JPH1036829A - Luminescent material for organic electroluminescence element and organic electroluminescence element comprising the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a luminescent material for an org. electroluminescence element which is useful for obtaining an organic EL element having high luminescence efficiency, luminance, and excellent stability in terms of repeated use by comprising a specified compd. having the max. wavelength for luminescence in a predetermined near infrared region. SOLUTION: This luminescent material comprises a phthalocyanine compd. having the max. wavelength for luminescence in a near infrared region of 780 to 2500nm, pref. represented by the formula [wherein ring A<1> to A<4> represent a cycloalkyl, aryl, or heterocycle; X represents a halogen, -R<1> , OR<2> , -OSi(R<3> R<4> R<5> ), -OCOR<6> , -OCON(R<7> R<8> ), -OCOCOOR<9> , -OCOCOSR<10> , -OCOOCON(R<11> R<12> ), -OPZ(R<11> R<12> ), -OPZ(OR<15> OR<16> ), -OPZ(SR<17> SR<18> ), -OPZN(R<19> R<20> )N(R<21> R<22> ); R<1> to R<22> represent H (except for R<1> , R<13> , and R<14> ) or a (cyclo)alkyl, aryl, or heterocyclic group; Z represents O or S; M represents a monovalent to tetravalent metal; and p and n are 1, 2, and 0 to 2 depending upon the valency of M].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescence (EL) device used for a flat light source, a light source for display and communication.

[0002]

2. Description of the Related Art An EL device using an organic substance is expected to be used as an inexpensive, large-area, full-color display device of a solid light emitting type, and many developments have been made. Generally EL
Is composed of a light-emitting layer and a pair of opposed electrodes sandwiching the layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side and holes are injected from the anode side. Further, the electrons are recombined with holes in the light emitting layer, and energy is emitted as light when the energy level returns from the conduction band to the valence band.

[0003] Conventional organic EL devices have a higher driving voltage and lower luminous brightness and luminous efficiency than inorganic EL devices.
In addition, the characteristic deterioration was remarkable, and it had not been put to practical use.
2. Description of the Related Art In recent years, an organic EL in which a thin film containing an organic compound having high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less is laminated.
Devices have been reported and are of interest (see Applied Physics Letters, vol. 51, p. 913, 1987). In this method, the metal chelate complex is converted into a phosphor layer,
High brightness green light emission is obtained by using an amine compound for the hole injection layer, and the brightness is 100 c at a DC voltage of 6 to 7 V.
d / m ² and maximum luminous efficiency of 1.5 lm / W,
Has performance close to the practical range. However, the organic EL elements up to now have improved luminous efficiency in green due to the improved structure. However, an organic EL device that emits light in the near infrared region does not yet have a sufficient light emission output.

An organic EL element emitting light in the near-infrared region can be used as a light source for short-distance, small-capacity optical communication, a light source for an image sensor used in a facsimile, and a light source for autofocus used in a camera. It is possible.

At present, a light source for short-distance, small-capacity optical communication,
An LED is used as a light source for an image sensor. However, since an organic EL element is easy to control a response speed and a luminous intensity, and the manufacturing cost is relatively low, the LED is used.
It is expected as a light source to replace The optical loss minimum wavelength of an optical fiber used for optical communication is 700 nm.
Therefore, when an organic EL element is used as a light source for optical communication, a light-emitting element which emits light in a region of 700 nm or more is required.

[0006]

SUMMARY OF THE INVENTION The object of the present invention is to
An object of the present invention is to provide an organic EL device having high luminous efficiency in a near infrared wavelength region of 0 nm to 2500 nm and having excellent stability when used repeatedly. As a result of extensive studies by the present inventors, it has been found that an organic EL device using at least one organic EL device material of the compound represented by the general formula [1] has high luminous efficiency in the near-infrared region and is repeatedly used. The present inventors have found that the stability at the time is also excellent, and have reached the present invention.

