which a pyrrolopyridine compound is blended as a dopant and a hole transport layer material and an electron transport layer material are both blended as a host.

  In addition, this invention solves the said subject by providing the display panel using such an organic EL element.

  Furthermore, this invention solves the said subject by providing the information display apparatus using such an organic EL element.

In addition, this invention solves the said subject by providing the light absorber containing the pyrrolopyridine compound represented by General formula 1.

(In general formula 1, X is a methylene group, an ethylene group, a propylene group, a phenylene group or biphenylene group, R ₁ is the .R ₂ to R ₅ represents a hydrogen atom or a substituent, each independently, a hydrogen atom Alternatively, it represents a substituent, and the bonding position of these substituents may be any of the ortho, meta, and para positions in each phenyl group to which they are bonded, and the ortho, meta, and para positions in each phenyl group. The substituents may be the same or different, and the adjacent groups are bonded to each other, including the carbon atom to which they are bonded, A cyclic structure may be formed, n represents 1 or 2. However, when n is 1, X represents a phenylene group, and when n is 2, a pyrrolopyridine compound represented by the general formula 1 Is 2 through X Embody, _{R 1} is absent.)

  This invention is based on the creation of a novel pyrrolopyridine compound and the discovery of its industrially useful properties. The pyrrolopyridine compound used in the present invention has an absorption maximum near a wavelength of 230 to 500 nm, more specifically, near 250 to 450 nm, an emission maximum such as a fluorescence maximum near a wavelength of 450 to 550 nm, and when excited, It is a material with excellent thermal stability having a characteristic of emitting green-red light to red light, a melting point exceeding 250 ° C., and a decomposition point exceeding 400 ° C. Since the pyrrolopyridine compound of this invention has the above-mentioned excellent characteristics and can form a stable thin film, it is extremely useful, for example, as a light-emitting agent for organic EL devices. In addition, the pyrrolopyridine compound used in the present invention has an absorption maximum in the wavelength range of 230 to 500 nm, more specifically, in the vicinity of 250 to 450 nm, and has a large molecular extinction coefficient, so that the chromaticity of light emission by the organic EL element is adjusted. It is also useful as a material. Since the organic EL device obtained using the pyrrolopyridine compound of the present invention is excellent in luminous efficiency and durability, it can be used as a light emitter in general lighting, for example, by forming it in a panel shape, image information, character information, etc. It can be used very advantageously in a wide variety of information display devices that visually display the information.

  Further, as described above, the pyrrolopyridine compound of the present invention has an absorption maximum in the vicinity of a wavelength of 230 to 500 nm, more specifically, in the vicinity of 250 to 450 nm, and has a large molecular extinction coefficient at the absorption maximum. It is also extremely useful as a light absorber for absorbing and shielding light from the ultraviolet region to the visible region in ambient light such as.

It is the schematic of the organic EL element by this invention. 1 is a schematic view of a display panel according to the present invention. It is the schematic of the information display apparatus by this invention.

  As described above, the present invention relates to a pyrrolopyridine compound represented by the general formula 1 and its use.

General formula 1:

  In General Formula 1, X represents a methylene group, an ethylene group, a propylene group, a phenylene group, or a biphenylene group.

In General Formula 1, R _{1 to} R ₅ each independently represents a hydrogen atom or a substituent. Examples of the substituent in R _{1 to} R ₅ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isopropenyl group, a 1-propenyl group, a 1-propynyl group, a 2-propenyl group, a butyl group, an isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl, 1,3-butadienyl group, pentyl group, isopentyl group, neopentyl group, tert-pentyl group, 1-methylpentyl group, 2-methylpentyl group, 2-pentenyl Group, 2-pentene-4-ynyl group, hexyl group, isohexyl group, 5-methylhexyl group, heptyl group, octyl group, nonyl group, decyl group, dodecyl group and other aliphatic hydrocarbon groups, cyclopropyl group, cyclobutyl Group, cyclopentyl group, cyclopentenyl group, cyclopentadienyl group, cyclohexyl group, Hexenyl group, cyclohexadienyl group, cycloheptyl group, cyclooctyl group, cyclooctadienyl group and other alicyclic hydrocarbon groups, phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, xylyl group , Mesityl group, o-cumenyl group, m-cumenyl group, p-cumenyl group, biphenylyl group, naphthyl group, anthryl group, phenalenyl group, phenanthryl group, pyrenyl group and other aromatic hydrocarbon groups, hydroxyl group, methoxy group, ethoxy group Group, propoxy group, propyloxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, allyloxy group, aryloxy group, phenoxy group , Ether groups such as toluyloxy group and naphthyloxy group, Estoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, acetoxy group, benzoyloxy group and other ester groups, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group , Diisopropylamino group, butylamino group, dibutylamino group, isobutylamino group, diisobutylamino group, sec-butylamino group, tert-butylamino group, pentylamino group, dipentylamino group, hexylamino group, cyclohexylamino group, piperidino Group, phenylamino group, N, N-diphenylamino group, naphthylamino group, N, N-naphthylphenylamino group, N, N-dinaphthylamino group, amino group such as N-carbazolyl group, fluoro group, chloro A halogen group such as a group, a bromo group and an iodo group, a hydroxy group, a carboxy group, a cyano group, a nitro group, a benzyl group, and a substituent by a combination thereof.

In the general formula 1, when R _{2 to} R ₅ are substituents, the bonding position of these substituents may be any of ortho, meta, and para positions in each phenyl group to which they are bonded. In the case where substituents are bonded to two or more positions of ortho position, meta position and para position in each phenyl group, these substituent groups may be the same or different, and adjacent ones are bonded to each other. However, it may contain a carbon atom to which they are bonded to form a cyclic structure such as, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, piperidine ring, pyrrolidine ring, morpholine ring, or urolidine ring. In this case, some or all of R _{2 to} R ₅ apparently do not exist as independent substituents.

N represents 1 or 2. However, when n is 1, X represents a phenylene group, and when n is 2, the pyrrolopyridine compound represented by the general formula 1 dimerizes via X, and R ₁ does not exist. The compound in which the pyrrolopyridine compound represented by the general formula 1 is dimerized via X has a significantly higher fluorescence intensity than the monomer composed of one molecule of the pyrrolopyridine compound represented by the general formula 1. And has a characteristic of long-wavelength emission.

  Specific examples of the pyrrolopyridine compound according to the present invention include those represented by chemical formulas 1 to 25. Each of these has an absorption maximum near a wavelength of 230 to 500 nm, more specifically, around 250 to 450 nm. Furthermore, the pyrrolopyridine compound represented by Chemical Formulas 1 to 25 has a light emission maximum such as a fluorescence maximum near a wavelength of 450 to 550 nm, and emits green to red light when excited. Moreover, the pyrrolopyridine compound of the present invention has a melting point exceeding 250 ° C. and a decomposition point exceeding 400 ° C.

As is well known, the melting point and decomposition point of an organic compound are used as indicators of thermal stability, and the higher the melting point and decomposition point, the greater the thermal stability. However, the pyrrolopyridine compound of the present invention is extremely useful in the field of organic EL devices that require an organic compound having luminous ability and excellent thermal stability. Incidentally, the melting point and decomposition point of the pyrrolopyridine compound according to the present invention can be determined by, for example, general-purpose differential scanning calorimetry (hereinafter abbreviated as “DSC analysis”). In addition, any of the pyrrolopyridine compounds according to the present invention has one or a plurality of absorption maxima in the visible region, and the molecular extinction coefficient (ε) at the absorption maxima is relatively large as 3.0 × 10 ³ or more. It is extremely useful as a light absorber for absorbing and blocking light from the ultraviolet region to the visible region in ambient light such as artificial light.

