JP2002124383A - Electroluminescence element and color conversion filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an electroluminescence element and a color conversion filter, that are improved in the conversion efficiency by using a rare earth complex phosphor, and have high luminance and are superior in preservation characteristics. SOLUTION: The electroluminescence element contains a rare-earth complex phosphor that emits light in a maximum wavelength, that is different from maximum luminous wavelength emitted from the luminous material and the luminous material absorbing the luminance of the luminous material. The rare- earth complex phosphor contains at least one of the anion of the compound, as expressed in formula (1) or formula (2) as a ligand.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroluminescence device (hereinafter, also simply referred to as an "EL device") and a color conversion filter, and more specifically, to a consumer or industrial device such as a light-emitting multi-color or full-color display and a display panel. The present invention relates to an electroluminescence element and a color conversion filter which are suitably used for display devices for personal computers.

[0002]

2. Description of the Related Art Electronic display devices include a light emitting type and a light receiving type. Examples of the light emitting type include a CRT (cathode ray tube), a PDP (plasma display), and an ELD.
(Electroluminescence display), VFD
(Fluorescent display tube).

[0003] Among them, the ELD will be described. EL
D (electroluminescence display) is a light-emitting element made of a material that emits light by an electric field or an electric field, or a combination of a plurality of them. Organic and inorganic materials are used for the light-emitting element, and electrons and positive light are used as a light-emitting mechanism. There are a carrier injection type using recombination of holes and an accelerated electron type using collision energy of accelerated electrons. In general, inorganic materials have a longer life and are more stable than organic materials. On the other hand, the development range of materials is narrow, and there is a limitation in molecular design. In terms of mechanism, the recombination type generally has an advantage that the driving voltage is lower than that of the accelerated electron type, and carrier injection type ELDs have been actively studied in recent years because of the advantage.

The following three types of light emitting elements are specifically mentioned. -Inorganic LED (Material is composed of inorganic compounds such as GaN and GaInN, and the light emission mechanism is carrier injection type. Simply LED
(Light emitting diode). Organic LED (the material is composed of an organic compound such as a triarylamine derivative or a stilbene derivative, and the light emission mechanism is a carrier injection type. Also referred to as an organic EL (electroluminescence) or OLED.) Inorganic EL (the material is ZnS: Mn.) And an inorganic LE such as ZnS: Tb, and the emission mechanism is an accelerated electron type.
Since this is older than D, it may be simply called electroluminescence (EL). ) Carrier-injection-type organic LEDs, which have attracted particular attention in recent years
Since a thin film made of an organic compound has been used, a thin film having a high luminous intensity has been obtained.

For example, US Pat. No. 3,530,325 discloses a light-emitting device using single crystal anthracene or the like,
JP-A-59-194393 discloses a combination of a hole injection layer and an organic luminescent layer.
No. 1 is a combination of a hole injection layer and an organic electron injection transport layer, Jpn. Journal of Applier
d Physics, vol 127, no. 2nd 269
Pp. 271 to 271 each disclose a combination of a hole transfer layer, a light emitting layer and an electron transfer layer, and the emission intensity has been improved by these.

An inorganic EL requires a high AC voltage to drive a light emitting element, whereas an organic EL requires a high voltage.
D can emit light at a voltage of several volts to several tens of volts. In addition, since it is a self-luminous type, it has a high viewing angle dependency, has high visibility, and is omitted because it is a thin-film type completely solid-state element. It attracts attention from the viewpoint of space, portability, and the like.

On the other hand, a method of emitting multicolored fluorescence using a phosphor has been applied to CRTs, PDPs, VFDs and the like.

However, in this case, there is a problem in that the emission is high in energy, that is, the emission wavelength is short, such as electron beam or far ultraviolet ray. In other words, the above-mentioned phosphor is specifically an inorganic phosphor, and its stability is much higher than that of an organic fluorescent dye, and there are many known ones that can withstand long-term use. Few of them excite the light in the long wavelength range from the near ultraviolet to the visible region, and in particular, none of them emit red light at all.

[0009] Near ultraviolet light that can be emitted from the electroluminescent material is about 350 nm or more.
It is presumed that the light has a maximum emission wavelength of about 400 nm, and the use of an organic fluorescent dye as such a phosphor excited by near-ultraviolet light is disclosed in JP-A-3-152897, JP-A-9-245511, and JP-A-9-245511. -258860.

However, organic fluorescent dyes are generally susceptible to the surrounding environment. For example, depending on the type of medium such as a solvent or a resin, the fluorescent wavelength may change (discolor) or cause quenching. In addition, most organic fluorescent dyes are extremely unstable to light and heat and can be decomposed in a few minutes to several hours under strong light of, for example, about 100,000 lux. Does not exist.

[0011] The method described in the patent is as follows:
A fluorescent dye that absorbs light from a luminous body and converts the color into a green region or a red region is used, and a fluorescent conversion film that emits fluorescence in the green region has a Stokes shift (difference between absorption wavelength and emission wavelength). Is small and can transmit a part of the light emitted by the electroluminescent material, and can convert the light of the luminous body with relatively high efficiency. In addition to requiring a shift, the conversion efficiency is extremely low because the light of the illuminant is hardly available. Specifically, several kinds of fluorescent dyes having different excitation wavelengths are used in combination, and for example, light-to-light conversion of a plurality of fluorescent dyes such as a fluorescent dye that receives yellow light and emits red light upon receiving yellow light ( Photoluminescence) must be used at another stage, and high efficiency was not possible in principle.

[0012]

In the prior art, the blue, green, and red emission luminances are not well balanced, including the problems of discoloration, low conversion efficiency, and extinction. However, there is a problem that the color display has low visibility and low brightness.

[0013] It is an object of the present invention to provide an electroluminescent device which is improved in conversion efficiency by using a rare earth complex-based phosphor, has high luminance and is excellent in storage stability. It is an object of the present invention to provide a color conversion filter that improves the conversion efficiency by using a color filter, has high luminance, and has excellent storage stability.

[0014]

The object of the present invention is achieved by the following constitution.

1. An electroluminescent device containing a light-emitting material and a rare-earth complex-based phosphor that emits light at a maximum emission wavelength different from the maximum emission wavelength emitted from the light-emitting material by absorbing light emitted from the light-emitting material, wherein the rare-earth complex-based phosphor is An electroluminescent device comprising, as a ligand, at least one anion of the compound represented by the general formula (1) or (2).

2. In the rare earth complex phosphor, the aromatic ring formed by Z ₁ in the general formula (1) is a substituted or unsubstituted benzene ring, X ₁ and Y ₁ are oxygen atoms, and R ₁₁ is a hydrogen atom. 2. The electroluminescent device according to the above 1, wherein the compound is an anionic ligand of a compound which is a hydrocarbon aromatic ring or a nitrogen-containing aromatic ring.

3. The rare earth complex-based phosphor is characterized in that the phosphor is contained as an anionic ligand of a compound in which R ₂₃ is a hydrogen atom and R ₂₁ and R ₂₂ are both substituted and unsubstituted aromatic rings in the general formula (2). 2. The electroluminescent device according to the above 1, wherein

4. Rare earth complex based fluorescent material, .sigma.p positive of R ₂₁ in the general formula (2), σp is negative substitution of R _22, in that it contains as anionic member ligand compound is an unsubstituted aromatic ring 4. The electroluminescent device according to the item 3, wherein the device is characterized in that:

5. 4. The electroluminescent device according to the item 3, wherein the compound represented by the general formula (2) is a compound represented by the general formula (3) or (4).

6. In a light-emitting material and an electroluminescence device containing a rare-earth complex-based phosphor that emits light at a maximum emission wavelength different from the maximum emission wavelength emitted from the light-emitting material by absorbing light emitted from the light-emitting material, the rare-earth complex-based phosphor is An electroluminescent device comprising, as a ligand, at least one selected from the compounds represented by the general formulas (5), (6) and (7).

7. In the rare earth complex-based phosphor, X ₅ is an oxygen atom in the general formula (5) or (6), and R ₅₁ , R ₅₂ , R ₅₃ , R ₆₁ and R ₆₂ are each an alkoxy group or an alkyl group. 7. The electroluminescent device according to the item 6, wherein the device contains at least one of ligands of a compound.

