JP2001011065A - New benzopyran compound, luminescent element material and light emission element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound capable of luminescing with high brightness and efficiency low-voltage drive, excellent in stability when used repeatedly, capable of uniform planar luminescence and useful for uses such as a filter dye, a color changing filter, a photosensitive material, sensitizing coloring matter, laser coloring matter and a luminescent element material. SOLUTION: This new compound is expressed by formula I [wherein R1 to R5, Rn1 and Rn2 are each H or a substituent with proviso that at least one of Rn1 and Rn2 is an aryl or an aromatic heterocycle; X is O, S or N-R (wherein R is H, an aliphatic hydrocarbon group, an aryl or a heterocycle); and Y is C-G1(G2) (wherein G1 and G2 are each H or a substituent with proviso that at least one of G1 and G2 is a substituent], and is e.g. a compound of formula II. The compound of formula I is obtained by reacting a thiocarbonyl compound of formula III with a compound (e.g. 1,3-indandione) having at least one active hydrogen of the formula G1-CH2-G2 in the presence of a base, and if necessary, in an added state with an activator preferably at 0 to 150 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a dye for a filter,
Compounds suitable for use as color conversion filters, photographic light-sensitive materials, sensitizing dyes, pulp dyes, laser dyes, medical diagnostic fluorescent agents, light-emitting device materials, synthetic intermediates thereof, and light-emitting devices using them Things.

[0002]

2. Description of the Related Art Light-emitting elements using organic substances are expected to be used as inexpensive large-area, full-color display elements of the solid-state light-emitting type, and many developments have been made. In general, a light emitting element includes a light emitting layer and a pair of opposed electrodes sandwiching the light emitting layer. Light emission occurs when an electric field is applied between both electrodes.
Electrons are injected from the cathode, and holes are injected from the anode.
Further, the electrons and holes are recombined in the light emitting layer, and the energy is emitted as light when the energy level returns from the conduction band to the valence band.

[0003] Conventional light-emitting elements have a high driving voltage and low light emission luminance and light emission efficiency. In addition, the characteristic deterioration was remarkable, and it had not been put to practical use. In recent years, a light emitting device in which a thin film containing an organic compound having high fluorescence quantum efficiency and emitting light at a low voltage of 10 V or less is laminated has been reported (Applied
Physics Letters, 51, 913, 1987
Years), has attracted interest. This method uses a metal chelate complex, a fluorescent band layer, and an amine compound for a hole injection layer,
High-luminance green light emission is obtained, and the luminance reaches several 1000 cd / m ² at a DC voltage of 6 to 7 V. However, in consideration of a practical device, development of a further higher luminance and higher efficiency light emitting device is desired. Further, in consideration of utilization as a full-color display and a light source, it is necessary to emit three primary colors or white in practical use. The above-described element uses an 8-quinolinol Al complex (Alq) as a light-emitting material, emits green light, and the development of light-emitting elements having other light-emitting colors is desired. Until now, various light emitting materials that emit light other than green light have been developed, but they have problems such as low light emission luminance, low light emission efficiency, and low durability, and have not been put to practical use.

Further, a conventional light-emitting device having high luminous efficiency is obtained by doping a light-emitting material such as a fluorescent dye in a charge transport material in a small amount, and it is difficult to obtain reproducibility of device characteristics in manufacturing. In addition, there are problems such as a decrease in luminance and a change in color when used for a long time due to low durability of the dye. As a means to solve this, the development of a material that has both a charge transport function and a light emitting function is desired.However, in the materials developed so far, if a fluorescent dye is used at a high concentration as a charge transport material, concentration quenching and the like will occur. There are problems such as difficulty in emitting high-luminance light and deterioration of device characteristics due to aggregation over time. On the other hand, organic light-emitting devices that achieve high-luminance light emission are devices in which organic substances are stacked by vacuum deposition. However, in view of simplification of the manufacturing process, workability, enlargement of the area, etc., the coating method is used. Device fabrication is desirable. However, a device manufactured by a conventional coating method is inferior to a device manufactured by a vapor deposition method in terms of luminous luminance and luminous efficiency, and high luminance and highly efficient luminescence have been major issues.
Further, in a device in which an organic low-molecular compound is dispersed and applied in an organic polymer medium, there is a problem that it is difficult to emit uniform planar light due to aggregation of the organic low-molecular compound when light is emitted for a long time.

In recent years, a variety of fluorescent materials have been used for filter dyes, color conversion filters, photographic materials, sensitizing dyes, pulp dyes, laser dyes, fluorescent materials for medical diagnosis, and materials for light emitting devices. Although the demand is increasing, there are not many compounds having high color purity from green to red and high fluorescence intensity, and thus development of new materials has been desired. At the same time, there has been a demand for an intermediate that can be easily converted to a compound having a high color purity from green to red and a high fluorescence intensity.

[0006]

SUMMARY OF THE INVENTION A first object of the present invention is to emit light with high luminance and high efficiency by driving at a low voltage, having excellent stability in repeated use, and capable of emitting uniform planar light. An element material and a light-emitting element are provided. A second object of the present invention is to provide a red light emitting device material and a light emitting device having excellent color purity. A third object of the present invention is to provide a synthetic intermediate useful in synthesizing a red light emitting device material having excellent color purity.

[0007]

This object has been achieved by the following means. (1) A light-emitting element material, which is a compound represented by the following general formula (I).

[0008]

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(Where R₁ , R_Two , R_Three , R_Four , R_Five ,
R_n1And R_n2Represents a hydrogen atom or a substituent, respectively.
You. Where R_n1, R_n2At least one is an aryl group
Or an aromatic heterocyclic group. X is O, S or NR
(R is a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or
Represents a heterocyclic group. ). Y is CG₁ (G_Two )
(G ₁ , G_Two Represents a hydrogen atom or a substituent, respectively.
Where G₁ , G_Two At least one represents a substituent. )
Represents )

(2) A compound represented by the following general formula (Ia).

[0011]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ and R
₅ represents a hydrogen atom or a substituent. Ar ₁ and Ar ₂ each represent an aryl group or an aromatic heterocyclic group. Y
Represents CG ₁ (G ₂ ) (G ₁ and G ₂ each represent a hydrogen atom or a substituent, provided that at least one of G ₁ and G ₂ represents a substituent). (3) A compound represented by the following general formula (II).

[0013]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ and R
₅ represents a hydrogen atom or a substituent. Ar ₁ and Ar ₂ each represent an aryl group or an aromatic heterocyclic group. X
Represents O, S or N—R (R represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group). )

(4) In a light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer are formed between a pair of electrodes, at least one of the light-emitting elements has the general formula described in (1), (2) or (3). A light-emitting element comprising the compound represented by (I), (Ia) or (II). (5) In a light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes, at least one of the light-emitting elements has the general formula (I) according to (1), (2) or (3). A light emitting device comprising a layer in which a compound represented by formula (Ia) or (Ia) is dispersed in a polymer.