Chemical formula 1:

Chemical formula 2:

Chemical formula 3:

Chemical formula 4:

Chemical formula 5:

Chemical formula 6:

Chemical formula 7:

Chemical formula 8:

Chemical formula 9:

Chemical formula 10:

Chemical formula 11:

Chemical formula 12:

Chemical formula 13:

Chemical formula 14:

Chemical formula 15:

Chemical formula 16:

Chemical formula 17:

Chemical formula 18:

Chemical formula 19:

Chemical formula 20:

Chemical formula 21:

Chemical formula 22:

Chemical formula 23:

Chemical formula 24:

Chemical formula 25:

Although the pyrrolopyridine compound of the present invention can be prepared by various methods,
For example, tetrabenzoylethane, p-toluidine, and p-toluenesulfonic acid represented by Chemical Formula 26 are each taken in an appropriate amount in the reaction vessel, or tetrabenzoylethane, phenylenediamine, and p-toluene represented by Chemical Formula 26 in the reaction vessel. Take an appropriate amount of each toluenesulfonic acid, dissolve it in a suitable solvent, add an acid catalyst such as tosylic acid, etc., and then react at ambient temperature or above ambient temperature while heating and stirring by heating under reflux. Then, after adding aminoacetonitrile, it can be obtained by appropriately dissolving in a solvent and reacting at ambient temperature or above ambient temperature while heating and stirring by heating under reflux or the like.

Chemical formula 26:

  Examples of the solvent include hydrocarbons such as pentane, hexane, cyclohexane, octane, benzene, toluene, xylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, trichloroethylene, tetrachloroethylene, chlorobenzene, Halogens such as bromobenzene and α-dichlorobenzene, methanol, ethanol, 2,2,2-trifluoroethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol, cyclo Hexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol, diethylene glycol, triethylene glycol Alcohols such as coal and glycerin and phenols, diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl-18-crown-6, methylcarb Ethers such as Thor, ethyl carbitol, ketones such as acetone, ethyl methyl ketone, cyclohexanone, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, propionic anhydride, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, Formamide, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, hexamethylphosphate triamide, phosphate Acids and acid derivatives such as limethyl, nitriles such as acetonitrile, propionitrile, succinonitrile, and benzonitrile, nitro compounds such as nitromethane and nitrobenzene, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, and water are necessary. Depending on the, these are used in combination.

  In the case of using a solvent, generally, when the amount of the solvent is increased, the efficiency of the reaction is lowered. On the other hand, when the amount is decreased, it becomes difficult to uniformly heat and stir or a side reaction is likely to occur. Therefore, it is desirable that the amount of the solvent is up to 100 times the weight of the raw material compound, usually 5 to 50 times. Although depending on the type of raw material compound and reaction conditions, the reaction is completed within 10 hours, usually 0.5 to 5 hours. The progress of the reaction can be monitored by a general method such as thin layer chromatography, gas chromatography, high performance liquid chromatography and the like. The pyrrolopyridine compound according to the present invention can be produced in a desired amount by this method or according to this method.

  Although the pyrrolopyridine compound thus obtained may be used as it is in the reaction mixture depending on the application, it is usually prior to use, for example, dissolution, separation, gradient, filtration, extraction, concentration, thin-layer chromatography. Purified by general methods for purifying similar compounds such as column chromatography, gas chromatography, high performance liquid chromatography, distillation, sublimation, crystallization, etc., these methods are applied in combination as necessary . Although depending on the type of pyrrolopyridine compound and the use of the organic EL device, the pyrrolopyridine compound applied to the organic EL device of the present invention is usually prior to use, for example, a method such as distillation, crystallization and / or sublimation. It is desirable to purify to a higher degree.

Among them, sublimation is particularly excellent because high-purity crystals can be easily obtained by one operation, and the loss of the pyrrolopyridine compound accompanying the operation is small, and the solvent is not taken into the crystals. ing. The sublimation method to be applied may be a normal pressure sublimation method or a reduced pressure sublimation method, but the latter reduced pressure sublimation method is usually applied. In order to sublimate the pyrrolopyridine compound of the present invention under reduced pressure, for example, an appropriate amount of the pyrrolopyridine compound is charged into a sublimation purification apparatus, and the apparatus is maintained at a reduced pressure lower than 10 ⁻² Torr, preferably 10 ⁻³ Torr or lower. The pyrrolopyridine compound is heated at a temperature as low as possible below the melting point so as not to decompose. When the purity of the pyrrolopyridine compound to be subjected to sublimation purification is relatively low, the sublimation rate is suppressed by adjusting the degree of vacuum or heating temperature so that impurities are not mixed, and when the pyrrolopyridine compound is difficult to sublimate. Promotes sublimation by passing a rare gas through the sublimation purification apparatus. The size of the crystals obtained by sublimation can be adjusted by adjusting the temperature of the condensation surface in the sublimation purification apparatus. When the condensation surface is kept at a temperature slightly lower than the heating temperature and gradually crystallized, Relatively large crystals are obtained.

  As described above, the pyrrolopyridine compound used in the present invention has an absorption maximum in the vicinity of a wavelength of 230 to 500 nm, more specifically, in the vicinity of 250 to 450 nm, and has an emission maximum such as a fluorescence maximum in the vicinity of a wavelength of 450 to 550 nm. When excited, it emits green to red light, has a melting point exceeding 250 ° C., and a decomposition point exceeding 400 ° C. Therefore, the pyrrolopyridine compound of the present invention can be used extremely advantageously as a light-emitting agent for organic EL devices that emits green to red light, alone or in combination with other light-emitting compounds. The organic EL element in the present invention means all electroluminescent elements using such a pyrrolopyridine compound, and in particular, recombines an anode for applying a positive voltage, a cathode for applying a negative voltage, holes and electrons. A light emitting layer for extracting light emission, and if necessary, a hole injecting / transporting layer for injecting and transporting holes from the anode, an electron injecting / transporting layer for injecting and transporting electrons from the cathode, and holes Single-layer and stacked organic EL devices that are provided with a hole blocking layer that suppresses movement from the light-emitting layer to the electron injection / transport layer are important applications.

  As is well known, the operation of an organic EL element is essentially a process in which electrons and holes are injected from an electrode, a process in which electrons and holes move in a solid, and an electron and holes are recombined. It consists of a process of generating a term exciton or a triplet exciton and a process of emitting the exciton, and these processes are not essentially different in either a single layer type or a stacked type organic EL element. However, in the single layer type organic EL element, the characteristics of the above four processes can be improved only by changing the molecular structure of the light emitting compound, whereas in the laminated type organic EL element, it is required in each process. Since functions can be shared among multiple materials and each material can be optimized independently, in general, it is easier to achieve the desired performance by configuring a stacked type than configuring a single layer type. .

  Therefore, the organic EL element of the present invention will be described by taking a stacked organic EL element as an example. FIG. 1 is a schematic view of the stacked organic EL element according to the present invention, in which 1 is a substrate, Usually, aluminosilicate glass, aluminoborosilicate glass, quartz glass, soda lime glass, barium silicate glass, barium borosilicate glass, borosilicate glass, or aramid, polyacrylate, polyarylate, polyimide, polyurethane, Plastics such as polyether ketone, polyether sulfone, polyester, polyethylene, polyethylene terephthalate, polyolefin, polycarbonate, polysulfone, polyvinyl chloride, polypropylene, polymethyl acrylate, epoxy resin, phenol resin, fluorine resin, melamine resin Alumina, silicon, quartz, a plate-like substrate materials, including ceramics such as silicon carbide, is used to form the sheet or film, if necessary, it is used by laminating. Among them, for example, aluminosilicate glass, aluminoborosilicate glass, quartz glass, borosilicate glass, barium borosilicate glass, etc., which have a low alkali content and a low thermal expansion coefficient, have a smooth surface, are free from scratches, and are easy to polish. Excellent compatibility with the glass for masks and the adjacent conductive film, hardly permeate moisture, for example, aramid, epoxy, phenol, polyarylate, polyimide, polyester, aromatic polyether, Polyolefin-based, melamine-based, and fluorine-based plastics are preferable, and an opaque ceramic material such as silicon is used in combination with a transparent electrode material.

