JP2005071773A - Full-color picture display device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a full-color picture display device which can display a full-color picture in high luminance which is not deteriorated in color even if a long period has passed. <P>SOLUTION: The color picture display device comprises a color filter formed by arranging pixels composed of a blue color separation element transmitting a blue color, a green color separation element transmitting a green color, and a red color separation element transmitting a red color in parallel in a matrix form, and a white color emitting compound containing a white organic fluorescence compound which is a single compound emitting a white color by electromagnetic wave energy. As the white organic fluorescence compound, a white organic fluorescence compound as expressed by a formula (1) or (2) is preferable. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a full-color image display device, and more particularly to a full-color image display device capable of displaying a full-color image with no luminance deterioration even after a long period of time with high luminance.

  According to Patent Document 1, conventionally, two methods have been considered in order to perform full-color display using an organic electroluminescent element. One is a method in which the blue, green, and red light emitting portions are arranged in a planar shape. Another method is to divide the light from the white light emitting element into blue, red and green pixels using a color filter. This method requires an organic electroluminescence device that emits white light, but the white light-emitting devices using conventional tetraphenylbutadiene derivatives (Patent Documents 2 and 3) have insufficient light emission characteristics (Patent Document 1). .

JP-A-7-142169

Japanese Patent Laid-Open No. 4-88079

JP-A-5-94875 In addition, according to the above-mentioned patent document 1, white light emitting organic electric field elements have 1) low luminous efficiency and high luminance cannot be obtained, and 2) blue, green, and red It is said that there is a problem that it is difficult to balance each emission luminance, and 3) there is no long-term stability due to deterioration such as crystallization of the organic layer.

  The invention proposed in Patent Document 1 is as described in claim 1, “An organic electroluminescent element having at least a hole transport layer and an organic light emitting layer sandwiched between an anode and a cathode on a substrate. The organic light-emitting layer is formed by sequentially laminating a blue light-emitting layer and a green light-emitting layer from the hole transport layer side, and the green light-emitting layer has a region containing a red fluorescent dye. A light emitting element.

  In the organic electroluminescent device described in Patent Document 1, since the fluorescent dyes contained in the blue light emitting layer and the green light emitting layer are different, the blue light emitted from the blue light emitting layer and the green light emitted from the green light emitting layer are different. It is difficult to display a clear full-color image without turbidity unless the brightness is finely adjusted, and the time-dependent characteristics of the fluorescent dye contained in the blue light-emitting layer and the fluorescent dye contained in the green light-emitting layer are different. The color image is assumed to have a problem that the color image changes or fades with time.

  The object of the present invention is to solve the above-mentioned problems. That is, the present invention can display a full-color image with high luminous efficiency and high luminance, and can balance the emission luminance of blue, green and red, and display a stable full-color image over a long period of time. An object of the present invention is to provide a full-color image display device capable of performing the above.

Means for solving the problems are as follows:
A color filter formed by arranging pixels in which a blue separating element that transmits blue, a green separating element that transmits green, and a red separating element that transmits red are arranged in a matrix, and a single element that emits white light by electromagnetic energy A color image display device comprising a white light-emitting compound containing a white organic fluorescent compound as a compound,
As the white organic fluorescent light-emitting compound, a white organic fluorescent compound represented by the following formula (1) or (2) is suitable.

(However, R ¹ represents a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl group. R ² represents a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl group.)

(However, R ¹ represents a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl group. R ³ and R ⁴ are a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl group, and each is the same group. Or a different group.)

According to the present invention, a white light-emitting element containing a white fluorescent light-emitting compound having a specific structure having a fluorescent light-emitting region of 400 to 700 nm and having a luminance of 2000 Cd / m ² or more while being a single substance is adopted. It is possible to provide a full-color image display device capable of displaying an image with good color purity and high luminance without deterioration of the full-color image with the passage of time.

  A full-color image display device of the present invention will be described with reference to the drawings.

  As shown in FIG. 1, a full color image display device as an example of the present invention includes a color filter layer 1, a white light emitting layer 2, a barrier layer 3, electrode layers 4a and 4b, an insulating isolation layer 5, And a transparent substrate 6.

  The transparent substrate 6 may be a sheet that is transparent and has a mechanical strength on which other members of the present invention such as the color filter layer 2 can be mounted, and may be doped or undoped silicon, oxidized It can be formed of silicon, plastic, glass, metal material or the like. Suitable plastics that can be formed on the transparent substrate 6 include, for example, polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, polyamide imide, polyimide, polyaryl ether nitrile, and thermoplastic. Examples thereof include resin materials such as polyester resins such as polyethylene terephthalate, polybutylene terephthalate, and polybutylene naphthalate.

  The thickness of the transparent substrate 1 can be appropriately determined according to the scale of the full-color image display device, and is, for example, 50 to 1000 μm, preferably 200 to 500 μm.

  The color filter layer 1 includes red, blue and green primary color separation elements 1 a to 1 c arranged on the surface of the transparent substrate 6.

  The blue color separation element 1a in the color filter layer 1 contains, for example, a blue pigment. Examples of the blue pigment include copper phthalocyanine pigments, indanthrone pigments, indophenol pigments, cyanine pigments, dioxane pigments, and the like. The above can be used together. The green color separation element 1b in the color filter layer 1 contains, for example, a green pigment. Examples of the green dye include halogen polysubstituted phthalocyanine pigments, halogen polysubstituted copper phthalocyanine pigments, triphenylmethane basic dyes, isoindoline pigments, and isoindolinone pigments. One kind can be used alone, or two or more kinds can be used in combination. The red color separation element 1c in the color filter layer 1 contains, for example, a red pigment. Examples of the red pigment include perylene pigments, lake pigments, azo pigments, quinacridone pigments, anthraquinone pigments, anthracene pigments, isoindoline pigments, and isoindolinone pigments. One kind can be used alone, or two or more kinds can be used in combination.

  The color filter layer 1 can be formed, for example, by incorporating the dye into a binder resin. When the dye is blue, a blue color separation element 1a is formed, and when the dye is green, the color is green. A color separation element 1b is formed, and if the pigment is red, a red color separation element 1c is formed.

  The binder resin may be a transparent resin, and examples thereof include transparent resins such as polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, and carboxymethyl cellulose.

  A photosensitive resin can also be employed as the binder resin. When the photosensitive resin is used as the binder resin, the color filter layer 1 can be formed by a photolithography method. Examples of the photosensitive resin include photo-curing resist materials having reactive vinyl groups such as acrylic resin, methacrylic resin, polyvinyl cinnamate resin, and cyclized rubber.

  The color filter layer 1 can be formed by the photolithography method, the printing method, the vapor deposition method, or the like.

  According to the photolithographic method, a photoresist mask layer is provided on the surface of the transparent substrate 6 to leave a photoresist portion through an exposure operation and a cleaning operation, and then a predetermined pigment for a color filter is added to a predetermined binder resin. The color separation solution 1a to 1c for each color can be formed by casting or vapor-depositing a color filter solution dissolved in the contained solution and finally removing the photoresist portion.

  According to the printing method, the color separation elements 1a to 1c for each color can be manufactured on the surface of the transparent substrate 6 by a technique such as gravure printing, letterpress printing, intaglio printing, and planographic printing.

  In the vapor deposition method, the blue dye or pigment, the green dye or pigment, and the red dye or pigment are attached to the surface of the transparent substrate 6 by vapor deposition so that a desired pattern of a color separation element is obtained. Each color separation element is formed. This vapor deposition method can reduce the thickness of the color separation elements 1a to 1c, eliminates the need to use an expensive resist material, and further reduces the cost. Since it is not used, there is an advantage that a color filter layer with high color purity can be formed.