[0007]

That is, the present invention provides a 780
It is a light emitting material for an organic electroluminescent element material, which is composed of a phthalocyanine compound and has a maximum light emission wavelength in a near infrared region in a wavelength range of from nm to 2500 nm.

Further, the present invention is the luminescent material for an organic electroluminescent device according to claim 1, wherein the phthalocyanine compound is represented by the following general formula [1]. General formula [1]

[0009]

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Wherein the rings A ^{1 to} A ⁴ are each independently
Represents a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. The substituent X is a halogen atom or a substituent independently represented by the general formulas [2] to [13] (provided that R ^{1 to} R ²² are each independently a hydrogen atom (provided that
R ¹ , R ¹³ and R ¹⁴ ), a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, and a substituted or unsubstituted heterocyclic group. Z represents an oxygen atom or a sulfur atom. ). M represents a monovalent to tetravalent metal atom. p is 2 when M is a monovalent metal, and 1 when M is a divalent to tetravalent metal.
Represents n represents 0 when M is a monovalent or divalent metal, represents 1 when M is a trivalent metal, and represents 2 when M is a tetravalent metal. ]

[0011]

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[0012]

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Further, the present invention is the above-mentioned light-emitting material for an organic electroluminescence device, wherein M is a trivalent or tetravalent metal atom.

Further, the present invention provides an organic electroluminescent device in which an organic compound thin film including a light emitting layer is formed between a pair of electrodes, wherein the light emitting layer is a layer containing the light emitting material for an organic electroluminescent device. Is an organic electroluminescence element.

Further, the present invention is the above-mentioned organic electroluminescence device, wherein the light-emitting layer is a layer containing 3% by weight or more of a light-emitting material for an organic electroluminescence device.

Further, the present invention is the above-mentioned organic electroluminescence device, wherein a hole injection layer is formed between the light emitting layer and the anode.

Further, the present invention is the above-mentioned organic electroluminescence device, wherein an electron injection layer is formed between the light emitting layer and the cathode.

The rings A ^{1 to} A ⁸ of the compound represented by the general formula [1] in the present invention each independently represent a substituted or unsubstituted cycloalkyl, a substituted or unsubstituted aryl ring, or a substituted or unsubstituted ring. Represents a heterocyclic ring. Specific examples of cycloalkyl include a cyclopentane ring and a cyclohexane ring, and specific examples of an aryl ring include
There are a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a diphenylanthracene ring, a pyrene ring, a fluorene ring and the like, and specific examples of the heterocycle include a pyridine ring, a pyrazine ring, a pyrimidine ring, a triazine ring,
Examples include a quinoxaline ring, a pyrrolidine ring, a dioxane ring, a piperidine ring, a morpholine ring, a furan ring, and a thiophene ring.