8. Rare earth complex-based phosphor is a compound of the above formula (5) or (6), wherein X ₅ is an oxygen atom and R ₅₁ , R ₅₂ , R ₅₃ , R ₆₁ and R ₆₂ are each a fluorine-substituted alkyl group. 8. The electroluminescent device according to the above 7, wherein the device contains at least one ligand of

9. The rare earth complex phosphor according to any one of the above items 6 to 8, wherein the phosphor contains at least one anion of the compound represented by the general formula (1) or (2) as a ligand. The electroluminescent device according to the above.

10. In the rare earth complex phosphor, the aromatic ring formed by Z ₁ in the general formula (1) is a substituted or unsubstituted benzene ring, X ₁ and Y ₁ are oxygen atoms, and R ₁₁ is a hydrogen atom. 10. The electroluminescent device according to the item 9, wherein the compound is contained as an anionic ligand of the compound.

[11] The rare earth complex phosphor is represented by the general formula
In (2), R_{twenty three}Is a hydrogen atom, R _{twenty one}And R_{twenty two}Together
Anionic coordination of substituted or unsubstituted aromatic ring compounds
10. The element according to the item 9, wherein
Castroluminescence element.

12. The rare earth complex phosphor is represented by the general formula
In (2), R_{twenty one}Is positive, R _{twenty two}Is negative.
In other words, an anionic ligand of a compound which is an unsubstituted aromatic ring
12. The element according to the above item 11, wherein
Castroluminescence element.

13. 12. The electroluminescent device according to the above item 11, wherein the compound represented by the general formula (2) is a compound represented by the general formula (3) or the general formula (4).

14. 14. The electroluminescent device according to any one of 1 to 13, wherein the binder used for the color conversion layer containing the rare earth complex-based phosphor is a low-polarity resin.

15. Wherein the maximum emission wavelength of the rare earth complex phosphor is from 600 to 700 nm.
15. The electroluminescent device according to any one of 14.

16. Maximum emission wavelength of light emitting material is 430n
m or less, any one of the above 1 to 15
Item 14. The electroluminescent device according to item 5.

17. The maximum emission wavelength of the light-emitting material is 400 to
16. The electroluminescent device according to the above 15, wherein the wavelength is 430 nm.

18. The electroluminescent device according to any one of 1 to 17, wherein the light emitting material is an organic LED material.

19. A color conversion filter comprising a rare earth complex-based phosphor containing at least one anion of the compound represented by the general formula (1) or (2) as a ligand.

20. In the rare earth complex phosphor, the aromatic ring formed by Z ₁ in the general formula (1) is a substituted or unsubstituted benzene ring, X ₁ and Y ₁ are oxygen atoms, and R ₁₁ is a hydrogen atom. 20. The color conversion filter as described in 19 above, wherein the color conversion filter contains an anionic ligand of a compound which is a hydrocarbon aromatic ring or a nitrogen-containing aromatic ring.

21. The rare earth complex phosphor is represented by the general formula
In (2), R_{twenty three}Is a hydrogen atom, R _{twenty one}And R_{twenty two}Together
Anion configuration of a compound that is a substituted or unsubstituted aromatic ring
20. The method according to the above 19, which is contained as a ligand.
Color conversion filter.

22. The rare earth complex-based phosphor contains as an anionic ligand of a compound in which R ₂₁ has a positive σp value and R ₂₂ has a negative σp value in the general formula (2) and is a substituted or unsubstituted aromatic ring. 22. The color conversion filter as described in 21 above, wherein

23. 22. The color conversion filter as described in 21 above, wherein the compound represented by the general formula (2) is a compound represented by the general formula (3) or (4).

24. A color conversion filter comprising a rare earth complex-based phosphor having at least one of the compounds represented by formulas (5), (6) and (7) as a ligand.

25. In the rare earth complex-based phosphor, X ₅ is an oxygen atom in the general formula (5) or (6), and R ₅₁ , R ₅₂ , R ₅₃ , R ₆₁ and R ₆₂ are each an alkoxy group or an alkyl group. 25. The color conversion filter according to the above item 24, which contains at least one ligand of a compound.

26. Rare earth complex-based phosphor is a compound of the above formula (5) or (6), wherein X ₅ is an oxygen atom and R ₅₁ , R ₅₂ , R ₅₃ , R ₆₁ and R ₆₂ are each a fluorine-substituted alkyl group. At least one of the ligands of
28. The color conversion filter as described in 25 above, wherein the color conversion filter contains:

27. 27. The rare earth complex-based phosphor according to any one of the above items 24 to 26, wherein at least one of the anion forms of the compound represented by the general formula (1) or (2) is contained as a ligand. The color conversion filter according to 1.

28. In the rare earth complex phosphor, the aromatic ring formed by Z ₁ in the general formula (1) is a substituted or unsubstituted benzene ring, X ₁ and Y ₁ are oxygen atoms, and R ₁₁ is a hydrogen atom. 28. The color conversion filter as described in 27 above, wherein the color conversion filter contains a compound having a hydrocarbon aromatic ring or a nitrogen-containing aromatic ring as an anionic ligand.

29. The rare earth complex phosphor is represented by the general formula
In (2), R_{twenty three}Is a hydrogen atom, R _{twenty one}And R_{twenty two}Together
Anionic coordination of substituted or unsubstituted aromatic ring compounds
28. The color as described in 27 above, wherein the color is contained as a child.
Conversion filter.

30. The rare earth complex phosphor is represented by the general formula
In (2), R_{twenty one}Is positive, R _{twenty two}Is negative.
In other words, an anionic ligand of a compound which is an unsubstituted aromatic ring
29. The color change according to 29 above, wherein
Exchange filter.

31. 30. The color conversion filter as described in 29 above, wherein the compound represented by the general formula (2) is a compound represented by the general formula (3) or the general formula (4).

Hereinafter, the present invention will be described in more detail. The light-emitting material of the present invention is a material that emits light by an electric or electric field, specifically, a material that emits light when a hole and an electron are injected from an anode and a cathode, respectively, and recombine, or an accelerated electron. Materials that emit light due to the collision energy.

To emit light by an electric field or an electric field means, for example, that a light-emitting material contained in the light-emitting layer has a pair of opposed electrodes with a light-emitting layer interposed therebetween and a current is applied to the electrodes. This is because electrons injected from one of a pair of counter electrodes sandwiching the light-emitting layer and holes injected from the other electrode recombine in the light-emitting layer, and the light-emitting material has a higher energy level. It is presumed that this is caused by emitting energy as light when the excited luminescent material returns to its original ground state.

The light emitting material of the present invention is not particularly limited as long as it emits light by an electric or electric field. For example, an inorganic light emitting material such as gallium nitride (GaN) (inorganic LED)
Materials), and organic light-emitting materials (also referred to as organic LED materials).
It is preferable to use a material from the viewpoint of luminous efficiency.

Hereinafter, the electroluminescent device of the present invention will be described. The “electroluminescent elements” referred to in the present invention are the three types described above, and the “electroluminescent material” indicates a material constituting them.

An electroluminescent element is usually constituted by including a single layer or a plurality of layers between two electrodes. The constituent layers include a hole injection layer (or a charge injection layer, a hole injection layer, A charge transport layer, a hole transport layer), an electron injection layer (or an electron transport layer), and the like.

The hole injection layer and the electron injection layer may have a further laminated structure if necessary.
Anode / first hole injection layer / second hole injection layer (hole transport layer)
The light emitting layer may have a layer structure such as a light emitting layer / second electron injection layer (electron transport layer) / first electron injection layer / cathode.

Next, an example of the layer structure of the electroluminescent device of the present invention will be shown (however, as described above, the description of a plurality of hole injection layers and / or electron injection layers is omitted, but it is a matter of course that the (1) substrate / color conversion layer / substrate / anode / light-emitting layer / cathode (2) substrate / color conversion layer / substrate / anode / hole injection layer / light-emitting layer / Cathode (3) substrate / color conversion layer / substrate / anode / emission layer / electron injection layer / cathode (4) substrate / color conversion layer / substrate / anode / hole injection layer / emission layer / electron injection layer / cathode ( 5) substrate / anode / light-emitting layer / cathode / color conversion layer / substrate (6) substrate / anode / hole injection layer / light-emitting layer / cathode / color conversion layer / substrate (7) substrate / anode / light-emitting layer / electron injection Layer / cathode / color conversion layer / substrate (8) substrate / anode / hole injection layer / light emitting layer / electron injection /
Cathode / color conversion layer / substrate (9) substrate / color conversion layer / anode / light-emitting layer / cathode (10) substrate / color conversion layer / anode / hole injection layer / light-emitting layer /
Cathode (11) substrate / color conversion layer / anode / light-emitting layer / electron injection layer /
Cathode (12) Substrate / Color conversion layer / Anode / Hole injection layer / Emitting layer /
Electron injection layer / cathode Here, the substrate in contact with the color conversion layer and the substrate in contact with the anode may be the same or different, and the outside of each element may be covered with a substrate.

