JPWO2006046416A1 - Arylsilane compounds and their uses - Google Patents

Abstract

Provided are novel arylsilane compounds having a plurality of coumarin residues in the same molecule, and uses thereof. This aryl silane compound is stable in addition to efficiently absorbing visible light in the violet to blue range, and emits blue light when many of them are excited. It will have a wide variety of uses in various fields that require organic compounds having such properties, such as photochemical polymerization, solar cells, optical filters, dyeing, dye lasers, and analysis. In particular, the arylsilane compound includes a light emitting layer material such as a host compound and a guest compound constituting a light emitting layer of an organic EL element, and a color adjusting material for adjusting the chromaticity of electroluminescence to a desired level. It is extremely useful as a material for organic EL elements.

Description

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

  With the advent of the information era, photochemical polymerization has been frequently used in a wide variety of fields. Now, its application goes beyond the field of synthetic resins, holography, printing plates, printed circuits, integration. It has extended to the field of information recording such as circuits and electronic circuits. Photochemical polymerization is a technique for polymerizing a polymerizable compound by light irradiation. Broadly speaking, photopolymerization that initiates polymerization by direct light irradiation and activation of the polymerizable compound, and a photosensitizer There is photosensitization polymerization in which a polymerizable compound is polymerized by irradiating light in a coexisting state to generate active species of a photosensitizer. In any photochemical polymerization, the start and stop of polymerization can be controlled by blinking of the exposure light source, and the polymerization degree and polymerization rate can be easily controlled by selecting the intensity and wavelength of the exposure light source. Moreover, since photochemical polymerization generally has a low polymerization initiation energy, it can be polymerized even at low temperatures. In the field of information recording such as printing plates and holograms, such advantages of photochemical polymerization are bought, and visible light such as second harmonics of argon ion laser, helium ion laser, and Nd-YAG laser is obtained. There is a rapidly increasing demand for photopolymerizable compositions that can be polymerized by irradiation.

  Since most of the polymerizable compounds and polymerization initiators blended in the photopolymerizable composition absorb only ultraviolet rays, a photosensitizer is indispensable when attempting to polymerize the polymerizable composition with visible light. It becomes a technical element. The characteristics that photosensitizers should have include a large molecular extinction coefficient in the visible region, the ability to sensitize various polymerizable compounds and polymerization initiators, high sensitization efficiency, solubility in solvents, etc. It is mentioned that it is excellent in compatibility with the blending component of, and is stable. Representative organic compounds having photosensitizing ability include, for example, merocyanine dyes disclosed in JP-A No. 54-151024, cyanine dyes disclosed in JP-A No. 58-29803, and JP-A No. 59. -56403, a stilbene dye disclosed in JP-A-63-23901, a coumarin derivative disclosed in JP-A-63-33103, a methylene blue derivative disclosed in JP-A-6-329654, and disclosed in JP-A-6-329654 However, these have advantages and disadvantages, and are photopolymerizable compositions composed of a plurality of materials such as a polymerizable compound, a polymerization initiator, and a binder resin, and have various characteristics as described above. There has not yet been found anything that can always be demonstrated. Therefore, in the field of new application of photochemical polymerization, for example, in the field of information recording and electronic equipment, a material other than a photosensitizer such as a polymerizable compound and a binder resin is first selected, and then In fact, it is a fact that a search is made for trials and errors for a variety of organic compounds suitable for those polymerizable compounds and polymerization initiators.

  By the way, in the field of information display devices, organic EL elements are in the spotlight as next-generation display elements. 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 organic EL elements emit light themselves, they have the advantage of reducing power consumption and are said to be excellent light emitting elements in principle (for example, edited by Hiroyuki Sakabe, “Organic Photonics”, Agne Inc.) See Jofusha, March 20, 1995, 1st edition, pages 136-160, and Yoshinori Saito, Journal of the Institute of Electronics, Information and Communication Engineers, Vol. 84, No. 11, pages 767-774 (2001) ).

  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. (For example, 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). However, conventionally known coumarin derivatives exhibit remarkable electroluminescence in the green to red range in organic EL elements, but exhibit electroluminescence characteristics that are practically satisfactory in the blue range, which is a shorter wavelength visible range. There were few things.

  In view of such circumstances, an object of the present invention is to widen the range of materials that can be selected in preparing a photopolymerizable composition and the like by providing a novel organic compound that absorbs visible light having a short wavelength. Is an issue.

  Furthermore, the subject of this invention is providing the organic material useful in the organic EL element aiming at light emission of a blue region.

  The present inventor paid attention to the arylsilane compound, and intensively studied and searched. As a result, the arylsilane compound having a plurality of coumarin residues in the same molecule, in particular, having a tetraarylsilane structure and a plurality of aromatic rings thereof. In addition, for example, it has been found that a product obtained by binding a coumarin residue represented by the general formula 1 efficiently absorbs visible light in a violet to blue region. Such arylsilane compounds are stable, and when many of them are excited, they emit visible light in the blue region. Therefore, in various fields that require organic compounds having such properties as light absorbers and luminescent agents. Very useful. In particular, when such an arylsilane compound is applied to an organic EL device as a material for a light emitting layer, it emits light with high brightness in a blue region, and the light emission is stably maintained for a long time at room temperature.