Specific examples of the substituents on the above-mentioned rings include chlorine, bromine, iodine, halogen atoms of fluorine,
Methyl group, ethyl group, propyl group, butyl group, sec-
Substituted or unsubstituted alkyl groups such as butyl group, tert-butyl group, pentyl group, hexyl group, heptyl group, octyl group, stearyl group, trichloromethyl group, phenyl group, naphthyl group, 3-methylphenyl group, 3-methoxyphenyl Substituted or unsubstituted aryl groups, such as a group, 3-fluorophenyl group, 3-trichloromethylphenyl group, 3-trifluoromethylphenyl group, and 3-nitrophenyl group, toxic group, n-butoxy group, tert-butoxy group, trichloro Methoxy group, trifluoroethoxy group, pentafluoropropoxy group, 2,2,3,3-
Tetrafluoropropoxy group, 1,1,1,3,3,3
Substituted or unsubstituted alkoxy groups such as -hexafluoro-2-propoxy group, 6- (perfluoroethyl) hexyloxy group, phenoxy group, p-nitrophenoxy group, p-tert-butylphenoxy group, 3-fluorophenoxy A substituted or unsubstituted aryloxy group such as a pentafluorophenyl group, a 3-trifluoromethylphenoxy group, a methylthio group, an ethylthio group,
t-butylthio group, hexylthio group, octylthio group,
A substituted or unsubstituted alkylthio group such as a trifluoromethylthio group, a phenylthio group, a p-nitrophenylthio group, a p-tert-butylphenylthio group, a 3-fluorophenylthio group, a pentafluorophenylthio group,
Substituted or unsubstituted arylthio groups such as 3-trifluoromethylphenylthio group, cyano group, nitro group, amino group, methylamino group, diethylamino group, ethylamino group, diethylamino group, dipropylamino group, dibutylamino group, Mono- or di-substituted amino group such as diphenylamino group, bis (acetoxymethyl) amino group, bis (acetoxyethyl) amino group, bisacetoxypropyl) amino group, acylamino group such as bis (acetoxybutyl) amino group, hydroxyl group, siloxy group Group, acyl group, methylcarbamoyl group, dimethylcarbamoyl group, ethylcarbamoyl group, diethylcarbamoyl group, propyl carbamoyl group, butylcarbamoyl group, carbamoyl group such as phenylcarbamoyl group, carboxylic acid group, sulfonic acid group, imide group, Kuropentan group, cycloalkyl groups such as cyclohexyl group, a phenyl group, a tolyl group, a naphthyl group, a biphenyl group, o, m, p-terphenyl group,
Aryl groups such as anthranyl group, phenanthrenyl group, fluorenyl group, 9-phenylanthranyl group, 9,10-diphenylanthranyl group, pyrenyl group, pyrrole group, pyrroline group, pyrazole group, pyrazoline group, imidazole group, triazole group, pyridine group , Pyridazine group, pyrimidine group, pyrazine group, triazine group, indole group, purine group, quinoline group, isoquinoline group, sinoline group, quinoxaline group, benzoquinoline group, fluorenone group, dicyanofluorene group, carbazole group, oxazole group, oxazi Azole group, thiazole group, thiadiazole group, triazole group, imidazole group, benzoxazole group, benzothiazole group, benzotriazole group, benzimidazole group, bisbenzoxazole group, bisbenzo There are heterocyclic groups such as azole group, bisbenzimidazole group, anthrone group, dibenzofuran group, dibenzothiophene group, anthraquinone group, acridone group, phenothiazine group, pyrrolidine group, dioxane group, piperidine group, morpholine group, and piperazine group. .

Representative examples of the substituents R ^{1 to} R ²² constituting the general formulas [2] to [13] include a methyl group, an ethyl group and n
-Butyl group, t-butyl group, stearyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3 , 3,3-pentafluoropropyl group, 1,1,1,3,3,3-hexafluoro-2-propyl group, 2,2,3,3,4,4-hexafluorobutyl group, 2-methoxy Substituted or unsubstituted alkyl groups such as ethyl group, substituted or unsubstituted cycloalkyl groups such as cyclopentane group and cyclohexyl group, phenyl group, naphthyl group, biphenyl group, p-nitrophenyl group, pt-butylphenyl Group, pentafluorophenyl group, pyridine group, pyrazine group, pyrimidine group, pyridazine group, triazine group, indole group, quinoline machine, acridine group, etc. Ku is unsubstituted aryl group, a pyrrolidine group, dioxane group, piperidine group, morpholine group, include a substituted or unsubstituted heterocyclic ring such as piperazine, substituted is substituted with these substituents R ¹ to R ²² The group may be an aryl group, a cycloalkyl group, an aryloxy group, an arylthio group, a heterocyclic group which may contain an oxygen atom or a sulfur atom, and the like. In the general formula [9], R ¹¹ and R ¹² may be combined to form a 5- or 6-membered ring which may contain a nitrogen atom.