Incidentally, between the anode and the light emitting layer or the hole injection layer,
Further, a buffer layer (electrode interface layer) may be present between the cathode and the light emitting layer or the electron injection layer.

The substrate preferably used for the electroluminescent device of the present invention is not particularly limited in the type of glass, plastic, etc., and is not particularly limited as long as it is transparent. Examples of the substrate preferably used for the electroluminescence device of the present invention include glass, quartz, and a light-transmitting plastic film.

As the light-transmitting plastic film,
For example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, polyarylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose A film made of acetate propionate (CAP) or the like can be used.

As the anode in this electroluminescence device, a material having a large work function (4 eV or more), such as a metal, an alloy, an electrically conductive compound, and a mixture thereof is preferably used. Specific examples of such an electrode material include metals such as Au, and conductive transparent materials such as CuI, indium tin oxide (ITO), SnO ₂ , ZnO, and zinc-doped indium oxide (IZO). The anode may be formed by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering, and forming a pattern of a desired shape by a photolithography method, or (100 μm Above), a pattern may be formed via a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.

When light is extracted from the anode, the transmittance is desirably greater than 10%, and the sheet resistance of the anode is preferably 10 ³ Ω / □ or less.
The thickness of the anode can be appropriately selected depending on the material, but is 10 nm.
About 1 μm, preferably 10 to 200 nm
Is more preferable.

On the other hand, as the cathode, a metal having a small work function (less than 4 eV) (sometimes referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof are used as the electrode material. Specific examples of such an electrode material include potassium, sodium, and sodium.
Potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium /
Examples include an aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, indium, a lithium / aluminum mixture, and a rare earth metal.

Among them, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂
A mixture of an electron-injecting metal and a metal having a higher work function than this, such as an O ₃ ) mixture or a lithium / aluminum mixture, is preferred.

However, when the above-mentioned cathode buffer layer is coated on the surface of the cathode and used, the work function restriction is released, and for example, as described in JP-A-11-224783, By using a fluoride of an alkali metal or an alkaline earth metal for the layer (referred to as “electron injection layer” in the patent specification), the cathode is made of I
It is also possible to use a substance having a large work function, such as TO, SnO ₂ , In ₂ O ₃ , or ZnO: Al, which is usually used as an anode and has a large work function.
As described on page 145, line 15 to line 28, published by NTT Co., Ltd. on November 30, 998, lithium fluoride (film thickness 0.5 to 0.5) was used as the cathode buffer layer. It is known that by using 1 μm), aluminum can be used as a cathode material. Examples of the cathode material when using such a cathode buffer layer include silver, copper, Elements defined as "metal" in the periodic table, such as platinum and gold, can be used.

The above-mentioned cathode can be manufactured by forming a thin film of the above-mentioned electrode material by a method such as vapor deposition or sputtering. Further, JP-A-11-8
It can also be produced by a plating method as described in No. 074.

The sheet resistance of the cathode is preferably 10 ³ Ω / □ or less. The thickness of the cathode is 10 nm to 100 μm.
m, more preferably 50 to 2000 nm.

In order to transmit light, it is preferable that the electrode located between the light emitting layer and the color conversion layer of the electroluminescence element is transparent or translucent, because the light emitting efficiency is improved.

Here, that the electrode is transparent or translucent means that the visible light transmittance at 400 nm to 700 nm is 20%.
It means that it is at least 50%, preferably at least 50%, more preferably 50-70%.

Next, the light emitting layer will be described. The light emitting layer is a layer that emits light by recombination of electrons and holes injected from the electrode or the electron injection layer and the hole injection layer, and a light emitting portion is adjacent to the light emitting layer even in the light emitting layer. It may be an interface with a layer.

The material used for the light emitting layer is a light emitting material, and is preferably an organic compound or complex that emits fluorescence or phosphorescence, and may be any of known materials used for the light emitting layer of an organic EL device. Can be selected and used.

The light-emitting material may have the above-mentioned hole injection function and electron injection function in addition to the light-emitting performance, and most of the above-mentioned hole injection material and electron injection material can be used as the light-emitting material.

The light emitting material may be a polymer material such as p-polyphenylenevinylene or polyfluorene. Further, a polymer material in which the light emitting material is introduced into a polymer chain or a polymer material in which the light emitting material is a polymer main chain is used. May be used.

Further, a dopant (guest material) may be used in combination in the light emitting layer, and an arbitrary one can be selected from known ones used as dopants in EL devices.

Specific examples of the dopant include, for example, quinacridone, DCM, coumarin derivative, rhodamine, rubrene, decacyclene, pyrazoline derivative, squarylium derivative, europium complex and the like.

In the present invention, the luminescent material preferably has a maximum emission wavelength of 430 nm or less due to an electric or electric field, and further has a maximum emission wavelength of 400 to 430 nm from the viewpoint of achieving both conversion efficiency and storage stability. It is preferable to have one.

Also, on the CIE chromaticity chart, “Color name and chromaticity coordinates of color stimulus (color of light)” described on page 108 of the New Edition of Color Science Handbook, 4th Edition, Japan Society of Color Science, 108 Bl in "Relationship with"
ue, Blueish Purple or Purple
It is preferable that it is the area | region of.

The thickness of the light emitting layer is not particularly limited, but is preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and further preferably 1 nm to 1 μm.
0 nm to 500 nm.

The hole injection layer provided as necessary in the present invention has a function of transmitting the holes injected from the anode to the light emitting layer. The hole injection layer is provided between the anode and the light emitting layer. , Many holes are injected into the light emitting layer at a lower electric field. In addition, due to the barrier between electrons injected into the light emitting layer from the cathode or the electron injection layer and electrons present at the interface between the light emitting layer and the hole injection layer, the light is accumulated at the interface in the light emitting layer and the light emission efficiency is improved. This is an excellent element.

The material used for this hole injection layer (hereinafter referred to as
The hole injection material is not particularly limited as long as it has the above-mentioned function, and any conventionally known material can be selected and used.

The hole injecting material has one of a hole injecting property and an electron blocking property, and may be an organic substance or an inorganic substance.

Organic hole injecting materials include, for example, JP-A-63-295695, JP-A-2-191694, JP-A-3-792, and JP-A-5-23468.
No. 1, JP-A-5-239455, JP-A-5-239455
299174, JP-A-7-126225,
JP-A-7-126226, JP-A-8-10017
Various organic compounds described in JP-A No. 2,650 / 955A1 and the like can be used. For example,
Phthalocyanine derivative, tetraarylbendicine compound, aromatic tertiary amine, hydrazone derivative, carbazole derivative, triazole derivative, imidazole derivative,
Oxadiazole derivatives having an amino group, polythiophene and the like. Two or more of these compounds may be used in combination, and when they are used in combination, they may be stacked as separate layers or mixed.

When the hole injecting layers are stacked and used (when the functions of the hole injecting and the hole transporting are selectively used), a preferable combination can be selected from the above compounds and used. At this time, it is preferable to stack the layers of the compound having the smaller ionization potential in order from the anode (ITO or the like) side. Further, it is preferable to use a compound having a good thin film property (film forming property) (for example, a star burst type compound described in JP-A-4-308688 or the like is a typical example) on the anode surface.

Further, as an inorganic hole injecting material, p-type-S
i, p-type SiC or the like can be used.

The thickness of the hole injection layer is not particularly limited, but is preferably 5 nm to 5 μm.

Further, the electron injection layer used as necessary may have a function of transmitting electrons injected from the cathode to the light emitting layer, and a function of facilitating the injection of electrons from the cathode. Has the function of transporting and the function of blocking holes. Note that the electron injecting and transporting layer may be provided separately for a layer having an injection function and a layer having a transporting function.