General formula 1:

(In General Formula 1, R ^{1 to} R ⁴ each independently represents a hydrogen atom or a substituent.)

  That is, this invention solves the said subject by providing the arylsilane compound which has multiple coumarin residues in the same molecule.

  In particular, as a preferred embodiment, the present invention solves the above problems by providing an arylsilane compound having a tetraarylsilane structure and having a coumarin residue bonded to a plurality of aromatic rings. is there.

  Furthermore, this invention solves the said subject by providing the arylsilane compound by which a coumarin residue is represented with General formula 1 as a more preferable embodiment.

General formula 1:

(In General Formula 1, R ^{1 to} R ⁴ each independently represents a hydrogen atom or a substituent.)

  Furthermore, this invention solves the said subject by providing the material for organic EL elements containing such an arylsilane compound.

  Furthermore, this invention solves the said subject by providing the organic EL element which uses such an arylsilane compound.

  Furthermore, 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.

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 a block diagram of the information display apparatus by this invention.

Explanation of symbols

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

  As described above, the present invention relates to an arylsilane compound having a plurality of coumarin residues in the same molecule and use thereof.

As is well known, an arylsilane is an organic compound in which one or more of the hydrogen atoms in silane (SiH ₄ ) are substituted with an aromatic ring such as a benzene ring, a pyridine ring, a furan ring, a pyrrole ring, or a thiophene ring. . The arylsilane compound as used in the present invention means all compounds in which a coumarin residue is bonded to a plurality of aromatic rings. The site to which the coumarin residue is bonded in the aromatic ring may be any of the 2-position, 3-position and 4-position with respect to the site where the aromatic ring is bonded to the silicon atom. In the case of a ring, the 4-position (para-position) is usually selected in terms of ease of preparation. Although depending on the use of the arylsilane compound, in applications where the stability of the compound is important, those having a tetraarylsilane structure in which all of the hydrogen atoms are substituted with aromatic rings are preferred.

  As one of the preferred embodiments according to the present invention, for example, an arylsilane compound having a coumarin residue represented by the general formula 1 can be mentioned.

General formula 1:

In General Formula 1, R ^{1 to} R ⁴ each independently represent a hydrogen atom or a substituent. Examples of the substituent in R ^{1 to} R ⁴ include a methyl group, ethyl group, propyl group, isopropyl group, isopropenyl group, 1-propenyl group, 1-propynyl group, 2-propenyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-butenyl group, 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, Cyclohexenyl 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, methoxy group, ethoxy group , Ether groups such as propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, allyloxy group, phenoxy group, naphthyloxy group , Methoxycarbonyl group, ethoxycarbonyl group, propoxycal Ester group such as bonyl group, acetoxy group, benzoyloxy group, 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 -Amino groups such as diphenylamino group, naphthylamino group, N, N-naphthylphenylamino group, N, N-dinaphthylamino group and N-carbazoyl group, halogens such as fluoro group, chloro group, bromo group and iodo group Group, hydroxy group, Bokishi group, a cyano group, a nitro group, further include a substituent by combination thereof.

When R ^{1 to} R ⁴ are substituents, adjacent ones are bonded to each other and include the carbon atom to which they are bonded. For example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, piperidine ring, pyrrolidine A cyclic structure such as a ring, a morpholine ring, a urolidine ring, or a pyrone ring may be formed. In this case, R ^{1 to} R ⁴ are not present as independent substituents. When the arylsilane compound has a plurality of coumarin residues, these coumarin residues may be different from each other.

Specific examples of preferred arylsilane compounds according to the present invention include those represented by chemical formulas 1 to 17. Each of these has a major absorption maximum at a wavelength shorter than 480 nm, usually in the violet to blue region near 380 to 450 nm, and the molecular extinction coefficient at the absorption maximum wavelength (hereinafter, the molecular absorption coefficient at the absorption maximum wavelength is expressed as “ε Is also abbreviated as 1 × 10 ⁴ or more, specifically 5 × 10 ⁴ or more, and as a result, light in the same wavelength region is efficiently absorbed. Further, many of the arylsilane compounds represented by the chemical formulas 1 to 17 have emission maxima such as fluorescence maxima in a blue wavelength shorter than 500 nm, usually around 420 to 480 nm. Is emitted. Moreover, many of the arylsilane compounds of the present invention have a decomposition point exceeding 400 ° C., and the glass transition point reaches 100 ° C. or higher. As is well known, the decomposition point and glass transition point in an organic compound are used as indicators of thermal stability and stability in an amorphous state, and the higher the decomposition point and glass transition point, the greater the stability. However, the arylsilane compound of the present invention has a wide variety of uses in various fields that require an organic compound having light absorption ability and light emission ability and excellent thermal stability and stability in an amorphous state. The arylsilane compound of the present invention having a plurality of coumarin residues in the same molecule is characterized by significantly higher light absorbency and light emission ability than those having only one coumarin residue. Incidentally, the decomposition point and glass transition point of the arylsilane compound according to the present invention can be determined by, for example, general-purpose differential scanning calorimetry (hereinafter abbreviated as “DSC analysis”).

