JP2002367783A - Luminous element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a luminous element with good red color purity. SOLUTION: The luminous element contains between a pair of electrodes made on a substrate at least one of chemical compounds expressed in formula (I) and also contains as a principal component a compound of which a configuration of an alkenylene group, an imino group or a diazo group substituting a pyran ring and its analogs among stereoisomers of the compound in formula (I) has an s-transformer configuration against a double bond of both the pyran ring and its analogs. R<1> to R<5> in the formula stands respectively for H or substituents; X stands for O, S, N-RY<1> , RY<1> stands for H or a substituent; L11 , L12 stands respectively for a methine group, a substituent methine group or N; n stands for an integer of 1 to 3; and Ar stands for an arylene group or a bivalent aromatic heterocycle group. R<x> , R<y> stand for H or substituent and at least either of them stands for an electron absorption group. The compound expressed in formula (I) can be one forming a metal complex.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to fields such as backlights, flat panel displays, illumination light sources, display elements, electrophotography, organic semiconductor lasers, recording light sources, exposure light sources, reading light sources, signs, signboards, and optical communication devices. The present invention relates to a light emitting device that can be used for a light emitting device.

[0002]

2. Description of the Related Art At present, research and development of a variety of light emitting devices are being actively conducted. Among them, organic electroluminescent (EL) devices are ultra-thin, lightweight, high-speed response, and have a wide viewing angle. It has features such as low-voltage driving and is attracting attention as a promising light emitting element. In general, an organic EL device is composed of a light-emitting layer and a pair of opposed electrodes sandwiching the light-emitting layer. Electrons injected from a cathode and holes injected from an anode recombine to emit light from excitons generated. Is used.

At present, an organic EL device which emits light with high luminance at a low voltage has a laminated structure shown by Tang et al. (Applied Physics Letters, vol.
913, 1987). This device emits high-luminance green light by laminating an electron-transporting / light-emitting material and a hole-transporting material, and has a luminance of several thousand c at a DC voltage of 6 to 7 V.
d / m ² . However, considering use as a full-color display and a light source, three primary colors or white light emission is necessary for practical use. However, in the above-mentioned element, an aluminum complex of 8-quinolinol is used as a light-emitting material, and the light emission color is limited to green. Therefore, development of a light emitting element of another emission color is desired. So far, 4- (dicyanomethylene) -2-methyl- (4-dimethylaminostyryl) -4H-pyran (D
CM) and its derivatives, Nile red derivatives, Eu (II
I) Luminescent materials such as complexes have been developed, but have problems such as poor color purity, low luminance, low luminous efficiency, and low durability.

[0004] Various studies have been made, and as a result, JP-A-11-335661, JP-A-11-292875,
JP-A-11-335368, Japanese Patent Application No. 11-16113
When a device using a compound containing a cyclic acidic nucleus, such as the compound described in No. 0 or the like, was prepared and evaluated, it was found that the device was excellent in red color purity, emission luminance, emission efficiency, and durability. However, these alkenylene-substituted pyran compounds have variations in performance such as a decrease in color purity and a decrease in durability due to a difference in synthesis conditions, and it has been desired to avoid this and stabilize the performance.

[0005]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a light emitting device having a small variation in performance due to a difference in synthesis lot of a compound. A second object of the present invention is to provide a light emitting device having excellent red purity and excellent durability.

[0006]

This object has been achieved by the following. (1) An alkenylene group containing at least one compound represented by the following general formula (I) between a pair of electrodes provided on a substrate and substituting a pyran ring or an analog thereof among stereoisomers of the compound. , The imino group or the diazo group has a s-configuration with respect to the double bond of the pyran ring and its analog.
A light-emitting element comprising a transformer as a main component. General formula (I)

[0007]

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Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are
Each represents a hydrogen atom or a substituent. X is an oxygen atom,
R represents a sulfur atom or N—R ^Y1 , and R ^Y1 represents a hydrogen atom or a substituent. L ₁₁ and L ₁₂ may be the same or different and represent a methine group, a substituted methine group or a nitrogen atom, respectively. n represents an integer of 1 to 3. Ar represents an arylene group or a divalent aromatic heterocyclic group. R ^x and R ^y each represent a hydrogen atom or a substituent, and at least one of them represents an electron-withdrawing group. In addition, the general formula (I)
The compound represented by may form a metal complex. (2) Among the stereoisomers of the compound represented by formula (I), the configuration of the alkenylene group substituted on the pyran ring or its analog is s-trans with respect to the double bond of the pyran ring or its analog. The light-emitting device according to (1), wherein the compound is a compound represented by the general formula (II). General formula (II)

[0009]

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Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are
Each represents a hydrogen atom or a substituent. X is an oxygen atom,
R represents a sulfur atom or N—R ^Y1 , and R ^Y1 represents a hydrogen atom or a substituent. R ²¹ and R ²² each represent a hydrogen atom or a substituent. Ar represents an arylene group or a divalent aromatic heterocyclic group. R ^x and R ^y each represent a hydrogen atom or a substituent, and at least one of them represents an electron-withdrawing group. (3) The light-emitting device according to (2), wherein the compound represented by the general formula (II) is a compound represented by the general formula (III). General formula (III)

[0011]

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Wherein R ¹ , R ² , R ³ , R ⁴ and R ⁵ are
Each represents a hydrogen atom or a substituent. Z ² represents an atom group necessary for forming a 5- or 6-membered ring. X represents an oxygen atom, a sulfur atom, or N-R ^Y1 , and R ^Y1 represents a hydrogen atom or a substituent. R ²¹ and R ²² each represent a hydrogen atom or a substituent. Ar represents an arylene group or a divalent aromatic heterocyclic group. (4) The light-emitting device according to (3), wherein the compound represented by the general formula (III) is a compound represented by the general formula (IV). General formula (IV)