The material used for this electron injection layer (hereinafter referred to as
Examples of the electron injection material) include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthalene perylene, carbodiimide, fluorenylidenemethane derivatives, anthraquinodimethane and Anthrone derivatives, oxadiazole derivatives and the like can be mentioned. A series of electron-transporting compounds described in JP-A-59-194393 are disclosed as a material for forming a light-emitting layer in the publication, but can also be used as an electron injection material. Further, in the oxadiazole derivative, a thiadiazole derivative in which an oxygen atom of an oxadiazole ring is substituted with a sulfur atom, an arylamino group, a triazole derivative in which an alkylamino group is substituted,
A quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as an electron injecting material.

Metal complexes of 8-quinolinol derivatives, for example, tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-
Quinolinol) aluminum, tris (2-methyl-8)
-Quinolinol) aluminum, tris (5-methyl-
8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), and the like, and the central metal of these metal complexes is In, Mg, Cu, Ca, Sn, Ga or Pb.
Can also be used as the electron injecting material. In addition, Reference A, Chapter 1, Chapter 3, Chapter 39
Metal complex-based materials, metal-free metal phthalocyanines described on pages 48 to 48, or those whose terminals are substituted with an alkyl group, a sulfonic acid group, or the like, can also be preferably used as the electron injecting material. Further, similarly to the hole injection layer, an inorganic semiconductor such as n-type Si or n-type SiC can be used as the electron injection material.

The thickness of the electron injection layer is not particularly limited, but is preferably 5 nm to 5 μm.

The electron injecting layer may have a single layer structure containing one or more of the above electron injecting materials, or may have a laminated structure having a plurality of layers of the same composition or different compositions.

Note that, between the anode and the light emitting layer or the hole injection layer,
Further, a buffer layer (electrode interface layer) may be present between the cathode and the light emitting layer or the electron injection layer.

The buffer layer is a layer provided between the electrode and the organic layer for lowering the driving voltage and improving the luminous efficiency. The second layer, Chapter 2, “Electrode materials” of Document A (pages 123 to 123)
166), which includes an anode buffer layer and a cathode buffer layer.

As the anode buffer layer, a phthalocyanine buffer layer represented by copper phthalocyanine, an oxide buffer layer represented by vanadium oxide, an amorphous carbon buffer layer, and a conductive polymer such as polyaniline (emeraldine) and polythiophene are used. Polymer buffer layer and the like.

The cathode buffer layer includes a metal buffer layer represented by strontium and aluminum, an alkali metal compound buffer layer represented by lithium fluoride, an alkaline earth metal compound buffer layer represented by magnesium fluoride, and an oxide buffer layer. An oxide buffer layer typified by aluminum is exemplified.

It is desirable that the buffer layer is a very thin film.
A range of 0 nm is preferred.

As a method for forming a light emitting layer, a hole injection layer, an electron injection layer or a buffer layer, for example, a vacuum evaporation method,
It can be formed by thinning by a known method such as a spin coating method, a casting method, and an LB method.
In particular, a molecular deposition film is preferable. Here, the molecular deposition film refers to a thin film formed by depositing a compound from a gaseous state or a film formed by solidifying a compound from a molten state or a liquid state. Usually, this molecular deposition film is LB
It can be distinguished from the thin film (molecule accumulation film) formed by the method by the difference in the aggregated structure and the higher-order structure and the functional difference caused by the difference.

This light emitting layer is disclosed in JP-A-57-517.
As described in No. 81, after dissolving the luminescent material in a solvent together with a binder such as a resin to form a solution,
This can be formed into a thin film by a spin coating method or the like. The thickness of the light emitting layer formed in this manner is not particularly limited and can be appropriately selected depending on the situation. However, it is preferable to use the light emitting layer in the range of 5 nm to 5 μm.

Next, the color conversion layer will be described. The color conversion layer is
A layer containing at least one rare earth complex-based phosphor according to the claims of the present invention, which absorbs light emitted from the light emitting material and emits light at a maximum emission wavelength different from the maximum emission wavelength of the light emitting material. Things.

Here, the emission wavelength different from the maximum emission wavelength emitted from the light-emitting material means that the maximum emission wavelength of the rare earth complex-based phosphor is 1 to the maximum emission wavelength emitted by the light-emitting material.
It means a thing separated by 0 nm or more.

Hereinafter, the general formula (1) will be described. one
In general formula (1), X₁And Y₁Are oxygen atoms,
Sulfur atom or NR ₁₂And R₁₁And R₁₂Each
A hydrogen atom or a monovalent substituent, Z₁Is an aromatic ring (hereinafter, referred to as
Atom group necessary to form an aromatic ring)
You. R₁₁And R₁₂As a monovalent substituent represented by
For example, alkyl group, alkenyl group, alkynyl group, ant
Group, heterocyclic group, hetero group containing quaternized nitrogen atom
Ring group (eg, pyridinium group), hydroxy group, alcohol
Xy group (for example, ethyleneoxy group or propylene
Aryloxy group), aryloxy group
Group, acyloxy group, acyl group, alkoxycarbonyl
Group, aryloxycarbonyl group, carbamoyl group, c
Urethane group, carboxyl group, imide group, amino group, cal
Bonamide, sulfonamide, ureido, thiou
Raid group, sulfamoylamino group, semicarbazide
Group, thiosemicarbazide group, hydrazino group, quaternary
Monio group, (alkyl, aryl or heterocycle) thio
Group, mercapto group, (alkyl or aryl) sulfoni
Group, (alkyl or aryl) sulfinyl group, sulf
E group, sulfamoyl group, acylsulfamoyl group,
(Alkyl or aryl) sulfonylureido group, (A
Alkyl or aryl) sulfonylcarbamoyl, halo
Gen atom, cyano group, nitro group, phosphoric acid amide group, etc.
No.

The aromatic ring formed by Z ₁ includes a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring,
Examples thereof include a triazine ring, a pyrrole ring, a furan ring, and a thiazole ring. These aromatic rings may further have a substituent, and the substituents may form a ring. Examples of the substituent on the aromatic ring formed by Z ₁ include the aforementioned R
Substituents similar to the monovalent substituent described for ₁₁ and R ₁₂ can be mentioned.

From the viewpoint of luminous efficiency, the aromatic ring formed by Z ₁ is preferably a substituted or unsubstituted benzene ring, X ₁ and Y ₁ are oxygen atoms, R ₁₁ is a hydrogen atom,
This is the case with a hydrocarbon aromatic ring or a nitrogen-containing aromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of the nitrogen-containing aromatic ring include a pyrrole ring, an oxazole ring, a pyridine ring, a pyrimidine ring, and a benzimidazole ring. More preferably, the aromatic ring formed by Z ₁ is a substituted or unsubstituted benzene ring, X ₁ and Y ₁ are oxygen atoms, and R ₁ is a hydrogen atom.

Together with the anion of the compound represented by the general formula (1) (anion obtained by dehydrogenation of the compound), Ce, Pr, Nd, Pm,
Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Y
and cations such as b. Preferable are cations of Ce, Tb and Eu, more preferably Eu ³⁺ which shows good color purity in red.

Specific examples of the compound represented by the general formula (1) and the rare earth complex-based phosphor formed together with the anion of the compound are shown below, but the present invention is not limited thereto.

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Next, the general formula (2) will be described. In the general formula (2), R ₂₁ , R ₂₂ and R ₂₃ each represent a hydrogen atom or a monovalent substituent. R ₂₁ , R ₂₂ and R ₂₃
The monovalent substituent represented by R ₁₁ and R ₁₁
The same substituents as the monovalent substituents described in ₁₂ are exemplified, and the respective substituents may be bonded to each other to form a ring.

In the present invention, from the viewpoint of luminous efficiency, the general formula (2) is preferably a case where R ₂₃ is a hydrogen atom, and both R ₂₁ and R ₂₂ are aromatic rings, and more preferably σp of R ₂₁ value is positive, when the σp value of R ₂₂ is negative, it is time represented by the general formula (3) or general formula (4).

