CN102442939A

CN102442939A - Electronic transmission material with pyridylphenyl substituted anthracene compound, organic electroluminescence element, display device and illuminating device

Info

Publication number: CN102442939A
Application number: CN2011102730698A
Authority: CN
Inventors: 小野洋平
Original assignee: JNC Corp
Current assignee: JNC Corp
Priority date: 2010-09-16
Filing date: 2011-09-15
Publication date: 2012-05-09
Also published as: JP2012094823A; TW201213306A; KR20120029343A

Abstract

The present invention provides an electronic transmission material with pyridylphenyl substituted anthracene compound, an organic electroluminescence element, a display device and an illuminating device. The anthracene compound with pyridylphenyl is used the electronic transmission material for preparing the organic electroluminescence element which has the following advantages: long service life, and excellent driving voltage.

Description

Use replaces electron transport material, organic electroluminescent device, display unit and the means of illumination of anthracene compound through the pyridyl phenyl

Technical field

The present invention relates to a kind of through the substituted anthracene compound of pyridyl phenyl; More detailed; The present invention relates to a kind of 9; Two (4-(pyridin-4-yl) phenyl) anthracene compounds or 9 of 10-, two (3-(pyridin-4-yl) phenyl) anthracene compounds of 10-and the organic electroluminescent device, display unit and the means of illumination that use it.

Background technology

Before, use the display unit of carrying out electroluminescent luminous element to obtain various researchs, and then the organic electroluminescent device that comprises organic materials obtain positive research because of realizing lightweight or maximization easily because of realizing little electrification or slimming.Especially; Up to now; About having exploitation with the organic materials of the characteristics of luminescence headed by the blueness of one of three primary colors of light; And possess the exploitation of organic materials of the charge transport ability (might become semi-conductor or supraconductor) of electric hole, electronics etc., no matter macromolecular compound, low molecular compound all obtain positive research.

For example, report that the synthesis method that has intramolecularly to have the compound of pyridyl phenyl structure maybe is used for this compound the organic electroluminescent device (Japanese Patent Laid is opened 2003-282270 communique (patent documentation 1)) of organic compound layer.In the patent documentation 1, report has the compound that intramolecularly is had a pyridyl phenyl structure especially as the organic electroluminescent device of electron transport material.In addition, also report has the organic electroluminescent device (Japanese Patent Laid is opened 2009-173642 communique (patent documentation 2)) that is substituted with the compound of pyridyl phenyl on the center framework that uses anthracene.

[patent documentation 1] Japanese Patent Laid is opened the 2003-282270 communique

[patent documentation 2] Japanese Patent Laid is opened the 2009-173642 communique

Summary of the invention

Invent problem to be solved

As stated; The known electron transport material that has several kinds of intramolecularly to have the compound of pyridyl phenyl structure; But these material known to regard to the viewpoint of the long lifetime of the desired luminous element of electron transport material (material of electron transfer layer or electron injecting layer), do not have sufficient characteristic with regard to generally.Under this kind situation, a kind of electron transport material that improves the component life of luminous element of expectation exploitation.Especially, blue luminous element is the acquired character electron transport material more excellent than red or green luminous element not as yet, and a kind of electron transport material that is suitable for the long lifetime of blue luminous element of expectation exploitation.

In order to solve the means of problem

The inventor etc. are artificial to solve said problem and the result that makes great efforts to study; Discovery is set to possess and contains by the organic electroluminescent device of the represented compound of formula (1) as the organic layer of electron transport material; Can obtain the excellent especially organic electroluminescent device of life characteristic of element thus, thereby accomplish the present invention.

[1] a kind of electron transport material, it contains by the represented compound of formula (1):

[changing 4]

In the formula (1); Ar is that carbon number is 10～24 aryl; This aryl can be that 1～12 alkyl, carbon number are that 3～12 naphthenic base or carbon number are that 6～20 aryl replaces by carbon number; 4-pyridyl and

phenyl

3 or 4 all link, and in addition, can be replaced by deuterium by at least one hydrogen in the represented compound of formula (1).

[2] a kind of electron transport material, it contains by the represented compound of formula (1-1):

[changing 5]

In the formula (1-1), Ar is that carbon number is 10～24 aryl, and this aryl can be that 1～12 alkyl, carbon number are that 3～12 naphthenic base or carbon number are that 6～20 aryl replaces by carbon number, in addition, can be replaced by deuterium by at least one hydrogen in the represented compound of formula (1-1).

[3] a kind of electron transport material, it contains by the represented compound of formula (1-2):

[changing 6]

In the formula (1-2), Ar is that carbon number is 10～24 aryl, and this aryl can be that 1～12 alkyl, carbon number are that 3～12 naphthenic base or carbon number are that 6～20 aryl replaces by carbon number, in addition, can be replaced by deuterium by at least one hydrogen in the represented compound of formula (1-2).

[4] according to each described electron transport material in said [1] to [3], wherein Ar is xenyl, terphenylyl or naphthyl, and this naphthyl can be replaced by phenyl.

[5] according to each described electron transport material in said [1] to [3], wherein Ar be 3-xenyl, 4-xenyl, meta-terphenyl-5 '-Ji, 1-naphthyl or 2-naphthyl.

[6] a kind of organic electroluminescent device; It comprises: the pair of electrodes that comprises anode and negative electrode; Be configured in this pair of electrical interpolar luminescent layer, and be configured between said negative electrode and this luminescent layer and contain the electron transfer layer and/or the electron injecting layer of each described electron transport material in good grounds said [1] to [5].

[7] according to said [6] described organic electroluminescent device, one deck at least of wherein said electron transfer layer and electron injecting layer comprises also that to be selected from by hydroxyquinoline be at least a in the cohort formed of metal misfit thing, dipyridyl derivatives, phenanthroline derivative, borane derivative and benzimidizole derivatives.

[8] according to said [6] or [7] described organic electroluminescent device, one deck at least of wherein said electron transfer layer and electron injecting layer also comprises and is selected from least a in the cohort of being made up of organic misfit thing of organic misfit thing of the oxide compound of basic metal, earth alkali metal, rare earth metal, alkali-metal oxide compound, alkali-metal halogenide, earth alkali metal, the halogenide of earth alkali metal, the oxide compound of rare earth metal, the halogenide of rare earth metal, alkali-metal organic misfit thing, earth alkali metal and rare earth metal.

[9] a kind of display unit, it possesses each described organic electroluminescent device in said [6] to [8].

[10] a kind of means of illumination, it possesses each described organic electroluminescent device in said [6] to [8].

The effect of invention

According to preferred form of the present invention, can obtain to drive long especially organic electroluminescent device of life-span.In addition, preferred electron transport material of the present invention is particularly suitable for blue luminous element, according to this electron transport material, can make the luminous element of the blueness of the component life be equal to redness or green luminous element.And then, through using this organic electroluminescent device, can obtain the high performance display equipment of full-color demonstration etc.

Description of drawings

Fig. 1 is the summary section of the organic electroluminescent device of this example of expression.

[explanation of symbol]

100: organic electroluminescent device

101: substrate

102: anode

103: electric hole input horizon

104: electric hole transport layer

105: luminescent layer

106: electron transfer layer

107: electron injecting layer

108: negative electrode

Embodiment

1. by general formula (1), formula (1-1) and the represented compound of formula (1-2)

Below; To by general formula (1-1) represented 9; Two (4-(pyridin-4-yl) phenyl) anthracene compounds of 10-, and by general formula (1-2) represented 9; Two (3-(pyridin-4-yl) phenyl) anthracene compounds of 10-be elaborated (moreover, be to make the structure of formula (1-1) and formula (1-2) merge the epigyny that forms) by the represented structure of general formula (1).Compound of the present invention be especially make " 4-(pyridin-4-yl) phenyl " or " 3-(pyridin-4-yl) phenyl " in the pyridyl phenyl be substituted in 9 of the anthracene structure with 10; And especially make " volume is greater than the aryl of phenyl " in the aryl be substituted in 2 compound of anthracene structure; And be through selecting this kind substituting group; (Electroluminescence EL) reaches the more compound of the component life of excellence under the situation of element being used for organic electroluminescent.

Ar in formula (1-1) or the formula (1-2) is that carbon number is 10～24 aryl; This aryl can be that 1～12 alkyl, carbon number are that 3～12 naphthenic base or carbon number are that 6～20 aryl replaces by carbon number; In addition, can replace by deuterium by at least one hydrogen in the represented compound of formula (1-1) or formula (1-2).