[0013]

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Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ³¹ ,
R ³² , R ³³ and R ³⁴ each represent a hydrogen atom or a substituent. Z ³ represents an atom group necessary for forming a 5- or 6-membered ring. R ²¹ and R ²² each represent a hydrogen atom or a substituent. (5) In the light-emitting devices of (1) to (4), among the stereoisomers of the compound, the configuration of an alkenylene group, an imino group, or a diazo group substituted on a pyran ring or an analog thereof is different from that of the pyran ring or the analog thereof. S-
A light-emitting element, wherein the abundance of trans is 99% or more based on the sum of all isomers of the compound.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The light-emitting element of the present invention is an element in which a light-emitting layer or a plurality of organic compound layers including a light-emitting layer are formed between both an anode and a cathode. In addition to the light-emitting layer, a hole injection layer, a hole transport layer, and an electron injection layer are provided. , An electron transport layer, a protective layer, and the like, and each of these layers may have another function.

First, the compound represented by formula (I) of the present invention will be described. R ¹ , R ² , R ³ , R ⁴ and R ⁵
May be the same or different and represent a hydrogen atom or a substituent, respectively. Examples of the substituent represented by R ^{1 to} R ⁵ include an alkyl group (preferably having 1 to 2 carbon atoms).
0, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methyl, ethyl, iso-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 20 carbon atoms, more preferably having 2 carbon atoms)
-12, particularly preferably 2-8 carbon atoms, such as vinyl, allyl, 2-butenyl, 3-pentenyl and the like. ), Alkynyl group (preferably having 2 to 2 carbon atoms)
It has 0, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, and examples thereof include propargyl and 3-pentynyl. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms, particularly preferably having 6 to 12 carbon atoms, for example, phenyl, p-methylphenyl, naphthyl, anthryl, phenanthryl,
Pyrenyl and the like. ), An amino group (preferably having 0 to 20 carbon atoms, more preferably 0 to 12 carbon atoms, particularly preferably 0 to 6 carbon atoms, for example, amino, methylamino, dimethylamino, diethylamino, diphenylamino, dibenzylamino) And an alkoxy group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 12 carbon atoms, particularly preferably having 1 to 8 carbon atoms, and examples include methoxy, ethoxy, and butoxy). ,
Aryloxy group (preferably having 6 to 20 carbon atoms, more preferably having 6 to 16 carbon atoms, particularly preferably having 6 to 1 carbon atoms)
2, for example, phenyloxy, 2-naphthyloxy and the like. ), A heterocyclic oxy group (preferably having 2 to 20 carbon atoms, more preferably 3 to 16 carbon atoms, particularly preferably 4 to 12 carbon atoms, and examples thereof include pyridinooxy, pyrimidinooxy, pyridazinooxy, and benzimidazolyloxy. ), A silyloxy group (preferably having 3 to 40 carbon atoms, more preferably having 3 carbon atoms)
-30, particularly preferably 3-20 carbon atoms, for example, trimethylsilyloxy, t-butyldimethyloxy and the like. ), An acyl group (preferably having 1 to 2 carbon atoms)
0, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, such as acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, and particularly preferably having 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl and the like.), Aryloxycarbonyl Group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 1 carbon atoms)
6, particularly preferably having 7 to 10 carbon atoms, such as phenyloxycarbonyl. ), An acyloxy group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 10 carbon atoms,
For example, acetoxy, benzoyloxy and the like can be mentioned. ), An acylamino group (preferably having 2 to 20 carbon atoms,
More preferably, it has 2 to 16 carbon atoms, particularly preferably 2 to 10 carbon atoms, for example, acetylamino, benzoylamino and the like. ), An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, such as methoxycarbonylamino and the like), aryloxycarbonylamino Group (preferably having 7 to 7 carbon atoms)
20, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, such as phenyloxycarbonylamino. ), A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, methanesulfonylamino, benzenesulfonylamino and the like. ), A sulfamoyl group (preferably having 0 carbon atoms)
-20, more preferably 0-16 carbon atoms, particularly preferably 0-12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like. ), A carbamoyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 carbon atom)
To 16 and particularly preferably 1 to 12 carbon atoms, for example, carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like. ), An alkylthio group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, such as methylthio and ethylthio, etc.), and an arylthio group (preferably carbon Equations 6 to 20,
More preferably, it has 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, such as phenylthio. ), A heterocyclic thio group (preferably having 2 to 20 carbon atoms,
More preferably, it has 3 to 16 carbon atoms, particularly preferably 4 to 12 carbon atoms, and examples thereof include pyridinothio, pyrimidinothio, pyridazinothio, benzimidazolylthio, thiadiazolylthio and the like. ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, such as mesyl and tosyl. ), A sulfinyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, methanesulfinyl, benzenesulfinyl and the like. ), Ureido group (preferably 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms)
12, for example, ureide, methylureide, phenylureide and the like. ), A phosphoric amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 1 carbon atoms)
6, particularly preferably 1 to 12 carbon atoms, for example, diethylphosphoramide, phenylphosphoramide and the like. ), Hydroxy, mercapto, halogen (eg, fluorine, chlorine, bromine, iodine), cyano, sulfo, carboxyl, nitro, hydroxamic acid, sulfino, hydrazino,
Imino group, heterocyclic group (preferably having 1 to 30 carbon atoms, more preferably having 1 to 12 carbon atoms, and the hetero atom includes, for example, a nitrogen atom, an oxygen atom, and a sulfur atom. Imidazolyl, pyridyl, quinolyl, furyl, thienyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzothiazolyl, carbazolyl, azepinyl and the like; a silyl group (preferably having 3 to 40 carbon atoms, more preferably 3 carbon atoms); -30, particularly preferably 3-24 carbon atoms,
For example, trimethylsilyl, triphenylsilyl and the like can be mentioned. ) And the like. These substituents may be further substituted. When there are two or more substituents, they may be the same or different. When possible, they may be connected to each other to form a ring.