The arylsilane compound of the present invention should in no way be limited to those having only two coumarin residues in the same molecule. In addition, the aromatic ring in the arylsilane compound according to the present invention may be monocyclic, for example, a ring assembly type such as a naphthalene ring, anthracene ring, biphenyl ring, terphenyl ring, quinoline ring, indole ring, or a condensed ring. It may be a part of a polycyclic aromatic hydrocarbon group or heterocyclic group, or a combination thereof. Such an aromatic ring may have a substituent, and examples of the individual substituent include aliphatic hydrocarbon groups such as a methyl group, an ethyl group, and a propyl group, a methoxy group, an ethoxy group, and a propoxy group. Halogen groups such as an ether group, a fluoro group, and a chloro group are exemplified. Although depending on the end use of the arylsilane compound, among the four hydrogen atoms constituting the silane molecule, the hydrogen atom that is not substituted by the aromatic ring in the arylsilane compound of the present invention is the chemistry of the arylsilane compound. For the purpose of enhancing general stability, for example, it may be substituted with a substituent such as R ^{1 to} R ⁴ in formula 1 such as an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.

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:

Although the arylsilane compound of the present invention can be prepared by various methods, a method utilizing a condensed ring closure reaction between an arylalkylnitrile residue and a salicylaldehyde is preferable if importance is attached to economy. When this method is used, for example, the silane compound having a plurality of arylalkylnitrile residues represented by the general formula 3 in the same molecule and the general formula 2 having R ^{1 to} R ⁴ corresponding to the general formula 1 are used. By reacting with the salicylaldehyde compound, the arylsilane compound of the present invention is produced in good yield. Ar in the general formula 3 represents an aromatic ring.

General formula 2:

General formula 3:

  Specifically, silane compound and salicylaldehyde compound are each taken in a suitable amount in the reaction vessel, and if necessary, dissolved in a solvent as appropriate, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, Basic compounds such as potassium hydrogen carbonate, ammonia, triethylamine, piperidine, pyridine, pyrrolidine, aniline, N, N-dimethylaniline, N, N-diethylaniline, hydrochloric acid, sulfuric acid, nitric acid, acetic acid, acetic anhydride, trifluoroacetic acid, Add an appropriate amount of acidic compounds such as p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, and Lewis acidic compounds such as aluminum chloride, zinc chloride, tin chloride, titanium tetrachloride, and then heat and stir by heating and refluxing. While reacting at ambient temperature or above ambient temperature. That.

  Examples of the solvent include hydrocarbons such as pentane, hexane, cyclohexane, octane, isooctane, benzene, toluene, xylene, carbon tetrachloride, chloroform, 1,2-dichloroethane, 1,2-dibromoethane, trichloroethane, tetrachloroethane. , Halides such as chlorobenzene, bromobenzene, α-dichlorobenzene, methanol, ethanol, 2,2,2-trifluoroethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, isobutyl alcohol, isopentyl Alcohol, cyclohexanol, ethylene glycol, propylene glycol, 2-methoxyethanol, 2-ethoxyethanol, phenol, benzyl alcohol, cresol, diethylene glycol, tri Alcohols and phenols such as tylene glycol and glycerin, diethyl ether, diisopropyl ether, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, anisole, 1,2-dimethoxyethane, diethylene glycol dimethyl ether, dicyclohexyl-18-crown-6, methyl Ethers such as carbitol and ethyl carbitol, acetic acid, acetic anhydride, trichloroacetic acid, trifluoroacetic acid, ethyl acetate, butyl acetate, ethylene carbonate, propylene carbonate, propionic anhydride, formamide, N-methylformamide, N, N- Acids and acid derivatives such as dimethylformamide, N-methylacetamide, N, N-dimethylacetamide, hexamethylphosphoric triamide, triethyl phosphate, acetonitrile, propylene Nitriles such as nitrile, succinonitrile and benzonitrile, nitro compounds such as nitromethane and nitrobenzene, sulfur-containing compounds such as dimethyl sulfoxide and sulfolane, water and the like can be mentioned, and these are used in combination as necessary.

  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 as large as the whole raw material compound, usually 5 to 50 times in mass ratio. 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 arylsilane compound according to the present invention can be prepared in a desired amount by the above-described method or according to this method.

  Although the arylsilane compound thus obtained may be used as a reaction mixture depending on the application, it is usually prior to use, for example, dissolution, separation, decantation, filtration, extraction, concentration, thin layer chromatography. And purified by general methods for purifying related compounds such as gas chromatography, high performance liquid chromatography, distillation, sublimation, crystallization, etc., and these methods are applied in combination as necessary. When the arylsilane compound of the present invention requires a high-purity luminescent organic compound, for example, when used as a laser working substance in a dye laser, a material for a light emitting layer in an organic EL element, or a material for adjusting chromaticity, it is used. Prior to this, it is desirable to carry out high purification by a method such as distillation, crystallization and / or sublimation.