As Ar " carbon number is 10～24 aryl " preferred carbon number is 12～24 aryl, and special preferred carbon number is 18～24 aryl.

As the concrete example of " carbon number is 10～24 aryl ", can enumerate: as the second cycle line aryl (4-) xenyl is as (the 1-of condensation second cycle line aryl for 2-, 3-; 2-) naphthyl is as the terphenylyl of three ring system aryl (meta-terphenyl-2 '-Ji, meta-terphenyl-4 '-Ji, meta-terphenyl-5 '-Ji, ortho-terphenyl-3 '-Ji, ortho-terphenyl-4 '-Ji, p-terphenyl-2 '-Ji, meta-terphenyl-2-base, meta-terphenyl-3-base, meta-terphenyl-4-base, ortho-terphenyl-2-base, ortho-terphenyl-3-base, ortho-terphenyl-4-base, p-terphenyl-2-base, p-terphenyl-3-base, p-terphenyl-4-yl), as anthracene-(1-, 2-, 9-) basic, the acenaphthene-(1-of condensation three ring system aryl; 3-, 4-, 5-) base, fluorenes-(1-, 2-, 3-; 4-, 9-) Ji 、 Fu-(1-, 2-) base, (1-, 2-; 3-, 4-, 9-) phenanthryl is the triphenylene-(1-of aryl as the condensation Fourth Ring; 2-) base, pyrene-(1-, 2-, 4-) base, tetracene-(1-, 2-; 5-) base is aryl De perylene-(1-, 2-, 3-) base etc. as the condensation five rings.

Preferably " carbon number is 10～24 aryl " is xenyl, terphenylyl or naphthyl, more preferably meta-terphenyl-5 '-Ji or 1-naphthyl.

Can be any of straight chain and side chain as substituent " carbon number is 1～12 alkyl " of Ar.That is, carbon number is that 1～12 straight chained alkyl or carbon number are 3～12 branched-chain alkyl.More preferably carbon number is 1～6 alkyl (carbon number is 3～6 branched-chain alkyl), and then more preferably carbon number is 1～4 alkyl (carbon number is 3～4 branched-chain alkyl).As concrete example; Can enumerate methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec.-butyl, the tertiary butyl, n-pentyl, isopentyl, neo-pentyl, tert-pentyl, n-hexyl, 1-methyl amyl, 4-methyl-2-amyl group, 3; 3-dimethylbutyl or 2-ethyl-butyl etc.; Preferable methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec.-butyl or the tertiary butyl, more preferably methyl, ethyl or the tertiary butyl.

Concrete example as Ar substituent " carbon number is 3～12 naphthenic base " can be enumerated: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, methylcyclopentyl, suberyl, methylcyclohexyl, ring octyl group or Dimethylcyclohexyl etc.

As Ar substituent " carbon number is 6～20 aryl " preferred carbon number is 6～12 aryl, and special preferred carbon number is 6～10 aryl.As concrete example, except that phenyl, can enumerate the base of explaining in the concrete example of said " carbon number is 10～24 aryl ", preferred phenyl, (2-, 3-, 4-) xenyl, (1-, 2-) naphthyl etc., special preferred phenyl.

When Ar had substituting group, substituent quantity for example was maximum commutable quantity, preferred 1～3, and more preferably 1～2, and then more preferably 1.

As the Ar concrete example of (containing substituent structure), can enumerate following base.

[changing 7]

[changing 8]

[changing 9]

In addition, constitute by all or part of of the Wasserstoffatoms in the anthracene skeleton of the represented compound of general formula (1-1) and general formula (1-2) or Wasserstoffatoms in the pyridyl phenyl or the Wasserstoffatoms among the Ar and can be deuterium.Compound by the deuterated situation under, Wasserstoffatoms in the preferred pyridyl phenyl or the Wasserstoffatoms among the Ar are by deuterate.

As concrete example, for example can enumerate by following formula (1-1-1)～represented compound of formula (1-1-12) by the represented compound of said general formula (1-1).Among the following compound, preferably by following formula (1-1-2)～formula (1-1-4), formula (1-1-7) and the represented compound of formula (1-1-10).

[changing 10]

As concrete example, for example can enumerate by following formula (1-2-1)～represented compound of formula (1-2-12) by the represented compound of said general formula (1-2).Among the following compound, preferably by following formula (1-2-1), formula (1-2-2), formula (1-2-4), formula (1-2-7) and the represented compound of formula (1-2-10).

[changing 11]

2. by the method for manufacture of the represented compound of general formula (1-1) and general formula (1-2)

Secondly, the method for manufacture to compound of the present invention describes.Compound of the present invention is gone up basically and can be used known compound; And utilize known synthesis method; For example Suzuki coupling reaction (Suzuki Coupling Reaction) or root bank coupling reaction (Negishi Coupling Reaction) are (for example; On the books in " " metal catalytic cross-coupling reaction " second edition (brand-new revision expand the page volume) (Metal-Catalyzed Cross-Coupling Reactions-Second, Completely Revised and Enlarged Edition) " waits) synthesize.In addition, also can make up two reactions synthetic.Following illustration is synthesized the flow process by the represented compound of general formula (1-1) and general formula (1-2) through Suzuki coupling reaction or root bank coupling reaction.

When making compound of the present invention, can enumerate: (1) synthetic base that pyridyl (terminal group) and phenyl (intermediate base) key knot are formed, then with the method for this base key knot on 9,10 of anthracene; (2) make phenyl key knot on 9,10 of anthracene, then with the method for pyridine base key knot on this phenyl.In addition, in the key knot of phenyl in these methods and pyridyl or the key of anthracene and the phenyl knot, can use the coupling reaction of halogen functional group or trifluoro-methanyl sulfonate functional group and zinc chloride misfit thing or boric acid (boric acid ester) basically.

At first, to (1) the synthetic base that pyridyl (terminal group) and phenyl (intermediate base) key knot are formed, then the method for this base key knot on 9,10 of anthracene described.Moreover; Make phenyl key knot on 9,10 of anthracene about (2), then with the method for pyridine base key knot on this phenyl, as long as with reference to illustrated various coupling reactions in the method for (1); At first make phenyl key knot on 9,10 of anthracene, then pyridine base key knot is got final product on this phenyl.

< synthesizing of 4-(4-bromophenyl) pyridine or 4-(3-bromophenyl) pyridine >

At first, through the zinc chloride misfit thing of reactions formula (1) pyridine synthesis, secondly; Make the zinc chloride misfit thing and 1 of pyridine through reactions formula (2); 4-dibromobenzene or 1, the 3-dibromobenzene reacts, and can synthesize 4-(4-bromophenyl) pyridine or 4-(3-bromophenyl) pyridine thus.Moreover " ZnCl2TMEDA " in the reaction formula (1) is the Tetramethyl Ethylene Diamine misfit thing of zinc chloride.Here, illustration use the synthesis method of 4-bromopyridine as raw material, but also can be through using the 4-iodine pyridine, and synthetic 4-(4-bromophenyl) pyridine or 4-(3-bromophenyl) pyridine as raw material.In addition, use 1 here, 4-dibromobenzene or 1,3-dibromobenzene be as raw material, but also can synthesize through using 1-bromo-4-iodobenzene or 1-bromo-3-iodobenzene.In addition; Also can be through making 1; 4-dibromobenzene or 1, the coupling reaction that 3-dibromobenzene and 4-pyridine boric acid or 4-pyridine boric acid ester react replace reacting with the zinc chloride misfit thing of pyridine, and obtain 4-(4-bromophenyl) pyridine or 4-(3-bromophenyl) pyridine.

[changing 12]

Reaction formula (1)

Reaction formula (2)

In the said reaction formula (1), R representes straight chain or ramose alkyl, and preferred carbon number is that 1～4 straight chain or carbon number are branch's alkyl of 3～4.

< 2 by Ar substituted anthracene-9,10-hypoboric acid (or boric acid ester) synthetic >

At first, shown in following reaction formula (3), use suitable bromizating agent, obtain 2-(naphthalene-2-yl)-9 thus, the 10-dibromoanthracene 2 substituted anthracene brominations.As suitable bromizating agent, can enumerate bromine or N-bromination succimide (N-Bromo Succinimide, NBS) etc.Here, illustration 2 anthracenes by the 2-naphthyl substituted, but can and obtain to import 9 of various Ar, 10-dibromoanthracene be arranged through suitable change raw material.