The central metal M may be any metal atom having a valence of 1 to 4, but may be Li, Be, Mg, Ca,
Sr, Ba, Ti, Zr, Fe, Co, Ni, Cu, Z
n, V, Al, Ga, In, Si, Ge, Sn or the like is desirable, but is not limited thereto. n is different depending on the valence of the metal atom.
It is 1 in the case of a valent metal.

In the present invention, the compound represented by the general formula [1] can be produced, for example, by the following method. Phthalonitriles represented by the following general formula [15],
Alternatively, an isoindoline compound represented by the following general formula [16] or a corresponding phthalic anhydride or phthalimide and various metal salts of a metal represented by M in the general formula [1] are usually used as starting materials. By the method, the general formula [1
7] can be produced.
In the formula, the ring A corresponds to A ^{1 to} A ⁴ represented by the general formula [1], p represents 2 when M is a monovalent metal, 1 when M is 2 to ⁴ , and n represents M Is 0 when a monovalent or divalent metal, 1 when a trivalent metal, and 2 when a tetravalent metal
Is shown.

[0023]

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Next, W.S. K. The general procedure reported by Kroenke et al. (Inorg. Chem., 2,
1064, 1963), a phthalocyanine compound and an alcohol, a trialkylsilanol, an acylating agent, an oxalyl chloride derivative, a chlorophosphine having a linear, branched or cyclic alkyl or aryl group which may have various substituents. By reacting with any of the derivatives, phthalocyanine-based compounds represented by the general formulas [1] and [2] can be produced.

Hereinafter, typical examples of the compounds of the present invention are specifically shown in Table 1, but the present invention is not limited to the following typical examples.

[0026]

[Table 1]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

The organic EL device is a device in which one or more organic thin films are formed between an anode and a cathode. In the case of a single layer type, a light emitting layer is provided between an anode and a cathode. The light-emitting layer contains a light-emitting material and may further contain a hole-injection material or an electron-injection material for transporting holes injected from an anode or electrons injected from a cathode to the light-emitting material. The multilayer type is (anode / hole injection layer / light emitting layer /
There is an organic EL device having a multilayer structure of (cathode), (anode / light-emitting layer / electron injection layer / cathode), and (anode / hole injection layer / light-emitting layer / electron injection layer / cathode). The compounds of the general formulas [1] and [14] can transport carriers such as holes or electrons, but have a better hole injecting property. Layer and a hole-injecting light-emitting layer. In addition, an organic EL device using an organic thin film containing this compound emits near-infrared light when an electric field is applied, and thus is suitable for use as a near-infrared light emitting material.

The organic EL element has a multi-layer structure, so that a decrease in luminance and life due to quenching can be prevented. If necessary, a combination of two or more kinds of light emitting materials, doping materials, hole injection materials for transporting carriers, and electron injection materials can be used. Also,
The hole injection layer, the light-emitting layer, and the electron injection layer may each be formed in a layer structure of two or more layers, and an element structure in which holes or electrons are efficiently injected from the electrode and transported in the layer is selected. You.

As the conductive material used for the anode, 4
Those having a work function larger than eV are suitable, and A
u, Pt, Ag, Cu, Al and other metals, metal alloys, IT
Organic conductive resins such as O, NESA or polythiophene or polypyrrole are used.

As the conductive material used for the cathode, 4
Those having a work function smaller than eV are suitable. Examples of the material include metals such as Al, In, Mg, Li, and Ca, and alloys such as Mg / Ag, Li / Al, and Mg / In. The anode and the cathode may be formed by two or more layers if necessary. The anode and the cathode are manufactured by a known film forming method such as vapor deposition, sputtering, ion plating, and a plasma gun.

In an organic EL device, it is desirable that at least one of the anode and the cathode is sufficiently transparent in the emission wavelength region of the device in order to emit light efficiently. Further, it is desirable that the substrate is also transparent. The transparent electrode is set so as to secure a predetermined translucency by a method such as vapor deposition, sputtering, or ion plating using the above conductive material. The electrode on the light emitting surface desirably has a light transmittance of 10% or more.