Regardless of which method is used to form the color filter layer 1, each of the three primary color separation elements 1 a to 1 c in the color filter layer 1 only needs to have spectral characteristics that diverge into red, blue, and green. The blue separation element 1a in the preferred color filter layer 1 preferably has a spectral characteristic of 440 nm ≦ λ _1B ≦ 470 nm, 490 nm ≦ λ _2B ≦ 520 nm, and 50% ≦ T _1B ≦ 90%. The green separation element 1b preferably has a spectral characteristic of 520 nm ≦ λ _1G ≦ 540 nm, 490 nm ≦ λ _2G ≦ 510 nm, 570 nm ≦ λ _2G ≦ 590 nm, and 50% ≦ T _1G ≦ 90%. The red separation element 1c preferably satisfies 620 nm ≦ λ _1R ≦ 700 nm, 580 nm ≦ λ _2R ≦ 600 nm, and 70% ≦ T _1R ≦ 95%. Here, λ ₁ indicates the maximum transmittance wavelength, T ₁ is the maximum transmittance value, λ ₂ is the half-value wavelength of transmittance, and the subscript B attached to λ ₁ , T ₁ and λ ₂ is blue , G represents green, and R represents red. When the separation elements 1a to 1c of the respective colors satisfy the maximum transmittance wavelength, the maximum transmittance value, and the half-value wavelength of the transmittance, the color purity of each of the three primary colors is satisfied to an extent that is visually inconspicuous. The brightness of becomes higher.

  The thickness of the color filter layer 1 is usually preferably 2000 nm or less, particularly preferably 300 to 600 nm. Needless to say, if the thickness of the color filter layer 1 is too thin, the function as a color filter may not be sufficiently exhibited, and if the thickness is too large, the loss of light transmission may be increased.

  For example, the barrier layer 3 is formed on the surface of the color filter layer 1 on the side opposite to the surface in contact with the transparent substrate 6. The barrier layer 3 can protect the color filter layer 1 from etching and cleaning liquid when forming the electrode layer 4a, or can protect the white light emitting layer 2 from moisture and gas.

The barrier layer 3 is preferably formed of SiC _x or SiN _y . Here, X in SiC _x is preferably 1.8 to 2.2, and _y in SiN _y is preferably 0.1 to 0.5. Moreover, the thickness of the barrier layer 3 is usually preferably 5 to 50 nm, particularly preferably 10 to 30 nm.
The electrode layers 4 a and 4 b are disposed so as to sandwich the white light emitting layer 2 disposed adjacent to the barrier layer 3. The white light emitting layer 2, the electrode layer 4a disposed on one surface of the white light emitting layer 2, and the electrode layer 4b disposed on the other surface of the white light emitting layer 2 form a light generating layer.

  In the embodiment shown in FIG. 1, one electrode 4a extends in the X direction, for example, and is disposed so as to correspond to each of the color separation elements 1a to 1c, and the other electrode 4b extends in the X direction. It extends along the orthogonal direction, that is, the Y direction. When the electrodes 4a and 4b are energized, the portion of the white light emitting layer 2 sandwiched between the electrodes 4a and 4b emits white light. Accordingly, a plurality of electrodes 44 are disposed on one surface of the white light emitting layer 2 so that one color separation element can emit light by the electrodes 4a and 4b, and extend in a direction perpendicular to the electrodes 4a. A plurality of electrodes 4 b are disposed on the other surface of the white light emitting layer 2.

  The electrode 4a interposed between the barrier layer 3 and the white light emitting layer 2 is preferably made of a transparent metal because it is necessary to transmit the white color generated in the white light emitting layer 2 to the glass filter layer 1. . Examples of the electrode 4a may include tin-doped indium oxide, zinc-doped indium oxide, indium oxide, tin oxide, and zinc oxide. These oxides may be used alone as an electrode, or two of them. Thus, an electrode can be formed. The thickness of the electrode 4a is preferably 50 to 500 nm, and particularly preferably 50 to 300 nm. If the thickness of the electrode 4a is less than the lower limit, it may be difficult to form the electrode as a uniform and uniform film when forming the electrode, and if the upper limit is exceeded, the light transmittance may be reduced. is there.

  The electrode 4b interposed on the opposite side of the white light emitting layer 2 from the barrier layer 3 is an ordinary metal such as Al, Ag, In, Ti, Cu, Au, Mo, W, Pt, Pd and Ni. be able to. Suitable metals for the electrode 4b are Al and Ag. The thickness of the electrode 4b is preferably at least 50 nm, particularly preferably at least 100 nm, and usually 50 to 500 nm.

  In order to emit light from a predetermined portion of the white light emitting layer 2, it is generally preferable to adopt either the XY address method or the active matrix method. The XY address method is suitable for a small display, and the active matrix method is suitable for a larger display.

  In the XY addressing system, as shown in FIG. 1, a specific electrode 4a that is energized among a plurality of electrodes 4a arranged in parallel and a parallel arrangement in a direction orthogonal to the extending direction of the electrode 4a. The white light emitting layer 2 emits light at a portion where the specific electrode 4b energized among the plurality of electrodes 4b has a tolerance. Light is emitted in blue, green, red, or a mixed color according to the color in the color separation element corresponding to the white light emitting layer 2 that emits light.

  Examples of the white organic fluorescent compound in the present invention include a single compound that can emit white light having an emission spectrum ranging from 400 nm to 700 nm when irradiated with electromagnetic energy, for example, light energy. The full-color image display device according to the present invention has a white light-emitting layer containing a single compound capable of emitting white light as a light-emitting source. Therefore, as in the prior art, a red light-emitting layer containing a red light-emitting compound, green Since a light-emitting layer having a green light-emitting layer containing a green light-emitting compound and a blue light-emitting layer containing a blue light-emitting compound emitting blue light is not employed, a full-color image displayed on a full-color image display device has elapsed over time At the same time, the red light emission layer does not deteriorate red light emission, green light emission, or blue light emission. However, among these white organic fluorescent compounds, the white organic fluorescent compounds represented by the formulas (1) and (2) are preferable. Each of the white organic fluorescent compounds represented by the formulas (1) and (2) has a quinacridone skeleton represented by the formula (3).

  The compound represented by the formula (3) is well known as a pigment called quinacridone or pigment violet 19. This quinacridone is synthesized by using, for example, diethyl succinyl succinate and aniline as main raw materials and performing, for example, condensation, ring closure, and oxidation. Quinacridone itself is excellent in fastness, weather resistance and heat resistance (“Color Material Engineering Handbook” (edited by Color Material Association, P402).

  Therefore, the white organic fluorescent compound according to the present invention represented by the formula (1) or (2) is also excellent in fastness, weather resistance, light resistance and heat resistance.

In the formula (1), R ¹ represents a hydrogen atom, an alkyl group, an aryl group or an arylalkyl group. Examples of the alkyl group include an alkyl group having 1 to 30 carbon atoms, and a lower alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable. Two R ¹ may be the same or different. Examples of the aryl group when R ¹ is an aryl group include a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, and a group in which a substituent such as an alkyl group or an alkoxy group is bonded to these aromatic rings. . When R ¹ is an arylalkyl group, the arylalkyl group includes benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylpropyl group, 2-phenylpropyl group, 3-phenylpropyl group, 5-phenylbutyl group etc. can be mentioned, The phenyl group may be further substituted by substituents, such as an alkyl group. A preferred arylalkyl group is a benzyl group.