In the general formula (3), R₃₁And R₃₃Is water
An element atom or a σm value represents a positive monovalent substituent,₃₂Is water
An element atom or a σp value represents a positive monovalent substituent, and R₃₄And
And R ₃₆Represents a hydrogen atom or a monovalent substituent having a negative σm value.
Then R₃₅Represents a hydrogen atom or a monovalent substituent having a negative σp value.
You. Where R₃₁, R₃₂And R₃₃Are simultaneously hydrogen atoms
There is no, R₃₄, R₃₅And R₃₆Is a hydrogen source at the same time
You cannot be a child. R ₃₁, R₃₂, R₃₃, R₃₄, R₃₅You
And R₃₆As the monovalent substituent represented by₁₁
And R₁₂Substituents similar to the monovalent substituent described in
And is appropriately selected depending on the σp value or σm value. It
Each substituent may be bonded to each other to form a ring.
In the general formula (4), R₄₁And R₄₂Is a hydrogen atom or one
A valent substituent, Z_FourForms a five-membered heteroaromatic ring
And m4 and n4 represent 1 to 5.
You. R₄₁And R₄₂As a monovalent substituent represented by
R described above₁₁And R₁₂Same as the monovalent substituent described in
Substituents, each of which is bonded to each other
A ring may be formed. Z_FourAnd an aromatic ring formed by
So, Z₁Exemplified by an aromatic ring formed by
Among them, five-membered heteroaromatic rings are exemplified.
May further have a substituent, and the substituents form a ring with each other
You may. Z_FourSubstituents on the aromatic ring formed by
Is an example of R₁₁And R₁₂The monovalent placement mentioned in
Substituents similar to the substituents can be mentioned.

The σp value and σm of the substituent in the present invention
The value is a substituent constant defined by Hammet and described in, for example, "Structure-Activity Relationship of Drugs: Chemistry, No. 122, pages 96-103, published by Nankodosha".

Together with the anion of the compound represented by the general formulas (2), (3) and (4) (anion obtained by dehydrogenating the compound), C is used as a rare earth metal forming a complex.
e, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
and cations such as y, Ho, Er, Tm, and Yb. Preferred are cations of Ce, Tb and Eu, more preferably E which exhibits good color purity in red.
Specific examples of compounds represented by general formulas (2), (3) and (4), which are u ³⁺ , and rare earth complex phosphors formed together with an anion of the compound are shown below. It is not limited to these.

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Next, general formulas (5), (6) and (7) will be described. In the general formula (5), R ₅₁ , R ₅₂ and R ₅₃ represent a monovalent substituent, and X ₅ represents an oxygen atom or a sulfur atom. Examples of the monovalent substituent represented by R ₅₁ , R ₅₂ and R ₅₃ include the same substituents as those described above for R ₁₁ and R ₁₂ , and from the viewpoint of luminous efficiency, Preferably, it is an alkoxy group or an alkyl group, and more preferably, a fluorine-substituted alkyl group.

In the general formula (6), R₆₁And R₆₂Is
Represents a monovalent substituent. R₆₁And R ₆₂Represented by
As the substituent, the aforementioned R₁₁And R₁₂The monovalent mentioned in
Substituents similar to the substituents can be mentioned, which are favorable in terms of luminous efficiency.
Preferably, it is an alkoxy group or an alkyl group, more preferably
Preferably, it is a fluorine-substituted alkyl group.

In the general formula (7), R ₇₁ , R ₇₂ and R ₇₃ represent a hydrogen atom or a monovalent substituent. R ₇₁ , R
_The monovalent substituents represented by ₇₂ and R ₇₃ include the aforementioned R
_The monovalent substituents described for ₁₁ and R ₁₂ are mentioned, and from the viewpoint of luminous efficiency, R ₇₂ and R ₇₃ are preferably bonded to each other to form a nitrogen-containing aromatic ring. Examples of the formed nitrogen-containing aromatic ring include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, an imidazole ring, an oxazole ring, a thiazole ring, and a quinoline ring.The nitrogen-containing aromatic ring further has a substituent. And the substituents may form a ring, and among them, a pyridine ring is preferable.

Formulas (5), (6) and (7)
As a rare earth metal that forms a complex with the compound
Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, D
cations such as y, Ho, Er, Tm, and Yb;
You. Preferably, it is a cation of Ce, Tb and Eu.
And more preferably E which shows good color purity in red.
u ³⁺It is.

More preferably, the rare earth complex phosphor formed together with the compounds represented by the general formulas (5), (6) and (7) is further represented by the general formula (1) or (2) It is time to have at least one of the anion forms of the compound as a ligand. Preferred examples of the general formula (1) or (2) used in this case are the same as described above.

The following formulas (5), (6) and (7)
Specific examples of the ligand and the rare earth complex-based phosphor represented by are shown below, but the present invention is not limited to these.

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The rare earth complex phosphor contained in the electroluminescence device of the present invention preferably has a maximum emission in a region of 400 to 700 nm by light emitted from the light emitting material. More preferably, in the prior art, the light emission has a maximum light emission in a region of 600 nm to 700 nm where the light emission efficiency is low.

The rare earth complex phosphor contained in the electroluminescent device of the present invention contains at least one kind having a maximum emission wavelength of 180 nm or more on the long wavelength side with respect to the maximum emission wavelength emitted from the light emitting material. Is preferred.

Next, the composition of the color conversion layer will be described.
The color conversion layer is formed by dispersing a rare-earth complex-based phosphor with a binder represented by a photo-curable or thermo-curable resin and / or a filler represented by silica gel, alumina or the like, or a non-reactive resin. Or a composite made of a hybrid polymer, or may be made by laminating simple substances as they are. When the phosphor of the present invention is used by being dispersed or composited, it is preferable to use the phosphor or filler at a ratio of 0.0001 to 100 mol per 1 kg of the binder or the filler.

The photo-curable or thermo-cured resin cured product will be described. These compounds are subjected to light or heat treatment on a photocurable resin or a thermosetting resin composition film (resist or paste film) to generate radical species or ionic species and polymerize or crosslink to make them insoluble and infusible. It is a thing. Specifically, the acrylate-based polymer refers to (I) a composition film comprising an acrylic polyfunctional molymer and an acrylate oligomer having a plurality of acrylic groups and methacrylic groups, and a light or heat polymerization initiator, which is subjected to light or heat treatment, Radicals or thermal radicals are polymerized, (II) a composition comprising polyvinyl cinnamate and a sensitizer is dimerized and crosslinked by light or heat treatment, and (III) a linear or cyclic olefin. A composition film composed of a bis azide, in which nitrene is generated by light or heat treatment and then crosslinked with an olefin, (IV) A composition film composed of a monomer having an epoxy group and a photoacid generator is treated with light or heat treatment to form an acid (cation) ) Is generated and polymerized.

Explaining the non-reactive resin, the non-reactive resin does not generate radical species or ionic species by light or heat, that is, has a reactivity, contrary to the photo-curing or thermosetting resin. Not a resin. Specifically, a compound having a structure having no reactive vinyl group and generating a radical species or an ionic species by decomposing by light or heat, such as a polymerization initiator, a sensitizer, a bisazide or an acid generator. It is a resin not containing. More specifically, polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl chloride, polyvinyl acetate, polyvinyl butyral, polyethylene, polypropylene, polystyrene, polyester,
General-purpose polymers such as polypyridine and fluororesin are exemplified.

From the viewpoint of luminous efficiency, a low-polarity resin is preferable. The low-polarity resin described here is JIS-K-6
A dielectric constant of 3 or less measured by a test method specified in 911 or ASTM D150,
Specific examples include resins having a dielectric constant of 3 or less among resins described in “Plastic Molding Material Commerce Handbook (1998 edition, published by Chemical Industry Daily)”, and polyethylene, polypropylene, and polystyrene. Most of the dielectric constant of the fluorine-based resin is 3 or less.

The color conversion layer can take various forms depending on the application. The electroluminescent device of the present invention has at least one kind of rare earth complex-based phosphor, but may use an inorganic phosphor as needed.

For example, when a white planar light-emitting material is desired, a mixture of a blue light-emitting phosphor and a yellow light-emitting phosphor is used, or three kinds of blue light emission, green light emission and red light emission are used. A mixture of phosphors is used. In that case, patterning is not particularly required, and it is only necessary to apply a uniform thickness.

Further, for the purpose of full colorization, at least one of an inorganic phosphor or a rare earth complex phosphor having a maximum emission wavelength of 400 to 500 nm by light emitted from the light emitting material, and a maximum emission wavelength of 501 to 600 nm. It is preferable to have a color conversion layer having at least one of an inorganic phosphor or a rare earth complex phosphor having at least one of an inorganic phosphor or a rare earth complex phosphor having a maximum emission wavelength at 601 to 700 nm. .