  Reference numeral 2 denotes an anode, which is made of one or a plurality of metals or electrically conductive materials having low electrical resistivity and high light transmittance over the entire visible region, for example, vacuum deposition, sputtering, chemical It is adhered to one side of the substrate 1 by a method such as vapor deposition (CVD), atomic layer epitaxy (ALE), coating, or dipping, and the resistivity at the anode 2 is 1 kΩ / □ or less, preferably 5 to 50Ω / □. The film is formed by forming a single layer or a multilayer having a thickness of 10 to 1,000 nm, preferably 50 to 500 nm. Examples of the electrically conductive material in the anode 2 include metals such as gold, platinum, aluminum, and nickel, zinc oxide, tin oxide, indium oxide, and a mixed system of tin oxide and indium oxide (hereinafter abbreviated as “ITO”). And metal oxides such as aniline, thiophene, pyrrole, etc., and conductive oligomers and polymers having repeating units. Among these, ITO is characterized in that a low resistivity can be easily obtained and a fine pattern can be easily formed by etching using an acid or the like.

3 is a hole injecting / transporting layer, which is usually adhered to the anode 2 in the same manner as in the anode 2 to form a hole injecting / transporting layer material to a thickness of 1 to 1,000 nm. It is formed. As the material for the hole injection / transport layer, in order to facilitate the hole injection and transport from the anode 2, the ionization potential is small and, for example, at least 10 under an electric field of 10 ^{4 to} 10 ⁶ V / cm. Those exhibiting a hole mobility of ⁻⁶ cm ² / V · sec are preferred. As an individual hole injection / transport layer material, for example, arylamine derivatives, imidazole derivatives, oxadiazole derivatives, oxazole derivatives, triazole derivatives, chalcone derivatives, styrylanthracene derivatives, stilbene derivatives, which are widely used in organic EL devices, Tetraarylethene derivative, triarylamine derivative, triarylethene derivative, triarylmethane derivative, phthalocyanine derivative, fluorenone derivative, hydrazone derivative, N-vinylcarbazole derivative, pyrazoline derivative, pyrazolone derivative, phenylanthracene derivative, phenylenediamine derivative, poly Examples include arylalkane derivatives, polysilane derivatives, polyphenylene vinylene derivatives, porphyrin derivatives, etc. Used Te Align. Among these, monomers and multimers of arylamines such as monoarylamines, diarylamines, triarylamines and tetraarylamines, which are aromatic tertiary amines, are particularly preferable.

  4 is a light emitting layer, which is usually brought into close contact with the hole injection / transport layer 3 in the same manner as in the anode 2, and one or more of the pyrrolopyridine compounds according to the present invention are used alone, or an appropriate host compound Alternatively, it is formed by forming a film with a thickness of 1 to 1,000 nm, preferably 10 to 200 nm, together with one or more guest compounds. The pyrrolopyridine compound of the present invention is easy to form excitons such as singlet excitons and triplet excitons, and is suitable for emission energy levels such as fluorescence and phosphorescence. Alternatively, the light-emitting layer of the organic EL element can also be configured by combining with a plurality of host compounds or guest compounds. In particular, when the pyrrolopyridine compound of the present invention as a host compound is combined with an appropriate guest compound, an extremely high level of luminance, power efficiency, external quantum efficiency, and lifetime that cannot be easily achieved by a conventionally known host compound are obtained. Can be achieved. Further, when the pyrrolopyridine compound of the present invention is used as a guest compound, it is difficult to cause so-called “concentration quenching” of light emission by the light emitting layer material itself. The light emission luminance of the element can be increased. In the organic EL device according to the present invention in which the light emitting layer is constituted by combining the host compound and the guest compound, the guest compound is used up to an equimolar amount with respect to the host compound, usually 0.1 to 10 mol%, preferably 0.5 The light emitting layer 4 is formed by separating the both into a single layer or multiple layers and forming a film with a thickness of 1 to 1,000 nm, preferably 10 to 200 nm.

  When the pyrrolopyridine compound according to the present invention is used as a host compound, other host compounds used in combination with the pyrrolopyridine compound of the present invention include quinolinol metal complexes widely used in organic EL devices, such as anthracene, chrysene, coronene, Condensed polycyclic aromatic hydrocarbons such as triphenylene, naphthacene, naphthalene, phenanthrene, picene, pyrene, fluorene, perylene, benzopyrene and their derivatives, quarterphenyl, distyrylarylene, 1,4-diphenylbutadiene, stilbene, terphenyl Ring-assembled hydrocarbons such as tetraphenylbutadiene and biphenyl and their derivatives, oxadiazole, carbazole, pyridazine, benzimidazole, benzoxazole, benzothiazo Heterocyclic compounds and derivatives thereof, such as Le, quinacridone, rubrene and derivatives thereof, further, styryl polymethine dyes, such as adamantane derivatives.

  Among these host compounds, one particularly preferable one is, for example, a quinolinol metal complex. The quinolinol metal complex referred to in the present invention has a pyridine residue and a hydroxy group in the molecule, for example, quinolinols as ligands such as 8-quinolinols and benzoquinolin-10-ols, and the pyridine Receiving an electron pair from the nitrogen atom in the residue to form a coordinate bond with the ligand, usually monovalent, divalent or trivalent as the central atom, for example, lithium, sodium, potassium, beryllium, It means a complex in general made of a metal belonging to Group 1, Group 2, Group 12 or Group 13 or an oxide thereof in the periodic table such as magnesium, calcium, zinc, boron, aluminum, gallium and indium. When the ligand is either 8-quinolinols or benzoquinolin-10-ols, they may have one or more substituents, and 8 or 10 to which a hydroxy group is attached. Carbon other than the carbon at the position, for example, halogen group such as fluoro group, chloro group, bromo group, iodo group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert -Aliphatic hydrocarbon groups such as butyl, pentyl, isopentyl, neopentyl, tert-pentyl, methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert -Butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, phenoxy group, benzyloxy group Any ether group, acetoxy group, benzoyloxy group, methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, etc. ester group, cyano group, nitro group, sulfo group, and one or more substituents by combinations thereof Does not prevent them from joining. When the quinolinol metal complex has two or more ligands in the same molecule, these ligands may be the same as or different from each other.

  Examples of individual quinolinol metal complexes include tris (8-quinolinolato) aluminum, tris (3,4-dimethyl-8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, and tris (4-methoxy-). 8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum, tris (5-chloro-8-quinolinolato) aluminum, tris (5- Bromo-8-quinolinolato) aluminum, tris (5,7-dichloro-8-quinolinolato) aluminum, tris (5-cyano-8-quinolinolato) aluminum, tris (5-sulfonyl-8-quinolinolato) aluminum, tris (5 Propyl-8-quinolinolato) aluminum, aluminum complexes such as bis (2-methyl-8-quinolinolato) aluminum oxide, bis (8-quinolinolato) zinc, bis (2-methyl-8-quinolinolato) zinc, bis (2,4 -Dimethyl-8-quinolinolato) zinc, bis (2-methyl-5-chloro-8-quinolinolato) zinc, bis (2-methyl-5-cyano-8-quinolinolato) zinc, bis (3,4-dimethyl-8) -Quinolinolate) zinc, bis (4,6-dimethyl-8-quinolinolato) zinc, bis (5-chloro-8-quinolinolato) zinc, zinc complexes such as bis (5,7-dichloro-8-quinolinolato) zinc, bis (8-quinolinolato) beryllium, bis (2-methyl-8-quinolinolato) beryllium, bis 2,4-dimethyl-8-quinolinolato) beryllium, bis (2-methyl-5-chloro-8-quinolinolato) beryllium, bis (2-methyl-5-cyano-8-quinolinolato) beryllium, bis (3,4 Dimethyl-8-quinolinolato) beryllium, bis (4,6-dimethyl-8-quinolinolato) beryllium, bis (5-chloro-8-quinolinolato) beryllium, bis (4,6-dimethyl-8-quinolinolato) beryllium, bis ( Beryllium complexes such as 10-hydroxybenzo [h] quinolinolato) beryllium, bis (8-quinolinolato) magnesium, bis (2-methyl-8-quinolinolato) magnesium, bis (2,4-dimethyl-8-quinolinolato) magnesium, bis (2-Methyl-5-chloro-8-quinolino Lato) magnesium, bis (2-methyl-5-cyano-8-quinolinolato) magnesium, bis (3,4-dimethyl-8-quinolinolato) magnesium, bis (4,6-dimethyl-8-quinolinolato) magnesium, bis ( 5-chloro-8-quinolinolato) magnesium, magnesium complexes such as bis (5,7-dichloro-8-quinolinolato) magnesium, indium complexes such as tris (8-quinolinolato) indium, tris (5-chloro-8-quinolinolato) Examples include gallium complexes such as gallium and calcium complexes such as bis (5-chloro-8-quinolinolato) calcium, and these are used in combination as necessary.