Among these, sublimation is particularly excellent because high-purity crystals can be obtained by a single operation, and the loss of the arylsilane compound accompanying the operation is small, and the solvent is not taken into the crystals. . 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 arylsilane compound of the present invention under reduced pressure, for example, an appropriate amount of the arylsilane 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. In order not to decompose the arylsilane compound, heating is performed at a temperature as low as possible below the melting point. When the purity of the arylsilane compound to be subjected to sublimation purification is relatively low, the sublimation rate is suppressed by adjusting the degree of vacuum and heating temperature so that impurities are not mixed, and when the arylsilane compound is difficult to sublimate. Promotes sublimation by ventilating a rare gas or the like into 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.

  The use of the arylsilane compound according to the present invention will be described. The arylsilane compound of the present invention has light absorption / emission characteristics and stability as described above, and various fields including information recording and solar power generation. For example, amide, alcohol, ketone, nitrile, and halogen-based organic solvents exhibit practically undissolvable solubility and absorb visible light in the purple to blue range As a light-absorbing material that cuts off or uses the energy, for example, information recording, printing, printed circuit, solar power generation, electrical machinery equipment, telecommunication equipment, optical equipment, clothing, bedding products, It is extremely useful in a wide variety of fields including health supplies and agricultural materials.

  That is, the arylsilane compound according to the present invention absorbs photographic materials and visible light in the field of information recording, and increases the number of polymerizable compounds and polymerization initiators used in optical cards, plate making, thermal transfer recording, thermal recording, and the like. It is useful as a sensitizer or photothermal exchange agent for accelerating polymerization. Most of the arylsilane compounds of the present invention have an absorption maximum wavelength, for example, argon laser, krypton ion laser, gas laser such as helium-neon leather, semiconductor laser such as CdS laser, distributed feedback type or Bragg reflection type. Since it is close to the oscillation wavelength of a general-purpose visible laser having a wavelength of around 500 nm, specifically 450 to 550 nm, including a solid-state laser such as an Nd-YAG laser, such a visible laser, mercury As a photosensitizer of a photopolymerizable composition using a lamp, a metal halide lamp, a xenon lamp or the like as an exposure light source, for example, the field of information recording such as a thin film hologram, a volume hologram, an optical recording medium, offset plate making, gravure plate making, Screen plate making, direct plate making, digital Fields of printing such as Elect plate making, flexo plate making, printing circuit fields such as etching resist ink, plating resist ink, solder resist ink, character ink, electrophotography such as copying machines, facsimiles, printers, etc. It is extremely useful in the field of optical wiring such as optical SMT) and self-forming connection technology (optical soldering), and further in various fields such as paints, adhesives, packaging materials, and dental forming materials.

  As another application as a sensitizer, for example, in the field of photovoltaic power generation, when the arylsilane compound according to the present invention is supported on the semiconductor electrode of a dye-sensitized wet solar cell, the sensitivity of the semiconductor electrode to visible light is improved. In addition, the photoelectric conversion efficiency of the solar cell can be significantly improved. Since the arylsilane compound of the present invention exhibits light resistance that is practically unaffected by ambient light such as natural light and artificial light, a solar cell using the arylsilane compound of the present invention as a photosensitizer is long. Even if it is used for a long time, there is an actual advantage that it is difficult to cause a decrease in electromotive force due to the photosensitizer.

  In the fields of telecommunications equipment, electromechanical equipment, and optical equipment, the arylsilane compound according to the present invention is used as a filter material, for example, when applied to color filters, color conversion filters, image pickup tubes, semiconductor light receiving elements, optical fibers, etc. Block the hue light or convert it to light of another hue, reduce the ambient temperature rise due to noise derived from visible light, radiated heat rays, etc., or bring the visibility to the desired level There are benefits that can be adjusted. As another application as a filter material, in the field of agricultural materials, for example, by applying it to glass substrates for greenhouses, plastic substrates for vinyl houses formed into sheets or films, fruit trees, grains, vegetables, flowers It is possible to control the growth of plants by adjusting the wavelength distribution of light reaching useful plants such as ornamental plants, garden plants, edible plants, and medicinal plants.