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION First, a compound represented by the general formula (I) of the present invention will be described.
The compound to be formed will be described in detail. R₁ , R_Two , R
_Three , R_Four And R_Five Represents a hydrogen atom or a substituent
Represent. R ₁ , R_Two , R_Three , R_Four And R_Five The position represented by
Examples of the substituent include an alkyl group (preferably having 1 carbon atom).
-20, more preferably 1-12 carbon atoms, particularly preferably
Has 1 to 8 carbon atoms, for example, methyl, ethyl, iso
-Propyl, tert-butyl, n-octyl, n-de
Syl, n-hexadecyl, cyclopropyl, cyclopen
Tyl, cyclohexyl and the like. ), Alkene
Group (preferably having 2 to 20 carbon atoms, more preferably
2-12, particularly preferably 2-8 carbon atoms, for example
For example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.
Is mentioned. ), Alkynyl group (preferably having 2 carbon atoms)
-20, more preferably 2-12 carbon atoms, particularly preferably
Has 2 to 8 carbon atoms, for example, propargyl, 3-pen
Tinyl and the like. ), An aryl group (preferably
C6-30, more preferably C6-20, especially
It preferably has 6 to 12 carbon atoms, for example, phenyl, p
-Methylphenyl, naphthyl and the like. ), A
A mino group (preferably having 0 to 20 carbon atoms, more preferably
A prime number of 0 to 10, particularly preferably a carbon number of 0 to 6,
For example, amino, methylamino, dimethylamino, diethyl
Amino, diphenylamino, dibenzylamino, etc.
I can do it. ), An alkoxy group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 12 carbon atoms, particularly preferably charcoal
A prime number of 1 to 8, for example, methoxy, ethoxy, butoki
And the like. ), An aryloxy group (preferably
Has 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms,
Preferably has 6 to 12 carbon atoms, e.g.
Xy, 2-naphthyloxy and the like. ), Reed
Group (preferably having 1 to 20 carbon atoms, more preferably
Number 1 to 16, particularly preferably carbon number 1 to 12, for example
For example, acetyl, benzoyl, formyl, pivaloyl, etc.
Is mentioned. ), An alkoxycarbonyl group (preferably
Has 2 to 20 carbon atoms, more preferably 2 to 16 carbon atoms,
Preferably has 2 to 12 carbon atoms, such as methoxy
Rubonyl, ethoxycarbonyl and the like. ),
Aryloxycarbonyl group (preferably having 7 to 2 carbon atoms)
0, more preferably 7 to 16 carbon atoms, particularly preferably charcoal
A prime number of 7 to 10, for example, phenyloxycarbonyl
And the like. ), Acyloxy group (preferably charcoal
A prime number of 2 to 20, more preferably a carbon number of 2 to 16, particularly preferably
It preferably has 2 to 10 carbon atoms, such as acetoxy,
Nzoyloxy and the like. ), Acylamino group
(Preferably 2 to 20 carbon atoms, more preferably 2 carbon atoms
To 16 and particularly preferably 2 to 10 carbon atoms, for example,
Acetylamino, benzoylamino, etc.
You. ), Alkoxycarbonylamino groups (preferably charcoal
A prime number of 2 to 20, more preferably a carbon number of 2 to 16, particularly preferably
Preferably it has 2 to 12 carbon atoms, for example, methoxycarbo
Nylamino and the like. ), Aryloxycal
A bonylamino group (preferably having 7 to 20 carbon atoms, more preferably
Or 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms.
And, for example, phenyloxycarbonylamino
No. ), Sulfonylamino group (preferably carbon
1 to 20, more preferably 1 to 16 carbon atoms, particularly preferably
Or methanesulfonyl having 1 to 12 carbon atoms
Amino, benzenesulfonylamino, etc.
You. ), A sulfamoyl group (preferably having 0 to 2 carbon atoms)
0, more preferably 0 to 16, particularly preferably carbon
A prime number of 0 to 12, for example, sulfamoyl, methyls
Rufamoyl, dimethylsulfamoyl, phenylsulfur
Famoyl and the like. ), Carbamoyl group (preferably
Preferably it has 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms.
6, particularly preferably 1 to 12 carbon atoms, e.g.
Bamoyl, methylcarbamoyl, diethylcarbamoy
And phenylcarbamoyl. ), Al
A kirthio group (preferably having 1 to 20 carbon atoms, more preferably
Has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms.
And, for example, methylthio, ethylthio, etc.
You. ), An arylthio group (preferably having 6 to 20 carbon atoms,
More preferably, the number of carbon atoms is 6 to 16, particularly preferably the number of carbon atoms
6 to 12, for example, phenylthio and the like.
You. ), A sulfonyl group (preferably having 1 to 20 carbon atoms,
More preferably 1 to 16 carbon atoms, particularly preferably 1 carbon atom
~ 12, for example, mesyl, tosyl, etc.
You. ), A sulfinyl group (preferably having 1 to 20 carbon atoms,
More preferably, the number of carbon atoms is 1 to 16, particularly preferably the number of carbon atoms
1-12, for example, methanesulfinyl, benzene
Sulfinyl and the like. ), Ureido group (preferred)
Or 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms
6, particularly preferably 1 to 12 carbon atoms.
Ide, methylureide, phenylureide, etc.
It is. ), A phosphoric amide group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, particularly preferably charcoal
A prime number of 1 to 12, for example, diethylphosphoramide,
Phenylphosphoric acid amide and the like. ), Hydroxy
Group, mercapto group, halogen atom (for example, fluorine atom,
Chlorine atom, bromine atom, iodine atom), cyano group, sulfo
Group, carboxyl group, nitro group, hydroxamic acid group,
Rufino group, hydrazino group, imino group, heterocyclic group (preferably
Preferably it has 1 to 20 carbon atoms, more preferably 1 to 1 carbon atoms.
2, and the hetero atom includes, for example, a nitrogen atom, an acid
Elemental atom, sulfur atom, specifically, for example, imidazolyl,
Lysyl, quinolyl, furyl, piperidyl, morpholino,
Benzoxazolyl, benzimidazolyl, benzthia
Zolyl and the like. ), Silyl group (preferably charcoal
A prime number of 3 to 40, more preferably a carbon number of 3 to 30, still more preferably
Preferably it has 3 to 24 carbon atoms, for example, trimethylsilyl.
And triphenylsilyl. )
I can do it. These substituents may be further substituted. Ma
When there are two or more substituents, they may be the same or different
Good. When possible, they may be linked to each other to form a ring.
You may.

The substituent is preferably an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an amino group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbonylamino group, a sulfonylamino group,
A sulfamoyl group, a carbamoyl group, a hydroxy group, and a heterocyclic group, more preferably an alkyl group, an alkenyl group, an aralkyl group, an aryl group, an acyl group, an amino group, a carbonylamino group, a sulfonylamino group, a heterocyclic group, and a substituent. Are linked to form a benzene ring, more preferably an alkyl group, an aralkyl group, an aryl group, an acyl group, an amino group, a carbonylamino group, a sulfonylamino group, a hydroxy group, a heterocyclic group, or a substituent is linked. To form a benzene ring.

R ₁ is preferably a hydrogen atom, an alkyl group, an aryl group, an acyl group, a carbonylamino group, a sulfonylamino group, a halogen atom, a cyano group, a sulfo group, a carboxyl group, a nitro group, a hydroxamic acid group, a sulfino group. , A hydrazino group, an imino group, and a heterocyclic group. More preferably a hydrogen atom, an aryl group, an acyl group,
Carbonylamino group, sulfonylamino group, halogen atom, cyano group, sulfo group, carboxyl group, nitro group,
An aromatic heterocyclic group, more preferably a hydrogen atom,
Acyl group, carbonylamino group, sulfonylamino group,
A cyano group, a carboxyl group, a nitro group, and an aromatic heterocyclic group, particularly preferably a hydrogen atom, a cyano group, and an aromatic heterocyclic group (for example, benzoxazole, benzothiazole, benzimidazole, triazole and the like); And most preferably a hydrogen atom. R ₂ is preferably a hydrogen atom or an alkyl group, more preferably a hydrogen atom or a lower alkyl group, and further preferably a hydrogen atom or a methyl group. R ₃ , R ₄ and R ₅ are preferably a hydrogen atom or an alkyl group, more preferably a lower alkyl group, and particularly preferably a hydrogen atom.