  As guest compounds used in the present invention, for example, acridone derivatives, oxazone derivatives such as Nile Red, quinacridone derivatives, JP 2001-76875 A, JP 2001-76876 A, and JP No. 2001-329257, JP 2002-226484 A, JP 2003-249371 A, JP 2003-249372 A, JP 2004-6222 A, etc. Diketopyrrolopyrrole derivatives, 1,1,4,4-tetraphenyl-1,3-butadiene, 4,4'-bis (2,2-diphenylvinyl) biphenyl, 4,4'-bis [(1,1 , 2-triphenyl) ethenyl] biphenyl and other anthracene derivatives 9,10-diphenylanthracene, 9,10-bis (phenylethyl) anthracene, chrysene, coronene, decacyclene, tetracene, tetraphenylcyclopentadiene, 4,4-bis (9 ″ -ethynylanthracenyl) biphenyl, pyrene, Perylene, dibenzo [f, f] diindeno [1,2,3-cd: 1 ′, 2 ′, 3′-lm] perylene, 1,4-bis (9′-ethynylanthcenyl) benzene, pentaphenylcyclo Polycyclic aromatic compounds such as pentadiene and rubrene and their derivatives, triarylamine derivatives, pyrazine derivatives, 4- (dicyanomethylene) -2-tert-butyl-6- (1,1,7,7-tetramethyl) Pyran derivatives such as eurolidyl-9-enyl) -4H-pyran, benzimidazole derivatives Benzoxazole derivatives, benzothiazole derivatives, polyterphenylene vinylene and its derivatives, polythienylene vinylene and its derivatives, polythiophene and its derivatives, polynaphthylene vinylene and its derivatives, poly-N-vinylcarbazole and its derivatives, polyphenylene vinylene and Derivatives thereof, polyfluorenes and derivatives thereof, etc., and these are used in combination as necessary, and as described above, the pyrrolopyridine compound according to the present invention can be used only as a host compound in an organic EL device. In the case where the pyrrolopyridine compound according to the present invention is used as the guest compound, the pyrrolopyridine compound according to the present invention and the host compound as described above are used in the present invention. A light emitting layer of an organic EL device is constituted by appropriately combining with other than the pyrrolopyridine compound.

  5 is an electron injecting / transporting layer, which is usually adhered to the light emitting layer 4 in the same manner as in the anode 2 and is an organic compound having a high electron affinity, or, for example, an anthraquinodimethane derivative, anthrone derivative, Oxadiazole derivatives, carbodiimides, distyrylpyrazine derivatives, diphenylquinone derivatives, silazane derivatives, thiopyran dioxide derivatives, triazole derivatives, heterocyclic tetracarboxylic acid derivatives, phthalocyanine derivatives, fluorenone derivatives, as in the light emitting layer 4 It is formed by forming one or more of a quinolinol metal complex, or an electrically conductive oligomer or polymer having aniline, thiophene, pyrrole or the like as a repeating unit to a thickness of 10 to 500 nm. When using a plurality of electron injecting / transporting layer materials, even if the plurality of electron injecting / transporting layer materials are uniformly mixed to form a single layer, the materials for each electron injecting / transporting layer are not mixed. It may be formed in a plurality of adjacent layers. When providing the hole blocking layer, prior to the formation of the electron injecting / transporting layer 5, it is brought into close contact with the light emitting layer 4 by the same method as in the anode 2, for example, 2-biphenyl-4-yl-5- ( 4-tert-butylphenyl)-[1,3,4] oxadiazole, 2,2-bis [5- (4-biphenyl) -1,3,4-oxadiazol-2-yl-1,4 Oxadiazole compounds such as -phenylene] hexafluoropropane, 1,3,5-tris- (2-naphthalen-1-yl- [1,3,4] oxadiazol-5-yl) benzene A thin film is formed from the hole blocking layer material. The thickness of the hole blocking layer is set in the range of 1 to 100 nm, usually 5 to 50 nm in consideration of the thickness of the electron injection / transport layer 5 and the operating characteristics of the organic EL element.

  6 is a cathode, which is usually in close contact with the electron injection / transport layer 5 and has a work function lower than that of the compound used in the electron injection / transport layer 5 (usually 5 eV or less). For example, lithium, magnesium, calcium, It is formed by vapor deposition of metals such as sodium, potassium, silver, copper, aluminum, indium, ytterbium, alloys, metal oxides, or electrically conductive compounds. The thickness of the cathode 6 is not particularly limited, and the thickness is usually set so that the resistivity is 1 kΩ / □ or less, taking into consideration the electrical conductivity, the manufacturing cost, the thickness of the entire device, the light transmittance, and the like. Is set to 10 nm or more, preferably 50 to 500 nm. In addition, in order to improve adhesiveness between the cathode 6 and the electron injection / transport layer 5 containing an organic compound, for example, an aromatic diamine compound, a quinacridone compound, a naphthacene compound, an organic silicon compound is used as necessary. An interface layer containing an organic phosphorus compound or the like may be provided. Further, in order to facilitate the movement of electrons from the cathode 6 to the electron injection / transport layer 5, in the same manner as in the anode 2, the cathode 6 is moved to the side in contact with the electron injection / transport layer 5, for example, fluorine. A thin film with a thickness of 0.1 to 2 nm may be formed using an alkali metal compound such as lithium fluoride or lithium oxide or an alkaline earth metal compound.

As described above, the organic EL device of the present invention includes an anode, a light emitting layer and a cathode on a substrate, and further, if necessary, a hole injection / transport layer, an electron injection / transport layer, a hole blocking layer, and the like. It can be obtained by integrally forming adjacent layers while being in close contact with each other. In forming each layer, it is desirable to perform an integrated operation under high vacuum, specifically, 10 ⁻⁵ Torr or less in order to minimize oxidation and decomposition of organic compounds, and adsorption of oxygen and moisture. . In forming the light emitting layer, for example, by mixing the host compound and the guest compound at a predetermined ratio in advance, or by controlling the deposition rate of both in vacuum deposition independently of each other, The blending ratio of both in the light emitting layer is adjusted. In order to minimize deterioration in the usage environment, the organic EL device constructed in this way is partially or wholly sealed with, for example, sealing glass or a metal cap in an inert gas atmosphere, or protected. It is desirable to form a layer, apply a moisture-proof paint, or cover with a protective layer made of an ultraviolet curable resin or the like. Furthermore, although depending on the structure of the organic EL element, in order to efficiently extract the light emitted from the light emitting layer to the outside of the element, it is moved to an appropriate place in the element as necessary, for example, an annular plate, one-dimensional or two-dimensional. A diffraction means for changing the incident angle of light emission with respect to the light emission extraction surface of the element, such as a three-dimensional reflection type or transmission type diffraction grating, is provided alone or in combination, and the interface between the organic layer and the inorganic layer in the element or light emission You may make it suppress the total reflection in the interface of an extraction surface and air | atmosphere.