R ¹ and R ² are preferably a hydrogen atom, an aliphatic hydrocarbon group, an aryl group, a heterocyclic group, a 5-membered or 6-membered ring linked with Ar and alkenylene group,
¹ and R ² are linked to form a 5- to 7-membered ring, more preferably a hydrogen atom, an alkyl group, an aryl group, or an Ar and alkenylene group to form a 5- or 6-membered ring; R ¹ and R ² are linked to form a 5- to 7-membered ring, more preferably an alkyl group having 1 to 5 carbon atoms, or a 5- or 6-membered ring linked to an Ar and alkenylene group. , R ¹ and R ² are linked to form a 5- to 7-membered ring, particularly preferably a methyl group, an ethyl group, or a 5- or 6-membered ring linked to Ar and an alkenylene group; ¹ and R ² are linked to form a 5- to 7-membered ring. R ³ is preferably a hydrogen atom,
Preferred are an alkyl group, an aryl group, a halogen atom and a cyano group, more preferably a hydrogen atom and an alkyl group, and further preferably a hydrogen atom. R ⁴ is preferably a hydrogen atom, an alkyl group, an aryl group, an aromatic heterocyclic group,
R ⁵ is linked to form a ring, more preferably a hydrogen atom or an alkyl group, further preferably a hydrogen atom. R ⁵ is preferably a hydrogen atom, an alkyl group, an aryl group, an aromatic heterocyclic group, or a ring formed by linking to R ^4, and more preferably an alkyl group (preferably an alkyl group having 2 to 20 carbon atoms). Group, more preferably a branched or cyclic alkyl group having 3 to 20 carbon atoms, further preferably a branched or cyclic alkyl group having a quaternary carbon having 4 to 12 carbon atoms, particularly preferably ter.
t-butyl group. ), An aryl group (preferably an aryl group having a substituent at the o-position, more preferably an alkyl-substituted phenyl group having a substituent at the o-position having 7 to 30 carbon atoms, and still more preferably a 2,6-dimethyl substitution A phenyl group, particularly preferably a 2,4,6-trimethylphenyl group), and particularly preferably a tert-butyl group,
It is a 4,6-trimethylphenyl group, most preferably a tert-butyl group.

X represents an oxygen atom, a sulfur atom or N—R ^Y1 , and R ^Y1 represents a hydrogen atom or a substituent. As the substituent represented by R ^Y1 , for example, an alkyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, for example, methyl, ethyl, i
so-propyl, tert-butyl, n-octyl, n
-Decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl and the like. ), An alkenyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms,
For example, vinyl, allyl, 2-butenyl, 3-pentenyl and the like can be mentioned. ), An alkynyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 12 carbon atoms, particularly preferably having 2 to 8 carbon atoms, for example, propargyl,
Pentynyl and the like. ), An aryl group (preferably having 6 to 30 carbon atoms, more preferably having 6 to 20 carbon atoms,
Particularly preferably, it has 6 to 12 carbon atoms, and examples thereof include phenyl, p-methylphenyl, and naphthyl. ), An acyl group (preferably having 1 to 20 carbon atoms, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 1 carbon atoms).
2, for example, acetyl, benzoyl, formyl, pivaloyl and the like. ), An alkoxycarbonyl group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 16 carbon atoms, particularly preferably having 2 to 12 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl and the like.), Aryloxycarbonyl A group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 10 carbon atoms, such as phenyloxycarbonyl), and a sulfamoyl group (preferably having 0 to 0 carbon atoms). 20, more preferably 0 carbon atoms
To 16, particularly preferably 0 to 12 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl and the like. ), A carbamoyl group (preferably having 1 to 20 carbon atoms,
More preferably, it has 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, and examples thereof include carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl. ), A sulfonyl group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 16 carbon atoms, particularly preferably having 1 to 12 carbon atoms, and examples thereof include mesyl and tosyl). It has 1 to 20, more preferably 1 to 16 carbon atoms, particularly preferably 1 to 12 carbon atoms, for example, methanesulfinyl, benzenesulfinyl and the like.), A heterocyclic group (preferably 1 to 20 carbon atoms, More preferably, it has 1 to 12 carbon atoms, and as the hetero atom, for example, a nitrogen atom, an oxygen atom, a sulfur atom, specifically, for example, imidazolyl, pyridyl, furyl, piperidyl, morpholino, benzoxazolyl, benzimidazolyl, benzothiazolyl And the like.) And the like. These substituents may be further substituted. When there are two or more substituents, they may be the same or different. If possible, they may be linked to form a ring. The substituent represented by R ^Y1 is preferably an alkyl group, an alkenyl group,
It is an alkynyl group, an aryl group, or a heterocyclic group, more preferably an alkyl group, an aryl group, or an aromatic heterocyclic group, and still more preferably an alkyl group or an aryl group. X is preferably an oxygen atom, N- ^RY1 , more preferably an oxygen atom.