R _n1 and R _n2 each represent a hydrogen atom or a substituent (provided that at least one of R _n1 and R _n2 is an aryl group or an aromatic heterocyclic group). The substituents represented by R _n1 and R _{n2 have the same} meanings as those of R _{1 to} R ₅ in formula (I). R _n1 and R _n2 are preferably an aryl group or a heterocyclic group.

R_n1, R_n2Good as an aryl group represented by
Preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms
(Examples include a phenyl group and a naphthyl group.)
And more preferably a phenyl group having 6 to 20 carbon atoms,
More preferably, it is a phenyl group having 6 to 12 carbon atoms. Ma
R if possible_n1And R_n2, R_n1And R_Four , R_n2And R
_Five May be connected to each other to form a ring.

The heterocyclic group represented by R _n1 and R _n2 is preferably a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms, and these are monocyclic. Or a condensed ring may be further formed with another ring, more preferably an aromatic heterocyclic group, further preferably an aromatic heterocyclic group containing a nitrogen atom or a sulfur atom. Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole,
Purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine phenanthroline, phenazine, tetrazole,
Examples include benzimidazole, benzoxazole, benzothiazole, benzotriazole, and tetrazaindene. Preferably as a heterocycle, thiophene,
Triazole, oxazole, triazine and quinoline are more preferable, and thiophene, triazine and quinoline are more preferable. More preferably, it is thiophene.

The aryl group and the heterocyclic group represented by R _n1 and R _n2 may have a substituent. Examples of the substituent include those described as the substituents of R _{1 to} R ₅ in formula (I). Can be applied. R _n1 and R _n2 are more preferably an aryl group or an aromatic heterocyclic group, further preferably an aryl group, and particularly preferably a phenyl group having 6 to 12 carbon atoms (for example, a phenyl group, a p-methylphenyl group, m
-Methylphenyl group, naphthyl group and the like. )
It is.

X is O, S or NR (R is a hydrogen atom,
Represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. ). The aliphatic hydrocarbon group represented by R is a linear, branched or cyclic alkyl group (preferably having 1 carbon atom).
-30, more preferably 1-20 carbon atoms, even more preferably 1-12 carbon atoms, for example, methyl, ethyl, is
o-propyl, tert-butyl, n-octyl, n-
Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like can be mentioned. ), An alkenyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, still more preferably having 2 to 12 carbon atoms,
For example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like can be mentioned. ), An alkynyl group (preferably having 2 to 30 carbon atoms, more preferably having 2 to 20 carbon atoms, still more preferably having 2 to 12 carbon atoms, for example, propargyl, 3
-Pentynyl and the like. ), Preferably an alkyl group or an alkenyl group, more preferably a methyl group, an ethyl group, a propyl group, a butyl group, or an allyl group.

The aryl group represented by R is preferably a monocyclic or bicyclic aryl group having 6 to 30 carbon atoms, more preferably a phenyl group having 6 to 20 carbon atoms, and still more preferably a phenyl group having 6 to 20 carbon atoms. ~ 12 phenyl groups.

The heterocyclic group represented by R is a 3- to 10-membered saturated or unsaturated heterocyclic ring containing at least one of N, O and S atoms, and these may be monocyclic. Or a condensed ring with another ring. The heterocyclic group is preferably an aromatic heterocyclic group, and more preferably an aromatic heterocyclic group containing a nitrogen atom or a sulfur atom. Specific examples of the heterocycle include, for example, pyrrolidine, piperidine, piperazine, morpholine, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole,
Triazine, indole, indazole, purine, thiazoline, thiazole, thiadiazole, oxazoline,
Oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine phenanthroline, phenazine, tetrazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, tetrazaindene, and the like.
Preferably as a heterocycle, thiophene, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole, thiadiazole, oxadiazole, quinoline, phthalazine, quinoxaline, quinazoline, cinnoline, tetrazole, thiazole, oxazole, Benzimidazole, benzoxazole, benzothiazole, benzotriazole, more preferably thiophene, imidazole, pyridine, quinoline, thiazole, oxazole, benzimidazole, benzoxazole, benzthiazole, benzotriazole, more preferably thiophene, pyridine , Quinoline.

The aliphatic hydrocarbon group, aryl group and heterocyclic group represented by R may have a substituent, and examples of the substituent include the substituents represented by R _{1 to} R ₅ in formula (I). Can be applied. R is preferably an alkyl group, an alkenyl group, or an aryl group, and more preferably an alkyl group or a phenyl group. X is preferably O, NR, and more preferably O.

Y is CG₁ (G_Two ) (G₁ , G_Two Is hydrogen
Represents an atom or a substituent. Where G₁, G_Two At least
And one represents a substituent. ) And G₁ , G_Two Represented by
Is a hydrogen atom or a substituent represented by R in general formula (I).₁ ~
R_Five Are synonymous with those of G₁ , G_Two Preferred as
Is an electron-withdrawing group (for electron-withdrawing groups, Hammett's σ _p
A group having a value of 0 or more. ) Or G₁ , G_Two and
The carbon atom to which it is bonded is linked to form a ring
is there.

The electron-withdrawing groups represented by G ₁ and G ₂ are preferably a cyano group, an oxycarbonyl group, an acyl group,
It is a sulfonyl group, a carbamoyl group or a sulfamoyl group, more preferably a cyano group.

As G ₁ , G ₂ and the carbon atom to which G ₁ and G ₂ are bonded to form a ring, those usually used as an acidic nucleus in a merocyanine dye are preferred, and specific examples thereof include the following. . (A) 1,3-dicarbonyl nucleus: for example, 1,3-indandione nucleus, 1,3-cyclohexanedione, 5,5-
Dimethyl-1,3-cyclohexanedione, 1,3-dioxane-4,6-dione and the like. (B) Pyrazolinone nucleus: For example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1- (2-benzothiazoyl)-
3-methyl-2-pyrazolin-5-one and the like. (C) isoxazolinone nucleus: for example, 3-phenyl-2
-Isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one and the like. (D) Oxindole nucleus: for example, 1-alkyl-2,
3-dihydro-2-oxindole and the like. (E) 2,4,6-triketohexahydropyrimidine nucleus: for example, barbituric acid or 2-thiobarbituric acid and derivatives thereof. Derivatives include, for example, 1-alkyl compounds such as 1-methyl and 1-ethyl, and 1,3-dimethyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl.
Dialkyl, 1,3-diphenyl, 1,3-di (p-
1,3-diaryl compounds such as chlorophenyl) and 1,3-di (p-ethoxycarbonylphenyl), 1-ethyl-
1-alkyl-1-aryl such as 3-phenyl, 1,
And 1,3-diheterocyclic substituents such as 3-di (2-pyridyl). (F) 2-thio-2,4-thiazolidinedione nucleus: for example, rhodanine and its derivatives. Derivatives include, for example, 3-methylrhodanine, 3-ethylrhodanine, 3
-3-alkyl rhodanines such as allyl rhodanine, 3-
3-arylrhodanines such as phenylrhodanine, 3-
3-position heterocyclic substituted rhodanine such as (2-pyridyl) rhodanine and the like. (G) 2-thio-2,4-oxazolidinedione (2-
Thio-2,4- (3H, 5H) -oxazoledione nucleus: For example, 3-ethyl-2-thio-2,4-oxazolidinedione and the like. (H) thianaphthenone nucleus: for example, 3 (2H) -thianaphthenone-1,1-dioxide and the like. (I) 2-thio-2,5-thiazolidinedione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidinedione. (J) 2,4-thiazolidinedione nucleus: For example, 2,4-
Thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, etc. (k) Thiazolin-4-one nucleus: For example, 4-thiazolinone, 2-ethyl-4-thiazolinone and the like. (L) 4-thiazolidinone nucleus: for example, 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-one and the like. (M) 2,4-Imidazolidinedione (hydantoin)
Core: For example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione and the like. (N) 2-thio-2,4-imidazolidinedione (2-
Thiohydantoin) nucleus: For example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione and the like. (O) Imidazolin-5-one nucleus: for example, 2-propylmercapto-2-imidazolin-5-one. (P) 3,5-pyrazolidinedione nucleus: for example, 1,2-
Diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione, etc.