In the formula (1), two R ^{2 s} are each a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl group, and may be the same group or different groups. Examples of the alkyl group include an alkyl group having 1 to 30 carbon atoms, and a lower alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable. Two R ² may be the same or different. When R ² is an aryl group, the aryl group includes a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, and a group in which a substituent such as an alkyl group and an alkoxy group is bonded to these aromatic rings, such as p-alkoxyphenyl. Groups and the like. When R ² is an arylalkyl group, the arylalkyl group includes benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylpropyl group, 2-phenylpropyl group, 3-phenylpropyl group, 5-phenylbutyl group etc. can be mentioned, The phenyl group may be further substituted by substituents, such as an alkyl group. A preferred arylalkyl group is a benzyl group.

In the formula (2), R ¹ has the same meaning as mentioned in the formula (1).

In the formula (2), R ³ and R ⁴ are a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl group, and may be the same group or different groups. Examples of the alkyl group include an alkyl group having 1 to 30 carbon atoms, and a lower alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group, and a propyl group is particularly preferable. R ³ and R ⁴ bonded to one carbon may be the same or different. When R ³ or R ⁴ is an aryl group, the aryl group includes a phenyl group, a naphthyl group, an anthranyl group, a biphenyl group, and a group in which a substituent such as an alkyl group and an alkoxy group is bonded to these aromatic rings, such as p. -Alkoxyphenyl group etc. can be mentioned. When R ³ or R ⁴ is an arylalkyl group, the arylalkyl group includes benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylpropyl group, 2-phenylpropyl group, 3-phenylpropoxy group. And the like, and a phenyl group may be further substituted with a substituent such as an alkyl group. A preferred arylalkyl group is a benzyl group.

The white organic fluorescent compound represented by the formula (1) or (2) has a substituent of R ¹ , R ² , R ³ and R ⁴ , so that the solubility in a solvent is improved. The coating property is improved by being dissolved in the material, and the sublimation temperature is lowered, so that the workability by vapor deposition is improved, and the compatibility with the polymer compound is improved, so that it can be included in the polymer film. Become.

  The white organic fluorescent compound represented by the formula (1) can be produced, for example, according to the following reaction formula.

In the above formula, R is a lower alkyl group, and R ¹ and R ² have the same meaning as described above. The above reaction formula is, for example, dialkyl 2,5-dihydroxy-1,4-cyclohexadiene-1,4-dicarboxylate (compound (4) in the above reaction formula) and 3-amino-9-alkylcarbazole. It proceeds by heating compound (5) in an appropriate solvent. The dehydration reaction proceeds to obtain a compound (6) crosslinked with an amino group. In the dehydration reaction, an appropriate dehydrating agent such as concentrated sulfuric acid can be used.

  When the dehydration reaction product is further treated with concentrated sulfuric acid or the like, a dehydrogenation reaction occurs as shown in the following formula.

When R ¹ is a hydrogen atom, the dehydrogenation reaction product is reacted with, for example, R ¹ Hal (where Hal represents a halogen atom) in DMF, for example, to thereby convert the dehydrogenation reaction product into an alkyl group. It can be made.

  Next, a ring closure reaction is performed according to the following reaction formula.

  The ring closure reaction is performed by heating in an appropriate solvent, preferably by heating in an appropriate solvent such as dichlorobenzene in the presence of an organic acid catalyst such as p-toluenesulfonic acid. ,proceed. As a ring-closed compound, there is a white organic fluorescent compound containing a carbazole skeleton represented by the above formula (8).

  The compound represented by (8) in the above reaction formula is also the white organic fluorescent compound according to the present invention represented by the above formula (1).

  When the compound represented by (9) is reacted instead of the compound represented by (5), a white organic fluorescent compound represented by the formula (2) is obtained.

However, in the formula (9), R ¹ , R ³ and R ⁴ have the same meaning as described above.

  Dialkyl 2,5-dihydroxy-1,4-cyclohexadiene-1,4-dicarboxylate (compound (4) in the above reaction formula) and a compound such as 2-amino-fluorene represented by the above formula (9) ( The reaction with 9) proceeds by heating them in an appropriate solvent. A white organic fluorescent compound represented by the formula (2) according to the present invention can be obtained by subjecting this reaction product to a dehydrogenation reaction and a ring closure reaction in the same manner as described above.

  The white organic fluorescent compound according to the present invention emits light in the region of 400 to 700 nm and can be used for an organic EL device capable of emitting white light.

  The white light emitting layer 2 shown in FIG. 1 is a layer containing a white organic fluorescent compound having a specific structure in the present invention. The white light emitting layer 2 can be formed as a polymer film in which the specific white organic fluorescent compound in the present invention is dispersed in a polymer, and the white organic fluorescent compound is deposited on the electrode 4a. It can be formed as a deposited film.

  As the polymer in the polymer film, polyvinyl carbazole, poly (3-alkylenethiophene), polyimide containing arylamine, polyfluorine, polyphenylene vinylene, poly-α-methylstyrene, vinylcarbazole / α-methylstyrene copolymer A coalescence etc. can be mentioned. Among these, polyvinyl carbazole is preferable.

  The content of the white organic fluorescent compound in the polymer film is usually 0.01 to 2% by weight, preferably 0.05 to 0.5% by weight.

  The thickness of the polymer film is usually 30 to 500 nm, preferably 100 to 300 nm. If the thickness of the polymer film is too thin, the amount of emitted light may be insufficient, and if the thickness of the polymer film is too large, the driving voltage may become too high, which may be undesirable.

  The polymer film is formed by a coating method such as a spin casting method, a coating method, and a dip method using a solution obtained by dissolving the polymer and the white organic fluorescent compound in the present invention in an appropriate solvent. Can do.

  When the said white light emitting layer 2 is a vapor deposition film, the thickness of the vapor deposition film is generally 0.1-100 nm although it changes with layer structures etc. in a white light emitting layer. When the thickness of the deposited film is too small or too large, the same problem as described above may occur.

  For light emission, when an electric field is applied between the electrode (cathode) and the electrode (anode), electrons are injected from the cathode side, holes are injected from the anode, and electrons are recombined with holes in the light emitting layer. This is a phenomenon in which energy is emitted as light when the energy level returns from the conduction band to the valence band.

In addition to the white light emitting layer 2 shown in FIG. 1, a white light emitting layer having the following laminated structure can be exemplified.
(1) (electrode: anode) / hole injection layer / white organic fluorescent compound-containing layer / (electrode: cathode)
(2) (electrode: anode) / white organic fluorescent compound-containing layer / electron injection layer / (electrode: cathode)
(3) (electrode: anode) / hole injection layer / white organic fluorescent compound-containing layer / electron injection layer / (electrode: cathode)
(4) (electrode: anode) / organic semiconductor layer / white organic fluorescent compound-containing layer / (electrode: cathode)
(5) (electrode: anode) / organic semiconductor layer / electron barrier layer / white organic fluorescent compound-containing layer / (electrode: cathode)
(6) (electrode: anode) / hole injection layer / white organic fluorescent compound-containing layer / adhesion improving layer / (electrode: cathode)
The hole injection layer is not necessarily required for the white light emitting layer used in the present invention, but is preferably used for improving the white light emitting performance. This hole injection layer is a layer that assists hole injection into the white organic fluorescent compound-containing layer, and has a high hole mobility and a small ionization energy of usually 5.5 eV or less. As such a hole injection layer, a material that transports holes to the light emitting layer with a lower electric field is preferable. Further, when an electric field having a hole mobility of, for example, 10 ⁴ to 10 ⁶ V / cm is applied, at least 10 It is still more preferable if it is ⁻⁶ cm / V · sec. Such a hole injection material is not particularly limited as long as it has the above-mentioned preferable properties, and conventionally used as a charge transport material for holes in a photoconductive material, or a positive electrode of an EL element. Any known material used for the hole injection layer can be selected and used.