Ar is an arylene group (preferably having 6 carbon atoms)
To 30, more preferably 6 to 20 carbon atoms, particularly preferably an arylene group having 6 to 16 carbon atoms) or a divalent aromatic heterocyclic group (which may further have a condensed ring, preferably azine, azole, Thiophene, aromatic hetero ring formed from furan ring, coumarin ring, preferably having 2 to 3 carbon atoms
0, more preferably an aromatic heterocyclic group having 2 to 20 carbon atoms, particularly preferably 2 to 12 carbon atoms). The arylene group or the divalent aromatic heterocyclic group represented by Ar may have a substituent, and examples of the substituent include R ¹ to
Those exemplified as the substituents of R ⁵ can be applied. As a substituent of Ar, preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, a halogen atom, a cyano group, a heterocyclic group,
A silyl group, more preferably an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, a cyano group, or an aromatic heterocyclic group, and still more preferably an alkyl group or an aryl group. ,
It is an alkoxy group or an aromatic heterocyclic group, particularly preferably an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. The following are specific examples of Ar.

[0020]

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[0021]

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[0022]

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[0023]

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[0024] L ¹¹ and L ¹² may be the same or different from each other, each a methine group, a substituted methine group or a nitrogen atom, also via the substituent of the substituted methine group at L ¹¹ or L ¹² each other or L, ¹¹ and L ¹² may be linked to form a 4- to 6-membered ring. L ¹¹ if possible,
L ¹² may combine with Ar, R ³ and R ^Y1 to form a ring. As the substituent of the substituted methine group, those exemplified as the substituents represented by R ^{1 to} R ⁵ can be applied, and preferably, an alkyl group, an aryl group, an aralkyl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group Group, a cyano group and a halogen atom, more preferably an alkyl group and an alkoxy group, still more preferably a lower alkyl group (preferably having 1 to 4 carbon atoms). L ¹¹ and L ¹² are preferably an unsubstituted methine group, an alkyl-substituted methine group, or an alkoxy-substituted methine group, and more preferably an unsubstituted methine group, or L ₁₂ is
And a 5- or 6-membered ring, more preferably an unsubstituted methine group. n represents an integer of 1 to 3, preferably 1 or 2, and more preferably 1. Specific examples of the groups represented by L ¹¹ , L ¹² and Ar include the following.

[0025]

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R ^x and R ^y may be the same or different and represent a hydrogen atom or a substituent, and at least one of them represents an electron-withdrawing group. R ^x and R ^y may be linked to form a ring. As the substituents represented by R ^x and R ^y , for example, those exemplified as the substituents of R ^{1 to} R ⁵ can be applied. As the substituent represented by R ^x and R ^y , preferably an alkyl group, an alkenyl group, an aryl group, an alkoxy group, an aryloxy group, a carbonyl group, a thiocarbonyl group, an oxycarbonyl group, an acylamino group, a carbamoyl group, a sulfonylamino Group, sulfamoyl group, sulfonyl group, sulfinyl group, phosphoryl group, imino group,
It is a cyano group, a halogen atom, a silyl group, or an aromatic heterocyclic group, and more preferably has a Hammett's σp value of 0.1.
Two or more electron-withdrawing groups, more preferably an aryl group, an aromatic heterocyclic group, a cyano group, a carbonyl group, a thiocarbonyl group, an oxycarbonyl group, a carbamoyl group,
A sulfamoyl group, a sulfonyl group, an imino group, a halogen atom, and a group in which R ^x and R ^y are linked to form a ring of an electron-withdrawing group, particularly preferably an aromatic heterocyclic group, a carbonyl group, a cyano group, an imino group; A group in which R ^x and R ^y are linked to form a ring of an electron-withdrawing group, most preferably a cyano group, in which R ^x and R ^y are linked to form a ring of an electron-withdrawing group. In particular, those in which R ^x and R ^y are linked to form a ring of an electron-withdrawing group are preferable.

As R ^x and R ^y and those in which the carbon atoms to which they are bonded are linked to form a ring, those which are usually used as acidic nuclei in merocyanine dyes are preferred, and specific examples thereof include the following. Can be (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. (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 and the like. (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) 2-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 and the like. (Q) Benzothiophen-3-one nucleus: For example, benzothiophen-3-one, oxobenzothiophen-3-one, dioxobenzothiophen-3-one and the like. (R) Indanone nucleus: For example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone and the like.

The ring formed by R ^x , R ^y 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, benzothiophen-3-one nucleus and indanone nucleus, more preferably 1,3-dicarbonyl nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including thioketone) , A 3,5-pyrazolidinedione nucleus, a benzothiophen-3-one nucleus and an indanone nucleus, and particularly preferably a 1,3-dicarbonyl nucleus;
A 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone body), and most preferably a 1,3-indandione nucleus.

The compound represented by the general formula (I) is a stereoisomer in which the configuration of an alkenylene group, an imino group or a diazo group substituted on a pyran ring or an analog thereof is a pyran ring or an analog thereof as shown below. There are an s-trans form and an s-cis form for the double bond of the body. Here, the s, means a single bond linking two double bonds (single bonds between the pyran ring and its analogs and L ^11), which double bond to a single bond in the trans Are s-trans and those in cis are s-cis. The compound of the present invention is mainly composed of an s-trans form, and its abundance is more than 50%, preferably 90% or more, more preferably 95% or more based on the sum of all isomers of the compound. And particularly preferably 99% or more.

[0030]

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Next, the general formula (II) will be described. Among the stereoisomers of the compound represented by the general formula (I), the configuration of the alkenylene group substituted on the pyran ring or an analog thereof is s- with respect to the double bond of the pyran ring or the analog.
The compound which is trans is preferably a compound represented by the general formula (II). Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ ,
X, Ar, R ^X and R ^Y have the same meanings as those in formula (I), and the preferred ranges are also the same.