The ring formed by G ₁ , G ₂ and the carbon atom to which they are bonded is preferably a 1,3-dicarbonyl nucleus, a pyrazolinone nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (also a thioketone compound). ), 2-thio-
2,4-thiazolidinedione nucleus, 2-thio-2,4-oxazolidinedione nucleus, 2-thio-2,5-thiazolidinedione nucleus, 2,4-thiazolidinedione nucleus, 2,4-
Imidazolidinedione nucleus, 2-thio-2,4-imidazolidinedione nucleus, 2-imidazolin-5-one nucleus, 3,
5-pyrazolidinedione nucleus, more preferably 1,
A 3-dicarbonyl nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body) and a 3,5-pyrazolidinedione nucleus, and particularly preferably a 1,3-dicarbonyl nucleus and barbituric acid Derivatives, 2-thiobarbituric acid derivatives.

Y is preferably a dicyanomethylene group, a 1,3-dicarbonyl nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone compound),
5-pyrazolidinedione nucleus, more preferably 1,
It is a 3-dicarbonyl nucleus, a barbituric acid derivative, or a 2-thiobarbituric acid derivative, and more preferably a 1,3-dicarbonyl nucleus (preferably a 1,3-dicarbonyl nucleus is a 1,3-indandione nucleus. ).

The compound represented by the general formula (I) may be a multimer or may be linked to the polymer chain via R _{1 to} R ₅ , R _n1 , R _n2 , X and Y.

Of the compounds represented by the general formula (I), a compound represented by the general formula (Ia) is preferred.

[0034]

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[0035] _{(wherein, R 1, R 2, R} 3, R 4, R 5 and Y have the same meanings as those in formula (I), respectively, .Ar _1, Ar ₂ is the same preferred range Represents an aryl group or an aromatic heterocyclic group.)

Ar₁, Ar_TwoAs an aryl group represented by
Preferably a monocyclic or bicyclic aryl having 6 to 30 carbon atoms
And more preferably phenyl having 6 to 20 carbon atoms
And more preferably a phenyl group having 6 to 12 carbon atoms.
You. If possible, Ar₁ And Ar _Two , Ar₁ And R_Four , Ar
_Two And R_Five May be connected to each other to form a ring.

The aromatic heterocyclic group represented by Ar ₁ or Ar ₂ is preferably an aromatic heterocyclic group containing a nitrogen atom or a sulfur atom. Specific examples of the aromatic heterocycle include, for example, thiophene, furan, pyrrole, imidazole, pyrazole, pyridine, pyrazine, pyridazine, triazole, triazine, indole, indazole,
Purine, thiazoline, thiazole, thiadiazole, oxazoline, oxazole, oxadiazole, quinoline, isoquinoline, phthalazine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, acridine phenanthroline, phenazine, tetrazole,
Examples include benzimidazole, benzoxazole, benzothiazole, benzotriazole, and tetrazaindene. As the aromatic hetero ring, preferably, thiophene, triazole, oxazole, triazine, quinoline, more preferably thiophene, triazine,
Quinoline. More preferably, it is thiophene.

The aryl group and the aromatic heterocyclic group represented by Ar ₁ and Ar ₂ may have a substituent. Examples of the substituent include the substituents represented by R _{1 to} R ₅ in formula (I). Can be applied.

Ar ₁ and Ar ₂ are preferably an aryl group, more preferably a phenyl group having 6 to 12 carbon atoms, still more preferably a phenyl group, a p-methylphenyl group, an m-methylphenyl group, a naphthyl. Group.

Among the compounds represented by the general formula (Ia), a compound represented by the general formula (Ib) is preferred.

[0041]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
Ar ₁ and Ar ₂ have the same meanings as those in formula (Ia), respectively, and their preferred ranges are also the same. Q
Represents an atom group forming a 5- or 6-membered ring. )

Q represents an atomic group forming a 5- or 6-membered ring, and Q is preferably a 1,3-dicarbonyl nucleus, a pyrazolinone nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone compound). ), 2-thio-2,4-thiazolidinedione nucleus, 2-thio-2,4-oxazolidinedione nucleus, 2-thio-2,5-thiazolidinedione nucleus, 2,4-thiazolidinedione nucleus, 2,4- An imidazolidinedione nucleus, a 2-thio-2,4-imidazolidinedione nucleus, a 2-imidazoline-5-one nucleus, and a 1,3-pyrazolidinedione nucleus, more preferably a 1,3-dicarbonyl nucleus; 2,4,6-triketohexahydropyrimidine nucleus (including thioketone body), particularly preferably 1,3-dicarbonyl nucleus, barbituric acid derivative, 2-thiobarbituric acid derivative And most preferably 1,3-
A dicarbonyl nucleus (preferably a 1,3-dicarbonyl nucleus is a 1,3-indandione nucleus).

Next, the compound represented by formula (II) of the present invention will be described in detail. R ₁ , R ₂ , R ₃ , R ₄ ,
R ₅ and X have the same meanings as those in formula (I), and the preferred ranges are also the same. Also,
Ar ₁ and Ar ₂ have the same meanings as those in formula (Ia), respectively, and their preferred ranges are also the same.

Among the compounds represented by the general formula (II), a compound represented by the general formula (II-a) is preferable.

[0046]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ and R ₅
Each has the same meaning as those in formula (I),
The same applies to the preferred range. Ar ₁ and Ar ₂ have the same meanings as those in formula (Ia), respectively, and their preferred ranges are also the same. )

Specific examples of the compound represented by formula (I) are shown below, but the present invention is not limited thereto.

[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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Specific examples of the compound represented by formula (II) are shown below, but the present invention is not limited thereto.

[0064]

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[0065]

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[0066]

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[0067]

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[0068]

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[0069]

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The method for synthesizing the compound represented by the general formula (II) of the present invention will be described below. The compound represented by the general formula (II) can be synthesized by various methods, and an example is shown in Scheme 1.

[0071]

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(Wherein, R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and X have the same meanings as those in the general formula (I), respectively, and Ar ₁ and Ar ₂ each represent a general formula (Ia) And R ₂₁ represents a leaving group and includes, for example, a halogen atom, an alkoxy group, and an azole group.)