  Further, together with the arylsilane compound according to the present invention and, if necessary, one or more of other materials that absorb light in the ultraviolet region, visible region and / or infrared region, a light shielding agent, a heat ray shielding agent, a heat insulating agent, Apparel in general as a heat-retaining agent, especially clothing that uses heat-retaining and storage fibers and fibers that have disguise performance for reconnaissance by ultraviolet rays, visible light, infrared rays, etc., other than clothing, for example, drape, pleats, shirring, lace , Casement, print, venetian blind, roll screen, roman shade, shutter, goodwill, blanket, duvet, duvet, duvet cover, sheets, cushion, pillowcase, pillowcase, cushion, mat, carpet, sleeping bag, automobile Interior materials, bedding products such as window glass, window glass, paper diapers, diaper covers, glasses, mono Filters for information display devices that use health supplies such as le and ronet, insoles, shoe linings, footwear, furoshiki, umbrellas, parasols, stuffed animals, lighting devices, cathode ray tube displays, liquid crystal displays, plasma displays, etc. , Panels and screens, sunglasses, sun visors, sunroofs, gas ranges, electric ranges, microwave ovens, ovens and other viewing windows, as well as packaging materials for filling, packing or containing these items, filling materials When used in containers, etc., unnecessary temperature changes, eye strain caused by excessive visible light, aging of photoreceptor cells, damage caused by environmental light such as natural light and artificial light in living organisms and articles such as cataract In addition to preventing or reducing inconveniences and inconveniences, the chromaticity, color tone, color, texture, etc. of the product can be adjusted. Or, there is a practical benefits that can adjust the light transmitted through or reflected from the article to the desired color balance. In addition, the arylsilane compound of the present invention, like the conventionally known organic dye compounds that absorb visible light, is a falsification preventing ink, a falsification / counterfeiting bar code ink, a light absorbing ink, a light absorbing paint, and a photo or film positioning. Marking agents, sorting dyes for recycling plastics, preheating aids for molding PET bottles, and pharmaceuticals for treating general tumors that are sensitive to visible light It can be used as an active ingredient, or as an ingredient that helps the action of the active ingredient.

  In addition to the various uses as the light-absorbing material described above, the arylsilane compound of the present invention, when excited, emits fluorescence in the blue region shorter than 500 nm, usually in the blue region near 420 to 480 nm. For example, it is useful as a fluorescent whitening agent or a laser acting substance in a dye laser that requires an organic compound that exhibits light-emitting ability. When the arylsilane compound of the present invention is used for a dye laser, the arylsilane compound is purified in the same manner as in the case of constructing a known dye-based laser oscillation device, dissolved in a solvent as appropriate, and, for example, cyclohexane is used. Add a suitable amount of heptatriene, cyclooctatetraene, piperidine, and benzophenone and benzotriazole triplet quenchers, adjust the pH of the solution to an appropriate level, filter, and then dye cell in the laser oscillation device Enclose in. The arylsilane compound of the present invention provides an amplification gain in a very wide wavelength region in the visible region, and can greatly change the oscillation wavelength by changing the pH of the solvent. It has high heat resistance and light resistance and is not easily deteriorated even when used for a long time. Thus, the arylsilane compound according to the present invention is used in combination with one or a plurality of other organic dye compounds that function as a laser acting substance, if necessary, and an appropriate narrowing technique is used as necessary. By applying it, it is possible to construct a narrow-band dye laser that oscillates at an arbitrary wavelength in an extremely wide wavelength range from the ultraviolet region to the infrared region. Such a variable wavelength dye laser is extremely useful as a laser light source in so-called picosecond / femtosecond analysis in the field of spectroscopic analysis or separation of isotopes such as plutonium and uranium by a laser method.

  Slightly special uses utilizing the light-absorbing ability of the arylsilane compound according to the present invention include, for example, enzyme reaction, antigen-antibody reaction, signal transduction inside and outside cells, formation of complex between proteins, hybridization between protein and nucleic acid, or between nucleic acids. Luminescence for labeling enzymes, substrates, antigens, antibodies, soluble receptors, proteins, glycolipids, nucleic acids, etc. in qualitative and quantitative analysis using specific reactions found between substances of biological origin The use as an agent is mentioned. The biological material labeled with the arylsilane compound of the present invention is extremely useful in the field of research and diagnosis as, for example, a biosensor.

  By the way, as described above, the arylsilane compound used in the present invention has a light emission maximum such as a fluorescence maximum in a wavelength shorter than 500 nm, usually around 420 to 480 nm, and emits visible light in a blue region when excited. Moreover, since it has excellent thermal stability and stability in an amorphous state, it is extremely advantageous in organic EL elements that emit visible light in the blue range as materials for organic EL elements such as light emitting layer materials and chromaticity adjusting materials. Can be used. The organic EL element as used in the present invention means an organic EL element using an arylsilane compound as described above, and in particular, an anode for applying a positive voltage, a cathode for applying a negative voltage, holes and electrons. A light emitting layer that recombines and extracts light emission, and if necessary, a hole injection / transport layer that injects and transports holes from the anode, and an electron injection / transport that injects and transports electrons from the cathode. Single layer type and stacked type organic EL devices provided with a layer, a hole blocking layer that suppresses movement of holes from the light emitting layer to the electron injection / transport layer, and the like 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 laminated. Among them, for example, aluminosilicate glass, aluminoborosilicate glass, quartz glass, borosilicate glass, barium borosilicate glass, etc., both have a low alkali content and a low thermal expansion coefficient, have a smooth surface, no scratches, and are easy to polish. Excellent compatibility with glass for photomasks and adjacent conductive films, and hardly permeates 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.