  The method of using the organic EL device according to the present invention will be described. The organic EL device of the present invention applies a relatively high voltage pulsed voltage intermittently or a relatively low voltage non-voltage depending on the application. A pulsed voltage (usually 2 to 50 V) is applied continuously for driving. The organic EL device of the present invention emits light only when the potential of the anode is higher than that of the cathode. Therefore, the voltage applied to the organic EL element of the present invention may be direct current or alternating current, and the waveform and cycle of the applied voltage may be appropriate. When alternating current is applied, in principle, the organic EL element of the present invention repeatedly increases and decreases in luminance or blinks according to the waveform and period of the applied alternating current. In the case of the organic EL device shown in FIG. 1, when a voltage is applied between the anode 2 and the cathode 6, holes injected from the anode 2 pass through the hole injection / transport layer 3 to the light emitting layer 4, and the cathode Electrons injected from 6 reach the light emitting layer 4 through the electron injection / transport layer 5. As a result, recombination of holes and electrons occurs in the light emitting layer 4, and target light emission is emitted through the anode 2 and the substrate 1 from the excited light emitting layer material generated thereby.

  The organic EL device of the present invention is excellent in durability and has high luminous efficiency. As a result, it is easy to increase luminance while suppressing power consumption, so that character information, image information, etc. Therefore, it has various uses as an information display device for visually displaying the above information and a light source (light emitter) in general illumination. That is, in the information display device, the organic EL element of the present invention is formed into a panel shape having a desired shape and size, for example, with a light weight by a conventional method, and a video display, a television receiver, and a telephone in a computer-related device. , Game machines, calculators, cameras, watches, car navigation devices, consumer and commercial electromechanical devices, electronic devices, optical devices in general, and general instruments that require visual display of information Applicable to signs, information boards, advertising panels, etc. In this case, the organic EL element according to the present invention is used alone or, if necessary, other organic EL elements that emit visible light in the blue, green, and / or red range, and the chromaticity and color tone of light emission. It is driven by applying a simple matrix type or active matrix type drive circuit widely used in this field while combining with appropriate filters for adjustment. For lighting applications, the organic EL device of the present invention is formed into a panel having a desired shape and size, for example, by using a conventional method, and is used as an energy saving and space saving light source for indoor lighting and outdoor lighting. Applied to general lighting such as, backlighting of liquid crystal elements, lighting used for physiotherapy to treat depression, and further, livestock, poultry, seafood, insects, fruit trees, grains, vegetables, flowers It is applied to lighting to control the photoperiodicity and phototaxis of animals and plants such as. In addition, the organic EL element of this invention which uses the reflecting mirror which functions as a micro optical resonator for the anode and the cathode is useful as, for example, a thresholdless laser operating in a small current region.

  By the way, as described above, the pyrrolopyridine compound of the present invention has an absorption maximum in the vicinity of a wavelength of 230 to 500 nm, more specifically, in the vicinity of 250 to 450 nm, and has a light emission maximum such as a fluorescence maximum in the vicinity of a wavelength of 450 to 550 nm. And emits green to red light when excited and has a melting point exceeding 250 ° C. and a decomposition point exceeding 400 ° C. In addition to being used as a material for a light emitting layer in an organic EL element, organic EL It is also useful as a chromaticity adjusting material for adjusting the chromaticity of light emitted by the element to a desired level. Thus, the organic EL element referred to in the present invention is not limited to the one containing the pyrrolopyridine compound of the present invention as a material for the light emitting layer, and in addition, the chromaticity of electroluminescence by the light emitting compound is adjusted. For this purpose, in the part other than the light emitting layer, the pyrrolopyridine compound of the present invention is used alone, or the pyrrolopyridine compound of the present invention is used in combination with one or more kinds of other compounds having light absorption ability. It encompasses all elements.

  The pyrrolopyridine compounds of the present invention all have an absorption maximum in the vicinity of a wavelength of 230 to 500 nm, more specifically, in the vicinity of 250 to 450 nm, and have a large molecular extinction coefficient at the absorption maximum, so natural light, artificial light, etc. It is also extremely useful as a light absorber for absorbing and shielding light from the ultraviolet region to the visible region in ambient light.

  When the pyrrolopyridine compound of the present invention is used as a light absorber, the pyrrolopyridine compound may be used alone or in combination with one or more other organic dye compounds. When the pyrrolopyridine compound of the present invention is used as a light absorber, for example, in clothing, the light absorber effectively blocks light from the ultraviolet region to the visible region contained in environmental light such as natural light and artificial light. The Rukoto.

  Many of the pyrrolopyridine compounds of the present invention exhibit a remarkable light-shielding ability in a minute amount, and even when blended with an article, the intended color, tone and texture of the article are not substantially impaired. Therefore, the pyrrolopyridine compound of the present invention can be suitably used as a light absorber applied to various articles. In particular, the pyrrolopyridine compound of the present invention can be suitably used as a light absorber for clothing. Applicable clothing includes, for example, business suits, sack suits, three sets, blazers, cardigan jackets, jackets and vests such as blousons, boleros, sacks, shirts, dress shirts, formal shirts, sports shirts , Shirts such as aloha shirts, cutter shirts, open collar shirts, polo shirts, tea shirts, slacks, lapel trousers, knickerbockers, gaucho pants, pedal pushers, jeans, etc. Ties such as Thailand, undershirts, briefs, zulose, scanties, shorts, trunks and other underwear, lingerie, petticoats, camisole, bra, stockings, panty stockings , Foundations such as girdle, body suit, blouse such as chori, midi blouse, set-in blouse, skirts such as divided skirt, midi skirt, mini skirt, trumpet skirt, wrap skirt, apron dress, basic dress, Dresses such as camisole dress, chemise dress, coat dress, house dress, jumper dress, sack dress, sheath dress, shift dress, sweater such as pullover, cardigan, boat neck sweater, bulky sweater, crew neck sweater, turtleneck, Balma Khan, Duffle coat, Duster coat, Inverness, Raglan, Trench coat, Lane coat, etc. Outfit, Tailcoat, Tuxedo, etc. Hat, beret, borderless cap, alpine, boater, busby, derby, fedora, fez, hunting cap, opera hat, sombrero, breton, cloche, pillbox, picture hat, snood, tamo shunter, talk, turban, bonnet, casquette Socks such as hats, ankle socks, bobby socks, crew socks, knee socks, over knee socks, sweatshirts, three quarter socks, tube socks, and more, anorak, towel, towel towel, bath towel, handkerchief, hand towel, fur, In addition to general clothes such as gloves, mittens, mufflers, scarves, ribbons, stomachbands, uniforms, jerseys, Japanese clothes, swimsuits, wetsuits, work clothes, fire fighting clothes, military uniforms, flying clothes, diving suits, space suits, etc. And general clothing materials such as interlinings and linings for preparing these garments.

  The use of the pyrrolopyridine compound of the present invention as a light absorber is not limited to clothing, and various types of materials other than clothing that need to absorb and shield light from the ultraviolet region to the visible region in ambient light such as natural light and artificial light. The present invention can be advantageously applied to various articles. Examples of individual items other than clothing include drapes, laces, casements, prints, venetian blinds, roll screens, shutters, goodwill, blankets, duvets, duvet covers, duvet covers, duvet cotton, sheets, cushions, pillows , Pillow covers, cushions, mats, carpets, sleeping bags, tents, interior decorations for automobiles, window glass, window bedding, hygiene items such as paper diapers, diaper covers, glasses, monocles, lownets, shoes Insoles, shoe linings, saddles, furoshikis, umbrellas, parasols, stuffed animals, lighting devices, television receivers and personal computers using, for example, cathode ray tube displays, liquid crystal displays, electroluminescent displays, plasma displays, etc. Filters, panels and screens for video display devices such as , Sunglasses, sunroofs, sun visors, PET bottles, warehouses, greenhouses, cold water bottles, optical fibers, prepaid cards, microwave ovens, ovens and other viewing windows, as well as items that do not like exposure to natural light, artificial light, or other environmental light It can also be used extremely advantageously in packaging materials, filling materials, containers, etc. for packaging, filling or storage.

  When the pyrrolopyridine compound of the present invention is used in the above-mentioned various articles as a light absorber, it can not only prevent or reduce obstacles and inconveniences in organisms and articles, but also adjusts the light transmitted and reflected to the desired color balance. There are real benefits that can be made.