The synthesis method of (F) is a synthesis method based on thiocarbonylation of (C), and is described in New Experimental Chemistry Lecture 14 (p. 817-821) (Maruzen) or an organic person reaction (Japan). (Chemical Society of Japan) (p. 169-170)
It can be synthesized by the method described in (Asakura Shoten). Specifically, there is a method using Lawessons reagent and the like. Lawessons
The equivalent of the reagent is preferably from 0.5 to
The equivalent is 5 equivalents, more preferably 0.5 to 2 equivalents, still more preferably 0.5 to 1 equivalent, particularly preferably 0.5 to 0.6 equivalent. The solvent is preferably a hydrocarbon (eg, benzene, toluene, xylene, hexane, etc.) or an ether (eg, tetrahydrofuran, 1,4-dioxane, etc.), and more preferably a hydrocarbon. And more preferably toluene and xylene. The reaction temperature is preferably from 10 to 200 ° C, more preferably from 50 to 200 ° C.
150 ° C. (C) can be synthesized from various intermediates. For example, the synthesis method from (E) and the 1,3-
A synthesis method for forming a ring with the carbonyl compound (B), (A)
, Via the intermediate (D) to form a ring with the carbonyl compound (J). The synthesis method of (E) to (C) is based on an Ullmann-type reaction using an aryl halide or an aromatic heterocyclic halide as a catalyst (preferably copper, palladium or a salt thereof) and a base. This is a synthesis method, for example, by the method described in Japanese Patent Application Laid-Open No. 4-225364.
The synthesis method from (A) to (C) is a reaction for forming a ring in the presence of a Lewis acid. As the Lewis acid, a metal chloride or metal bromide is preferable, a metal chloride is more preferable, and a metal chloride is more preferable. Has zinc chloride. The equivalent of the Lewis acid catalyst is preferably 1 to 10 equivalents, more preferably 1 to 5 equivalents, still more preferably 1 to 2 equivalents, and particularly preferably 1 to 1.2 equivalents to (A). Is equivalent. The solvent is preferably a solvent having a boiling point of 90 ° C. or higher, more preferably hydrocarbons (for example, toluene, xylene, etc.) and acetoacetate, further preferably acetoacetate. Particularly preferred is ethyl acetoacetate. The reaction temperature is preferably 50 to 250 ° C, more preferably 9 to 250 ° C.
0-200 ° C. The synthesis method from (A) to (D) is a synthesis method based on a carbonylation reaction of an aromatic ring,
For example, New Laboratory Chemistry Course 14 (pp. 683-695, p. 7)
99-802) (Maruzen). (D) is synthesized from (C) in the presence of a base in the presence of (J),
This is a reaction for forming a ring, and the equivalent of the base is preferably 0.01 to 10 equivalents, more preferably 0.01 to 5 equivalents, and still more preferably 0.01 to 5 equivalents to (A). 2 equivalents, particularly preferably 0.01 to
1.2 equivalents. Examples of the solvent include hydrocarbons (eg, benzene, toluene, xylene, etc.), nitriles (eg, acetonitrile, etc.), and alcohols (eg, methanol, ethanol, isopropanol, butanol, etc.). , Ethers (eg, tetrahydrofuran, 1,4-dioxane, diethyl ether, etc.), amides (eg, dimethylformamide, dimethylacetamide, etc.) are preferred, and the reaction temperature is preferably 0 to 150 ° C. , More preferably 15 to 120 ° C.

The method for synthesizing the compound represented by formula (I) of the present invention will be described below. The compound represented by the general formula (I) can be synthesized by various methods, one example of which is shown in Scheme 2.

[0075]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ ,
R _n1 , R _n2 , G ₁ , G ₂ and X have the same meanings as those in formula (I), and the preferred ranges are also the same. )

The method of synthesizing (H) is a reaction between the compound (I) having active hydrogen and the thiocarbonyl compound (G) in the presence of a base. In some cases, an activating agent may be added. Preferably, the activator is an acid halide, a silver salt,
More preferably, it is a silver salt, and still more preferably, silver nitrate. Preferred examples of the solvent include hydrocarbons (eg, benzene, toluene, xylene, etc.), nitriles (eg, acetonitrile, etc.), and alcohols (eg, methanol, ethanol, isopropanol, butanol, etc.). ), Ethers (for example, tetrahydrofuran, 1,4-dioxane, diethyl ether, etc.), amides (dimethylformamide,
And dimethylacetamide. And the like, more preferably nitriles and alcohols, and still more preferably acetonitrile, methanol, ethanol and isopropanol. The reaction temperature is preferably from 0 to 1
It is 50 degreeC, More preferably, it is 15-120 degreeC.

The light emitting device of the present invention is a device in which a light emitting layer or a plurality of organic compound thin layers including a light emitting layer are formed between a pair of electrodes of an anode and a cathode. It may have a layer, an electron injection layer, an electron transport layer, a protective layer, and the like, and each of these layers may have another function. Various materials can be used for forming each layer.

The anode supplies holes to the hole injection layer, the hole transport layer, the light emitting layer, etc., and may be made of a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof. It is possible to use a material having a work function of 4 eV or more. Specific examples include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), or metals such as gold, silver, chromium, and nickel, and furthermore, these metals and conductive metal oxides. Mixtures or laminates, inorganic conductive substances such as copper iodide and copper sulfide, organic conductive materials such as polyaniline, polythiophene, and polypyrrole, and laminates of these with ITO, and the like. Oxides,
In particular, ITO is preferable in terms of productivity, high conductivity, transparency, and the like. The thickness of the anode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 500 nm.

As the anode, a layer formed on a soda lime glass, a non-alkali glass, a transparent resin substrate or the like is usually used. When glass is used, it is preferable to use non-alkali glass in order to reduce ions eluted from the glass. Further, when soda lime glass is used, it is preferable to use a glass coated with a barrier coat such as silica. The thickness of the substrate is not particularly limited as long as it is sufficient to maintain the mechanical strength. When glass is used, the thickness is usually 0.2 mm or more, preferably 0.7 mm or more. Various methods are used for producing the anode depending on the material. For example, in the case of ITO, an electron beam method, a sputtering method, a resistance heating evaporation method, a chemical reaction method (such as a sol-gel method), and a coating of a dispersion of indium tin oxide are used. The film is formed by the method described above. The anode can be cleaned or otherwise treated to lower the device's drive voltage,
It is also possible to increase the luminous efficiency. For example, in the case of ITO, UV-ozone treatment, oxygen plasma treatment and the like are effective.

The cathode supplies electrons to the electron injecting layer, the electron transporting layer, the light emitting layer and the like. The cathode has good adhesion and ionization potential between the negative electrode and the adjacent layer such as the electron injecting layer, the electron transporting layer and the light emitting layer. It is selected in consideration of stability and the like. As the material of the cathode, a metal, an alloy, a metal oxide, an electrically conductive compound, or a mixture thereof can be used, and specific examples thereof include an alkali metal (eg, Li, Na, K, etc.) or a fluoride thereof, and an alkaline earth metal. Metals such as Mg, Ca
Etc.) or its fluorides, gold, silver, lead, aluminum,
Sodium-potassium alloy or a mixed metal thereof, lithium-aluminum alloy or a mixed metal thereof, magnesium-silver alloy or a mixed metal thereof, indium, rare earth metals such as ytterbium, and the like, preferably having a work function of 4 eV or less. The material is more preferably aluminum, a lithium-aluminum alloy or a mixed metal thereof, a magnesium-silver alloy or a mixed metal thereof, or the like. The thickness of the cathode can be appropriately selected depending on the material, but is usually preferably in the range of 10 nm to 5 μm, more preferably 50 nm to 1 μm, and still more preferably 100 nm to 1 μm. A method such as an electron beam method, a sputtering method, a resistance heating evaporation method, or a coating method is used for manufacturing the cathode, and a metal can be evaporated alone or two or more components can be simultaneously evaporated. Further, an alloy electrode can be formed by depositing a plurality of metals at the same time, or an alloy prepared in advance may be deposited. The sheet resistance of the anode and the cathode is preferably low, and is preferably several hundred Ω / □ or less.