  In FIG. 1, reference numeral 2 denotes an anode, which is made of one or more of a metal or an electrically conductive material having a low electrical resistivity and a high light transmittance over the entire visible region. Chemical vapor deposition (CVD), atomic layer epitaxy (ALE), vacuum deposition, immersion, screen printing, sputtering, electrochemical polymerization (electrolytic polymerization), electrochemical deposit (electrodeposition), coating, heat It is adhered to one side of the substrate 1 by a diffusion method, thermal transfer method, optical transfer method, photolithography method, photopolymer method, or the like, and the resistivity at the anode 2 is 1 kΩ / □ or less, preferably 5 to 50Ω. / □ 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.

In FIG. 1, reference numeral 3 denotes a hole injection / transport layer. Usually, the hole injection / transport layer material is formed in a thickness of 1 to 1,000 nm by being in close contact with the anode 2 by the same method as in the anode 2. It is formed by doing. 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.

  In FIG. 1, reference numeral 4 denotes 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 arylsilane compounds according to the present invention are used alone or appropriately. 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 of the above host compounds or guest compounds. Since the arylsilane compound of the present invention easily generates excitons such as singlet excitons and triplet excitons, and is suitable for the energy level of light emission such as fluorescence and phosphorescence, a conventionally known light emitting layer material In contrast, the light emitting layer of the organic EL device can be constituted by itself or in combination with one or a plurality of host compounds or guest compounds. In particular, when the arylsilane compound of the present invention as a host compound is combined with an appropriate guest compound, extremely high levels of light emission 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 arylsilane 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 material for the light emitting layer itself, so by increasing the compounding ratio with respect to the host compound in the light emitting layer. 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 usually equimolar to the host compound in an amount of usually 0.1 to 10 mol%, preferably 0.8. The light emitting layer 4 is formed by using 5 to 5 mol% and separating both into a single layer or multiple layers and forming a film of 1 to 1,000 nm, preferably 10 to 200 nm.

  When the arylsilane compound according to the present invention is used as a host compound, other host compounds used in combination with the arylsilane compound of the present invention include quinolinol metal complexes widely used in organic EL devices, such as anthracene, chrysene, coronene, Condensed polycyclic hydrocarbons such as triphenylene, naphthacene, naphthalene, phenanthrene, picene, pyrene, fluorene, perylene, benzopyrene and their derivatives, quarterphenyl, distyrylarylene, 1,4-diphenylbutadiene, stilbene, terphenyl, tetra Ring-assembled hydrocarbons such as phenylbutadiene and biphenyl and their derivatives, such as oxadiazole, carbazole, pyridazine, benzimidazole, benzoxazole, and benzothiazole. Heterocyclic compounds and derivatives thereof, quinacridone, rubrene and their derivatives, furthermore, 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, This means a general complex composed 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 any of 8-quinolinols or benzoquinolin-10-ols, they may have one or more substituents, the 8-position where the hydroxy group is bonded or To carbons other than carbon at 10 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-butyl group, pentyl group, isopentyl group, neopentyl group, aliphatic hydrocarbon group such as tert-pentyl group, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, phenoxy group, benzyloxy An ether group such as an acetoxy group, a benzoyloxy group, a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a cyano group, a nitro group, a sulfo group, Does not prevent multiple 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 ( Magnesium complexes such as 5-chloro-8-quinolinolato) magnesium and 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 derivatives thereof, polythienylene vinylene and derivatives thereof, polythiophene and derivatives thereof, polynaphthylene vinylene and derivatives thereof, poly-N-vinylcarbazole and derivatives thereof, polyphenylene vinylene and Derivatives thereof, polyfluorenes and derivatives thereof, etc., and these are used in combination as necessary, and as described above, the arylsilane compound according to the present invention can be used only as a host compound in an organic EL device. When the aryl silane compound according to the present invention is used as the guest compound, the aryl silane compound according to the present invention and the host compound as described above can be used. A light emitting layer of the organic EL device is constituted by appropriately combining with other than the arylsilane compound.

  In FIG. 1, reference numeral 5 denotes 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 an anthraquinodimethane derivative, for example. In anthrone derivatives, oxadiazole derivatives, carbodiimides, distyrylpyrazine derivatives, diphenylquinone derivatives, silazane derivatives, thiopyrandioxide derivatives, triazole derivatives, heterocyclic tetracarboxylic acid derivatives, phthalocyanine derivatives, fluorenone derivatives, in the light emitting layer 4 The quinolinol metal complex similar to the above, and further, one or a plurality of electrically conductive oligomers or polymers having aniline, thiophene, pyrrole or the like as a repeating unit are formed 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.

  In FIG. 1, reference numeral 6 denotes 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). , Calcium, sodium, potassium, silver, copper, aluminum, indium, ytterbium, and other metals, 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 in consideration of the electrical conductivity, the manufacturing cost, the thickness of the element itself, 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 use 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 It is desirable to apply a moisture-proof paint or to cover it 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 usually has a light emission maximum such as a fluorescence maximum in a blue region of 450 to 490 nm, although it depends on the structure and blending ratio of the arylsilane compound, the host compound used in combination, and the guest compound. Such luminescence is usually in the range of 0.01 to 0.20 and in the range of 0.02 to 0.70 on the xy chromaticity diagram by the International Commission on Illumination (CIE). .