[changing 13]

Reaction formula (3)

Moreover; About having the anthracene of substituting group (being the 2-naphthyl in the said reaction formula (3)) on 2; Through 2 by halogen or the substituted anthracene of fluoroform sulphonate and Suzuki coupling corresponding to the boric acid (or boric acid ester) of said substituent base, but have substituent anthracene on the Synthetic 2 position.In addition, as additive method, can enumerate and utilize 2 by halogen or the substituted anthracene of fluoroform sulphonate and root bank coupled synthesis method corresponding to the zinc misfit thing of said substituent base.And then; Also can enumerate utilize 2-anthracene boric acid (or boric acid ester) with by halogen or the substituted Suzuki coupled synthesis method of fluoroform sulphonate corresponding to said substituent base; And then, also can enumerate utilize 2-anthracene zinc misfit thing with by halogen or the substituted root bank coupled synthesis method of fluoroform sulphonate corresponding to said substituent base.

Secondly; Shown in following reaction formula (4), use organolithium reagent with 2-(naphthalene-2-yl)-9,10-dibromoanthracene lithiumation; Perhaps use magnesium or organomagnesium reagent to process Grignard reagent; React with trimethyl borate, triethyl borate or triisopropyl borate ester etc. then, but Synthetic 2-(naphthalene-2-yl) anthracene-9 thus, 10-hypoboric acid ester.And then, utilize reactions formula (5) with this 2-(naphthalene-2-yl) anthracene-9, the hydrolysis of 10-hypoboric acid ester, but Synthetic 2-(naphthalene-2-yl) anthracene-9 thus, 10-hypoboric acid.

[changing 14]

Reaction formula (4)

Reaction formula (5)

In the said reaction formula (4), R representes straight chain or ramose alkyl, and preferred carbon number is that 1～4 straight chain or carbon number are branch's alkyl of 3～4.

In addition, shown in following reaction formula (6), use organolithium reagent with 2-(naphthalene-2-yl)-9,10-dibromoanthracene lithiumation; Perhaps use magnesium or organomagnesium reagent to process Grignard reagent, then with two (tetramethyl ethylene ketone closes) two boron or 4,4; 5,5-tetramethyl--1,3; 2-dioxa borine reacts, and can synthesize other 2-(naphthalene-2-yl) anthracene-9 thus, 10-hypoboric acid ester.In addition, shown in following reaction formula (7), utilize palladium catalyst and alkali to make 2-(naphthalene-2-yl)-9,10-dibromoanthracene and two (tetramethyl ethylene ketone closes) two boron or 4; 4,5,5-tetramethyl--1,3; 2-dioxa borine carries out coupling reaction, can synthesize identical 2-(naphthalene-2-yl) anthracene-9 thus, 10-hypoboric acid ester.

[changing 15]

Reaction formula (6)

Reaction formula (7)

In the said reaction formula (6), R representes straight chain or ramose alkyl, and preferred carbon number is that 1～4 straight chain or carbon number are branch's alkyl of 3～4.

Moreover in said reaction formula (4), reaction formula (6) or reaction formula (7), even if use muriate, iodide or fluoroform sulphonate to replace like 2-(naphthalene-2-yl)-9, the bromide of 10-dibromoanthracene and so on also can likewise synthesize.

At last; Shown in following reaction formula (8); In the presence of palladium catalyst and alkali, make synthetic 2-(naphthalene-2-yl) anthracene-9 in this way, 10-hypoboric acid or 2-(naphthalene-2-yl) anthracene-9; The 4-of 10-hypoboric acid ester class and 2 times of moles (4-bromophenyl) pyridine or 4-(3-bromophenyl) pyridine react, and can synthesize compound of the present invention thus.

[changing 16]

Reaction formula (8)

In addition, shown in following reaction formula (9), in the presence of palladium catalyst and alkali, make boric acid or the borate ester and the 2-(naphthalene-2-yl)-9 of the pyridyl benzene of 2 times of moles, the 10-dibromoanthracene reacts, and can synthesize compound of the present invention thus.Moreover the boric acid of pyridyl benzene or borate ester can be synthetic by 4-(4-bromophenyl) pyridine or 4-(3-bromophenyl) pyridine through the method according to said reaction formula (4)～reaction formula (7).

[changing 17]

Reaction formula (9)

As the concrete example of employed palladium catalyst in the Suzuki coupling reaction, can enumerate tetrakis triphenylphosphine palladium (0): Pd (PPh ₃) ₄, two (triphenylphosphine) palladium chloride (II): PdCl ₂(PPh ₃) ₂, acid chloride (II): Pd (OAc) ₂, three (dibenzalacetones), two palladiums (0): Pd ₂(dba) ₃, three (dibenzalacetones), two palladiums (0) chloroform misfit thing: Pd ₂(dba) ₃CHCl ₃, or two (dibenzalacetone) palladium (0): Pd (dba) ₂

In addition, in order to promote reaction, also can in these palladium compounds, add phosphine compound sometimes.Concrete example as this phosphine compound; Can enumerate: three (tertiary butyl) phosphine, tricyclohexyl phosphine, 1-(N; The N-dimethylamino methyl)-2-(di-t-butyl phosphino-) ferrocene, 1-(N, N-dibutylamino methyl)-2-(di-t-butyl phosphino-) ferrocene, 1-(methoxymethyl)-2-(di-t-butyl phosphino-) ferrocene, 1,1 '-two (di-t-butyl phosphino-) ferrocene, 2; 2 '-two (di-t-butyl phosphino-s)-1; 1 '-dinaphthalene, 2-methoxyl group-2 '-(di-t-butyl phosphino-)-1,1 '-dinaphthalene or 2-dicyclohexyl phosphino--2 ', 6 '-dimethoxy-biphenyl.

As the concrete example of employed alkali in the reaction, can enumerate: yellow soda ash, salt of wormwood, cesium carbonate, sodium hydrogencarbonate, sodium hydroxide, Pottasium Hydroxide, hydrated barta, sodium ethylate, sodium tert-butoxide, sodium acetate, Tripotassium phosphate or Potassium monofluoride.

In addition, as the concrete example of employed solvent in the reaction, can enumerate: benzene,toluene,xylene, 1; 2; 4-Three methyl Benzene, N, dinethylformamide, THF, diethyl ether, t-butyl methyl ether, 1,4-dioxan, methyl alcohol, ethanol, cyclopentyl methyl ether or Virahol.These solvents can suit to select, and can use separately, also can be used as mixed solvent.

< 2 by Ar substituted anthracene-9,10-two zinc misfit things synthetic >

At first, shown in following reaction formula (10), use organolithium reagent with 2-(naphthalene-2-yl)-9,10-dibromoanthracene lithiumation perhaps uses magnesium or organomagnesium reagent to process Grignard reagent, then with zinc chloride or zinc chloride Tetramethyl Ethylene Diamine misfit thing (ZnCl ₂TMEDA) react, but Synthetic 2-(naphthalene-2-yl) anthracene-9 thus, 10-two zinc misfit things.

[changing 18]

Reaction formula (10)

In the said reaction formula (10), R representes straight chain or ramose alkyl, and preferred carbon number is that 1～4 straight chain or carbon number are branch's alkyl of 3～4.Moreover even if use muriate or iodide to replace like 2-(naphthalene-2-yl)-9, the bromide of 10-dibromoanthracene and so on also can likewise synthesize.In addition, about 2 methods that import other substituting groups (Ar), as illustrated in said Suzuki coupling reaction one hurdle to anthracene.

At last; Shown in following reaction formula (11), in the presence of the palladium catalyst, make synthetic 2-(naphthalene-2-yl) anthracene-9 in this way; 4-(4-bromophenyl) pyridine of 10-two zinc misfit things and 2 times of moles or 4-(3-bromophenyl) pyridine react, and can synthesize compound of the present invention thus.

[changing 19]

Reaction formula (11)

In addition; Shown in following reaction formula (12); In the presence of the palladium catalyst; Make 2-(naphthalene-2-yl)-9, the 10-dibromoanthracene with to react according to the method for said reaction formula (10) 4-pyridyl benzene zinc misfit thing by 4-(4-bromophenyl) pyridine or 2 times of moles of 4-(3-bromophenyl) pyridine institute's synthetic, can synthesize compound of the present invention thus.