The material of the light emitting layer can inject holes from the anode or the hole injection layer or the hole transport layer when applying an electric field, and also can inject electrons from the cathode or the electron injection layer or the electron transport layer. Any material can be used as long as it can form a layer having a function, a function of transferring injected charges, and a function of providing a field of recombination of holes and electrons to emit light. Preferably, the light-emitting layer contains the compound of the present invention, but other light-emitting materials of the compound of the present invention can also be used. For example, benzoxazole derivatives,
Benzimidazole derivatives, benzothiazole derivatives,
Styrylbenzene derivatives, polyphenyl derivatives, diphenylbutadiene derivatives, tetraphenylbutadiene derivatives, naphthalimide derivatives, coumarin derivatives, perylene derivatives, perinone derivatives, oxadiazole derivatives, aldazine derivatives, cyclopentadiene derivatives, bisstyrylanthracene derivatives, quinacridone derivatives, Pyrrolopyridine derivatives, thiadiazolopyridine derivatives, cyclopentadiene derivatives, styrylamine derivatives, aromatic dimethylidin compounds, various metal complexes represented by 8-quinolinol derivatives and rare earth complexes, polythiophene, polyphenylene, polyphenylenevinylene, etc. And polymer compounds. The thickness of the light emitting layer is not particularly limited, but is usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 500 nm. The method for forming the light-emitting layer is not particularly limited, but resistance heating evaporation, electron beam, sputtering, molecular lamination,
A coating method (such as a spin coating method, a casting method, or a dip coating method), an LB method, an inkjet method, or a printing method is used, and resistance heating evaporation and a coating method are preferable.

The material of the hole injection layer and the hole transport layer has one of a function of injecting holes from the anode, a function of transporting holes, and a function of blocking electrons injected from the cathode. Anything should do. Specific examples thereof include carbazole derivatives, triazole derivatives, oxazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, and styryl anthracene derivatives , Fluorenone derivative, hydrazone derivative, stilbene derivative, silazane derivative, aromatic tertiary amine compound, styrylamine compound, aromatic dimethylidin compound, porphyrin compound, polysilane compound,
Examples thereof include poly (N-vinylcarbazole) derivatives, aniline-based copolymers, thiophene oligomers, and conductive polymer oligomers such as polythiophene. The thicknesses of the hole injection layer and the hole transport layer are not particularly limited, but are usually preferably in the range of 1 nm to 5 μm, more preferably 5 nm to 1 μm, and still more preferably 10 nm to 5 μm.
00 nm. The hole injection layer and the hole transport layer may have a single-layer structure composed of one or more of the above-described materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the hole injection layer and the hole transport layer include a vacuum deposition method, an LB method, and a method in which the hole injection / transport agent is dissolved or dispersed in a solvent and coated (spin coating method, casting method, dip coating method). Such),
An ink jet method and a printing method are used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. Examples of the resin component include polyvinyl chloride, polycarbonate, polystyrene, polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, and poly (N -Vinyl carbazole), hydrocarbon resins, ketone resins, phenoxy resins, polyamides, ethyl cellulose, vinyl acetate, ABS resins, polyurethanes, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, silicone resins, and the like.

The material of the electron injecting layer and the electron transporting layer is not limited as long as it has a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. Good. Specific examples thereof include triazole derivatives, oxazole derivatives, oxadiazole derivatives,
Heterocyclic tetracarboxylic anhydrides such as fluorenone derivatives, anthraquinodimethane derivatives, anthrone derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, carbodiimide derivatives, fluorenylidenemethane derivatives, distyrylpyrazine derivatives, naphthalene perylene, and phthalocyanine derivatives And various metal complexes typified by metal complexes of 8-quinolinol derivatives, metal phthalocyanines, and metal complexes having benzoxazole or benzothiazole as ligands. The thickness of the electron injection layer and the electron transport layer is not particularly limited, but is usually 1 nm to 5 μm.
m, more preferably 5 nm to 1
μm, and more preferably 10 nm to 500 nm. The electron injection layer and the electron transport layer may have a single layer structure composed of one or more of the above-mentioned materials, or may have a multilayer structure composed of a plurality of layers having the same composition or different compositions. Examples of the method for forming the electron injecting layer and the electron transporting layer include a vacuum evaporation method, an LB method, a method in which the electron injecting and transporting agent is dissolved or dispersed in a solvent and coated (spin coating, casting, dip coating, etc.), An ink jet method, a printing method, or the like is used. In the case of the coating method, it can be dissolved or dispersed together with the resin component. As the resin component, for example, those exemplified in the case of the hole injection transport layer can be applied.

As the material of the protective layer, any material may be used as long as it has a function of preventing a substance that promotes element deterioration such as moisture and oxygen from entering the element. As a specific example,
In, Sn, Pb, Au, Cu, Ag, Al, Ti, N
metal such as i, MgO, SiO, SiO ₂ , Al ₂ O ₃ ,
GeO, NiO, CaO, BaO, Fe 2 O 3, Y 2 O 3
, TiO _{2 and} other metal oxides, MgF ₂ , LiF, Al
F ₃ , metal fluoride such as CaF ₂ , polyethylene, polypropylene, polymethyl methacrylate, polyimide,
Polyurea, polytetrafluoroethylene, polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer Copolymer obtained, a fluorine-containing copolymer having a cyclic structure in the copolymer main chain, a water-absorbing substance having a water absorption of 1% or more,
A moisture-proof substance having a water absorption of 0.1% or less can be used. There is no particular limitation on the method for forming the protective layer. For example, a vacuum deposition method, a sputtering method, a reactive sputtering method,
BE (molecular beam epitaxy) method, cluster ion beam method, ion plating method, plasma polymerization method (high frequency excitation ion plating method), plasma CVD method, laser CVD method, thermal CVD method, gas source CVD method, coating Method, inkjet method, and printing method can be applied.

[0086]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. Synthesis Example 1 Synthesis of Exemplified Compound 41

[0087]

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Method for synthesizing intermediate (a) 98.6 g of diphenylamine, 3-iodoanisole 1
50 g, 55 g of copper powder, 1.5 g of iodine, and 210 g of potassium carbonate were heated with vigorous stirring at 200 ° C. for 100 hours under a nitrogen atmosphere, cooled to room temperature, dissolved in 1000 mL of ethyl acetate, and filtered through celite. The filtrate was evaporated under reduced pressure, and purified by silica gel column chromatography (hexane: chloroform = 8: 2 (v / v)) to obtain 144 g of intermediate (a) (yield 90%).

Synthesis of Intermediate (b) 73 g of Intermediate (a) is dissolved in 150 mL of methylene chloride and cooled to 0 ° C. in an ice bath. Under a nitrogen atmosphere, 75 mL of BBr _{3 is} slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 3 hours, then the reaction solution was slowly added dropwise to a beaker containing ice, extracted with chloroform and an aqueous solution of sodium hydroxide until the aqueous phase reached pH 7, and then extracted with an organic phase. Was distilled off under reduced pressure to obtain 68 g of intermediate (b) (yield: 99%).