  Specific examples of hole injection materials include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styryl. Anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilanes, aniline copolymers, and the like can be given. Although the above-mentioned materials can be used as the material for the hole injection layer, it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.

  Specific examples of the hole injection material, that is, the hole transport material include triphenylamine compounds such as N, N′-diphenyl-N, N′-di (m-tolyl) -benzidine (TPD), α-NPD, and the like. Hydrazone compounds, stilbene compounds, heterocyclic compounds, π-electron starburst hole transport materials, and the like.

  The hole injection layer can be formed by thinning the above-described compound by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. Although the film thickness as a positive hole injection layer does not have a restriction | limiting in particular, Usually, they are 5 nm-5 micrometers. This hole injection layer may be composed of one or more of the above-mentioned materials, or a layer in which a hole injection layer made of a compound different from the hole injection layer is laminated. It may be.

  The white organic fluorescent compound-containing layer is a layer containing the white organic fluorescent compound in the present invention, and is formed by depositing a polymer film or white organic fluorescent compound obtained by mixing with a polymer as described above. It can be formed as a deposited film.

  The electron injection layer is a layer that assists injection of electrons into the white organic fluorescent compound-containing layer. Examples of the material used for the electron injection layer include oxadiazole derivatives such as 2- (4-tert-butylphenyl) -5- (4-biphenyl) -1,3,4-oxadiazole and 2,5 -Bis (1-naphthyl) -1,3,4-oxadiazole, 2,5-bis (5′-tert-butyl-2′-benzoxazolyl) thiophene and the like can be mentioned. As the electron transporting substance, for example, a metal complex material such as a quinolinol aluminum complex (Alq3) or a benzoquinolinol beryllium complex (Bebq2) can be preferably used.

  The adhesion improving layer is a layer made of a material having a particularly good adhesion to the electrode in the electron injection layer. The material used for the adhesion improving layer is particularly preferably a metal complex of 8-hydroxyquinoline or a derivative thereof.

  Specific examples of the metal complex of 8-hydroxyquinoline or its derivative include metal chelate oxanoid compounds containing an oxine (generally 8-quinolinol or 8-hydroxyquinoline) chelate.

The organic semiconductor layer is a layer that assists the injection of sex holes or electrons into the white organic fluorescent compound-containing layer, and preferably has a conductivity of 10 ⁻¹⁰ S / cm or more. As a material for such an organic semiconductor layer, a conductive oligomer such as a thiophene-containing oligomer or an arylamine oligomer, a conductive dendrimer such as an arylamine dendrimer, or the like can be used.

(Example 1)
<Dehydration reaction>
In a 1000 ml three-necked flask, 25.0 g (1.2 × 10 ⁻¹ mol) of 3-amino-9-ethylcarbazole and 13.6 g (6.0 × 10 ⁻² mol) of a compound represented by the formula (10) And 200 ml each of acetic acid and ethyl alcohol were added. The mixture was heated to 120 ° C. with a silicone oil bath and reacted for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and poured into ice.

  Filter using a glass filter. The solid matter remaining in the filter was washed successively with methyl alcohol cooled to 5 ° C. and petroleum ether, and then vacuum-dried to obtain a brick-colored powder (35.2 g).

  An IR chart of the powder is shown in FIG. This brick-colored powder is represented by the following formula (11).

<Dehydrogenation reaction>
In a 1000 ml three-necked flask, 25.0 g of the powder obtained by the dehydration reaction was added, 500 ml of o-dichlorobenzene was added, 1.0 g of 95% sulfuric acid at room temperature was gradually added dropwise, and the mixture was stirred for 30 minutes. The mixture was heated and stirred up to 160 ° C. using an oil bath and reacted for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and poured into ice.

  Chloroform extraction was carried out 3 times using a separatory funnel, followed by washing with water twice, and then sodium sulfate was added to remove the water, followed by filtration and concentration to dryness using an evaporator. The obtained solid was sequentially washed with ethyl acetate and petroleum ether, and then vacuum-dried to obtain a red powder (13.1 g).

  The IR chart of this red powder is shown in FIG. 3, and the NMR chart is shown in FIG. This red powder is represented by the following formula (12).

<Ring ring reaction>
In a 500 ml three-necked flask, 10.0 g (1.6 × 10 ⁻² mol) of the red powder is added, and 13.7 g (7.2 × 10 ⁻² mol) of p-toluenesulfonic acid hydrate is added. Furthermore, 200 ml of O-dichlorobenzene was added. The mixture was heated and stirred to 160 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, it was concentrated and solidified using an evaporator. The obtained solid was sequentially washed with methyl alcohol, acetone, and petroleum ether cooled to 5 ° C., and then dried in vacuo to obtain a brown powder (9.4 g). To purify, add 700 ml of xylene to 1000 ml Meyer, add 2.0 g of the obtained brown powder and 2.0 g of activated carbon, boil for 3 minutes using a mantle heater, and concentrate the filtrate filtered while hot using an evaporator. Allowed to dry.

  The obtained solid was washed with petroleum ether and then vacuum dried to obtain a maroon powder. The IR chart of this maroon powder is shown in FIG. 5, and the NMR chart is shown in FIG.

  This maroon powder has a structural formula represented by the following formula (1a).

５ｍｌのメスフラスコに、ポリビニルカルバゾール７０ｍｇ、ｔ−ブチルフェニル−ジフェニル−１，３，４−オキザジアゾール（ＰＢＤ）２９ｍｇ、及び前記あずき色粉体（化合物(１ａ)） １ｍｇを秤量し、ジクロロエタンを加えて５ｍｌになるように白色有機蛍光化合物含有溶液を調製した。この白色有機蛍光化合物含有溶液は、超音波洗浄器（（株）エスエヌディ製、ＵＳ−２）で超音波を２０分間照射することにより、十分に均一なものにされた。ＩＴＯ基板（５０×５０ｍｍ、三容真空工業（株）製）をアセトンで１０分間超音波洗浄した後に２−プロパノールで１０分間超音波洗浄し、窒素でブローして乾燥させた。その後に、ＵＶ照射装置（（株）エム・ディ・エキシマ製、波長１７２ｎｍ）で３０秒間ＵＶを照射して洗浄した。スピンコータ（ミカサ（株）製、１Ｈ−Ｄ７）を用いて洗浄乾燥の終了したＩＴＯ基板に、調製しておいた前記白色有機蛍光化合物含有溶液を滴下し、回転数１，５００ｒｐｍ、回転時間３秒にてスピンコートして製膜した。製膜した基板を、５０℃の恒温槽中で３０分乾燥させた後に、真空蒸着装置（大亜真空技研（株）製、ＶＤＳ−Ｍ２−４６型）でアルミ合金（Ａｌ：Ｌｉ＝９９：１重量比、（株）高純度化学研究所製）電極を、４×１０^-6Torrで約１５０ｎｍの厚みに蒸着し、ＥＬ素子を製作した。