R^{twenty one}And R^{twenty two}Is a hydrogen atom or
Represents a substituent, and if possible, R ^{twenty one}And R^{twenty two}Is other
It may combine with a substituent to form a ring. R^{twenty one}, R^{twenty two}In table
The substituent is, for example, R in general formula (I)
¹~ R^FiveThe substituents represented by are applicable.
You. R^{twenty one}, R^{twenty two}Preferably a hydrogen atom, alkyl
Group, aryl group, aralkyl group, alkoxy group, aryl
Ruoxy, alkylthio, arylthio, cyano
Group, a halogen atom, more preferably a hydrogen atom,
Alkyl and alkoxy groups, more preferably hydrogen
And a lower alkyl group (preferably having 1 to 4 carbon atoms)
And particularly preferably a hydrogen atom.

Next, the general formula (III) will be described. Among the compounds represented by the general formula (II), more preferred are the compounds represented by the general formula (III). Where R ¹ ,
R ² , R ³ , R ⁴ , R ⁵ , X, Ar, R ²¹ and R ²² have the same meanings as those in formula (II), respectively.
The same applies to the preferred range. Z ² represents an atom group necessary for forming a 5- or 6-membered ring.

The ring formed by Z ² is preferably 1,
3-dicarbonyl nucleus, pyrazolinone nucleus, 2,4,6-triketohexahydropyrimidine nucleus (including thioketone), 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, 1,3 -A pyrazolidinedione nucleus, a benzothiophen-3-one nucleus, and an indanone nucleus, more preferably a 1,3-dicarbonyl nucleus, a 2,4,6-triketohexahydropyrimidine nucleus (including a thioketone compound),
A benzothiophen-3-one nucleus, an indanone nucleus,
More preferred are 1,3-dicarbonyl nuclei, barbituric acid derivatives and 2-thiobarbituric acid derivatives, and particularly preferred are 1,3-dicarbonyl nuclei (preferably 1,3-dicarbonyl nuclei are preferably 1,3-indandione). It is a nucleus.) The ring formed by Z ² may have a substituent, and examples of the substituent include those described as substituents for R ¹ and R ² .

Next, the general formula (IV) will be described. Among the compounds represented by the general formula (III), more preferred are the compounds represented by the general formula (IV). Wherein R ¹ , R ² ,
R ³ , R ⁴ , R ⁵ , R ²¹ and R ²² are each represented by the general formula (II
It has the same meaning as those in I), and the preferred range is also the same. Z ³ represents an atom group necessary for forming a 5- or 6-membered ring. R ³¹ , R ³² , R ³³ and R ³⁴ each represent a hydrogen atom or a substituent. As the substituents represented by R ³¹ to R ³⁴ , for example, those exemplified as the substituents of R ^{1 to} R ⁵ can be applied, and each may be bonded to form a ring. As the ring formed by Z ³ , for example, a compound represented by the general formula (I
Of the rings formed by Z ² in II), those having a 1,3-dicarbonyl structure in the ring, for example, 1,3-dicarbonyl
Cyclopentanedione, 1,3-cyclohexanedione, 1,3-indandione, 3,5-pyrazolidinedione, 2,4,6-triketohexahydropyrimidine nucleus and the like, and preferably 1,3- Indanzion,
3,5-pyrazolidinedione, barbituric acid or 2-
Thiobarbituric acid and its derivatives, more preferably 1,3-indandione, 1,2-diaryl-
3,5-pyrazolidinedione, more preferably 1,3-indandione, 1,2-diphenyl-3,5
-Pyrazolidinedione, particularly preferably 1,3-
Indansion. The ring formed by Z ³ may have a substituent, and examples of the substituent include those described as the substituents of R ^{1 to} R ⁵ .

The compound represented by the formula (I) may have a low molecular weight, or a high molecular weight compound having a residue connected to the polymer main chain (preferably a mass average molecular weight of 1000).
５5,000,000, more preferably 5,000 to 2,000
000, more preferably 10,000 to 1,000,000)
Alternatively, a high molecular weight compound having a compound represented by the general formula (I) in its main chain (preferably a mass average molecular weight of 1,000 to 1,000)
5,000,000, more preferably 5,000 to 20,000
00, more preferably 10,000 to 1,000,000). In the case of a high molecular weight compound, it may be a homopolymer, or may be a copolymer with another polymer.If it is a copolymer, it may be a random copolymer or a block copolymer. There may be. The compound used in the present invention is preferably a low molecular weight compound. Further, the compound represented by the general formula (I) may be contained in a state where a metal chelate is formed.

Specific examples of the compound represented by formula (I) of the present invention include, for example, JP-A-11-292875, JP-A-11-335661, and JP-A-11-335368.
No., Japanese Patent Application No. 11-161130, Japanese Patent Application No. 2001-16
980 and the like, among the stereoisomers of those bonded to the pyran ring and its analogs, the configuration of the alkenylene group, imino group or diazo group substituted on the pyran ring and its analogs is the same as that of the pyran ring and its analogs. Examples of the double bond include s-trans, and the following specific examples are more preferable, but the present invention is not limited thereto.

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The above compounds may be any other compounds provided that the configuration of the alkenylene group, imino group or diazo group substituted on the pyran ring or its analog is s-trans to the double bond of the pyran ring or its analog. May form a tautomer or a metal complex. Preferably, the alkenylene group substituted on the pyran ring or its analog is a trans form.

The compounds represented by the general formula (I) of the present invention are described, for example, in JP-A-11-335661 and JP-A-11-335661.
It can be synthesized by referring to the methods described in JP-A-292875, JP-A-11-335368, Japanese Patent Application No. 11-161130 and the like, but it is preferable to shield light during crystallization of the final target product.