Synthesis of Intermediate (c) 36.0 g of the intermediate (b), 22.5 g of zinc chloride and 100 mL of ethyl acetoacetate were heated at 150 ° C. for 6 hours.
Extraction operation was performed with chloroform and brine, the organic phase was recovered, the solvent was distilled off under reduced pressure, and silica gel column chromatography (hexane: ethyl acetate = 17: 3 (v / v)).
And then recrystallized from hexane-ethyl acetate to give 23.8 g of intermediate (c) (yield 5).
3%).

Synthesis of Exemplified Compound 101 Intermediate (c) 15.5 g, Lawesson's reagent
A mixture of 5 g and 150 mL of toluene was stirred for 3 hours while heating in a 110 ° C. oil bath. After cooling to room temperature, 1000 mL of toluene was added, and celite filtration was performed.
The filtrate was concentrated under reduced pressure. 150 mL of ethanol was added, the mixture was heated and allowed to stand, and the precipitated solid was collected by filtration to obtain 10.3 g of Exemplified Compound 101 (yield: 63%). Melting point: 1
77-178 ° C

Synthesis of Exemplified Compound 41 A mixture of 6.8 g of silver nitrate and 100 mL of acetonitrile was
Stir at room temperature for 5 minutes, 3.2 g of 1,3-indandione
, Followed by Exemplified Compound 101,6.
After adding 8 g and stirring at room temperature for 30 minutes, 5.5 mL of triethylamine was added dropwise and stirred at room temperature for 4 hours. Thereafter, 300 mL of chloroform was added, the mixture was filtered through celite, the filtrate was recovered, the solvent was distilled off under reduced pressure, and silica gel column chromatography (chloroform: methanol = 100: 1).
(V / v)), 1.8 g of Exemplified Compound 41 (20% yield) was obtained. Melting point: 295-297 ° C. ¹ H-NMR (CDCl ₃ ) δ 8.20 (s, 1H), 7.74 (d,
2H), 7.60 (m, 2H), 7.13 to 7.46 (m,
12H), 6.96 (m, 1H), 2.53 (s, 3H)

Synthesis Example 2 Synthesis of Exemplified Compound 42

Synthesis of Exemplified Compound 42 A mixture of 4.6 g of silver nitrate and 80 ml of acetonitrile was
The mixture was stirred at room temperature for 5 minutes, and 2.6 g of 2H-cyclopenta <b> naphthalene-1,3-dione was added.
01 and 4.6 g were added, and the mixture was stirred at room temperature for 1 hour. Then, 3.9 mL of triethylamine was added dropwise, and the mixture was stirred at room temperature for 1 hour. Thereafter, 2000 mL of chloroform was added, the mixture was filtered through Celite, the filtrate was collected, the solvent was distilled off under reduced pressure, and purification was performed by silica gel column chromatography (chloroform: methanol = 100: 1 (v / v)). Recrystallization from ethanol gave Exemplified Compound 4
2.0 g (yield 30%) was obtained. Melting point: 300 ° C. or higher, ¹ H-NMR (CDCl ₃ ) δ 8.36 (s,
1H), 8.22 (d, 2H), 8.02 (m, 2H), 7.
78 (m, 2H), 7.45 (d, 2H), 7.19 to 7.
40 (m, 7H), 7.00 (m, 1H), 2.59 (s,
3H)

Synthesis Example 3 Synthesis of Exemplified Compound 44

Synthesis of Exemplified Compound 115 9H-Tribenzo <b, d, f> azepine 2.5 g, te
Dissolve 1.4 g of rt-butyl sodium in 20 ml of xylene, and under a nitrogen atmosphere, 40 mg of palladium acetate,
130 mg of -butylphosphine were added. Then, m-
Slowly add 1.9 g of bromoanisole,
And then cooled to room temperature, chloroform,
An extraction operation was performed with a saline solution, the organic phase was recovered, the solvent was distilled off under reduced pressure, and silica gel column chromatography was performed.
9- (m-methoxyphenyl) tribenzo <b, d, f
> Azepine was obtained. The solid obtained is thoroughly dried, dissolved in 15 ml of methylene chloride and cooled to 0 ° C. in an ice bath. Under a nitrogen atmosphere, 12 ml of a 1 M BBr ₃ methylene chloride solution is slowly added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 8 hours, and the reaction solution was slowly added dropwise to a beaker containing ice.
The aqueous phase is pH 7 with chloroform and aqueous sodium hydroxide.
The organic phase was distilled off under reduced pressure until 9- (m-hydroxyphenyl) tribenzo <b,
d, f> 2.8 g of azepine (81% yield) was obtained. 9-
(M-hydroxyphenyl) tribenzo <b, d, f>
After heating 2.8 g of azepine, 2.0 g of zinc chloride and 15 mL of ethyl acetoacetate at 150 ° C. for 4 hours, the solvent was distilled off under reduced pressure, extracted with chloroform and water, and the organic phase was recovered. The solvent was distilled off, and the residue was purified by silica gel column chromatography to give 7- (9-tribenzo <b, d, f> azepino) -4-methylcoumarin 1.9.
g (57% yield). 7- (9-tribenzo <b,
d, f> azepino) -4-methylcoumarin 1.7 g, L
A mixture of 0.90 g of awesson reagent and 15 ml of toluene was stirred for 3 hours while heating in a 110 ° C. oil bath. After cooling to room temperature, 100 mL of toluene was added, the mixture was filtered through celite, and the filtrate was concentrated under reduced pressure. Purification was performed by silica gel column chromatography (chloroform), and 0.72 g of Exemplified Compound 115 (yield 41) was obtained.
%)Obtained. Method for synthesizing Exemplified Compound 44 A mixture of 500 mg of silver nitrate and 20 ml of acetonitrile was stirred at room temperature for 5 minutes, 282 mg of 2H-cyclopenta <b> naphthalene-1,3-dione was added, and subsequently 600 mg of Exemplified Compound 115 was added. After stirring for 30 minutes, 2.0 mL of triethylamine was added dropwise, and the mixture was added at room temperature for 3 minutes.
Stirred for hours. Thereafter, 20 mL of chloroform was added, the mixture was filtered through celite, the filtrate was collected, the solvent was distilled off under reduced pressure, and purification was carried out by silica gel column chromatography (chloroform: methanol = 100: 1 (v / v)) to give the exemplified compound. 82 mg (21% yield) of 44 were obtained. Melting point: 300 ° C. or higher ¹ H-NMR (CDCl ₃ ) δ 8.24 (m, 3H), 8.03 (d
d, 2H), 7.75 (m, 2H), 7.70 (dd, 2
H), 7.56 to 7.60 (m, 8H), 7.45 (dd,
2H), 6.78 (d, 1H), 6.62 (dd, 1H),
2.47 (s, 3H)

Example 1 Evaluation of Light-Emitting Element Fabrication Example 1 IT was placed on a glass substrate of 25 mm × 25 mm × 0.7 mm.
O was formed to a thickness of 150 nm to obtain a transparent support substrate. After etching and washing this transparent support substrate, 40 mg of poly (N-vinylcarbazole) and PBD (2-
(4-biphenylyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole) 12 m
g, 0.5 mg of the compound shown in Table 1 was dissolved in 1,2-dichloroethane (3 ml) and spin-coated on a washed ITO substrate. The thickness of the resulting organic thin layer was about 120 nm. A mask (a mask having a light emitting area of 5 mm × 5 mm) patterned on the organic thin layer is provided, and magnesium: silver = 10: 1 is co-deposited at 50 nm in a vapor deposition apparatus, and then 50 nm of silver is vapor deposited to form a light emitting element. Created. Using Toyo Technica Source Measure Unit Model 2400,
A DC constant voltage is applied to the light emitting element to emit light, and the luminance is measured by a luminance meter BM-8 manufactured by Topcon Corporation, and the emission wavelength and CIE chromaticity coordinates are measured by a spectrum analyzer PMA-1 manufactured by Hamamatsu Photonics, Inc.
1 was measured. Also, the fabricated device was heated at 60 ° C. for 2 hours.
After leaving for 3 hours under the condition of 0% RH (driving voltage 15
V) The presence or absence of a dark spot on the light emitting surface was evaluated. Table 1 shows the results.