In a 5 ml volumetric flask, weigh 70 mg of polyvinylcarbazole, 29 mg of t-butylphenyl-diphenyl-1,3,4-oxazodiazole (PBD), and 1 mg of the maroon powder (compound (1a)), and add dichloroethane. A white organic fluorescent compound-containing solution was prepared so as to be 5 ml. This white organic fluorescent compound-containing solution was made sufficiently uniform by irradiating ultrasonic waves with an ultrasonic cleaner (US-2, manufactured by SND Corporation) for 20 minutes. An ITO substrate (50 × 50 mm, Sanyo Vacuum Industry Co., Ltd.) was ultrasonically cleaned with acetone for 10 minutes, then ultrasonically cleaned with 2-propanol for 10 minutes, and blown with nitrogen to dry. Then, it was cleaned by UV irradiation for 30 seconds with a UV irradiation apparatus (manufactured by M.D. Excimer, wavelength 172 nm). The prepared white organic fluorescent compound-containing solution is dropped onto an ITO substrate that has been cleaned and dried using a spin coater (Mikasa Co., Ltd., 1H-D7), and the rotational speed is 1,500 rpm and the rotational time is 3 seconds. Spin-coated to form a film. The substrate thus formed was dried in a constant temperature bath at 50 ° C. for 30 minutes, and then an aluminum alloy (Al: Li = 99: with a vacuum vapor deposition apparatus (VDS-M2-46 type, manufactured by Daia Vacuum Engineering Co., Ltd.)). An EL device was manufactured by evaporating an electrode having a weight ratio of 1 (manufactured by Kojundo Chemical Laboratory Co., Ltd.) to a thickness of about 150 nm at 4 × 10 ⁻⁶ Torr.

The EL device was measured for luminance and chromaticity while gradually increasing the voltage with BM-7 Fast manufactured by Topcon Corporation. As a result, a result was obtained in which the voltage was 21 V, the current was 9.69 mA, the luminance was 2,300 Cd / m ² , the chromaticity X was 0.33, and the chromaticity Y was 0.33.

<Luminescent characteristics (2)>
The white organic fluorescent compound (1a) was dissolved in mixed xylene to a concentration of 10 mg / L to prepare a sample solution. This sample solution was loaded into an F-4500 type spectrofluorometer manufactured by Shimadzu Corporation, and the fluorescence spectrum was measured under the following conditions. The obtained fluorescence spectrum is shown in FIG.

Measurement conditions Measurement mode Wavelength scan Excitation wavelength 365nm
Fluorescence start wavelength 400nm
Fluorescence end wavelength 700nm
Scanning speed 1200nm / min Excitation side slit 5.0nm
Fluorescent side slit 5.0nm
Photomultiplier voltage 700V
As can be seen from FIG. 7, the white organic fluorescent compound obtained in this example shows fluorescence emission of 400 to 700 nm and covers the entire region.

(Example 2)
<Dehydration reaction>
In a 1000 ml three-necked flask, 25.0 g (1.4 × 10 ⁻¹ mol) of 3-amino-fluorene represented by the following formula (13) and 15.7 g (7. 0 × 10 ⁻² mol), and 200 ml each of acetic acid and ethyl alcohol were further added.

  The mixture was heated and stirred to 120 ° C. using a silicone oil bath and reacted for 4 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and poured into ice.

  Filter using a glass filter. The solid matter remaining in the filter was washed successively with methyl alcohol cooled to 5 ° C. and petroleum ether, and then vacuum-dried to obtain an orange powder (34.0 g).

  An IR chart of the orange powder is shown in FIG. This orange powder is represented by the following formula (14).

<Dehydrogenation reaction>
Place 25.0 g of the orange powder obtained in the dehydration reaction in a 1000 ml three-necked flask, add 500 ml of O-dichlorobenzene, slowly drop 1.0 g of 95% sulfuric acid at room temperature, and stir for 30 minutes. After that, the mixture was heated and stirred up to 160 ° C. using a silicone oil bath and reacted for 2 hours. After completion of the reaction, the reaction mixture was cooled to room temperature and poured into ice.

  Chloroform extraction was performed 3 times using a separatory funnel, and after washing with water twice, sodium sulfate was added to remove moisture, followed by filtration, and concentration to dryness using an evaporator. The obtained solid was washed with ethyl acetate and petroleum ether, and then vacuum-dried to obtain a red powder (20.5 g).

  An IR chart of this red powder is shown in FIG. This red powder was a compound represented by the formula (15).

<Ring ring reaction>
In a 500 ml three-necked flask, 10.0 g (1.7 × 10 ⁻² mol) of the red powder is added, and 15.3 g (8.0 × 10 ⁻² mol) of p-toluenesulfonic acid hydrate is added. Furthermore, 200 ml of O-dichlorobenzene was added. The mixture was heated and stirred up to 160 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the mixture was concentrated to dryness using an evaporator. The obtained solid was sequentially washed with methyl alcohol, acetone, and petroleum ether cooled to 5 ° C., and then vacuum-dried to obtain a brown powder (8.2 g). To purify, add 700 ml of xylene to 1000 ml Meyer, add 2.0 g of the obtained brown powder and 2.0 g of activated carbon, boil for 3 minutes using a mantle heater, and concentrate the filtrate filtered while hot with an evaporator. Solidified.

  The obtained solid was washed with petroleum ether and then vacuum dried to obtain a maroon powder.

  An IR chart of this adzuki colored powder is shown in FIG.

  The structure of this adzuki colored powder is represented by the following formula (2a).

(Example 3)
<Benzylation reaction>
10.0 g (1.6 × 10 ⁻² mol) of the compound having the structure represented by the same formula (12) as prepared in Example 1 was put in a 500 ml pressure bottle, and 17.1 g of benzyl bromide (7 .6 × 10 ⁻² mol) was added, and then 200 ml of N, N-dimethylformamide (DMF) was added. Using a silicone oil bath, the inside of the pressure bottle was heated to 150 ° C. with stirring and reacted for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated using an evaporator, poured into ice water, and neutralized with sodium hydroxide. Chloroform extraction was performed 3 times using a separatory funnel, and water washing was performed twice. Next, sodium sulfate was added to remove moisture, filtered, and concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG. This brown powder has a structure represented by formula (16).

<Ring ring reaction>
In a 500 ml three-necked flask, 5.0 g (6.1 × 10 ⁻³ mol) of the compound represented by the above formula (16) was added, and 5.2 g (2.7 × 10 ^{− −} p-toluenesulfonic acid monohydrate was added. ² mol) and 200 ml of o-dichlorobenzene was added. The mixture was heated to 160 ° C. with a silicone oil bath and reacted for 20 hours. After completion of the reaction, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with methyl alcohol, acetone and petroleum ether cooled to 5 ° C., and then vacuum-dried to obtain a brown solid.

  Using a Soxhlet extraction apparatus, 1.0 g of the brown solid was extracted with 250 ml of xylene over 24 hours. After completion of extraction, the mixture was concentrated to dryness using an evaporator, and the resulting solid was washed with petroleum ether and dried in vacuo to obtain a brown powder. An IR chart of this brown powder is shown in FIG. This brown solid was a compound having a structure represented by the formula (1b).

<Luminescent characteristics (3)>
As in <Luminescent characteristics (1)> of Example 1, in a 5 ml volumetric flask, 70 mg of polyvinylcarbazole, 29 mg of t-butylphenyl-diphenyl-1,3,4-oxazole, and the maroon powder (compound (1a)) Instead of preparing a white organic fluorescent compound-containing solution so that 1 mg is weighed and adding dichloroethane to 5 ml, in a 5 ml volumetric flask, 70 mg of polyvinylcarbazole has a structure represented by the formula (17) A white organic fluorescent compound-containing solution was prepared by adding 29.7 mg of BND and 0.3 mg of the white organic fluorescent compound represented by the formula (1b) to 5 ml by adding dichloroethane. Using this white organic fluorescent compound-containing solution, an EL device was manufactured in the same manner as in <Light-Emitting Characteristics (1)> of Example 1, and a luminance meter BM-7 manufactured by Topcon Co., Ltd. was used for this EL device. Luminance and chromaticity were measured at.