  The organic EL device of the present invention has excellent durability and 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 gonorrhea, and further, livestock, poultry, seafood, insects, fruit trees, grains, vegetables, Applicable to lighting to control photoperiodism and phototaxis of flora and fauna. Note that the organic EL element of the present invention using a reflecting mirror functioning as a micro-optical resonator at the anode and the cathode is useful as, for example, a thresholdless laser operating in a small current region.

By the way, the arylsilane compound of the present invention has an absorption maximum in a violet to blue region near a wavelength of 380 to 450 nm, and has a molecular extinction coefficient of 1 × 10 ⁴ or more, preferably 5 × 10 ^{4 at the} absorption maximum wavelength. Since it is large as mentioned above, it is useful as a chromaticity adjusting material for adjusting the chromaticity of light emission by the organic EL element to a desired level in addition to the use as a light emitting layer material in the organic EL element. Thus, the organic EL element referred to in the present invention is not limited to the one containing a specific arylsilane compound as a material for the light emitting layer, and in addition to that, the chromaticity of electroluminescence by the light emitting compound is adjusted. General organic EL devices that use a specific arylsilane compound in the light emitting layer or other than the light emitting layer for the purpose, or use a specific arylsilane compound and one or more of other compounds having light absorption in combination Will be included.

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

<Arylsilane compound>
In a reaction vessel, 3.6 g of the compound represented by Chemical Formula 18, 3.3 g of 4-diethylaminosalicylaldehyde, 5.9 g of acetic acid and 10 ml of piperidine were taken and reacted by heating at 170 ° C. for 4 hours, and then the reaction mixture was mixed with chloroform. And extracted. The chloroform layer was collected by tilting, washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and then chloroform was distilled off. The obtained oil was purified by silica gel column chromatography using a chloroform / ethyl acetate mixed solution as a developing solvent and crystallized to obtain 3 g of an arylsilane compound crystal of the present invention represented by Chemical Formula 4.

Chemical formula 18:

A portion of the crystal was taken and the visible absorption spectrum and fluorescence spectrum in a methylene chloride solution were measured by a conventional method, and an absorption maximum (ε = 8.27 × 10 ⁴ ) and a fluorescence maximum were observed near wavelengths of 406 and 467 nm, respectively. It was done. When the melting point, decomposition point, and glass transition point were measured by ordinary DSC analysis, the arylsilane compound of this example had a melting point near 243 ° C., a glass transition point near 121 ° C., and a decomposition point near 448 ° C. Indicated. 2. When a ¹ H-nuclear magnetic resonance spectrum in a chloroform-d solution was measured by a conventional method, the chemical shift δ (ppm, TMS) was 1.22 (12H, t, J = 7.2 Hz, CH ₃ −). _{43 (8H, q, J =} 7.2Hz, -CH 2 -), 6.54 (2H, d, J = 2.4Hz, ArH), 6.60 (2H, dd, J 1 = 8.7Hz, Peaks were observed at positions of J ₂ = 2.4 Hz, ArH), 7.31 to 7.47 (8H, m, ArH) and 7.60 to 7.74 (14H, m, ArH). In mass spectrometry using a conventional method, a molecular ion peak (M + H) ⁺ having a mass (m / e) of 767.4 was observed. In addition, the arylsilane compound of this example exhibited the solubility which has no practical problem in ordinary amide-based, alcohol-based, ketone-based, nitrile-based and halogen-based organic solvents.

  The arylsilane compound of this example, which has excellent solubility in solvents and thermal properties, and has an absorption maximum and emission maximum in the short wavelength visible region, for example, information recording, printing, printed circuit, solar power generation, electromechanical equipment, Absorbs short-wave visible light by absorbing short-wave visible light in various fields including telecommunications equipment, optical equipment, clothing, bedding, health supplies, and agricultural materials. It is useful as a light emitting material in materials, dye lasers, analysis and the like. In addition, the arylamine compound of this example, which emits fluorescence in the blue region when excited, is useful as an organic EL device material such as a light emitting layer material and a chromaticity adjusting material in an organic EL device aiming at light emission in the blue region.

<Arylsilane compound>
The arylsilane compound obtained by the method of Example 1 was charged into a water-cooled sublimation purification apparatus and purified by heating in an ordinary manner while keeping the apparatus at a reduced pressure.

  The arylsilane compound of this example can be advantageously used in various fields that require high-purity organic compounds that absorb or emit short-wavelength visible light.

  Although the arylsilane compound according to the present invention has slight differences in the charging conditions and yield depending on the structure, for example, all of the arylsilane compounds including those represented by the above chemical formulas 1 to 17 are the methods of Examples 1 and 2. Or the desired amount can be obtained according to those methods.