  Further, in order to apply the pyrrolopyridine compound of the present invention to a product as described above as a light absorbent, depending on the shape, size, purpose of use, etc., normal mixing, coating, spraying, dipping, fixing, etc. Apply the method. In order to temporarily or semipermanently carry the pyrrolopyridine compound of the present invention on various kinds of articles including clothing as a light absorber, for example, one or more of the pyrrolopyridine compounds of the present invention may be added as necessary. Support material, microencapsulating agent, binder, monomer, oligomer, multifunctional reagent, glue, adhesive, colorant, flame retardant, wrinkle remover, deodorant, water repellent, oil repellent, antistatic agent , Conductive agent, water-absorbing agent, moisture-proofing agent, fragrance, antioxidant, insecticide, antifungal agent, antibacterial agent, antiallergic agent, blood circulation promoter, surfactant, emulsion stabilizer, chelating agent, etc. Along with more than seeds, for example, water, pentane, hexane, cyclohexane, petroleum ether, petroleum benzine, isooctane, octane, benzene, toluene, xylene, carbon tetrachloride, chloroform, 1,2-di Loroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, bromobenzene, dichlorobenzene, methanol, ethanol, 1-propanol, 2-propanol, 2,2,2-trifluoroethanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl alcohol , Cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol, diethylene glycol, triethylene glycol, glycerin, diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4- Dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether , Dicyclohexyl-18-crown-6, methyl carbitol, ethyl carbitol, furfural, acetone, methyl ethyl ketone, cyclohexanone, formic acid, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate , Formamide, N-methylformamide, N, N-dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, hexamethylphosphate triamide, triethyl phosphate, acetonitrile, propionitrile, succinonitrile, benzo It is dissolved or suspended in a general-purpose solvent such as nitrile, nitromethane, nitrobenzene, ethylenediamine, pyridine, piperidine, morpholine, dimethyl sulfoxide, sulfolane, or a mixture thereof. Turbine and store in a sealed container with a general propellant if necessary. The solutions and suspensions thus obtained can impart a light-shielding capability to a desired part or the whole of the article by applying or spraying them on various kinds of articles or by immersing the article in them. Can do. Among these light absorbers, those that can be easily removed by washing or washing include, for example, horticulture, picnics, hiking, trekking, mountaineering, swimming, skiing, in addition to regular outings and athletics. When going out to places exposed to strong ultraviolet rays, such as golf, cycling, tide-hunting, fishing, etc., light-absorbing agent should be applied by temporarily shading clothing before washing and washing or washing as necessary after wearing. It can be easily detached.

  Further, in order to make the pyrrolopyridine compound of the present invention semipermanently supported on clothing as a light absorber, one or more pyrrolopyridine compounds of the present invention are used as they are, or, for example, fine porous Urethane resin, acrylic resin, aminoplast resin, epoxy resin, glyoxal resin, ethylene urea resin, silicon resin in a microencapsulated state using fine particles of silica, activated carbon, melamine resin, acrylate resin, urea resin, etc. Along with a binder such as above, if necessary, it is dispersed in an aqueous medium containing a higher alcohol or a surfactant. A cloth or a sewing product is immersed in this dispersion, and excess dispersion is removed by centrifugation or the like. After drying at 180 ° C. or lower, preferably 140 ° C. or lower, if necessary, dry heat according to a conventional method. Set or wet heat set. When this method is used, the light absorbent can be carried semipermanently on the clothes, and the washing resistance is also improved. Such light absorbers include, for example, clothing, bedding products, sanitary products, filters such as lighting devices and image display devices, panels and screens, sunroofs, PET bottles, tents, plastic houses, etc. In the case of blending into the article, an appropriate amount of such a light absorber may be contained in an appropriate process until the preparation of the article is completed.

  Hereinafter, embodiments of the present invention will be described based on examples.

<Light emitting agent for organic EL elements>
To the reaction vessel, 30 ml of acetic acid was added, 2.00 g of tetrabenzoylethane represented by the chemical formula 26, 1.42 g of p-toluidine, and 30 mg of p-toluenesulfonic acid were added and heated to reflux for 24 hours. After heating and refluxing, 1.42 g of p-toluidine was added and reacted after 8 hours and 16 hours, respectively, allowed to cool, left to stand for 1 day, crystallized, and N- (p-methylphenyl) -2,5-diphenyl-3,4-dibenzoylpyrrole (intermediate product) was obtained. Next, 0.8 g of an intermediate product and 0.45 g of aminoacetonitrile were added to an appropriate amount of n-butanol, and the mixture was heated to reflux for 48 hours. After heating to reflux, 12 hours, 24 hours, and 48 hours, aminoacetonitrile was added. .45 g of each was added and allowed to react, then slowly cooled and allowed to stand for 1 day, and the precipitate was filtered and washed with water. Subsequently, it melt | dissolved in tetrahydrofuran (THF), activated carbon was added and heated, the impurity was removed, and THF was distilled off. The obtained crude crystals were recrystallized with n-butanol, and 6-cyano-2-N- (p-methylphenyl) -1,3,4,7 represented by the chemical formula 2 which is a pyrrolopyridine compound of the present invention. -Yellow needle-like crystals of tetraphenylpyrrolo [3,4-c] pyridine were obtained. A portion of the crystal was taken and the visible absorption spectrum and the fluorescence spectrum in a methylene chloride solution were measured according to a conventional method. As a result, an absorption maximum (with side absorption at a wavelength of 394 nm) and a fluorescence maximum were observed at wavelengths of 260 nm and 499 nm, respectively. It was. Further, when ¹ H-NMR in a chloroform-d solution was measured according to a conventional method, the chemical shift δ (ppm, TMS) was 2.1 (3H, CH ₃ ) and 6.8 to 7.2 (24H, ArH). ) Was observed at a position. Furthermore, when a DSC analysis was performed using a commercially available DSC analyzer (trade name “DSC220U type” manufactured by Seiko Instruments Inc.) at a heating rate of 10 ° C./min, the melting point of the pyrrolopyridine compound of this example was 268.7 ° C. The decomposition point was 430.8 ° C.

  The pyrrolopyridine compound of this example, which is excellent in thermal stability and emits fluorescence in the green region when excited, is extremely useful as a light-emitting agent for organic EL devices, whether used alone or in combination with other host compounds or guest compounds.

<Light emitting agent for organic EL elements>
To the reaction vessel, 30 ml of acetic acid was added, 2.00 g of tetrabenzoylethane represented by Chemical Formula 26, 0.72 g of phenylenediamine, and 30 mg of p-toluenesulfonic acid were added and heated to reflux for 24 hours. After heating and refluxing, 0.72 g of phenylenediamine was added after 8 hours and 16 hours, respectively, reacted, slowly cooled, left to stand for 1 day, crystallized, and N- (p-methylphenyl) -2. , 5-Diphenyl-3,4-dibenzoylpyrrole (intermediate product) was obtained. Next, 0.8 g of an intermediate product and 0.45 g of aminoacetonitrile were added to an appropriate amount of n-butanol, and the mixture was heated to reflux for 48 hours. After heating to reflux, 12 hours, 24 hours, and 48 hours, aminoacetonitrile was added. .45 g of each was added and allowed to react, then slowly cooled and allowed to stand for 1 day, and the precipitate was filtered and washed with water. Subsequently, it melt | dissolved in N, N- dimethylformamide (DMF), activated carbon was added and heated, the impurity was removed, and DMF was depressurizingly distilled. The obtained crude crystals were recrystallized from n-butanol, and 1,4-di (6-cyano-2-N- (p-methylphenyl) -1 represented by the chemical formula 23 which is a pyrrolopyridine compound of the present invention. , 3,4,7-tetraphenylpyrrolo [3,4-c] pyridin-2-yl) benzene yellow-orange needles were obtained. A portion of the crystal was taken and the visible absorption spectrum and fluorescence spectrum in a methylene chloride solution were measured according to a conventional method, and an absorption maximum (with a secondary absorption spectrum at a wavelength of 425 nm) and a fluorescence maximum were observed, respectively. It was done. Further, when ¹ H-NMR in a chloroform-d solution was measured according to a conventional method, a peak was observed at a chemical shift δ (ppm, TMS) of 6.5 to 7.7 (44H, ArH). Furthermore, when a DSC analysis was performed using a commercially available DSC analyzer (trade name “DSC220U type” manufactured by Seiko Instruments Inc.) at a heating rate of 10 ° C./min, the melting point of the pyrrolopyridine compound of this example was 289.5 ° C. The decomposition point was 470 ° C.