As a result, a voltage of 21 V, current of 36.8 mA, luminance of 2400 Cd / m ² , chromaticity X of 0.34, and chromaticity Y of 0.35 were obtained. Moreover, the spectral radiance graph of this white organic fluorescent compound with this spectroradiometer is shown in FIG. From this spectral radiance graph, it can be recognized that white light was sufficiently emitted by the naked eye.

<Luminescent characteristics (4)>
An ITO substrate (50 × 50 mm, Sanyo Vacuum Industry Co., Ltd.) was ultrasonically cleaned with acetone for 10 minutes, then ultrasonically cleaned with 2-propanol for 10 minutes, and blown with nitrogen to dry. Thereafter, UV irradiation was performed with a UV irradiation apparatus (manufactured by M.D. Excimer, wavelength 172 nm) for 30 seconds to complete the cleaning of the ITO substrate.

The cleaned ITO substrate was set in a vacuum deposition apparatus (manufactured by Daia Vacuum Giken Co., Ltd., UDS-M2-46 type), and N, N′-diphenyl-N, N, under reduced pressure of 4 × 10 ⁻⁶ torr or less. N-di (m-tolyl) -benzidine (TPD) was vapor-deposited to a thickness of 68 nm, then the white organic fluorescent compound (1b) was vapor-deposited to a thickness of 0.6 nm, and the following formula (18) DPVBi having the structure shown was deposited to a thickness of 36 nm, finally tris (8-quinolinato) aluminum (Alq3) was deposited to 40 nm, and finally an aluminum alloy electrode (Al: Li = 99: 1 weight ratio, ( An EL device was manufactured by vapor-depositing a high purity chemical laboratory) to a thickness of 150 nm.

  The luminance and chromaticity of this EL element were measured in the same manner as in the light emission characteristic (3).

As a result, a voltage of 17 V, current of 21.8 mA, luminance of 4500 Cd / m ² , chromaticity X of 0.32, and chromaticity Y of 0.35 were obtained. Moreover, the spectral radiance graph of this white organic fluorescent compound with this spectroradiometer is shown in FIG. From this spectral radiance graph, it can be recognized that white light was sufficiently emitted by the naked eye.

Example 4
<Methylation reaction>
10.0 g (1.6 × 10 ⁻² mol) of the compound having the structure represented by the same formula (12) produced in Example 1 was put in a 500 ml pressure bottle, and 10.8 g (7. 6 × 10 ⁻² mol) was added, followed by 200 ml of N, N-dimethylformamide (DMF). Using a silicone oil bath, the inside of the pressure bottle was heated to 150 ° C. with stirring and reacted for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated using an evaporator, poured into ice water, and neutralized with sodium hydroxide. Chloroform extraction was performed 3 times using a separatory funnel, and water washing was performed twice. Next, sodium sulfate was added to remove moisture, filtered, and concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG. This brown powder has a structure represented by the formula (19).

<Ring ring reaction>
In a 500 ml three-necked flask, 5.0 g (7.5 × 10 ⁻³ mol) of the compound represented by the above formula (19) was put, and 8.0 g (4.2 × 10 ^{− −} p-toluenesulfonic acid monohydrate was added. ² mol) and 200 ml of o-dichlorobenzene was added. The mixture was heated to 160 ° C. with a silicone oil bath and reacted for 20 hours. After completion of the reaction, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with methyl alcohol, acetone and petroleum ether cooled to 5 ° C., and then vacuum-dried to obtain a brown solid.

  Using a Soxhlet extraction apparatus, 1.0 g of the brown solid was extracted with 250 ml of xylene over 24 hours. After completion of extraction, the mixture was concentrated to dryness using an evaporator, and the resulting solid was washed with petroleum ether and dried in vacuo to obtain a brown powder. An IR chart of this brown powder is shown in FIG. This brown solid was a compound having a structure represented by the formula (1d).

<Luminescent characteristics (5)>
In the same manner as in the above <light emission characteristic (4)>, TPD was vapor-deposited on the ITO substrate to a thickness of 71 nm, and then the white organic fluorescent compound (1d) was vapor-deposited to a thickness of 0.6 nm. , DPVBi was evaporated to a thickness of 40 nm, finally tris (8-quinolinato) aluminum (Alq3) was evaporated to a thickness of 41 nm, and finally an aluminum alloy electrode (Al: Li = 99: 1 weight ratio, Co., Ltd.) An EL element was manufactured by vapor-depositing a high-purity chemical laboratory) to a thickness of 150 nm.

  The luminance and chromaticity of this EL element were measured in the same manner as in the light emission characteristic (3).

As a result, a voltage of 16 V, current of 17.5 mA, luminance of 7000 Cd / m ² , chromaticity X of 0.35, and chromaticity Y of 0.34 were obtained. Moreover, the spectral radiance graph of this white organic fluorescent compound with this spectroradiometer is shown in FIG. From this spectral radiance graph, it can be recognized that white light was sufficiently emitted by the naked eye.

(Example 5)
<Ethylation reaction>
10.0 g (1.6 × 10 ⁻² mol) of the compound having the structure represented by the same formula (12) produced in Example 1 was placed in a 500 ml pressure bottle and iodoethane (C ₂ H ₅ I). ) 10.8 g (6.9 × 10 ⁻² mol) was added, and 200 ml of N, N-dimethylformamide (DMF) was further added. The mixture was heated and stirred to 150 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated using an evaporator, and then poured into ice water and neutralized with sodium hydroxide. Chloroform extraction was carried out 3 times using a separatory funnel, followed by washing with water twice. Then, sodium sulfate was added to remove water, and the mixture was filtered and concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Ring ring reaction>
In a 500 ml three-necked flask, 5.0 g (8.3 × 10 ⁻³ mol) of the ethylated reaction product was added, and 8.0 g (4.2 × 10 ⁻² mol) of p-toluenesulfonic acid monohydrate. Further, 200 ml of O-dichlorobenzene was added. The mixture was heated and stirred to 160 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with methyl alcohol, acetone, and petroleum ether cooled to 5 ° C., and then vacuum-dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Purification>
Using a Soxhlet apparatus, 1.0 g of the above ring-closing reaction product was added, 250 ml of xylene was added, heated to 185 ° C. using a silicone oil bath, and extracted for 24 hours. After completion, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder.

(Example 6)
<Butylation reaction>
10.0 g (1.6 × 10 ⁻² mol) of the compound having the structure represented by the same formula (12) produced in Example 1 was placed in a 500 ml pressure bottle, and n-butyliodine (C ₄ H ₉ I) 10.8 g (7.6 × 10 ⁻² mol) was added, and 200 ml of N, N-dimethylformamide (DMF) was further added. The mixture was heated to 150 ° C. with a silicone oil bath and reacted for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated using an evaporator, and then poured into ice water and neutralized with sodium hydroxide. Chloroform extraction was carried out 3 times using a separatory funnel, followed by washing with water twice. Then, sodium sulfate was added to remove water, and the mixture was filtered and concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Ring ring reaction>
In a 500 ml three-necked flask, 5.0 g (7.5 × 10 ⁻³ mol) of the butylated reaction product was put, and 7.2 g (3.7 × 10 ⁻² mol) of p-toluenesulfonic acid monohydrate was added. Further, 200 ml of O-dichlorobenzene was added. The mixture was heated and stirred to 160 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with methyl alcohol, acetone, and petroleum ether cooled to 5 ° C., and then vacuum-dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Purification>
Using a Soxhlet apparatus, 1.0 g of the above ring-closing reaction product was added, 250 ml of xylene was added, heated to 185 ° C. using a silicone oil bath, and extracted for 24 hours. After completion, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder.