When a plurality of kinds of light are obtained using a plurality of kinds of inorganic phosphors or rare earth complex phosphors, the purpose is to adjust the color of the light emitted from each phosphor to increase the color purity. Color filters may be used in an overlapping manner. In addition, a black matrix may be arranged in the gap between each fluorescent element (one pixel having a different fluorescent color) to block leakage light of light emission to enhance visibility of multicolor light emission.

Further, a transparent protective film may be laminated on the color conversion layer, if necessary. The thickness of each fluorescence conversion layer is usually 0.1 μm to 100 μm, preferably 1 μm to 60 μm.
m.

Next, a method for manufacturing the color conversion layer will be described. The color conversion layer may be a dispersion or solution of the rare earth complex-based phosphor of the present invention, and the phosphor of the present invention may be directly applied in a mosaic form using an inkjet method or a printing method, or may be a photo-curing type. Alternatively, a mosaic pattern may be produced using light or heat by using a thermosetting resin composition as a binder, and the pattern may be obtained by a normal printing technique or photolithography method.

The composition of the inorganic fluorescent substance which may be used in combination in the present invention is not particularly limited, but the crystal bases Y ₂ O ₂ S and Zn
Metal oxides such as ₂ SiO ₄ and Ca ₅ (PO ₄ ) ₃ Cl and sulfides such as ZnS, SrS and CaS are added to Ce, Pr, Nd, Pm, Sm, Eu, Gd, T
It is preferable to use a combination of rare earth metal ions such as b, Dy, Ho, Er, Tm, and Yb and metal ions such as Ag, Al, Mn, In, Cu, and Sb as an activator or a coactivator.

The inorganic phosphors preferably used in the present invention are shown below, but the present invention is not limited to these compounds.

[Blue emitting inorganic phosphor] (BL-1) Sr ₂ P ₂ O ₇ : Sn ⁴⁺ (BL-2) Sr ₄ Al ₁₄ O ₂₅ : Eu ²⁺ (BL-3) BaMgAl ₁₀ O ₁₇ : Eu ²⁺ (BL-4) SrGa ₂ S ₄ : Ce ³⁺ (BL-5) CaGa ₂ S ₄ : Ce ³⁺ (BL-6) (Ba, Sr) (Mg, Mn) Al
₁₀ O ₁₇ : Eu ²⁺ (BL-7) (Sr, Ca, Ba, Mg) ₁₀ (PO ₄ ) ₆
Cl ₂ : Eu ²⁺ (BL-8) BaAl ₂ SiO ₈ : Eu ²⁺ (BL-9) Sr ₂ P ₂ O ₇ : Eu ²⁺ (BL-10) Sr ₅ (PO ₄ ) ₃ Cl: Eu ^{2 +} (BL-11) (Sr, Ca, Ba) ₅ (PO ₄ ) ₃ C
^{l: Eu 2+ (BL-12} ) BaMg 2 Al 16 O 27: Eu 2+ (BL-13) (Ba, Ca) 5 (PO 4) 3 Cl: Eu
²⁺ (BL-14) Ba ₃ MgSi ₂ O ₈ : Eu ²⁺ (BL-15) Sr ₃ MgSi ₂ O ₈ : Eu ²⁺ [Green light emitting inorganic phosphor] (GL-1) (BaMg) Al ₁₆ O ₂₇ : Eu ²⁺ , Mn ²⁺ (GL-2) Sr ₄ Al ₁₄ O ₂₅ : Eu ²⁺ (GL-3) (SrBa) Al ₂ Si ₂ O ₈ : Eu ²⁺ (GL-4) (BaMg) ^{_{2 SiO 4: Eu 2+ (GL}} -5) Y 2 SiO 5: Ce 3+, Tb 3+ (GL-6) Sr 2 P 2 O 7 -Sr 2 B 2 O 5: Eu 2+ (GL-7 ) (BaCaMg) ₅ (PO ₄ ) ₃ Cl: Eu
_{^{2+ (GL-8) Sr 2}} Si 3 O 8 - 2 SrCl 2: Eu 2+ (GL-9) Zr 2 SiO 4, MgAl 11 O 19: Ce 3+,
Tb ³⁺ (GL-10) Ba ₂ SiO ₄ : Eu ²⁺ (GL-11) Sr ₂ SiO ₄ : Eu ²⁺ (GL-12) (BaSr) SiO ₄ : Eu ²⁺ [Red-emitting inorganic phosphor] _{(RL-1) Y 2 O} 2 S: Eu 3+ (RL-2) YAlO 3: Eu 3+ (RL-3) Ca 2 Y 2 (SiO 4) 6: Eu 3+ (RL-4) LiY 9 (SiO ₄ ) ₆ O ₂ : Eu ³⁺ (RL-5) YVO ₄ : Eu ³⁺ (RL-6) CaS: Eu ³⁺ (RL-7) Gd ₂ O ₃ : Eu ³⁺ (RL-8) ^{_{gd 2 O 2 S: Eu 3+}} (RL-9) Y (P, V) O 4: Eu 3+ (RL-10) Mg 4 GeO 5. ^{_{5 F: Mn 4+ (RL-}} 11) Mg 4 GeO 6: Mn 4+ following describes the color conversion filter of the present invention.

The color conversion filter of the present invention is a wavelength conversion element used for converting the color of a light source (emission color) to a desired color. The light source may be a laser other than the electroluminescence element of the present invention. Any light source such as light can be used. Basically, one more than the maximum wavelength of the light source
It is a wavelength conversion element capable of converting a wavelength to a longer wavelength of 0 nm or more.
No. 9-245511, No. 11-297777, etc. (for blue, green and red light emission by converting a blue light source into green and red and arranging them in stripes). Color conversion filter), and a white light emission filter (400 to 700 n) for illumination and backlight of a liquid crystal display.
m), a color conversion filter that emits a wide range of visible light in the m range, a neon sign and a filter for partial emission of automotive instruments (a color conversion filter that displays the necessary colors where needed). As an example.

To obtain a multicolored color conversion filter such as a color filter of a liquid crystal display,
The phosphor that obtains the required emission color may be patterned in a stripe, dot, or mosaic shape.As the patterning method, a conventional method for manufacturing a color filter for a liquid crystal display can be directly applied, and specifically, It can be produced by a pigment dispersion method, a printing method, an inkjet method, or the like.

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EXAMPLES The present invention will now be described specifically with reference to examples, but the embodiments of the present invention are not limited thereto.

Example 1 (Preparation of Organic LED Element) Example (1-1) After patterning a substrate (NA-45 manufactured by NH Techno Glass Co., Ltd.) on which 150 nm of ITO was formed on glass as an anode, The transparent support substrate provided with the ITO transparent electrode was ultrasonically washed with isopropyl alcohol, dried with dry nitrogen gas, and washed with UV ozone for 5 minutes.

This transparent support substrate was fixed to a substrate holder of a commercially available vacuum evaporation apparatus, and a N, N′-diphenyl-N, N′-bis (3
-Methylphenyl) [1,1′-biphenyl] -4,
200 mg of 4'-diamine (TPD), 200 mg of p-quarterphenyl (PQP) in another molybdenum resistance heating boat, and tris (8-hydroxyquinolinato) aluminum in another molybdenum resistance heating boat 200 mg of (Alq3) was charged and attached to a vacuum evaporation apparatus.

Next, after the pressure in the vacuum chamber was reduced to 4 × 10 ⁻⁴ Pa, the heating boat containing the TPD was energized to
Heat to 20 ° C. and evaporate at a rate of 0.1 to 0.3 nm / sec
By vapor-depositing on a transparent support substrate by c, a hole injection layer having a thickness of 60 nm was provided. Further, the heating boat containing the PQP was energized and heated to 220 ° C., and the vapor deposition rate was 0.1 to 0.3 n.
deposited on the hole injection layer at a rate of 40 nm
Was provided. Further, the heating boat containing Alq3 was energized and heated to 250 ° C., and the evaporation rate was set to 0.1.
deposited on the light emitting layer at a thickness of 20 nm / sec.
Was provided. In addition, the substrate temperature at the time of vapor deposition was room temperature. Next, a vacuum chamber was opened, a stainless steel rectangular perforated mask was placed on the electron injection layer, while 3 g of magnesium was placed in a molybdenum resistance heating boat, and silver was placed in a tungsten deposition basket with 0.1 g of silver. Put 5g,
After reducing the pressure of the vacuum chamber to 2 × 10 ⁻⁴ Pa again, the magnesium-containing boat was energized and the deposition rate was 1.5 to 2.0 n.
At this time, the silver basket was heated at the same time, silver was deposited at a deposition rate of 0.1 nm / sec, and a counter electrode composed of a mixture of magnesium and silver was formed. A luminescence device (UV-1) was produced.