Next, a light emitting device containing the compound represented by the general formula (I) of the present invention will be described. The method for forming the organic layer of the light emitting device containing the compound of the general formula (I) of the present invention is not particularly limited.
Methods such as electron beam, sputtering, molecular lamination, coating, inkjet, printing, and transfer are used, and resistance heating evaporation and coating are preferred in view of device characteristics, emission luminance, durability, and manufacturing aspects. .

The light-emitting device of the present invention is a device in which a light-emitting layer or a plurality of organic compound films including the light-emitting layer is formed between a pair of anode and cathode electrodes.
It may have a hole transport 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, and the like, 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 thereof include conductive metal oxides such as tin oxide, zinc oxide, indium oxide, and indium tin oxide (ITO), and metals such as gold, silver, chromium, and nickel, and furthermore, these metals and conductive metal oxides. Or a laminate, copper iodide, an inorganic conductive substance such as copper iodide, an organic conductive material such as polyaniline, polythiophene, and polypyrrole, and a laminate of these with ITO, and the like. Metal oxides, especially from the viewpoints of productivity, high conductivity, transparency, etc.
TO is preferred. 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, an alkali-free 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 the thickness 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 to produce the anode depending on the material.
In the case of O, a film is formed by a method such as an electron beam method, a sputtering method, a resistance heating evaporation method, a chemical reaction method (such as a sol-gel method), and the application of an ITO dispersion. The anode can be washed or otherwise treated to lower the driving voltage of the device or increase the luminous efficiency. For example, in the case of ITO, UV
-Ozone treatment, plasma treatment, etc. are effective.

The cathode supplies electrons to the electron injection layer, the electron transport layer, the light emitting layer and the like. The cathode has good adhesion, ionization potential, and the like between the cathode and the adjacent layers such as the electron injection layer, the electron transport 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. Specific examples thereof include alkali metals (for example, Li, Na, K, and Cs).
Or its fluoride, its oxide, alkaline earth metal (eg, Mg, Ca, etc.) or its fluoride, its oxide, gold, silver, lead, aluminum, sodium-potassium alloy, or a mixed metal thereof, Lithium-aluminum alloy, or a mixed metal thereof, a magnesium-silver alloy, or a mixed metal thereof, indium, rare earth metals such as ytterbium, and the like, preferably a material having a work function of 4 eV or less, more preferably aluminum, A lithium-aluminum alloy, a mixed metal thereof, a magnesium-silver alloy, a mixed metal thereof, or the like is used. 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.
Furthermore, it is possible to form an alloy electrode 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 contains at least one compound represented by the general formula (I) of the present invention, and the compound represented by the general formula (I) of the present invention may be used in combination of two or more. good. Further, another light emitting material of the compound represented by the general formula (I) of the present invention may be used in combination, and holes can be injected from an anode, a hole injection layer, or a hole transport layer when an electric field is applied. In addition, a layer having a function of injecting electrons from the cathode or the electron injection layer, the electron transport layer, a function of transferring injected charges, and a function of providing a field of recombination of holes and electrons and emitting light. Anything that can be formed may be used. The compound used for the light-emitting layer may be any of those emitting light from an excited singlet and those emitting light from an excited triplet.For example, in addition to the compound of the present invention, benzoxazole, benzimidazole, benzothiazole, styrylbenzene, polyphenyl, diphenyl Butadiene, tetraphenylbutadiene, naphthalimide, coumarin, perylene, perinone, oxadiazole, aldazine, pyrazine, cyclopentadiene, bisstyrylanthracene, quinacridone, pyrrolopyridine, thiadiazolopyridine, styrylamine, aromatic dimethylidin compound, 8- Metal complexes of quinolinol, various metal complexes typified by organometallic complexes and rare earth complexes, the above derivatives, and polymer compounds such as polythiophene, polyphenylene, and polyphenylenevinylene It is below. Although the thickness of the light emitting layer is not particularly limited, it is usually 1 nm.
~ 5 μm, more preferably 5n
m to 1 μm, more preferably 10 nm to 500 n
m.

The method for forming the light emitting layer is not particularly limited, but includes resistance heating evaporation, electron beam, sputtering, molecular lamination, coating (spin coating, casting, dipping, etc.), LB, and ink jet. A method such as a printing method, a printing method, and a transfer method is used, and a resistance heating evaporation method and a coating method are preferable. When a light emitting material is dissolved and applied to form a light emitting layer, the dissolving and applying operation is preferably performed under light shielding.