(Example 7)
<Hexylation reaction>
5.0 g (8.0 × 10 ⁻³ mol) of the compound having the structure represented by the same formula (12) produced in Example 1 was placed in a 500 ml pressure bottle and hexyl iodide (C ₆ H ₁₃ I) 12.9 g (4.5 × 10 ⁻² mol) was added, and 200 ml of N, N-dimethylformamide (DMF) was further added. The mixture was heated and stirred to 150 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated using an evaporator, and then poured into ice water and neutralized with sodium hydroxide. Chloroform extraction was carried out 3 times using a separatory funnel, followed by washing with water twice. Then, sodium sulfate was added to remove water, and the mixture was filtered and concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Ring ring reaction>
In a 500 ml three-necked flask, 5.0 g (5.8 × 10 ⁻³ mol) of the hexylated reaction product was placed, and 6.6 g (3.5 × 10 ⁻² mol) of p-toluenesulfonic acid monohydrate was added. ), And 200 ml of O-dichlorobenzene was further added. The mixture was heated and stirred to 160 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with methyl alcohol, acetone, and petroleum ether cooled to 5 ° C., and then vacuum-dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Purification>
Using a Soxhlet apparatus, 1.0 g of the above ring-closing reaction product was added, 250 ml of xylene was added, heated to 185 ° C. using a silicone oil bath, and extracted for 24 hours. After completion, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder.

(Example 8)
<Benzylation reaction>
10.0 g (1.6 × 10 ⁻² mol) of the compound having the structure represented by the same formula (12) produced in Example 1 was placed in a 500 ml pressure bottle and benzyl bromide (C ₆ H ₅ 17.2 g (7.6 × 10 ⁻² mol) of CH ₂ Br) was added, and 200 ml of N, N-dimethylformamide (DMF) was further added. The mixture was heated and stirred to 150 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated using an evaporator, and then poured into ice water and neutralized with sodium hydroxide. Chloroform extraction was carried out 3 times using a separatory funnel, followed by washing with water twice. Then, sodium sulfate was added to remove water, and the mixture was filtered and concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Ring ring reaction>
In a 500 ml three-necked flask, 5.0 g (6.9 × 10 ⁻³ mol) of the benzylation reaction product was added, and 5.2 g (2.7 × 10 ⁻² mol) of p-toluenesulfonic acid monohydrate was added. In addition, 200 ml of O-dichlorobenzene was added. The mixture was heated and stirred to 160 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with methyl alcohol, acetone, and petroleum ether cooled to 5 ° C., and then vacuum-dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

Example 9
<Methylbenzylation (tolylation) reaction>
10.0 g (1.6 × 10 ⁻² mol) of the compound having the structure represented by the same formula (12) produced in Example 1 was put in a 500 ml pressure bottle, and α-chloro-P-xylene (CH ₃ C ₆ H ₄ CH ₂ Cl) 15.8 g (1.1 × 10 ⁻¹ mol) was added, and 200 ml of N, N-dimethylformamide (DMF) was further added. The mixture was heated and stirred to 150 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated using an evaporator, and then poured into ice water and neutralized with sodium hydroxide. Chloroform extraction was carried out 3 times using a separatory funnel, followed by washing with water twice. Then, sodium sulfate was added to remove water, and the mixture was filtered and concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Ring ring reaction>
A 500 ml three-necked flask was charged with 5.0 g (5.4 × 10 ⁻³ mol) of methylbenzylation reaction product and 8.0 g (4.2 × 10 ⁻² mol) of p-toluenesulfonic acid monohydrate. Further, 200 ml of O-dichlorobenzene was added. The mixture was heated and stirred to 160 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with methyl alcohol, acetone, and petroleum ether cooled to 5 ° C., and then vacuum-dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Purification>
Using a Soxhlet apparatus, 1.0 g of the above ring-closing reaction product was added, 250 ml of xylene was added, heated to 185 ° C. using a silicone oil bath, and extracted for 24 hours. After completion, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder.

<Luminescent characteristics (6)>
In the emission characteristics (4), instead of “depositing TPD to a thickness of 68 nm to form a TPD layer”, a 45 nm α-NPD layer was formed, and “white organic fluorescent compound (1b) was made to a thickness of 0.6 nm. Instead of vapor-depositing and further vapor-depositing DPVBi having the structure represented by the following formula (18) to a thickness of 36 nm ", a light-emitting layer formed by doping 4.4% of the white light-emitting compound (1c) into DPVBi And an EL device similar to that described in the light emission characteristic (4) was manufactured except that the Alq3 layer 21 nm was laminated in this order instead of “depositing the Alq3 layer 40 nm”.

The light emission characteristics were measured in the same manner as in the light emission characteristics (3). As a result, the luminance was 10720 Cd / m ² , the chromaticity X was 0.35, and the chromaticity Y was 0.39 at a voltage of 18 V and a current of 30.9 mA. was gotten.

<Luminescent characteristics (7)>
An α-NPD layer 46 nm, a layer 31 nm obtained by doping 2.9% of the white light-emitting compound (1c) in CBP having the structure represented by the formula (20), and an Alq ₃ layer 19 nm were stacked in this order, An EL element similar to that described in the light emission characteristic (4) was manufactured.

The light emission characteristics were measured in the same manner as in the light emission characteristics (3). As a result, the luminance was 10120 Cd / m ² at a voltage of 17 V and a current of 36.1 mA, the chromaticity X was 0.32, and the chromaticity Y was 0.35. was gotten.

<Three primary color reproduction test>
The light spectrum shown in FIG. 35 is used for the EL element having the emission spectrum measured by the spectral radiance meter CS10000 manufactured by Minolta Co., Ltd. as shown in FIG. In combination with the color filters, the chromaticities of transmitted red, green and blue were measured.

  The red chromaticity X was 0.630 and the chromaticity Y was 0.341. This chromaticity value of red indicates that red is not red, such as orange and red, but crimson. The chromaticity X of green was 0.372 and the chromaticity Y was 0.575. This green chromaticity value X indicates pure green. The blue chromaticity X was 0.138, and the chromaticity Y was 0.095. This blue chromaticity X indicates pure blue.

  From the results of the three primary color reproduction tests, when a light emitting layer was formed using the white light emitting compound obtained in this example and the examples other than this example, and the light emitting layer and the color filter were combined, the color purity over time A full-color image display device capable of displaying a color image without lowering is provided.

(Example 10)
<Dimethylbenzylation (xylation) reaction>
10.0 g (1.6 × 10 ⁻² mol) of the compound having the structure represented by the same formula (12) produced in Example 1 was placed in a 500 ml pressure bottle, and 2,4-dimethylbenzyl chloride. (CH ₃ C ₆ H ₃ CH ₃ CH ₂ Cl) 15.8 g (1.0 × 10 ⁻¹ mol) was added, and 200 ml of N, N-dimethylformamide (DMF) was further added. The mixture was heated and stirred to 150 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated using an evaporator, and then poured into ice water and neutralized with sodium hydroxide. Chloroform extraction was carried out 3 times using a separatory funnel, followed by washing with water twice. Then, sodium sulfate was added to remove water, and the mixture was filtered and concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Ring-opening reaction>
In a 500 ml three-necked flask, 5.0 g (6.3 × 10 ⁻³ mol) of the dimethylbenzylation reaction product was placed, and 6.0 g (3.2 × 10 ⁻² mol) of p-toluenesulfonic acid monohydrate was added. ) And 200 ml of O-dichlorobenzene was further added. The mixture was heated and stirred to 160 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with methyl alcohol, acetone, and petroleum ether cooled to 5 ° C., and then vacuum-dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Purification>
Using a Soxhlet apparatus, 1.0 g of the above ring-closing reaction product was added, 250 ml of xylene was added, heated to 185 ° C. using a silicone oil bath, and extracted for 24 hours. After completion, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder.