The substrate may be a transparent substrate having mechanical and thermal strength, and examples thereof include a glass substrate and a plate-like or film-like material such as polyethylene, polyethersulfone, polypropylene, and polyimide. Can be

For forming each layer of the organic EL device of the present invention, any of dry film forming methods such as vacuum evaporation, sputtering, ion plating and plasma gun and wet film forming methods such as spin coating and dipping are applied. be able to. The thickness is not particularly limited, but each layer needs to be set to an appropriate thickness. If the film thickness is too thick,
In order to obtain a constant light output, a large applied voltage is required, resulting in poor efficiency. If the film thickness is too small, pinholes or the like are generated in the thin film, and sufficient light emission luminance cannot be obtained even when an electric field is applied. The normal film thickness is suitably in the range of 5 nm to 10 μm, but is more preferably in the range of 10 nm to 0.2 μm.

In the case of the wet film forming method, a material for forming each layer is dissolved or dispersed in a solvent such as chloroform, tetrahydrofuran, dioxane or the like to form a thin film, and any solvent may be used. In any organic layer, an appropriate resin or additive is used to improve film forming properties and prevent pinholes in the film. Such resins include polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone,
Polymethyl methacrylate, polymethyl acrylate,
Insulating resin such as cellulose, poly-N-vinylcarbazole, photoconductive resin such as polysilane, polythiophene,
A conductive resin such as polypyrrole can be used. Examples of the additive include an antioxidant, an ultraviolet absorber, and a plasticizer.

The hole-injecting material has the ability to transport holes, has an excellent hole-injecting effect on the light-emitting layer or the light-emitting material, and has an electron-injecting layer or electron of excitons generated in the light-emitting layer. Compounds that prevent transfer to a transport material and have excellent thin film forming ability can be used. Specifically, phthalocyanine, naphthalocyanine, porphyrin, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, polyarylalkane,
Stilbene, butadiene, benzidine-type triphenylamine, styrylamine-type triphenylamine, diamine-type triphenylamine and the like, and derivatives thereof, and polymer materials such as polyvinylcarbazole, polysilane, and a conductive polymer. However, the present invention is not limited to this.

The electron injecting material has a capability of transporting electrons, has an excellent electron injecting effect on the light emitting layer or the light emitting material, and has a hole injecting layer or a hole transporting function of excitons generated in the light emitting layer. Compounds that prevent transfer to a material and have excellent thin film forming ability are exemplified. For example, there are fluorenone, anthraquinodimethane, diphenoquinone, thiopyrandioxide, oxadiazole, thiadiazole, tetrazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone and the like, and derivatives thereof. However, the present invention is not limited to this. Alternatively, the electron injecting material may be sensitized by adding an electron accepting material to the hole injecting material and the electron donating material to the electron injecting material.

The compound of the general formula [1] of the present invention is desirably used as a luminescent material or as a doping material in a luminescent layer.
At least one of the hole injection material and the electron injection material may be contained in the same layer. Further, since the compound of the general formula [1] has a hole injection ability, it can be used for a hole injection layer.

In order to improve the stability of the organic EL device obtained according to the present invention with respect to temperature, humidity, atmosphere, etc., a protective layer is provided on the surface of the device or silicon oil is sealed to protect the entire device. It is also possible.

The organic EL device of the present invention can be used as a flat panel display such as a wall-mounted television or a flat light-emitting device.
It can be applied to light sources for copiers, printers, communications, etc., light sources for liquid crystal displays and instruments, display boards, marker lights, etc., and especially its industrial value in devices that make use of near-infrared light emission applications. Is very large.