[0098]

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As is clear from the results shown in Table 1, the device using the compound of the present invention can be driven at a low voltage and emits light at a high luminance, and generates less dark spots over time, as compared with the comparative compound. It exhibited excellent properties in terms of homogeneous planar light emission and durability. In particular, good light-emitting characteristics were obtained by a coating method with low light emission luminance.

[0100]

[Table 1]

Example 2 In the same manner as in Example 1, the ITO substrate was etched and washed,
PD (N, N ^'- bis (3-methylphenyl) -N, N
^' -Diphenylbenzidine) about 40 nm, the compounds shown in Table 2 about 20 nm, 2,5-bis (1-naphthyl) -1,
Approximately 40 nm of 3,4-oxadiazole is sequentially taken from 10 ^-3 to 1
Vapor deposition was carried out at a substrate temperature of room temperature in a vacuum of 0 ^-4 Pa.
Next, a cathode was vapor-deposited in the same manner as in Example 1 to produce a light-emitting device, which was evaluated. Table 2 shows the results. As is clear from the results in Table 2, the device using the compound of the present invention emitted light with higher luminance even in the vapor deposition method than the comparative compound.

[0102]

[Table 2]

Embodiment 3 After etching and cleaning the ITO substrate in the same manner as in Embodiment 1,
After vapor deposition of about 40 nm of PD, the compounds shown in Table 3 and A
1q (tris (8-hydroxyquinolinato) aluminum) was co-deposited at a deposition rate of 0.04 ° / sec and 4 ° / sec to a film thickness of about 60 nm. Next, Example 1
A light emitting device was prepared by evaporating a cathode in the same manner as described above, and was evaluated. Table 3 shows the results. As is evident from the results in Table 3, the device using the compound of the present invention had better color purity and higher luminance than the comparative compound even in the vapor-doped system.

[0104]

[Table 3]

Example 4 An ITO substrate was etched and washed in the same manner as in Example 3-1. After TPD was deposited to a thickness of about 40 nm, Exemplified Compound 42 was deposited to a thickness of about 40 nm, and then Alq (tris (8-hydroxyquinolinato) Aluminum) was deposited to a thickness of about 20 nm. Next, a cathode was vapor-deposited in the same manner as in Example 1 to produce a light-emitting element, and the result was evaluated. As a result, the minimum drive voltage was 5 V, and the maximum luminance was 16 V, 520 cd / m ² , λ max = 630 n.
m, CIE chromaticity (x, y) = (0.62, 0.37). No occurrence of dark spots was observed. As is clear from these results, the device using the compound of the present invention exhibited good color purity and high-luminance emission even in the non-doped system of the vapor deposition method.

Example 5 After etching and washing the ITO substrate in the same manner as in Example 1, about 60 nm of Exemplified Compound 42 was evaporated, and then Alq (tris (8-hydroxyquinolinato) aluminum) was evaporated to a thickness of about 40 nm. . Next, a cathode was vapor-deposited in the same manner as in Example 1 to produce a light-emitting element, and as a result of evaluation, the result was 420 cd / m ² at a minimum drive voltage of 6 V and a maximum luminance of 15 V,
λmax = 631 nm, CIE chromaticity (x, y) = (0.6
2, 0.37). As is evident from these results, it was found that the compound of the present invention was also effective as a hole-injecting / transporting and luminescent agent, and exhibited good color purity and high-luminance emission.

[0107]

According to the present invention, it is possible to obtain a light emitting device having better color purity, lower driving voltage, higher luminance and longer life than the conventional one. In addition, high-intensity light emission was able to be exhibited as a hole injection / transport and light emitting agent. In addition, good light-emitting characteristics can be obtained even by a coating method having low light emission luminance, and an element can be manufactured which is advantageous in terms of manufacturing cost and the like.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C07D 405/04 C07D 405/04 405/14 405/14 409/04 409/04 409/12 409/12 409 / 14 409/14 413/04 413/04 417/04 417/04 417/14 417/14 491/052 491/052 513/04 371 513/04 371 C09K 11/06 640 C09K 11/06 640 655 655 H05B 33/14 H05B 33/14 B (72) Inventor Tsuyoshi Nagatatsu 210 Nakanakanuma, Minamiashigara-shi, Kanagawa Prefecture Fuji Photo Film Co., Ltd. F-term (reference) 3K007 AB00 AB02 AB03 AB04 AB06 AB18 CA01 CA05 CB01 CB03 DA00 DB03 EB00 FA01 4C031 JA01 4C062 EE61 FF55 FF68 HH69 4C063 AA01 AA03 AA05 BB01 BB09 CC62 CC78 CC92 CC94 CC95 DD19 DD22 DD23 DD29 DD51 DD52 DD54 DD58 DD62 DD64 DD78 DD92 EE10 4C072 AA01 AA07 BB02 BB07 CC17 CC11 CC16 GG07

Claims (5)

[Claims] 1. A light emitting device material, which is a compound represented by the following general formula (I). Embedded image (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R _n1 and R _n2
Represents a hydrogen atom or a substituent, respectively. Where R _n1 ,
At least one of R _n2 is an aryl group or an aromatic heterocyclic group. X is O, S or NR (R is a hydrogen atom,
Represents an aliphatic hydrocarbon group, an aryl group or a heterocyclic group. ). Y represents CG ₁ (G ₂ ) (G ₁ and G ₂ each represent a hydrogen atom or a substituent, provided that G ₁ and G ₂
At least one represents a substituent. ). ) 2. A compound represented by the following general formula (Ia). Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a substituent. Ar ₁ and Ar ₂ each represent an aryl group or an aromatic heterocyclic group. Y represents C— G ₁
(G ₂ ) (G ₁ and G ₂ each represent a hydrogen atom or a substituent, provided that at least one of G ₁ and G ₂ represents a substituent). ) 3. A compound represented by the following general formula (II). Embedded image (Wherein, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ each represent a hydrogen atom or a substituent. Ar ₁ and Ar ₂ each represent an aryl group or an aromatic heterocyclic group. X represents O, S or NR (R represents a hydrogen atom, an aliphatic hydrocarbon group, an aryl group or a heterocyclic group) 4. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes,
A light-emitting device comprising at least one layer containing a compound represented by formula (I), (Ia) or (II) according to claim 1, 2 or 3. 5. A light-emitting element in which a light-emitting layer or a plurality of organic compound thin layers including a light-emitting layer is formed between a pair of electrodes,
A light-emitting device comprising at least one layer in which a compound represented by the general formula (I), (Ia) or (II) according to claim 1, 2 or 3 is dispersed in a polymer.