[changing 20]

Reaction formula (12)

As the concrete example of employed palladium catalyst in the root bank coupling reaction, can enumerate tetrakis triphenylphosphine palladium (0): Pd (PPh ₃) ₄, two (triphenylphosphine) palladium chloride (II): PdCl ₂(PPh ₃) ₂, acid chloride (II): Pd (OAc) ₂, three (dibenzalacetones), two palladiums (0): Pd ₂(dba) ₃, three (dibenzalacetones), two palladiums (0) chloroform misfit thing: Pd ₂(dba) ₃CHCl ₃, two (dibenzalacetone) palladium (0): Pd (dba) ₂, two (tri-tert phosphino-) palladiums (0) or (1,1 '-two (diphenylphosphino) ferrocene) dichloro palladium (II).

In addition, as the concrete example of employed solvent in the reaction, can enumerate: benzene,toluene,xylene, 1, N, dinethylformamide, THF, diethyl ether, t-butyl methyl ether, cyclopentyl methyl ether or 1,4-dioxan.These solvents can suit to select, and can use separately, also can be used as mixed solvent.

In addition, compound of the present invention also comprises the Wasserstoffatoms of at least a portion by the substituted compound of deuterium, and this kind compound can pass through to use desired position by the deuterated raw material, and with said likewise synthetic.

3. organic electroluminescent device

Anthracene compound with pyridyl phenyl of the present invention for example can be used as the material of organic electroluminescent device.Below, be elaborated according to graphic organic electroluminescent device to this example.Fig. 1 is the summary section of the organic electroluminescent device of this example of expression.

< structure of organic electroluminescent device >

Organic electroluminescent device 100 shown in Figure 1 comprises: substrate 101, be arranged on anode 102 on the substrate 101, be arranged on electric hole input horizon 103 on the anode 102, be arranged on electric hole transport layer 104 on the electric hole input horizon 103, be arranged on luminescent layer 105 on the electric hole transport layer 104, be arranged on electron transfer layer 106 on the luminescent layer 105, be arranged on the electron injecting layer 107 on the electron transfer layer 106 and be arranged on the negative electrode 108 on the electron injecting layer 107.

Moreover; Organic electroluminescent device 100 also can make the formation of production order below for example forming mutually on the contrary, promptly comprises: substrate 101, be arranged on negative electrode 108 on the substrate 101, be arranged on electron injecting layer 107 on the negative electrode 108, be arranged on electron transfer layer 106 on the electron injecting layer 107, be arranged on luminescent layer 105 on the electron transfer layer 106, be arranged on electric hole transport layer 104 on the luminescent layer 105, be arranged on the electric hole input horizon 103 on the electric hole transport layer 104 and be arranged on the anode 102 on the electric hole input horizon 103.

Said each layer is not all to be indispensable layer; Minimum component unit is set at the formation that comprises anode 102, luminescent layer 105, electron transfer layer 106 and/or electron injecting layer 107 and negative electrode 108, and electric hole input horizon 103 and electric hole transport layer 104 are the layers that can be provided with arbitrarily.In addition, said each layer can be made up of simple layer respectively, also can be made up of multilayer.

Form as the layer that constitutes organic electroluminescent device; Except that the construction form of said " substrate/anode/electric hole input horizon/electric hole transport layer/luminescent layer/electron transfer layer/electron injecting layer/negative electrode ", also can be the construction form of " substrate/anode/electric hole transport layer/luminescent layer/electron transfer layer/electron injecting layer/negative electrode ", " substrate/anode/electric hole input horizon/luminescent layer/electron transfer layer/electron injecting layer/negative electrode ", " substrate/anode/electric hole input horizon/electric hole transport layer/luminescent layer/electron injecting layer/negative electrode ", " substrate/anode/electric hole input horizon/electric hole transport layer/luminescent layer/electron transfer layer/negative electrode ", " substrate/anode/luminescent layer/electron transfer layer/electron injecting layer/negative electrode ", " substrate/anode/electric hole transport layer/luminescent layer/electron injecting layer/negative electrode ", " substrate/anode/electric hole transport layer/luminescent layer/electron transfer layer/negative electrode ", " substrate/anode/electric hole input horizon/luminescent layer/electron injecting layer/negative electrode ", " substrate/anode/electric hole input horizon/luminescent layer/electron transfer layer/negative electrode ", " substrate/anode/luminescent layer/electron transfer layer/negative electrode ", " substrate/anode/luminescent layer/electron injecting layer/negative electrode ".

Substrate 101 is the supporters that become organic electroluminescent device 100, uses quartz, glass, metal, plastics etc. usually.Substrate 101 forms tabular, membranaceous or sheet according to purpose, for example can use sheet glass, metal sheet, tinsel, plastic film, plastic sheet etc.Wherein, the transparent plastic plate of preferred glass plate and polyester, Rohm tech inc, polycarbonate, polysulfones etc.If glass substrate then can use soda-lime glass or non-alkali glass etc., in addition, thickness is also so long as be enough to keep the thickness of physical strength to get final product, as long as therefore for example there is 0.2mm above.The higher limit of thickness for example is below the 2mm, below the preferred 1mm.About the material of glass, because of few more good more from the released ion of glass, so more preferably non-alkali glass, owing to applied SiO ₂Deng the soda-lime glass of protective coating also have commercially availablely, therefore can use this soda-lime glass.In addition,, also can fine and closely woven choke films such as silicon dioxide film be set, especially be used as under the situation of substrate 101, the choke film preferably is set at plastic plate, film or thin slice that gas barrier property is low in the one side at least of substrate 101 in order to improve gas barrier property.

< anode in the organic electroluminescent device >

Anode 102 is effects that performance is injected electric hole to luminescent layer 105.Moreover, when between anode 102 and luminescent layer 105, being provided with electric hole input horizon 103 and/or electric hole transport layer 104, inject electric hole via these course luminescent layers 105.

As the material that forms anode 102, can enumerate mineral compound and organic cpds.As mineral compound; For example can enumerate: metal (aluminium, gold and silver, nickel, palladium, chromium etc.), MOX (oxide compound of indium, the oxide compound of tin, indium-tin-oxide (Indium Tin Oxide; ITO), indium-zinc oxide (Indium Zinc Oxide, IZO) etc.), metal halide (cupric iodide etc.), cupric sulfide, carbon black, ito glass or nesa glass etc.As organic cpds, for example can enumerate: gather electric conductive polymers such as Polythiophenes such as (3 methyl thiophenes), polypyrrole, polyaniline etc.In addition, can be from using as suitable selection the anodic material of organic electroluminescent device.

Therefore and indefinite as long as the resistance of transparency electrode can be to the enough electric currents of the luminous supply of luminous element,, but with regard to the viewpoint of the consumes electric power of luminous element, comparatively ideal is low resistance.For example; If the ito substrate below 300 Ω/ then as element electrode performance function, but also can be supplied with the substrate about 10 Ω/ now; Therefore it is desirable to use for example 100 Ω/～5 Ω/, the low resistance article of preferred 50 Ω/～5 Ω/ especially.The thickness of ITO can cooperate resistance value and at random select, but situation about between 100nm～300nm, using usually is more.

< the electric hole input horizon in the organic electroluminescent device, electric hole transport layer >

Electricity hole input horizon 103 is that performance will be moved and the electric hole come is injected in the luminescent layer 105 efficiently or the layer of the effect in the electric hole transport layer 104 from anode 102.Electricity hole transport layer 104 is layers that performance will transfer to the effect of luminescent layer 105 efficiently from electric hole that anode 102 is injected or from the electric hole that anode 102 is injected via electric hole input horizon 103.Electricity hole input horizon 103 and electric hole transport layer 104 are injected electric hole one or more in addition lamination, mixing of transport material respectively, and the mixture that perhaps injects transport material and polymer binder by electric hole forms.In addition, also can come form layers to the inorganic salt that electric hole injection transport material adds like iron(ic)chloride (III) and so on.

Inject transmission property material as electric hole, must between the electrode that is supplied to electric field, inject transmission efficiently from anodal electricity hole, comparatively ideal is the electric hole that electric hole injection efficiency is high and transmission is efficiently injected.Therefore, preferred ionization potential little and hol mobility big so when excellent in stability, manufacturing and when use be difficult for producing the material of the impurity that becomes trap.