<Light emitting agent for organic EL elements>
The pyrrolopyridine compounds of the present invention represented by the chemical formula 2 and the chemical formula 23 obtained in Example 1 and Example 2 were respectively charged into a water-cooled sublimation purification apparatus, and the apparatus was kept under reduced pressure by a conventional method. Each was purified by sublimation by heating.

  Both of the two types of pyrrolopyridine compounds of this example obtained by sublimation purification are extremely useful in organic EL devices that require a high-purity luminescent organic compound.

  The pyrrolopyridine compound used in the present invention includes, for example, those represented by chemical formula 1, chemical formula 3 to 22, chemical formula 24, and chemical formula 25 other than the above, although there are slight differences in the charging conditions and yield depending on the structure. In either case, the desired amount can be obtained by the method of Example 1 or 2, or according to the method.

<Organic EL device>
Using the organic EL device light-emitting agent according to the present invention, a stacked organic EL device having the structure shown in FIG. 1 was produced. That is, a glass substrate having a transparent ITO electrode having a thickness of 160 nm patterned with hydrobromic acid is ultrasonically cleaned with an organic alkali cleaning agent, pure water, acetone and ethanol, dried, and UV-exposed. After removing organic substances on the surface of the ITO electrode with ozone, it was transferred to a pretreatment chamber in a vacuum deposition apparatus. After depressurizing the pretreatment chamber to 1 × 10 ⁻⁶ Torr, an argon / oxygen mixture is introduced to 1 × 10 ⁻² Torr, and the ITO electrode surface is plasma-treated to clean the anode electrode with the ITO electrode. A substrate 1 was obtained.

The substrate 1 is moved into an organic vapor deposition chamber of a vacuum vapor deposition apparatus whose pressure is reduced to 1 × 10 ⁻⁶ Torr, an organic film forming mask is attached to the ITO electrode as the anode 2, the carbon crucible is heated, and the ITO in the substrate 1 is heated. A triphenylamine tetramer represented by chemical formula 27 (hereinafter abbreviated as “TPTE”) is vapor-deposited up to 40 nm as a hole injection / transport layer material on the side having the electrode. 3 was formed. Subsequently, as a host compound, one of the two types of pyrrolopyridine compounds of the present invention represented by Chemical Formula 2 and Chemical Formula 23 obtained by sublimation purification in Example 3 and as a guest compound are represented by Chemical Formula 28. 4- (dicyanomethylene) -2-tert-butyl-6- (1,1,7,7-tetramethylurolidyl-9-enyl) -4H-pyran (hereinafter referred to as “DCJTB”) Are formed by co-evaporation up to a thickness of 40 nm in a weight ratio of 100: 1 to form a light-emitting layer 4 in close contact with the hole injection / transport layer 3, and then tris (8-quinolinolate). Aluminum (hereinafter abbreviated as “AlQ ₃ ”) was evaporated to a thickness of 40 nm to form the electron injection / transport layer 5 in close contact with the light emitting layer 4.

Chemical formula 27:

Chemical formula 28:

Thereafter, the substrate 1 is moved into a metal vapor deposition chamber in a vacuum vapor deposition apparatus, and lithium fluoride and aluminum are vapor deposited in this order to a thickness of 0.5 and 150 nm, respectively, to form a cathode 6 that adheres closely to the electron injection / transport layer 5. After that, the entire device was sealed with a glass plate and an ultraviolet curable resin in a nitrogen atmosphere, and two types of organic EL devices of the present invention were obtained. The organic EL device thus obtained was examined for electroluminescence characteristics and lifetime by a conventional method. The lifetime was determined by setting the initial luminance to 2,400 cd / m ² at room temperature. Separately, for comparison, instead of the pyrrolopyridine compound according to the present invention, a pyrrolopyridine represented by Chemical Formula 29 or Chemical Formula 30 described in Patent Document 1 is used as a host compound, as an analogous compound of the pyrrolopyridine compound according to the present invention. An organic EL device was prepared using the compound and tested in the same manner as controls 1 and 2, respectively.

Chemical formula 29:

Chemical formula 30:

  As a result, in the organic EL device of this example and the control organic EL device, no light emission peculiar to the host compound was observed, indicating that the excitation energy was efficiently transferred from the host compound to the guest compound. ing.

However, when the two types of organic EL elements of this example are driven at a constant current at a current density of 11 mA / cm ² , the light emission luminance at room temperature is about 500 cd / cm ² or more, and the light emission luminance of the control 1 organic EL device. together show a high brightness of greater than about 1.2 times (about 410 cd / cm ^2), light emission luminance (about 380 cd / cm ²⁾ of the organic EL element of control 2 showed a high brightness of greater than about 1.3 times. The power efficiency and external quantum efficiency at that time were clearly higher than those of the organic EL elements of Controls 1 and 2. In addition, the organic EL device of this example has stable light emission, and no non-light emitting portion such as a dark spot was observed even when driven at high luminance (2,400 cd / m ² ) for 100 hours. On the other hand, when the organic EL elements of Controls 1 and 2 were tested in the same manner as the organic EL element of this example, a plurality of non-light emitting portions such as dark spots were already observed at the time of driving for 90 hours. From this result, the lifetime of the organic EL device of this example was estimated to be about 1.5 times longer than that of Controls 1 and 2.

  These results indicate that by using the pyrrolopyridine compound of the present invention as a luminescent agent, it is possible to realize an organic EL device having a long lifetime and high brightness and high efficiency.

<Display panel>
FIG. 2 shows an example of a simple matrix type display panel (20 electrode rows in the horizontal direction and 30 electrode rows in the vertical direction) mainly composed of the organic EL elements of the present invention. It can produce as follows.

  That is, after forming the anode 14 by the ITO transparent electrode on one side of the glass substrate 10 according to the method of Example 4, the anode 14 is processed into a stripe shape by a wet etching method. Next, the hole injection / transport layer 16 and the light emitting layer 18 are sequentially formed according to the method of Example 4, and the cathode 20 is formed in a stripe shape using a mechanical mask, and then a glass plate (not shown) and ultraviolet rays are formed. The organic EL element is sealed with a cured resin. In the display panel of this example, a heat radiating means such as a heat radiating plate or a cooling fan may be provided on the back side of the cathode 20 as needed in order to suppress a temperature rise during use.

<Information display device>
The block diagram of FIG. 3 shows an example of an information display device using a display panel manufactured by the method of Example 5. In FIG. 3, reference numeral 30 denotes a DC power supply with an output voltage of 4.5 V, and two booster circuits 32 and 34 are connected to the output terminals thereof. The booster circuit 32 can supply a DC voltage in the range of 5 to 12 V, and its output terminal is connected to the driver circuit 36. The other booster circuit 34 is for supplying a constant voltage of 5V to the microcomputer 38.

  The microcomputer 38 includes an I / O interface 38a for exchanging signals with the outside, a ROM 38b for recording a program, a RAM 38c for recording various data, and a CPU 38d for executing various operations. The microcomputer 38 is connected with a clock generation circuit for supplying an 8 MHz clock signal to the microcomputer 38 and two oscillation circuits 42 and 44, respectively. The two oscillation circuits 42 and 44 are connected to the microcomputer 38. , For supplying a signal of 5 to 50 Hz for controlling the display speed and a signal of 0.2 to 2 kHz for controlling the scanning frequency, respectively.