[0059]

The present invention will be described in more detail with reference to the following examples. Synthesis method of compound (15) To 100 parts of o-dichlorobenzene and 30 parts of tri-n-butylamine, 10 parts of 1,3-diiminoisoindoline and 15 parts of silicon tetrachloride were added, and heated and stirred at 160 to 170 ° C. for 8 hours. Thereafter, the mixture was cooled and diluted with 500 parts of methanol. The deposited precipitate was separated by filtration, washed with a mixed solution of methanol / water (4/1), and dried to obtain 10 parts of a green powder. As a result of molecular weight analysis, it was confirmed to be dihydroxysilicon phthalocyanine. Next, 5 parts of dihydroxysilicon phthalocyanine was stirred and dissolved in 50 parts of ethanol.
The mixture was heated and stirred at 110 ° C. for 10 hours. The deposited precipitate was separated by filtration, washed with water and dried to obtain 4 parts of a blue powder. As a result of molecular weight analysis, it was confirmed to be phthalocyanine compound (15). The results of elemental analysis of the product are shown below. Elemental analysis result: C ₃₆ H ₂₆ N ₈ O ₂ Si Calculated value (%): C: 68.57 H: 4.13 N: 17.8 Actual value (%): C: 67.89 H: 3.45 N: 17.3

Synthesis Method of Compound (31) 5 parts of dihydroxysilicon phthalocyanine synthesized by the above method was dissolved in 50 parts of ethyloxalyl chloride and 100 parts of pyridine by stirring, and the mixture was heated and stirred at 110 ° C. for 10 hours. The deposited precipitate was separated by filtration, washed with water and dried to obtain 4 parts of a blue powder. As a result of molecular weight analysis, it was confirmed that this powder was a phthalocyanine compound (31). The results of elemental analysis of the product are shown below. Elemental analysis calcd _{C 40 H 26 N 8 O 8} Si (%): C: 64.70 H: 3.50 N: 15.14 Found (%): C: 63.32 H : 4.05 N: 14.82

Synthetic method of compound (38) 5 parts of dihydroxysilicon phthalocyanine synthesized by the above-mentioned method was combined with 100 parts of pyridine and n-tributylamine 2
After stirring and dissolving in 5 parts, 10 parts of chlorodiphenylphosphine was added while cooling, and the mixture was heated and stirred at 100 ° C. for 2 hours. The precipitated precipitate was separated by filtration, washed with water and dried to obtain 4 parts of a phthalocyanine compound. As a result of molecular weight analysis, it was confirmed that this powder was a phthalocyanine compound (38). The results of elemental analysis of the product are shown below. Elemental analysis result: C ₆₆ H ₃₆ N ₈ O ₄ P ₂ Si Calculated value (%): C: 68.99 H: 3.69 N: 11.50 Actual value (%): C: 69.42 H: 3 .51 N: 10.67 Method for synthesizing compound (26) To 100 parts of o-dichlorobenzene and 30 parts of tri-n-butylamine, 10 parts of 1,3-diiminobenzo [f] isoindoline and 15 parts of silicon tetrachloride were added. 160-17
After heating and stirring at 0 ° C. for 8 hours, the mixture was cooled and diluted with 500 parts of methanol. The deposited precipitate was separated by filtration, washed with a mixed solution of methanol / water (4/1), and dried to obtain 10 parts of a green powder. As a result of molecular weight analysis, it was confirmed to be dihydroxysilicon naphthalocyanine. Next, 5 parts of dihydroxysilicon naphthalocyanine was stirred and dissolved in 50 parts of ethanol, and then heated and stirred at 110 ° C. for 10 hours. The deposited precipitate was separated by filtration, washed with water and dried to obtain 4 parts of a blue powder. As a result of the molecular weight analysis, the naphthalocyanine compound (2
6) was confirmed. The results of elemental analysis of the product are shown below. Elemental analysis _{C 52 H 34 N 8 O 2} Si Calculated (%): C: 75.12 H : 4.05 N: 13.5 Found (%): C: 76.39 H : 4.45 N: 14.2 Synthesis method of compound (17) To 100 parts of o-dichlorobenzene and 30 parts of tri-n-butylamine, 10 parts of 1,3-diiminoisoindoline and 15 parts of tin tetrachloride were added, and 160 to 170 ° C. After heating and stirring for 8 hours, the mixture was cooled and diluted with 500 parts of methanol.
The deposited precipitate was separated by filtration, washed with a mixed solution of methanol / water (4/1), and dried to obtain 10 parts of a green powder. As a result of molecular weight analysis, it was confirmed to be dihydroxytin phthalocyanine. Next, 5 parts of dihydroxytin phthalocyanine was stirred and dissolved in 50 parts of ethanol, and then heated and stirred at 110 ° C. for 10 hours. The deposited precipitate was separated by filtration, washed with water and dried to obtain 4 parts of a blue powder. As a result of molecular weight analysis, it was confirmed to be phthalocyanine compound (17). The results of elemental analysis of the product are shown below. Elemental analysis result: C ₃₆ H ₂₆ N ₈ O ₂ Sn Calculated value (%): C: 60.00 H: 3.61 N: 15.6 Actual value (%): C: 58.89 H: 3.41 N: 16.1