(Example 11)
<Naphthylation reaction>
5.0 g (8.0 × 10 ⁻³ mol) of the compound having the structure represented by the same formula (12) produced in Example 1 was placed in a 500 ml pressure bottle, and 1-chloromethylnaphthalene ( _{C 10 H 7 CH 2 Cl)} 9.6g (5.4 × 10 -2 mol) was added, was further added N, N- dimethylformamide (DMF) 200 ml. The mixture was heated and stirred to 150 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated using an evaporator, and then poured into ice water and neutralized with sodium hydroxide. Chloroform extraction was carried out 3 times using a separatory funnel, followed by washing with water twice. Then, sodium sulfate was added to remove water, and the mixture was filtered and concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Ring-opening reaction>
A 500 ml three-necked flask is charged with 5.0 g (6.0 × 10 ⁻³ mol) of a naphthylation reaction product and 6.9 g (3.6 × 10 ⁻² mol) of p-toluenesulfonic acid monohydrate. In addition, 200 ml of O-dichlorobenzene was further added. The mixture was heated and stirred to 160 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with methyl alcohol, acetone, and petroleum ether cooled to 5 ° C., and then vacuum-dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Purification>
Using a Soxhlet apparatus, 1.0 g of the above ring-closing reaction product was added, 250 ml of xylene was added, heated to 185 ° C. using a silicone oil bath, and extracted for 24 hours. After completion, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum-dried to obtain a brown color powder.

(Example 12)
<Anthracene reaction>
5.0 g (8.0 × 10 ⁻³ mol) of the compound having the structure represented by the same formula (12) produced in Example 1 was placed in a 500 ml pressure bottle, and 9-chloromethylanthracene (C ₁₄ H ₇ CH ₂ Cl) (8.6 g, 5.4 × 10 ⁻² mol) was added, and 200 ml of N, N-dimethylformamide (DMF) was further added. The mixture was heated and stirred to 150 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated using an evaporator, and then poured into ice water and neutralized with sodium hydroxide. Chloroform extraction was performed 3 times using a separatory funnel, followed by washing with water twice. Then, sodium sulfate was added to remove water, and the mixture was filtered and concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Ring ring reaction>
A 500 ml three-necked flask was charged with 5.0 g (5.3 × 10 ⁻³ mol) of an anthracene reaction product, and 5.1 g (2.6 × 10 ⁻² mol) of p-toluenesulfonic acid monohydrate. In addition, 200 ml of O-dichlorobenzene was further added. The mixture was heated and stirred to 160 ° C. using a silicone oil bath and reacted for 20 hours. After completion of the reaction, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with methyl alcohol, acetone, and petroleum ether cooled to 5 ° C., and then vacuum-dried to obtain a brown powder. An IR chart of this brown powder is shown in FIG.

<Purification>
Using a Soxhlet apparatus, 1.0 g of the above ring-closing reaction product was added, 250 ml of xylene was added, heated to 185 ° C. using a silicone oil bath, and extracted for 24 hours. After completion, the mixture was concentrated to dryness using an evaporator. The obtained solid was washed with petroleum ether and then vacuum dried to obtain a brown powder.

FIG. 1 is an explanatory diagram illustrating a part of an example of a color filter image display device. FIG. 2 is an IR chart showing the compounds obtained in Example 1 by dehydrating dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate and 3-amino-9-ethylcarbazole. FIG. 3 is an IR chart showing a compound obtained by dehydrogenating a dehydration reaction product in Example 1. 4 is an NMR chart showing a compound obtained by dehydrogenating a dehydration reaction product in Example 1. FIG. FIG. 5 is an IR chart showing a white organic fluorescent compound obtained by ring-closing reaction of a dehydrogenation reaction product in Example 1. 6 is an NMR chart showing the white organic fluorescent compound in Example 1. FIG. FIG. 7 is a graph showing the fluorescence spectrum of the white organic fluorescent compound in Example 1. FIG. 8 is an IR chart showing the compounds obtained in Example 2 by dehydrating dimethyl 1,4-cyclohexanedione-2,5-dicarboxylate and 2-amino-fluorene. FIG. 9 is an IR chart showing a compound obtained by dehydrogenating a dehydration reaction product in Example 2. FIG. 10 is an IR chart showing a white organic fluorescent compound obtained by ring-closing reaction of a dehydrogenation reaction product in Example 2. FIG. 11 is an IR chart of a compound having the structure of formula (16). FIG. 12 is an IR chart of a compound having the structure of formula (1b). FIG. 13 is a spectral radiance graph showing light emission characteristics of an organic EL device using a compound having the structure of formula (1b). FIG. 14 is a spectral radiance graph showing the emission characteristics of an organic EL device using a compound having the structure of formula (1b). FIG. 15 is an IR chart of the compound having the structure of formula (19). FIG. 16 is an IR chart of a compound having the structure of the formula (1d). FIG. 17 is a spectral radiance graph showing light emission characteristics of an organic EL device using a compound having the structure of the formula (1d). FIG. 18 is an IR chart of the brown powder of Example 5. FIG. 19 is an IR chart of the brown powder of Example 5. FIG. 20 is an IR chart of the brown powder powder of Example 6. FIG. 21 is an IR chart of the brown powder of Example 6. FIG. 22 is an IR chart of the brown powder of Example 7. FIG. 3 is an IR chart of the brown powder of Example 7. FIG. 24 is an IR chart of the brown powder of Example 8. FIG. 25 is an IR chart of the brown powder of Example 8. FIG. 26 is an IR chart of the brown powder of Example 9. FIG. 27 is an IR chart of the brown powder of Example 9. FIG. 28 is an IR chart of the brown powder powder of Example 10. FIG. 29 is an IR chart of the brown powder of Example 10. FIG. 30 is an IR chart of the brown powder of Example 11. FIG. 31 is an IR chart of the brown powder of Example 11. 32 is an IR chart of the brown powder of Example 12. FIG. FIG. 33 is an IR chart of the brown powder of Example 12. FIG. 34 is a graph showing an emission spectrum of the white light-emitting compound obtained in Example 9. FIG. 35 is a graph showing a light transmission spectrum of the color filter used in Example 3.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Color filter layer, 1a, 1b, 1c ... Color separation element, 2 ... White light emitting layer, 3 ... Barrier layer, 4a, 4b ... Electrode layer, 5 ... Insulation isolation Layer, 6... Transparent substrate, 7.

Claims (2)

  A color filter formed by arranging pixels in parallel in a blue separation element that transmits blue, a green separation element that transmits green, and a red separation element that transmits red, and a single element that emits white light by electromagnetic energy A color image display device comprising a white light-emitting compound containing a white organic fluorescent compound as a compound. A color image display device, wherein the white organic fluorescent compound is a white organic fluorescent compound represented by the following formula (1) or (2).

(However, R ¹ represents a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl group. R ² represents a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl group.)

(However, R ¹ represents a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl group. R ³ and R ⁴ are a hydrogen atom, an alkyl group, an aryl group, or an arylalkyl group, and each is the same group. Or a different group.)

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