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 is fine. Specific examples thereof include carbazole, imidazole, triazole, oxazole, oxadiazole, polyarylalkane, pyrazoline, pyrazolone, phenylenediamine, arylamine, amino-substituted chalcone, styryl anthracene, fluorenone, hydrazone, stilbene, silazane, and aromatic Tertiary amine compounds, styrylamines, aromatic dimethylidin compounds, porphyrin compounds, polysilane compounds,
Examples include poly (N-vinylcarbazole), aniline-based copolymers, thiophene oligomers and polymers, conductive polymer oligomers and polymers such as polythiophene, carbon films, and the above derivatives. The thickness of the hole injection layer and the hole transport layer is not particularly limited by the material, 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. It is. 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. As a method for forming the hole injection layer and the hole transport layer, a vacuum evaporation method, an LB method, an ink jet method, a printing method, a transfer method, and a method in which the hole injection material and the hole transport material are dissolved or dispersed in a solvent. Coating methods (spin coating, casting, dip coating, etc.) are 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, polyvinyl chloride, polycarbonate,
Polystyrene, polymethyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, poly (N-vinylcarbazole), hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane,
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 has one of a function of injecting electrons from the cathode, a function of transporting electrons, and a function of blocking holes injected from the anode. I just want it. Specific examples thereof include aromatic rings such as triazole, triazine, oxazole, oxadiazole, fluorenone, anthraquinodimethane, anthrone, diphenylquinone, thiopyrandioxide, carbodiimide, fluorenylidenemethane, distyrylpyrazine, and naphthaleneperylene. Examples include metal complexes of tetracarboxylic anhydrides, phthalocyanines, and 8-quinolinol derivatives, metal phthalocyanines, various metal complexes represented by metal complexes having benzoxazole or benzothiazole as ligands, and the above derivatives. The thickness of the electron injecting layer and the electron transporting 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 1 μm.
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-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 electron injection layer and the electron transport layer include a vacuum deposition method, an LB method, an ink jet method, a printing method, a transfer method, and a method of coating by dissolving or dispersing the electron injection material and the electron transport material in a solvent ( Spin coating, casting, dip coating, etc.) are 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 for 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 which promotes element deterioration such as moisture or 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,
Metal oxides such as TiO _2, SiN, a metal nitride such as _{SiNxOy, MgF 2, LiF, AlF} 3, metal fluorides such as CaF _2, polyethylene, polypropylene, polymethyl methacrylate, polyimide, polyurea, polytetrafluoroethylene, Polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer of chlorotrifluoroethylene and dichlorodifluoroethylene, copolymer obtained by copolymerizing a monomer mixture containing tetrafluoroethylene and at least one comonomer, copolymerization Examples include a fluorine-containing copolymer having a cyclic structure in the main chain, a water-absorbing substance having a water absorption of 1% or more, and a moisture-proof substance having a water absorption of 0.1% or less. There is no particular limitation on the method for forming the protective layer. For example, a chemical vapor deposition method (CVD)
Method), vacuum deposition method, sputtering method, reactive sputtering method, MBE (molecular beam epitaxy) method, cluster ion beam method, ion plating method, plasma polymerization method (high frequency excitation ion plating method), plasma CVD method, laser A CVD method, a thermal CVD method, a gas source CVD method, a coating method, an inkjet method, a printing method, and a transfer method can be applied.

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EXAMPLES Examples and comparative examples of the present invention will be described below by way of example, but the present invention is not limited to these examples.

Example 1 (Preparation of mixed sample of s-trans form and its isomer)
In the present invention, the content of the s-trans form was determined by high performance liquid chromatography (HPLC) as described below. Under light-shielding, 0.1 m was obtained by dissolving 1.0 g of the present compound (D-14) in 25 ml of tetrahydrofuran.
One sample was taken and further diluted 100-fold. Take 10 μl of this and perform high performance liquid chromatography (column: W
akosil-II5C18RS 4.6 × 150 mm,
Eluent THF / H ₂ O = 50/50 (volume ratio; 0.1%
Acetic acid, containing 0.1% triethylamine), flow rate 1 ml /
At a detection wavelength of 254 nm) and analyzed. As a result, the s-trans form of the compound of the present invention (N
^{MR, Cosy, Roesy, 1 H-} 13 C two-dimensional NMR
Was confirmed (peak area% = 100%). Next, a solution prepared by dissolving 1.0 g of the compound of the present invention (D-14) in 25 ml of tetrahydrofuran was allowed to stand in a light room all day and night, sampled in the same manner as described above, and analyzed by high performance liquid chromatography. -Immediately before the trans-form, generation of an isomer (area% = 10%) was confirmed at a retention time of 9.8 minutes (LC-MS has the same molecular weight as the s-trans-form, and NMR indicates a high magnetic field shift of vinyl protons from NMR) It was confirmed. The sample aged in a bright room was concentrated to dryness to prepare a sample (THF: H ₂ O = 50: 50 (volume ratio) solution) in which the isomer was mixed with the s-trans form. FIG. 1 shows the absorption spectrum (solute concentration: arbitrary) of a mixed sample of the s-trans form (solid line) and its isomer (broken line).
Is shown. For the isomer, a large side absorption was observed on the low wavelength side.

Example 2 (Evaluation of Device Performance) A transparent support substrate was prepared by forming a film of ITO to a thickness of 150 nm on a glass substrate of 25 mm × 25 mm × 0.7 mm (manufactured by Tokyo Sanyo Vacuum Co., Ltd.). . After etching and washing this transparent support substrate, put it in a vapor deposition device,
TPD (N, N'-diphenyl-N, N'-di (m-tolyl) -benzidine) was deposited to a thickness of 40 nm, and the compound of the present invention (D-14; s-trans-form in Example 1: contained thereon) Rate 100% (HPLC assay)) and Alq (tris (8-hydroxyquinolinato) aluminum) were co-deposited at a deposition rate of 0.004 nm / sec and 0.4 nm / sec, respectively, so that the film thickness became 40 nm. As the third layer, the electron transporting material (E-1) was deposited alone in a vacuum of 10 ⁻³ to 10 ⁻⁴ Pa at a substrate temperature of room temperature so as to have a thickness of 20 nm. Further, a mask (emission area becomes 4 mm × 5 mm) patterned on the organic thin film is mounted, and lithium fluoride is vapor-deposited to a thickness of 5 nm.
0 nm was vapor-deposited, and the element was subsequently sealed to produce an EL element (Element No. 101).