Example 1 A compound (45) was vacuum-deposited on a washed glass plate with an ITO electrode to form a 100-nm-thick light-emitting layer, on which an alloy obtained by mixing magnesium and silver at a ratio of 10: 1 was used. An electrode having a thickness of 150 nm was formed to obtain an organic EL device. The light emitting layer and the cathode were deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. This element has a DC voltage of 5
At V, an emission output of 0.97 W / m ² / sr was obtained.
FIG. 1 shows an emission spectrum of Example 1.

Examples 2 to 14 Organic EL devices were prepared in the same manner as in Example 1 except that the phthalocyanine compounds were changed to the compounds shown in Table 2, and the light emission output was measured. With this device, a light emission output shown in Table 2 was obtained at a DC voltage of 5 V.

[0064]

[Table 2]

Example 15 A phthalocyanine compound (26) was vapor-deposited on a washed glass plate with an ITO electrode to form a light emitting layer having a thickness of 80 nm, and then a tris (8-hydroxyquinoline) aluminum complex was vapor-deposited. An electron injection layer having a thickness of 10 nm was obtained. An electrode having a thickness of 100 nm was formed thereon using an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. With this device, a light emission output of 0.97 W / m ² / sr was obtained at a DC voltage of 5 V.

Examples 16 to 25 Organic EL devices were prepared in the same manner as in Example 15 except that the phthalocyanine compounds were changed to the compounds shown in Table 3, and the luminescence output was measured. With this device, the light emission output shown in Table 3 was obtained at a DC voltage of 5 V.

[0067]

[Table 3]

Example 26 N, N ′-(4
-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine was vacuum-deposited to obtain a hole injection layer having a thickness of 30 nm. Next, the phthalocyanine compound (20) was dissolved and dispersed in chloroform, and a 50-nm-thick light-emitting layer was obtained by spin coating. An electrode having a thickness of 150 nm was formed thereon with an alloy of magnesium and silver mixed at a ratio of 10: 1 to obtain an organic EL device. The hole injection layer and the cathode were deposited at a substrate temperature of room temperature in a vacuum of 10 ^-6 Torr. With this device, a light emission output of 1.90 W / m ² / sr was obtained at a DC voltage of 5 V.

Example 27 N, N ′-(4
-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine was vacuum-deposited to obtain a 20-nm-thick hole injection layer. Next, a phthalocyanine compound (26) was vapor-deposited to form a light-emitting layer having a thickness of 40 nm, and a tris (8-hydroxyquinoline) aluminum complex was vapor-deposited to obtain an electron injection layer having a thickness of 10 nm. An electrode having a thickness of 100 nm was formed thereon using an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain an organic EL device. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. With this device, a light emission output of 1.56 W / m ² / sr was obtained at a DC voltage of 5 V.