  A display panel 48 mainly composed of the organic EL element of the present invention is connected to the microcomputer 38 via driver circuits 36 and 46. The driver circuit 36 is a circuit that controls application of a DC voltage from the booster circuit to the display panel 48, and includes a plurality of transistors individually connected to the vertical electrode rows in the display panel 48. . Therefore, when any of the transistors in the driver circuit 36 is turned on, the voltage from the booster circuit 36 is applied to the vertical electrode row connected to the transistor. On the other hand, the driver circuit 46 includes a plurality of transistors individually connected to the horizontal electrode rows of the display panel 48, and when any of the transistors in the driver circuit 46 is turned on, the horizontal connection connected to the transistors is made. The electrode array in the direction is grounded.

  Since the information display device of this example is configured as described above, when the transistors in the driver circuits 36 and 46 are turned on in accordance with the instructions of the microcomputer 38, the display panel 48 has a predetermined interval between corresponding electrode rows in the vertical and horizontal directions. A voltage is applied, and the organic EL element located at the intersection emits light. Therefore, for example, one horizontal electrode row is selected by appropriately controlling the driver circuit 46, and connected to the vertical electrode row by appropriately controlling the driver circuit 36 while grounding the electrode row. If the transistors are sequentially turned on, the entire selected horizontal electrode row is scanned in the horizontal direction, and a given pixel is displayed. By repeating such scanning sequentially in the vertical direction, the entire screen can be displayed. Note that, since the driver circuit 36 in this example has a data register for one column of electrodes, it is preferable to drive the transistor based on the recorded data.

  The information to be displayed is supplied from the outside in accordance with the display speed and cycle, or for information having a certain pattern such as character information, the pattern is stored in the ROM 38b in advance. This may be data. When displaying a normal NTSC television broadcast, first, the received signal is separated into a horizontal synchronization signal and a vertical synchronization signal according to a horizontal frequency and a vertical frequency based on the broadcast standard, and a video signal is also displayed. The digital signal corresponding to the number of pixels of the display panel 48 is converted. The television broadcast can be displayed on the display panel 48 by supplying these signals to the microcomputer 38 in appropriate synchronization.

<Light absorber>
Two types of pyrrolopyridine compounds of the present invention represented by Chemical Formula 2 and Chemical Formula 23 having an absorption maximum in the ultraviolet region are uniformly mixed at a mass ratio of 2: 1, and N-methylpyrrolidone is added to the mixture at a mass ratio of 1: After adding at 100, according to a conventional method, silica particles having a fine porous structure (particle size 2 to 6 μm) were immersed in a solution to microencapsulate the organic dye compound, thereby obtaining the light absorber of the present invention. . Mixing microcapsules as light absorbers, in which a plurality of organic compounds are mixed with each other, into an acrylic ester binder (trade name “Blimar HA-16” manufactured by Nippon Reichhold) at a mass ratio of 1: 1. After that, a 120 g / l aqueous dispersion was prepared. A stocking made of nylon 6 processed yarn is immersed in this dispersion, and 3% of the microcapsules are adhered by dry weight, followed by dehydration with a centrifugal dehydrator, drying at 120 ° C., and dry heat setting at 140 ° C. for 3 minutes. did. After that, stockings with organic dye compound microcapsules attached to the right leg (test example) and similar stockings without organic dye compound attached to the left leg (comparative example) are respectively hand-sewn. Pantyhose was made.

  This pantyhose was tested on 20 women aged 18 to 38 years over a month, and the sunburn of the right leg was significantly less than that of the left leg. In addition, when all the subjects were surveyed regarding the trial findings, the pantyhose of this example, when worn, has a distinct cooling sensation on the right leg compared to the left leg, and it is difficult to stuffy and is repeatedly washed. Even so, many respondents said that the shading effect did not diminish.

  As described above, the pyrrolopyridine compound of the present invention is an electroluminescent material as a light emitting agent such as a host compound or a guest compound constituting a light emitting layer in the field of organic EL devices which is attracting attention as a next generation display device. As a chromaticity adjusting material for adjusting the chromaticity to a desired level, it is extremely useful as a light absorber applicable to various articles such as clothing.

1, 10 Substrate 2, 14 Anode 3, 16 Hole injection / transport layer 4, 18 Light emitting layer 5 Electron injection / transport layer 6, 20 Cathode 30 DC power source 32, 34 Booster circuit 36, 46 Driver circuit 38 Microcomputer 40 Clock Generator circuit 42, 44 Oscillator circuit 48 Display panel

Claims (7)

A pyrrolopyridine compound represented by the general formula 1.
General formula 1:

(In General Formula 1, X represents a methylene group, ethylene group, propylene group, phenylene group or biphenylene group, R ₁ represents a hydrogen atom or a substituent. R _{2 to} R ₅ each independently represents a hydrogen atom. Alternatively, it represents a substituent, and the bonding position of these substituents may be any of the ortho, meta, and para positions in each phenyl group to which they are bonded, and the ortho, meta, and para positions in each phenyl group. The substituents may be the same or different, and the adjacent groups are bonded to each other, including the carbon atom to which they are bonded, A cyclic structure may be formed, n represents 1 or 2. However, when n is 1, X represents a phenylene group, and when n is 2, a pyrrolopyridine compound represented by the general formula 1 Is 2 through X Embody, _{R 1} is absent.) A light-emitting agent for an organic electroluminescence device comprising a pyrrolopyridine compound represented by the general formula 1.
General formula 1:

(In General Formula 1, X represents a methylene group, ethylene group, propylene group, phenylene group or biphenylene group, R ₁ represents a hydrogen atom or a substituent. R _{2 to} R ₅ each independently represents a hydrogen atom. Alternatively, it represents a substituent, and the bonding position of these substituents may be any of the ortho, meta, and para positions in each phenyl group to which they are bonded, and the ortho, meta, and para positions in each phenyl group. The substituents may be the same or different, and the adjacent groups are bonded to each other, including the carbon atom to which they are bonded, A cyclic structure may be formed, n represents 1 or 2. However, when n is 1, X represents a phenylene group, and when n is 2, a pyrrolopyridine compound represented by the general formula 1 Is 2 through X Embody, _{R 1} is absent.) An organic electroluminescent device using a pyrrolopyridine compound represented by the general formula 1.
General formula 1:

(In general formula 1, X is a methylene group, an ethylene group, a propylene group, a phenylene group or biphenylene group, R ₁ is the .R ₂ to R ₅ represents a hydrogen atom or a substituent, each independently, a hydrogen atom Alternatively, it represents a substituent, and the bonding position of these substituents may be any of the ortho, meta, and para positions in each phenyl group to which they are bonded, and the ortho, meta, and para positions in each phenyl group. The substituents may be the same or different, and the adjacent groups are bonded to each other, including the carbon atom to which they are bonded, A cyclic structure may be formed, n represents 1 or 2. However, when n is 1, X represents a phenylene group, and when n is 2, a pyrrolopyridine compound represented by the general formula 1 Is 2 through X Embody, _{R 1} is absent.)   The organic electroluminescent device is an organic electroluminescent device comprising an anode, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode, and the pyrrolopyridine compound represented by the general formula 1 is used as a dopant in the light emitting layer. The organic electroluminescent device according to claim 3, wherein both the hole transport layer material and the electron transport layer are blended as a host.   The display panel using the organic electroluminescent element of Claim 3 or 4.   An information display device using the organic electroluminescent element according to claim 3. A light absorber comprising the pyrrolopyridine compound represented by the general formula 1.
General formula 1:

(In General Formula 1, X represents a methylene group, ethylene group, propylene group, phenylene group or biphenylene group, R ₁ represents a hydrogen atom or a substituent. R _{2 to} R ₅ each independently represents a hydrogen atom. Alternatively, it represents a substituent, and the bonding position of these substituents may be any of the ortho, meta, and para positions in each phenyl group to which they are bonded, and the ortho, meta, and para positions in each phenyl group. The substituents may be the same or different, and the adjacent groups are bonded to each other, including the carbon atom to which they are bonded, A cyclic structure may be formed, n represents 1 or 2. However, when n is 1, X represents a phenylene group, and when n is 2, a pyrrolopyridine compound represented by the general formula 1 Is 2 through X Embody, _{R 1} is absent.)

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