When a direct current of 10 volts was applied using the ITO electrode of the device as an anode and the opposite electrode made of magnesium and silver as a cathode, light emission with a maximum emission wavelength of 380 nm was obtained.

Example (1-2) Except that the luminous substance p-quarterphenyl (PQP) in Example (1-1) was replaced with the compound A-1, the same method as in Example (1-1) was used. The produced electroluminescence device (A-1) was produced.

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When a direct current of 10 V was applied using the ITO electrode of the device as an anode and the counter electrode made of magnesium and silver as a cathode, a maximum emission of 405 nm was obtained.

Example (1-3) The light-emitting substance p-quarterphenyl (PQ) of (1-1)
P) is 4,4'-bis (2,2'-diphenylvinyl)
(1-) except that it was replaced with biphenyl (DPVBi).
An electroluminescent device (B-1) manufactured in exactly the same manner as in 1) was manufactured.

When a direct current of 10 V was applied using the ITO electrode of the device as an anode and the opposite electrode made of magnesium and silver as a cathode, blue light with a maximum emission of 475 nm was obtained.

Example 2 (Preparation of Color Conversion Layer) Example (2-1) Mixed solution of toluene / ethanol = 1/1 (300 g)
3 g of the rare earth complex-based phosphor (CL-4) of the present invention was dissolved in 30 g of polyvinyl butyral (BX-1, manufactured by Sekisui Chemical Co., Ltd.) dissolved in An electroluminescent device containing the rare earth complex-based phosphor of the present invention is coated on a substrate of the luminescent device (A-1) (the surface opposite to the light emitting layer) with a wet film thickness of 150 μm and dried with hot air (NO. 1) was produced.

Similarly, except that the electroluminescent device and the rare earth complex-based phosphor were changed to the devices and compounds shown in Table 1, a similar method was used.
Electroluminescent devices (NO.2) to (NO.22) and (NO.26) to (NO.27) containing the color rare earth complex-based phosphor of the present invention were produced.

Comparative Example (2-1) The fluorescent pigment Solvent Yellow 116 was replaced with 1.0 g, basic violet 11 with 0.5 g and rhodamine 6G with 0.5 g instead of CL-4 of Example (2-1). A blue light-excited red-emitting electroluminescent device (No. 23) as a comparison was produced in the same manner as in Example (2-1) except for the above. Further, electroluminescent elements (NO. 24) and (NO. 25) in which the electroluminescent elements were changed to B-1 and UV-1 were produced.

Example (2) was repeated except that the fluorescent pigment coumarin 6 and 2.0 g and the fluorescent pigment Solvent Yellow 116 and 0.5 g were used in place of CL-4 of Example (2-1).
An electroluminescent element (No. 28) that emits blue light and emits green light for comparison was produced in the same manner as in the method of -1).

Further, the electroluminescent element was changed to B-
Electroluminescent element changed to No. 1 (No. 2)
9) was produced.

Example 3 (Evaluation) Example (3-1) (Evaluation of Luminous Efficiency, Lifetime, and Color Tone of Electroluminescent Element) 1 to NO. 29
Was subjected to continuous lighting by applying a DC voltage of 12 V in a dry nitrogen gas atmosphere at a temperature of 23 ° C., and the luminous efficiency (lm / W) at the start of lighting and the time required for halving the luminance were measured. The luminous efficiency of the sample No. The luminous efficiency of Sample No. 1 is represented by a relative value when the luminous efficiency is set to 100, and the time for halving the luminance is shown in Sample No. It was expressed as a relative value with the time when the luminance of 1 was reduced by half as 100. The results are shown in Tables 1 and 2.

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[Table 1]

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[Table 2]

From Tables 1 and 2, it was found that the electroluminescent element containing the rare earth complex-based phosphor of the present invention, which emits red light, has higher luminous efficiency and longer life than the comparative example. Further, the emission color of the sample of the present invention was more preferable.

Further, it was found that the electroluminescent device containing the rare earth complex-based phosphor of the present invention, which emits green light, has higher luminous efficiency and longer lifetime than the comparative example. Further, the luminescent color was more preferable than that of the comparative sample.

Example (3-2) In place of the electroluminescent element used in Example (3-1), an ultraviolet light emitting LED (U
When the same evaluation was performed using (V LED Lamp), the same result as that of Example (3-1) was obtained.

Example (3-3) (Low Polar Binder) 3 g of the rare earth complex phosphor (CL-54) of the present invention was dissolved in 300 g of a fluororesin for coating (Lumiflon LF-200, manufactured by Asahi Glass Co., Ltd.). Then, on the substrate (the surface opposite to the light emitting layer) of the electroluminescent device (A-1) produced in Example (1-2), a wet film was applied at a thickness of 150 μm, and dried with warm air to obtain a rare earth element of the present invention. An electroluminescent device (No. 30) containing a complex phosphor was produced.

Further, under the same conditions as in Example (3-1), the luminous efficiency and the time required for reducing the luminance by half were measured.
Table 3 shows the results.

Note that Lumiflon L used in this example was used.
The dielectric constant of F-200 showed a value of 2.2 as a result of an actual measurement by a test method specified in ASTM-D50.

The permittivity of polyvinyl butyral (manufactured by Sekisui Chemical Co., Ltd.) is described in the catalog as 3.1 to 4.2.

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[Table 3]

As shown in Table 3, the binder of the electroluminescent device (NO. 20) of the present invention was Lumiflon L
It was confirmed that the luminous efficiency was further improved by changing to F-200.

Also, it can be seen that when the Lumiflon LF-200 was changed to commercially available polyethylene, polypropylene and polystyrene, the improvement of the luminous efficiency was confirmed.

Example 4 Example (4-1) A color conversion layer was formed on a transparent substrate by the method described in JP-A-8-27997, and an anode, a hole injection layer, and a light emitting layer were formed on the color conversion layer. , An electron emission element in which an electron injection layer and a cathode were sequentially laminated, and an example (3-1)
When the same evaluation was performed, similar effects were confirmed in terms of luminous efficiency and lifetime.

Example 5 (Color conversion filter) A mixed solution of toluene / ethanol = 1/1 (300 g)
3 g of the rare earth complex phosphor (CL-4) of the present invention was dissolved in 30 g of butyral (BX-1) dissolved in
A 0 μm polyethersulfone (PES) film was coated at a wet film thickness of 150 μm and dried with warm air to prepare a color conversion filter (F-1) of the present invention.

Similarly, the color conversion filters (F-2) to (F-5) of the present invention were prepared in the same manner except that the compounds shown in Table 4 were used instead of CL-4.
Was prepared.

[0182]

[Table 4]

Example 6 Using the color conversion filter prepared in Example 5, using a light source (laser light, etc.) other than the light sources (A-1, B-1, UV-1) used in the present invention. When the color conversion efficiency was measured, good color conversion efficiency was obtained as in Example 3.

[0184]

As has been demonstrated in the examples, the rare earth complex-based phosphor of the present invention can confirm good visible light emission, and has excellent light emission luminance, light emission efficiency and light emission life. The rare earth complex-based phosphor color conversion filter of the present invention can provide good visible light emission even when a light source other than the electroluminescence element is used, and has excellent light emission luminance, light emission efficiency, and light emission life.