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Embodiment 3 After etching and cleaning the ITO substrate in the same manner as in Embodiment 2,
After depositing PD to a thickness of 40 nm, a mixed sample of the s-trans isomer and its isomer prepared in Example 1 and Alq
(Tris (8-hydroxyquinolinato) aluminum)
At a deposition rate of 0.004 nm / sec and 0.4 nm /
Co-evaporation so that the film thickness becomes 40 nm in seconds, and further, as the third layer, the electron transporting material (E-1) alone is evaporated to a thickness of 20 nm, and then the cathode is evaporated in the same manner as in Example 2. After sealing, an EL element was manufactured (element No. 10).
2). Furthermore, samples having different contents of the s-trans isomer of the compound were prepared, and similar devices were prepared (device Nos. 103 and 104).

Embodiment 4 After etching and cleaning the ITO substrate in the same manner as in Embodiment 2,
After evaporating PD to a thickness of 40 nm, the compounds shown in Table 1 (D-1)
6, D-52) and Alq (tris (8-hydroxyquinolinato) aluminum) were each deposited at a deposition rate of 0.00
Co-deposition at 4 nm / sec and 0.4 nm / sec so that the film thickness becomes 40 nm, and further as an electron transporting material (E
-1) was vapor-deposited alone by 20 nm, and then a cathode was vapor-deposited in the same manner as in Example 2, followed by sealing the element to produce an EL element (element Nos. 105 and 106).

(Method of Measuring Device Characteristics) Each device was evaluated as follows. Using Toyo Technica's Source Measure Unit 2400, apply a DC constant current to the EL element,
The devices of the comparative example and the present invention were made to emit light, and the luminance was measured using a luminance meter BM-8 manufactured by Topcon Corporation, the emission wavelength, and the CIE chromaticity coordinates were measured using a spectrum analyzer PM manufactured by Hamamatsu Photonics.
It measured using A-11. In addition, the element was set to have an initial
The device was driven at a constant current of 00 cd / m ² for 12 hours, and the luminance maintenance ratio ((luminance after driving / initial luminance) × 100 (%)) was measured. Table 1 shows the results.

[0073]

[Table 1]

As is clear from the results shown in Table 1, the device of the present invention is excellent in red purity and also excellent in durability (luminance maintenance ratio).

[0075]

According to the present invention, by defining the content of the S-trans isomer, a light emitting device excellent in red purity and durability with little variation in performance due to the difference in the synthesis lot of the compound can be obtained.

[Brief description of the drawings]

FIG. 1 Spectral absorption spectrum

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Teruichi Yanagi 210 Nakanakanuma, Minamiashigara, Kanagawa Prefecture Inside Fuji Photo Film Co., Ltd. (Reference) 3K007 AB04 EB00

Claims (5)

[Claims] 1. A method according to claim 1, wherein at least one compound represented by the following general formula (I) is contained between a pair of electrodes provided on the substrate,
Compounds in which the configuration of an alkenylene group, an imino group, or a diazo group substituted on a pyran ring or an analog thereof among the stereoisomers of the compound is s-trans to the double bond of the pyran ring or the analog thereof. A light-emitting element comprising, as a main component. General formula (I) In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent a hydrogen atom or a substituent. X is an oxygen atom, a sulfur atom, N
Represents -R ^Y1, R ^Y1 represents a hydrogen atom or a substituent. L
₁₁ and L ₁₂ may be the same or different from each other, each represents a methine group, a substituted methine group or a nitrogen atom. n
Represents an integer of 1 to 3. Ar represents an arylene group or a divalent aromatic heterocyclic group. R ^x and R ^y each represent a hydrogen atom or a substituent, and at least one of them represents an electron-withdrawing group. Further, the compound represented by the general formula (I) may form a metal complex. 2. Among the stereoisomers of the compound of the formula (I), the configuration of an alkenylene group substituted on a pyran ring or an analog thereof is s- with respect to the double bond of the pyran ring or the analog thereof. The light emitting device according to claim 1, wherein the compound is a compound represented by the following general formula (II), which is trans. General formula (II) In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent a hydrogen atom or a substituent. X is an oxygen atom, a sulfur atom, N
Represents -R ^Y1, R ^Y1 represents a hydrogen atom or a substituent. R
²¹ and R ²² each represent a hydrogen atom or a substituent. Ar represents an arylene group or a divalent aromatic heterocyclic group. R ^x and R ^y each represent a hydrogen atom or a substituent, and at least one of them represents an electron-withdrawing group. 3. The light emitting device according to claim 2, wherein the compound of the general formula (II) is a compound represented by the following general formula (III). General formula (III) In the formula, R ¹ , R ² , R ³ , R ⁴ and R ⁵ each represent a hydrogen atom or a substituent. Z ² represents an atom group necessary for forming a 5- or 6-membered ring. X is an oxygen atom, a sulfur atom,
Represents N—R ^Y1 , wherein R ^Y1 represents a hydrogen atom or a substituent.
R ²¹ and R ²² each represent a hydrogen atom or a substituent. Ar represents an arylene group or a divalent aromatic heterocyclic group. 4. A compound represented by the general formula (III):
4. The compound represented by V)
The light-emitting device according to item 1. General formula (IV) In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ³¹ , R ³² , R ³³ and R ³⁴ each represent a hydrogen atom or a substituent. Z
³ represents an atom group necessary for forming a 5- or 6-membered ring.
R ²¹ and R ²² each represent a hydrogen atom or a substituent. 5. The light-emitting device according to claim 1, wherein, among the stereoisomers of the compound, the configuration of an alkenylene group, an imino group, or a diazo group substituted on a pyran ring and an analog thereof is a pyran ring and The abundance ratio of s-trans to the double bond of the analog is 99% based on the sum of all isomers of the compound.
A light-emitting element characterized by the above.