Example 28 A N, N '-(4
-Methylphenyl) -N, N '-(4-n-butylphenyl) -phenanthrene-9,10-diamine was vacuum-deposited to obtain a hole injection layer having a thickness of 30 nm. Next, a tris (8-hydroxyquinoline) aluminum complex and a phthalocyanine compound (18) were vapor-deposited at a weight ratio of 5: 1 to form a light-emitting layer having a thickness of 30 nm, and then [2- ( 4-tert-butylphenyl)-
5- (biphenyl) -1,3,4-oxadiazole]
An electron injection layer having a thickness of 20 nm was obtained. On top of this, an alloy of magnesium and silver mixed at a ratio of 10: 1 with a thickness of 150 nm
Was formed to obtain an organic EL device. The hole injection layer, the light emitting layer, the electron injection layer and the cathode were deposited in a vacuum of 10 ^-6 Torr at a substrate temperature of room temperature. With this device, a light emission output of 2.90 W / m ² / sr was obtained at a DC voltage of 5 V.

All the organic EL devices shown in this example had the maximum emission wavelength in the near infrared wavelength region of 780 nm to 2500 nm, and the luminous efficiency in the near infrared region was high. The organic EL device of the present invention achieves improvement in luminous efficiency, luminous luminance and long life, and is used together with a luminescent substance, a doping material, a hole transport material, an electron transport material, a sensitizer, and a resin. It does not limit the electrode material, etc., and the element manufacturing method.

[0072]

According to the present invention, an organic EL device having a light emission output in the near infrared region can be obtained. That is, by using the compound shown in the present invention in an organic EL device, an organic EL device having light emission in the near infrared region which can be used as a light source for communication, a light source for autofocus, and a light source for a print head is produced. It became possible to do.

[Brief description of the drawings]

FIG. 1 is an EL spectrum of Example 1.

Claims (7)

[Claims] 1. A light-emitting material for an organic electroluminescence device material comprising a phthalocyanine-based compound and having a maximum light emission wavelength in a near infrared region in a wavelength range of 780 nm to 2500 nm. 2. The light emitting material for an organic electroluminescence device according to claim 1, wherein the phthalocyanine compound is represented by the following general formula [1]. General formula [1] [Wherein, rings A ^{1 to} A ⁴ each independently represent a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. The substituent X is a halogen atom or a substituent represented by any one of formulas [2] to [13] (provided that R ^{1 to} R
²² independently represent a hydrogen atom (however, except for R ¹ , R ¹³ and R ¹⁴ ), a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, Represents a substituted or unsubstituted heterocyclic group. Z represents an oxygen atom or a sulfur atom. ). M represents a monovalent to tetravalent metal atom. p represents 2 when M is a monovalent metal and 1 when M is a divalent to tetravalent metal. n represents 0 when M is a monovalent or divalent metal, represents 1 when M is a trivalent metal, and represents 2 when M is a tetravalent metal. ] Embedded image 3. The light emitting material for an organic electroluminescence device according to claim 2, wherein M is a trivalent or tetravalent metal atom. 4. An organic electroluminescence device having an organic compound thin film including a light-emitting layer formed between a pair of electrodes, wherein the light-emitting layer is a layer containing the light-emitting material for an organic electroluminescence device according to claim 1 or 2. An organic electroluminescence device characterized by the above-mentioned. 5. The organic electroluminescence device according to claim 4, wherein the light emitting layer is a layer containing 3% by weight or more of a light emitting material for an organic electroluminescence device. 6. The organic electroluminescence device according to claim 5, wherein a hole injection layer is formed between the light emitting layer and the anode. 7. The organic electroluminescence device according to claim 4, wherein an electron injection layer is formed between the light emitting layer and the cathode.