Claims (31)

[Claims] 1. An electroluminescence device containing a light-emitting material and a rare-earth complex-based phosphor that absorbs light emitted from the light-emitting material and emits light at a maximum emission wavelength different from the maximum emission wavelength emitted from the light-emitting material. An electroluminescent device, wherein the system phosphor contains at least one anion of a compound represented by the following general formula (1) or (2) as a ligand. Embedded image [Wherein, X ₁ and Y ₁ each represent an oxygen atom, a sulfur atom or N—R ₁₂ , R ₁₁ and R ₁₂ each represent a hydrogen atom or a monovalent substituent, and Z ₁ forms an aromatic ring. Represents the group of atoms required to perform [Chemical formula 2] [Wherein, R ₂₁ , R ₂₂ and R ₂₃ each represent a hydrogen atom or a monovalent substituent. ] 2. The rare earth complex-based phosphor according to claim 1, wherein the aromatic ring formed by Z ₁ in the general formula (1) is a substituted or unsubstituted benzene ring, X ₁ and Y ₁ are oxygen atoms, R ₁₁ is a hydrogen atom, electroluminescent device according to claim 1, characterized in that it contains as anionic member ligand compound is a hydrocarbon aromatic ring or a nitrogen-containing aromatic ring. 3. The rare earth complex-based phosphor is an anion ligand of a compound in which R ₂₃ is a hydrogen atom and R ₂₁ and R ₂₂ are both a substituted or unsubstituted aromatic ring in the general formula (2). The electroluminescent device according to claim 1, wherein the electroluminescent device is contained. 4. A rare earth complex based phosphor, .sigma.p positive of R ₂₁ in the general formula (2), σp is negative substitution of R _22, the compound is an unsubstituted aromatic ring anion body ligand The electroluminescent device according to claim 3, wherein: 5. A compound represented by the general formula (2):
The electroluminescent device according to claim 3, which is a compound represented by the following general formula (3) or (4). Embedded image [Wherein, R ₃₁ and R ₃₃ represent a hydrogen atom or a monovalent substituent having a positive σm value, R ₃₂ represents a hydrogen atom or a monovalent substituent having a positive σp value, and R ₃₄ and R ₃₆ Is a hydrogen atom or σm
R ₃₅ represents a hydrogen atom or σp
A value represents a negative monovalent substituent. However, R ₃₁ , R ₃₂ and R ₃₃ are not simultaneously hydrogen atoms, and R ₃₄ , R ₃₅
And R ₃₆ cannot be a hydrogen atom at the same time. [Formula 4] [Wherein, R ₄₁ and R ₄₂ represent a hydrogen atom or a monovalent substituent, Z ₄ represents an atomic group necessary for forming a 5-membered heteroaromatic ring, and m4 and n4 represent 1 to 5 Represents ] 6. An electroluminescence device containing a light-emitting material and a rare-earth complex-based phosphor that absorbs light emitted from the light-emitting material and emits light at a maximum emission wavelength different from the maximum emission wavelength emitted from the light-emitting material. An electroluminescent device, wherein the system phosphor contains at least one selected from compounds represented by the following general formulas (5), (6) and (7) as a ligand. Embedded image [Wherein, R ₅₁ , R ₅₂ and R ₅₃ represent a monovalent substituent,
X ₅ represents an oxygen atom or a sulfur atom. [Formula 6] [In the formula, R ₆₁ and R ₆₂ represent a monovalent substituent. [Formula 7] [Wherein R ₇₁ , R ₇₂ and R ₇₃ represent a hydrogen atom or a monovalent substituent. ] 7. The rare earth complex-based phosphor according to the formula (5)
Or, in the general formula (6), X ₅ is an oxygen atom,
7. The electroluminescent device according to claim 6, wherein R ₅₁ , R ₅₂ , R ₅₃ , R ₆₁ and R ₆₂ each contain at least one ligand as a ligand of a compound wherein the compound is an alkoxy group or an alkyl group. 8. The rare earth complex phosphor according to the general formula (5)
Or, in the general formula (6), X ₅ is an oxygen atom,
R ₅₁ , R ₅₂ , R ₅₃ , R ₆₁ and R ₆₂ each have at least 1
The electroluminescent device according to claim 7, comprising: 9. The rare earth complex phosphor according to the above general formula (1)
Or at least one of the anions of the compound represented by (2) is contained as a ligand.
The electroluminescent device according to any one of items 1 to 8, wherein 10. The rare earth complex-based phosphor, wherein the aromatic ring formed by Z ₁ in the general formula (1) is a substituted or unsubstituted benzene ring, X ₁ and Y ₁ are oxygen atoms, electroluminescent device according to claim 9, R ₁₁ is characterized in that it contains as anionic member ligand compound are hydrogen atoms. 11. A rare-earth complex phosphor as an anionic ligand of a compound in which R ₂₃ is a hydrogen atom and R ₂₁ and R ₂₂ are both substituted and unsubstituted aromatic rings in the general formula (2). The electroluminescent device according to claim 9, further comprising: 12. rare earth complex based phosphor, .sigma.p positive of R ₂₁ in the general formula (2), σp is negative substitution of R _22, the compound is an unsubstituted aromatic ring anion body ligand The electroluminescent device according to claim 11, wherein: 13. The electroluminescence according to claim 11, wherein the compound represented by the general formula (2) is a compound represented by the general formula (3) or (4). element. 14. The electroluminescent device according to claim 1, wherein the binder used for the color conversion layer containing the rare-earth complex phosphor is a low-polarity resin. 15. The rare-earth complex phosphor has a maximum emission wavelength of 600 to 700 nm.
15. The electroluminescent device according to any one of 14. 16. The light-emitting material has a maximum light emission wavelength of 430 nm.
16. Any one of claims 1 to 15, wherein
Item 14. The electroluminescent device according to item 5. 17. The light-emitting material has a maximum emission wavelength of 400 to 4
The electroluminescent device according to claim 15, wherein the thickness is 30 nm. 18. The electroluminescent device according to claim 1, wherein the light emitting material is an organic LED material. 19. A color conversion filter comprising a rare earth complex-based phosphor containing at least one anion of the compound represented by the general formula (1) or (2) as a ligand. 20. The rare earth complex-based phosphor, wherein the aromatic ring formed by Z ₁ in the general formula (1) is a substituted or unsubstituted benzene ring, X ₁ and Y ₁ are oxygen atoms, R ₁₁ is a hydrogen atom, a color conversion filter according to claim 19, characterized in that it contains as anionic member ligand compound is a hydrocarbon aromatic ring or a nitrogen-containing aromatic ring. 21. The rare earth complex-based phosphor as an anionic ligand of the compound of the formula (2) wherein R ₂₃ is a hydrogen atom and R ₂₁ and R ₂₂ are both substituted or unsubstituted aromatic rings. The color conversion filter according to claim 19, wherein the color conversion filter is contained. 22. An anion compound of a compound in which the rare earth complex phosphor is a substituted or unsubstituted aromatic ring in which R ₂₁ has a positive σp value and R ₂₂ has a negative σp value in the general formula (2). The color conversion filter according to claim 21, wherein the color conversion filter is contained as a ligand. 23. The color conversion according to claim 21, wherein the compound represented by the general formula (2) is a compound represented by the general formula (3) or the general formula (4). filter. 24. The formula (5), (6) or (7)
A color conversion filter comprising a rare earth complex-based phosphor having at least one of the compounds represented by the formula (1) as a ligand. 25. The rare earth complex phosphor of the formula (5) or (6), wherein X ₅ is an oxygen atom, and R ₅₁ , R ₅₂ , R ₅₃ , R ₆₁ and R ₆₂ are each an alkoxy group. 25. The color conversion filter according to claim 24, further comprising at least one ligand of a compound that is an alkyl group. 26. The rare earth complex phosphor of the formula (5) or (6), wherein X ₅ is an oxygen atom, and R ₅₁ , R ₅₂ , R ₅₃ , R ₆₁ and R ₆₂ are each substituted with fluorine. At least one of the ligands of the compound which is an alkyl group
26. The color conversion filter according to claim 25, comprising: 27. The rare earth complex-based phosphor contains at least one anion of the compound represented by the general formula (1) or (2) as a ligand. 27. The color conversion filter according to any one of 26. 28. The rare earth complex-based phosphor, wherein the aromatic ring formed by Z ₁ in the general formula (1) is a substituted or unsubstituted benzene ring, X ₁ and Y ₁ are oxygen atoms, R ₁₁ is a hydrogen atom, a color conversion filter according to claim 27, characterized in that it contains as anionic member ligand compound is a hydrocarbon aromatic ring or a nitrogen-containing aromatic ring. 29. The rare earth complex-based phosphor as an anionic ligand of a compound in which R ₂₃ is a hydrogen atom and R ₂₁ and R ₂₂ are both substituted and unsubstituted aromatic rings in the general formula (2). The color conversion filter according to claim 27, wherein the color conversion filter is contained. 30. A rare earth complex based phosphor, .sigma.p positive of R ₂₁ in the general formula (2), σp is negative substitution of R _22, the compound is an unsubstituted aromatic ring anion body ligand 30. The color conversion filter according to claim 29, wherein the color conversion filter comprises: 31. The color conversion according to claim 29, wherein the compound represented by the general formula (2) is a compound represented by the general formula (3) or (4). filter.