As the material that forms electric hole input horizon 103 and electric hole transport layer 104; The compound that can since previous, light conductive material, habitually practise as the charge transfer material in electric hole is used for the electric hole input horizon of p N-type semiconductorN, organic electroluminescent device and the material known of electric hole transport layer and selects to use material arbitrarily.The concrete example of these materials is carbazole derivative (N-phenyl carbazole, polyvinyl carbazole etc.), two (N-aryl carbazoles) or two carbazole derivative such as two (N-alkyl carbazoles), (main chain or side chain have the polymkeric substance, 1 of aromatic series tertiary amine base to triarylamine derivative, two (4-two-p-methylphenyl aminophenyl) hexanaphthenes of 1-, N, N '-phenylbenzene-N; N '-two (3-aminomethyl phenyl)-4,4 '-benzidine, N, N '-phenylbenzene-N; N '-dinaphthyl-4; 4 '-benzidine, N, N '-phenylbenzene-N, N '-two (3-aminomethyl phenyl)-4; 4 '-phenylbenzene-1; 1 '-diamines, N, N '-dinaphthyl-N, N '-phenylbenzene-4; 4 '-phenylbenzene-1; 1 ' diamines, 4,4 ', 4 " triphenylamine verivate, star burst shape sulfonamide derivatives etc. such as three (3-aminomethyl phenyl (phenyl) amino) triphenylamine), heterogeneous ring compound, polysilane etc. such as diphenyl ethylene derivatives, phthalocyanine derivates (no metal, copper phthalocyanine etc.), pyrazoline derivative, hydrazone based compound, benzofuran derivative or thiophene derivant, oxadiazoles verivate, derivatives of porphyrin.In the polymer system; Preferred side chain has said monomeric polycarbonate or styrene derivatives, polyvinyl carbazole and polysilane etc., but so long as the required film of making of formation luminous element can inject electric hole from anode; And then can transmit the compound in electric hole, then do not have special qualification.

In addition, strong because of its doping receives to influence this point also known for organic semi-conductor electroconductibility.This kind organic semiconductor substrate substance comprises good compound or the good compound of electronics acceptability of electronics supply property.For the electronics donor material of mixing, known have four cyano quinone bismethane (TCNQ) or 2,3,5; 6-tetrafluoro four cyano-1,4-benzoquinones bismethane stronger electronics receptors (for example, reference literature " M.Pfeiffer, A.Beyer; T.Fritz, K.Leo, Applied Physics communication (Appl.Phys.Lett.), 73 (22); 3202-3204 (1998) " and document " J.Blochwitz, M.Pheiffer, T.Fritz, K.Leo; Applied Physics communication (Appl.Phys.Lett.), 73 (6), 729-731 (1998) ") such as (F4TCNQ).They generate so-called electric hole through the electron migration process in the electronics supply type basic substance (electric hole transport materials).The conductivity of basic substance produces sizable variation according to the quantity and the rate of flow in electric hole.As the substrate substance with electric hole transport property, known have benzidine derivative (TPD etc.) for example or star burst shape sulfonamide derivatives (TDATA etc.), an or specific metal phthalocyanine (particularly zinc phthalocyanine ZnPc etc.) (Japanese Patent Laid is opened the 2005-167175 communique).

< luminescent layer in the organic electroluminescent device >

Luminescent layer 105 is through between the electrode that is supplied to electric field, makes the electric hole layer luminous with combining again from 108 injected electrons of negative electrode that injects from anode 102.As the material that forms luminescent layer 105; So long as luminous compound (luminance compound) gets final product with the combining again to excite of electronics by electric hole, preferably can form stable film shape and under solid state, show the compound of stronger luminous (fluorescence and/or phosphorescence) efficient.

Luminescent layer can be simple layer, also can comprise multilayer, and is formed by luminescent material (material of main part, dopant material) respectively.Material of main part and dopant material can be a kind of respectively, also can be multiple combinations.Dopant material can be included in the entire body material, also can be included in the part material of main part.As adulterating method, can form through common vapour deposition method with material of main part, also can mix back vapor deposition simultaneously in advance with material of main part.

The usage quantity of material of main part is according to the kind of material of main part and difference, as long as cooperate the characteristic of this material of main part to decide.The benchmark of the usage quantity of material of main part is preferably 50wt% (the weight percent)～99.999wt% of whole luminescent material, more preferably 80wt%～99.95wt%, and then more preferably 90wt%～99.9wt%.

The usage quantity of dopant material is according to the kind of dopant material and difference, as long as cooperate the characteristic of this dopant material to decide.The benchmark of the usage quantity of hotchpotch is preferably the 0.001wt%～50wt% of whole luminescent material, more preferably 0.05wt%～20wt%, and then more preferably 0.1wt%～10wt%.If said scope, then for example can prevent on the concentration quenching phenomenon this point preferred.

The luminescent material of the luminous element of this example can be fluorescence, also can be phosphorescent.

Material of main part does not have special qualification, can preferably use the condensed ring derivatives of previous anthracene known or pyrene etc. to be used as twinkler, with the polyphenylacetylene verivate in double styrene radical derivative, tetraphenylbutadiene verivate, coumarin derivatives, oxadiazoles verivate, Pyrrolopyridine derivatives, purple cyclic ketone derivative, cyclopentadiene derivant, thiadiazoles and pyridine derivate, Pyrrolopyrrole derivatives, fluorene derivatives, benzofluorene verivate, the polymer systems such as metal chelating combination oxine class (oxinoid) compound, bisstyryl anthracene derivant or diphenylethyllene benzene derivative headed by three (oxine) aluminium, gather benzene derivative and polythiofuran derivative.

In addition, as material of main part, can from chemical industry in June, 2004 numbers 13 pages, and wherein cited reference etc. in the compound put down in writing etc. suitable the selection use.

In addition, dopant material does not have special qualification, can use compound known, and can from various materials, select corresponding to desired illuminant colour.Particularly, for example can enumerate: phenanthrene, anthracene, pyrene, tetracene, pentacene 、 perylene, naphtho-pyrene, dibenzo pyrene, rubrene and 1, the condensed ring derivatives of 2-benzophenanthrene etc., benzoxazoles verivate, benzothiazole derivant; Benzimidizole derivatives, OR 10154, oxazole derivatives, oxadiazoles verivate; Thiazole derivative, imdazole derivatives, thiadiazoles derivative, triazole derivative; Pyrazoline derivative, diphenyl ethylene derivatives, thiophene derivant, tetraphenylbutadiene verivate; Cyclopentadiene derivant, double styrene radical derivatives (japanese patent laid-open 1-245087 communique) such as bisstyryl anthracene derivant or diphenylethyllene benzene derivative, bisstyryl arylene derivatives (japanese patent laid-open 2-247278 communique), diaza benzo two indene derivatives; Furan derivatives, benzofuran derivative, phenyl isobenzofuran, two (2,4; The 6-trimethylphenyl) isobenzofuran verivates such as isobenzofuran, two (2-aminomethyl phenyl) isobenzofuran, two (2-trifluoromethyl) isobenzofuran, phenyl isobenzofuran, diphenylene-oxide verivate, coumarin derivativess such as 7-dialkyl amido coumarin derivatives, 7-piperidyl coumarin derivatives, umbelliferone verivate, ayapanin verivate, 7-acetoxyl group coumarin derivatives, 3-benzothiazolyl coumarin derivatives, 3-benzimidazolyl-coumarin derivatives, 3-benzoxazolyl coumarin derivatives, dicyano methylene radical pyran derivate; Dicyano methylene radical thiapyran verivate, polymethine verivate, cyanine verivate, oxo benzanthrene verivate; The xanthene verivate, rhodamine verivate, fluorescein derivative, pyran derivate; Carbostyril derivative, acridine derivatives, oxazines verivate, oxidation crystalline 1,2-phenylene derivatives; Quinacridone derivative, quinazoline derivant, Pyrrolopyridine derivatives, furo pyridine derivate; 1,2,5-thiadiazoles and pyrene derivatives, pyrroles's methine verivate; Purple cyclic ketone derivative, Pyrrolopyrrole derivatives, salt derivative in side's acid, violanthrone verivate; The azophenlyene verivate, acridone derivatives, denitrogenation flavin derivatives, fluorene derivatives and benzofluorene verivate etc.