<Organic EL device>
Using the arylsilane compound according to the present invention as a material for the light emitting layer, 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 the organic substance 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. To the side having electrodes, as a material for a hole injection / transport layer, copper phthalocyanine represented by Chemical Formula 19 (hereinafter abbreviated as “CuPc”) and triphenylamine tetramer represented by Chemical Formula 20 (hereinafter referred to as “CuPc”) Abbreviated as “TPTE”) in this order to a thickness of 10 nm and 30 nm, respectively, to form a hole injection / transport layer 3. Subsequently, the arylsilane compound according to the present invention represented by the chemical formula 4 and the dipyrenylphenyladamantane compound (hereinafter referred to as “PY-AD”) which is the blue light emitting material represented by the chemical formula 21 are used as the light emitting layer material. ) In a weight ratio of 0.5: 100 to 1.5: 100 to a thickness of 40 nm to form a light emitting layer 4 that is in close contact with the hole injection / transport layer 3, and then tris. (8-quinolinolato) 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 19:

Chemical formula 20:

Chemical formula 21:

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 to obtain an organic EL device. With respect to the organic EL device thus obtained, the electroluminescence characteristics and the lifetime (driving time at which the initial luminance is reduced by half) were determined by ordinary methods. The lifetime was determined by setting the initial luminance to 2,400 cd / m ² at room temperature. Separately, for comparison, an organic EL element using only PY-AD as the material for the light emitting layer was prepared and tested in the same manner as a control. The results are shown in Table 1.

  As seen in Table 1, both the organic EL device of this example and the control organic EL device had a light emission maximum in the blue region near the wavelength of 450 to 470 nm. The coordinates of light emission on the xy diagram by CIE are as follows. In the case of the control organic EL element, x is 0.18 and y is 0.19. Also, in the organic EL element of this example, x is 0.16, y Was 0.23. In neither the organic EL element of this example nor the control organic EL element, light emission peculiar to the host compound was not recognized, which indicates that the excitation energy was efficiently transferred from the host compound to the guest compound.

However, as can be seen in the column of “Luminance Luminance” in Table 1, when the organic EL element of this example is driven at a constant current at a current density of 11 mA / cm ^2, it exhibits a high luminance of 473 cd / m ² at room temperature. The power efficiency and external quantum efficiency were also higher than those of the control organic EL device. None of the organic EL devices of the present invention sustained stable light emission, and no non-light-emitting portions such as dark spots were observed even when driven at high brightness (2,400 cd / m ² ) for 10 hours or longer. On the other hand, the lifetime of the control organic EL device when tested in the same manner was at most 5 hours. The lifetime of the organic EL device using the arylsilane compound represented by the chemical formula 4 is remarkably long, and the lifetime when continuously driven at a practical luminance of 300 cd / m ² is estimated to be 1,500 hours or more, and there is no practical problem. It was a thing.

  The above results show that by using the arylsilane compound of the present invention as a material for the light emitting layer, it is possible to realize a long-life, high-brightness, high-efficiency organic EL element that emits light in the blue region.

<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 3, 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 3, 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 4. 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 supplies a constant voltage of 5V to the microcomputer 38.

  The microcomputer 38 includes an I / O interface 38a that exchanges signals with the outside, a ROM 38b that records programs, a RAM 38c that records various data, and a CPU 38d that executes 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. 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. 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.

  As described above, the present invention is based on the creation of a novel arylsilane compound. The arylsilane compound according to the present invention is stable in addition to efficiently absorbing visible light in the purple to blue region, and emits blue light when many of them are excited. The organic compound having such properties has various uses in various fields including, for example, photochemical polymerization, solar cell, optical filter, dyeing, dye laser, and analysis. Furthermore, the arylsilane compound of the present invention is a material for a light emitting layer such as a host compound or a guest compound constituting a light emitting layer, or an electroluminescent chromaticity in the field of an organic EL device which is attracting attention as a next generation display device. It is extremely useful as a material for organic EL elements including a chromaticity adjusting material for adjusting the color to a desired level. Since the organic EL element of the present invention is excellent in luminous efficiency and durability, a wide variety of information for visually displaying character information and image information by forming a light emitter in general illumination, for example, a panel shape. It can be used very advantageously in display devices.

Claims (7)

  An arylsilane compound having a plurality of coumarin residues in the same molecule.   The arylsilane compound according to claim 1, which has a tetraarylsilane structure, and a coumarin residue is bonded to a plurality of aromatic rings. The arylsilane compound according to claim 1, wherein the coumarin residue is represented by the general formula 1.
General formula 1:

(In General Formula 1, R ^{1 to} R ⁴ each independently represents a hydrogen atom or a substituent.)   An organic electroluminescent element material comprising the arylsilane compound according to any one of claims 1 to 3.   The organic electroluminescent element using the arylsilane compound in any one of Claims 1 thru | or 3.   A display panel using the organic electroluminescent element according to claim 5.   The information display apparatus using the organic electroluminescent element of Claim 5.

Images