If carry out illustration, then, can enumerate: naphthalene, anthracene, phenanthrene, pyrene, triphenylene 、 perylene, fluorenes, indenes, 1 as blueness～blue-greenish colour dopant material by color development light; Aromatic hydrocarbon compound or derivatives thereofs such as 2-benzophenanthrene, furans, pyrroles, thiophene, thiophene are coughed up, 9-silicon fluorenes, 9,9 '-aromatic heterocyclic compounds or derivatives thereof such as spiral shell two silicon fluorenes, thionaphthene, cumarone, indoles, dibenzothiophene, diphenylene-oxide, imidazopyridine, phenanthroline, pyrazine, naphthyridines, quinoxaline, pyrrolopyridine, thioxanthene; The diphenylethyllene benzene derivative, tetraphenylbutadiene verivate, diphenyl ethylene derivatives; The aldazine verivate; Coumarin derivatives, oxazole derivatives and metal misfit things thereof such as imidazoles, thiazole, thiadiazoles, carbazole, oxazole, oxadiazoles, triazole, and with N; N '-phenylbenzene-N; N '-two (3-aminomethyl phenyl)-4,4 '-phenylbenzene-1,1 '-diamines is the aromatic amine derivative of representative etc.

In addition; As green～yellow dopant material; Can enumerate tetracene verivates such as coumarin derivatives, phthalimide derivative, Naphthalamide derivatives, purple cyclic ketone derivative, Pyrrolopyrrole derivatives, cyclopentadiene derivant, acridone derivatives, quinacridone derivative and rubrene etc.; And then, but also can enumerate to as said blueness～blue-greenish colour dopant material import compound that the substituting group of long wavelengthizations such as aryl, heteroaryl, aryl vinyl, amino, cyanic acid forms in the illustrative compound as preferable example.

And then, as orange～red-doped material, can enumerate two (Naphthalamide derivatives such as diisopropyl phenyl) perylene tetracarboxylic acid imide; Purple cyclic ketone derivative is with the rare earth misfit things such as Eu misfit thing as part such as methyl ethyl diketone or benzoyl acetone and phenanthroline etc., 4-(dicyano methylene radical)-2-methyl-6-(to the dimethylamino styryl)-4H-pyrans or its analogue; Metal phthalocyanine derivatives such as magnesium phthalocyanine, aluminium chlorine phthalocyanine, rhodamine compound, denitrogenation flavin derivatives; Coumarin derivatives, quinacridone derivative, Phenazoxine verivate; The oxazines verivate, quinazoline derivant, Pyrrolopyridine derivatives; Salt derivative in side's acid, violanthrone verivate, azophenlyene verivate; Phenazoxine ketone derivatives and thiadiazoles and pyrene derivatives etc., and then, but also can enumerate to as said blueness～blue-greenish colour and green～yellow dopant material import compound that the substituting group of long wavelengthizations such as aryl, heteroaryl, aryl vinyl, amino, cyanic acid forms in the illustrative compound as preferable example.And then, also can enumerate with three (2-phenylpyridine) iridium (III) be representative with iridium or platinum as the phosphorescent metal misfit thing of central metal as preferable example.

In addition, as hotchpotch, can from chemical industry in June, 2004 numbers 13 pages, and wherein cited reference etc. in the compound put down in writing etc. suitable the selection use.

Among the described dopant material, special You Xuan perylene verivate, borane derivative, the styryl derivative that contains amine, aromatic amine derivative, coumarin derivatives, pyran derivate, iridium misfit thing or platinum misfit thing.

Zuo Wei perylene verivate, for example can enumerate: 3,10-two (2,6-3,5-dimethylphenyl) perylene, 3,10-two (2; 4,6-trimethylphenyl) perylene, 3,10-Er Ben Ji perylene, 3,4-Er Ben Ji perylene, 2,5; 8,11-four-uncle Ding Ji perylene, 3,4,9,10-four benzene base perylenes, 3-(1 '-pyrenyl)-8; 11-two (tertiary butyl) perylene, 3-(9 '-anthryl)-8,11-two (tertiary butyl) perylene, 3,3 '-two (8,11-two (tertiary butyl) perylene base) etc.

In addition, also can use japanese patent laid-open 11-97178 communique, Japanese Patent Laid open 2000-133457 communique, Japanese Patent Laid open 2000-26324 communique, Japanese Patent Laid open 2001-267079 communique, Japanese Patent Laid open 2001-267078 communique, Japanese Patent Laid open 2001-267076 communique, Japanese Patent Laid open 2000-34234 communique, Japanese Patent Laid open the 2001-267075 communique, and Japanese Patent Laid open the De perylene verivate of putting down in writing in the 2001-217077 communique etc.

As borane derivative, for example can enumerate: 1,8-phenylbenzene-10-(two (2,4; The 6-trimethylphenyl) anthracene, 9-phenyl-10-(two (mesityl) boryl) anthracene, 4-(9 '-anthryl) two (2,4 boryl); The 6-trimethylphenyl) boryl naphthalene, 4-(10 '-phenyl-9 '-anthryl) two (mesityl) boryl naphthalene, 9-(two (2; 4,6-trimethylphenyl) anthracene, 9-(4 '-xenyl)-10-(two (2,4 boryl); The 6-trimethylphenyl) anthracene, 9-(4 '-(N-carbazyl) phenyl)-10-(two (mesityl) boryl) anthracene etc. boryl).

In addition, also can use the borane derivative of being put down in writing in International Publication the 2000/40586th trumpeter's volume etc.

As the styryl derivative that contains amine, for example can enumerate: N, N, N ', N '-four (4-xenyl)-4; 4 '-diaminobenzil, N, N, N ', N '-four (1-naphthyl)-4,4 '-diaminobenzil, N; N, N ', N '-four (2-naphthyl)-4,4 '-diaminobenzil, N; N '-two (2-naphthyl)-N, N '-phenylbenzene-4,4 '-diaminobenzil, N, N '-two (9-phenanthryl)-N; N '-phenylbenzene-4,4 '-diaminobenzil, 4,4 '-two [4 " two (diphenylamino) styryl]-biphenyl, 1,4-pair [4 '-two (diphenylamino) styryl]-benzene, 2; 7-pair [4 '-two (diphenylamino) styryl]-9,9-dimethyl fluorene, 4,4 '-two (9-ethyl-3-carbazole vinyl)-biphenyl, 4,4 '-two (9-phenyl-3-carbazole vinyl)-biphenyl etc.

In addition, also can use Japanese Patent Laid open the 2003-347056 communique, and Japanese Patent Laid open the styryl derivative of being put down in writing in the 2001-307884 communique etc. that contains amine.

As aromatic amine derivative; For example can enumerate: N; N, N, N-tetraphenyl anthracene-9; 10-diamines, 9; Two (4-diphenylamino-phenyl) anthracenes, 9 of 10-, two (4-two (1-naphthylamino) phenyl) anthracenes, 9 of 10-, two (4-two (2-naphthylamino) phenyl) anthracenes of 10-, 10-two-p-methylphenyl amino-9-(4-two-p-methylphenyl amino-1-naphthyl) anthracene, 10-diphenylamino-9-(4-diphenylamino-1-naphthyl) anthracene, 10-diphenylamino-9-(6-diphenylamino-2-naphthyl) anthracene, [4-(4-diphenylamino-phenyl) naphthalene-1-yl]-diphenylamine, [4-(4-diphenylamino-phenyl) naphthalene-1-yl]-diphenylamine, [6-(4-diphenylamino-phenyl) naphthalene-2-yl]-diphenylamine, 4; 4 '-two [4-diphenylamino naphthalene-1-yl] biphenyl, 4; 4 '-two [6-diphenylamino naphthalene-2-yl] biphenyl, 4,4 " two [4-diphenylamino naphthalene-1-yl]-p-terphenyl, 4,4 " two [6-diphenylamino naphthalene-2-yl]-p-terphenyl etc.

In addition, also can use Japanese Patent Laid to open the aromatic amine derivative of being put down in writing in 2006-156888 communique etc.

As coumarin derivatives, can enumerate tonka bean camphor-6, tonka bean camphor-334 etc.

In addition, also can use Japanese Patent Laid open 2004-43646 communique, Japanese Patent Laid open the 2001-76876 communique, and japanese patent laid-open 6-298758 communique etc. in the coumarin derivatives put down in writing.

As pyran derivate, can enumerate following DCM, DCJTB etc.

[changing 21]

In addition, also can use Japanese Patent Laid open 2005-126399 communique, Japanese Patent Laid open 2005-097283 communique, Japanese Patent Laid open 2002-234892 communique, Japanese Patent Laid open 2001-220577 communique, Japanese Patent Laid open the 2001-081090 communique, and Japanese Patent Laid open the pyran derivate of being put down in writing in the 2001-052869 communique etc.

As iridium misfit thing, can enumerate following Ir (ppy) 3 etc.

[changing 22]

In addition, also can use Japanese Patent Laid open 2006-089398 communique, Japanese Patent Laid open 2006-080419 communique, Japanese Patent Laid open 2005-298483 communique, Japanese Patent Laid open the 2005-097263 communique, and Japanese Patent Laid open the iridium misfit thing of being put down in writing in the 2004-111379 communique etc.

As platinum misfit thing, can enumerate following PtOEP etc.

[changing 23]

In addition, also can use Japanese Patent Laid open 2006-190718 communique, Japanese Patent Laid open 2006-128634 communique, Japanese Patent Laid open 2006-093542 communique, Japanese Patent Laid open the 2004-335122 communique, and Japanese Patent Laid open the platinum misfit thing of being put down in writing in the 2004-331508 communique etc.

< electron injecting layer in the organic electroluminescent device, electron transfer layer >

Electron injecting layer 107 be performance will from negative electrode 108 move and the electronic high-effective ground that comes is injected in the luminescent layer 105 or the effect in the electron transfer layer 106 layer.Electron transfer layer 106 is layers of bringing into play the effect that will transfer to luminescent layer 105 from 108 injected electrons of negative electrode or from negative electrode 108 via 107 injected electrons of electron injecting layer efficiently.With one or more lamination, mixing in addition of electric transmission injecting material, perhaps the mixture by electric transmission injecting material and polymer binder forms respectively for electron transfer layer 106 and electron injecting layer 107.

So-called electronics injects transport layer, is meant to administer from negative electrode to inject electronics, and then the layer of transmission electronic, comparatively ideally is the electron injection efficiency height and transmits institute's injected electrons efficiently.Therefore, preferred electron avidity is big and the electron migration rate big and then excellent in stability, is difficult for producing the material of the impurity that becomes trap during manufacturing and when using.But; Considering under the transmission equilibrated situation of electric hole and electronics; Main performance do not combine again and flows to time spent of doing of cathode side when can stop from anodic electricity hole efficiently; Even if electron transport ability is so not high, also can have the material identical luminous efficiency lifting effect high with electron transport ability.Therefore, the electronics in this example injects the function that transport layer also can comprise the layer that moves that can stop electric hole efficiently.

Material (electron transport material) as forming electron transfer layer 106 or electron injecting layer 107 can use by the represented compound of said general formula (1).In electron transfer layer 106 or the electron injecting layer 107 by the content of the represented compound of said general formula (1) according to the kind of compound and difference, as long as cooperate the characteristic of this compound to decide.Benchmark by the content of the represented compound of said general formula (1) is preferably the 1wt%～100wt% of whole electron transfer layer with material (or electron injecting layer is used material); More preferably 10wt%～100wt%; And then more preferably 50wt%～100wt%, special preferred 80wt%～100wt%.When separately (100wt%) do not use by the represented compound of said general formula (1), if below mixing with the other materials that details.

Form the material of electron transfer layer or electron injecting layer as other; The compound that can since previous, light conductive material, habitually practise as electron transport compound is used for the electron injecting layer of organic electroluminescent device and the known compound of electron transfer layer and at random selects to use.

As the material that is used for electron transfer layer or electron injecting layer; Preferably contain and be selected from least a in the following compound: comprise mainly the aromatic nucleus formed by more than one the atom that is selected from carbon, hydrogen, oxygen, sulphur, silicon and the phosphorus or the compound of assorted aromatic nucleus; Pyrrole derivative and condensed ring derivatives thereof, and metal misfit thing with electronics acceptability nitrogen.Particularly, can enumerate: the condensation ring system aromatic nucleus verivate of naphthalene, anthracene etc., with 4; 4 '-two (diphenylacetylene) biphenyl is the vinylbenzene base system aromatic nucleus verivate of representative, purple cyclic ketone derivative, coumarin derivatives; Naphthalamide derivatives; Quinone derivative such as anthraquinone or diphenoquinone, phosphorus oxide verivate, carbazole derivative and indole derivatives etc.As metal misfit thing, for example can enumerate: hydroxyl azoles misfit things such as phenylor oxazole misfit thing, azomethine misfit thing, tropolone metal misfit thing, flavonol metal misfit thing and benzoquinoline metal misfit thing etc. with electronics acceptability nitrogen.These materials can use separately, also can mix use with material different.Wherein, with regard to the viewpoint of weather resistance, preferably use 9, anthracene derivants such as two (2-naphthyl) anthracenes of 10-; 4,4 '-vinylbenzene base system aromatic nucleus verivates such as two (diphenylacetylene) biphenyl, 4; 4 '-two (N-carbazyl) biphenyl, 1,3, carbazole derivative such as 5-three (N-carbazyl) benzene.

In addition; Concrete example as other electron transport compounds; Can enumerate: pyridine derivate, naphthalene derivatives, anthracene derivant, phenanthroline derivative, purple cyclic ketone derivative, coumarin derivatives, Naphthalamide derivatives, anthraquinone derivative, diphenoquinone verivate, phenylbenzene quinone derivative 、 perylene verivate, oxadiazoles verivate (1; Two [(the 4-tert-butyl-phenyls) 1 of 3-; 3; 4-oxadiazoles base] phenylene etc.), thiophene derivant, triazole derivative (N-naphthyl-2; 5-phenylbenzene-1; 3,4-triazole etc.), thiadiazoles derivative, the metal misfit thing of oxine verivate, hydroxyquinoline be metal misfit thing, quinoxaline derivatives, quinoxaline derivatives polymkeric substance, benzazoles compound, gallium misfit thing, pyrazole derivatives, perfluorination crystalline 1,2-phenylene derivatives, pyrrolotriazine derivatives, pyrazines derivatives, benzoquinoline verivate (2,2 '-two (benzo [h] quinoline-2-yl)-9; 9 '-spiral shell two fluorenes etc.), imidazopyridine derivatives, borane derivative, benzimidizole derivatives (oligomerization pyridine derivate, dipyridyl derivatives, terpyridyl verivate (1 such as three (N-phenyl benzimidazolyl-2 radicals-yl) benzene etc.), benzoxazoles verivate, benzothiazole derivant, quinoline, terpyridyl; 3-two (4 '-(2,2 ': 6 ' 2 " the terpyridyl base)) benzene etc.), 7-naphthyridine derivatives (two (1-naphthyl)-4-(1,8-naphthyridines-2-yl) phenyl phosphine oxide etc.), aldazine verivate, carbazole derivative, indole derivatives, phosphorus oxide verivate, double styrene radical derivative etc.

In addition; Also can use the metal misfit thing with electronics acceptability nitrogen, for example can enumerate: hydroxyquinoline is hydroxyl azoles misfit things such as metal misfit thing or phenylor oxazole misfit thing, azomethine misfit thing, tropolone metal misfit thing, flavonol metal misfit thing and benzoquinoline metal misfit thing etc.

Said material can use separately, also can mix use with material different.

Among the said material, preferred hydroxyquinoline is metal misfit thing, dipyridyl derivatives, phenanthroline derivative or borane derivative.

Hydroxyquinoline is that metal misfit thing is by the represented compound of formula (E-1).

[changing 24]

In the formula, R ¹～R ⁶Be hydrogen or substituting group, M is Li, Al, Ga, Be or Zn, and n is 1～3 integer.

As hydroxyquinoline is the concrete example of metal misfit thing; Can enumerate: oxine lithium, three (oxine) aluminium, three (4-methyl-oxine) aluminium, three (5-methyl-oxine) aluminium, three (3; 4-dimethyl--oxine) aluminium, three (4; 5-dimethyl--oxine) aluminium, three (4; 6-dimethyl--oxine) aluminium, two (2-methyl-oxine) (phenol) aluminium, two (2-methyl-oxine) (2-methylphenol) aluminium, two (2-methyl-oxine) (3-methylphenol) aluminium, two (2-methyl-oxine) (4-methylphenol) aluminium, two (2-methyl-oxine) (2-phenylphenol) aluminium, two (2-methyl-oxine) (3-phenylphenol) aluminium, two (2-methyl-oxine) (4-phenylphenol) aluminium, two (2-methyl-oxine) (2; The 3-xylenol) aluminium, two (2-methyl-oxine) (2; The 6-xylenol) aluminium, two (2-methyl-oxine) (3; The 4-xylenol) aluminium, two (2-methyl-oxine) (3; The 5-xylenol) aluminium, two (2-methyl-oxines) (3,5-two-tert.-butyl phenol) aluminium, two (2-methyl-oxines) (2,6-phenylbenzene phenol) aluminium, two (2-methyl-oxine) (2; 4; 6-triphenyl phenol) aluminium, two (2-methyl-oxine) (2) aluminium, two (2-methyl-oxine) (2; 4; 5,6-tetramethyl phenol) aluminium, two (2-methyl-oxines) (1-how phenol) aluminium, two (2-methyl-oxines) (2-how phenol) aluminium, two (2,4-dimethyl--oxine) (2-phenylphenol) aluminium, two (2; 4-dimethyl--oxine) (3-phenylphenol) aluminium, two (2; 4-dimethyl--oxine) (4-phenylphenol) aluminium, two (2,4-dimethyl--oxine) (3, the 5-xylenol) aluminium, two (2; 4-dimethyl--oxine) (3; 5-two-tert.-butyl phenol) aluminium, two (2-methyl-oxine) aluminium-mu-oxo-two (2-methyl-oxine) aluminium, two (2,4-dimethyl--oxine) aluminium-mu-oxos-two (2,4-dimethyl--oxine) aluminium, two (2-methyl-4-ethyl-oxine) aluminium-mu-oxo-two (2-methyl-4-ethyl-oxine) aluminium, two (2-methyl-4-methoxyl group-oxine) aluminium-mu-oxo-two (2-methyl-4-methoxyl group-oxine) aluminium, two (2-methyl-5-cyanic acid-oxine) aluminium-mu-oxo-two (2-methyl-5-cyanic acid-oxine) aluminium, two (2-methyl-5-trifluoromethyl-oxine) aluminium-mu-oxo-two (2-methyl-5-trifluoromethyl-oxine) aluminium, two (10-hydroxy benzo [h] quinoline) beryllium etc.

Dipyridyl derivatives is by the represented compound of formula (E-2).

[changing 25]

In the formula, G representes to be merely the concatenating group of associative key or n valency, and n is 2～8 integer.In addition, the carbon atom that is not used in the key knot of pyridine-pyridine or pyridine-G can be substituted.

As the G of general formula (E-2), for example can enumerate following structural formula.Moreover the R in the following structural formula is independent respectively to be hydrogen, methyl, ethyl, sec.-propyl, cyclohexyl, phenyl, 1-naphthyl, 2-naphthyl, xenyl or terphenylyl.

[changing 26]

As the concrete example of pyridine derivate, can enumerate: 2,5-two (2,2 '-pyridine-6-yl)-1,1-dimethyl--3,4-phenylbenzene thiophene cough up, 2, and 5-pairs (2; 2 '-pyridine-6-yl)-1,1-dimethyl--3,4-two (mesityl) thiophene cough up, 2, and 5-two (2; 2 '-pyridine-5-yl)-1,1-dimethyl--3,4-phenylbenzene thiophene cough up, 2,5-two (2,2 '-pyridine-5-yl)-1,1-dimethyl--3; 4-two (mesityl) thiophene coughs up, 9,10-two (2,2 '-pyridine-6-yl) anthracene, 9,10-two (2; 2 '-pyridine-5-yl) anthracene, 9,10-two (2,3 '-pyridine-6-yl) anthracene, 9,10-two (2,3 '-pyridine-5-yl) anthracene, 9,10-two (2; 3 '-pyridine-6-yl)-2-phenylanthracene, 9,10-two (2,3 '-pyridine-5-yl)-2-phenylanthracene, 9,10-two (2,2 '-pyridine-6-yl)-2-phenylanthracene, 9,10-two (2; 2 '-pyridine-5-yl)-2-phenylanthracene, 9,10-two (2,4 '-pyridine-6-yl)-2-phenylanthracene, 9,10-two (2,4 '-pyridine-5-yl)-2-phenylanthracene, 9,10-two (3; 4 '-pyridine-6-yl)-2-phenylanthracene, 9,10-two (3,4 '-pyridine-5-yl)-2-phenylanthracene, 3,4-phenylbenzene-2,5-two (2,2 '-pyridine-6-yl) thiophene, 3; 4-phenylbenzene-2,5-two (2,3 '-pyridine-5-yl) thiophene, 6 ' 6 " two (2-pyridyl) 2,2 ': 4 ', 4 ": 2 ", 2 " '-the tetrad pyridine etc.

Phenanthroline derivative is by formula (E-3-1) or the represented compound of general formula (E-3-2).

[changing 27]

In the formula, R ¹～R ⁸Be hydrogen or substituting group, the base of adjacency key is each other tied and is formed condensed ring, and G representes to be merely the concatenating group of associative key or n valency, and n is 2～8 integer.In addition, as the G of general formula (E-3-2), for example can enumerate with dipyridyl derivatives one hurdle in illustrated G identical.

As the concrete example of phenanthroline derivative, can enumerate: 4,7-phenylbenzene-1,10-phenanthroline, 2,9-dimethyl--4,7-phenylbenzene-1; 10-phenanthroline, 9,10-two (1,10-phenanthroline-2-yl) anthracene, 2,6-two (1,10-phenanthroline-5-yl) pyridine, 1; 3,5-three (1,10-phenanthroline-5-yl) benzene, 9,9 '-two fluoro-two (1,10-phenanthroline-5-yl), 2; 9-dimethyl--4,7-biphenyl-1,10-phenanthrolene or 1, two (2-phenyl-1,10-phenanthroline-9-yl) benzene of 3-etc.

Especially, the situation that phenanthroline derivative is used for electron transfer layer, electron injecting layer is described.Long-time stable luminous in order to obtain; Expect the excellent material of a kind of thermostability or film formation property; Among the preferred phenanthroline derivative; Substituting group itself have 3-D solid structure, or through with the steric repulsion of phenanthroline skeleton or with have 3-D solid structure in abutting connection with substituent steric repulsion, perhaps linking has a plurality of phenanthroline skeletons.And then, when linking a plurality of phenanthroline skeleton, more preferably contain the compound of conjugated link(age), replacement or unsubstituted aromatic hydrocarbons, replacement or unsubstituted aromatic heterocycle in the connection unit.

Borane derivative is by the represented compound of formula (E-4), and details is opened in the 2007-27587 communique in Japanese Patent Laid and disclosed to some extent.

[changing 28]

In the formula, R ¹¹And R ¹²Respectively independent be Wasserstoffatoms, alkyl, can substituted aryl, replacement is silica-based, can substituted nitrogenous heterocyclic radical or at least one of cyanic acid, R ¹³～R ¹⁶Respectively independent be can substituted alkyl or can substituted aryl, and X is can substituted arylidene, Y be can substituted carbon number be below 16 aryl, replacement boryl or can substituted carbazyl, and n independently is respectively 0～3 integer.

Among the represented compound of said general formula (E-4), preferably by the represented compound of formula (E-4-1), more preferably by the represented compound of formula (E-4-1-1)～(E-4-1-4).As concrete example, can enumerate: 9-[4-(4-two (mesityl) boryl naphthalene-1-yl) phenyl] carbazole, 9-[4-(4-two (mesityl) boryl naphthalene-1-yl) naphthalene-1-yl] carbazole etc.

[changing 29]

In the formula, R ¹¹And R ¹²Respectively independent be Wasserstoffatoms, alkyl, can substituted aryl, replacement is silica-based, can substituted nitrogenous heterocyclic radical or at least one of cyanic acid, R ¹³～R ¹⁶Respectively independent is can substituted alkyl or can substituted aryl, R ²¹And R ²²Respectively independent be Wasserstoffatoms, alkyl, can substituted aryl, replacement first silica-based (silyl), can substituted nitrogenous heterocyclic radical or at least one of cyanic acid, X ¹Be substituted carbon number to be the arylidene below 20, n independently is respectively 0～3 integer, and m independently is respectively 0～4 integer.

[changing 30]

In various, R ³¹～R ³⁴Difference independently is any of methyl, sec.-propyl or phenyl, and, R ³⁵And R ³⁶Difference independently is any of hydrogen, methyl, sec.-propyl or phenyl.

Among the represented compound of said general formula (E-4), preferably by the represented compound of formula (E-4-2), more preferably by the represented compound of formula (E-4-2-1).

[changing 31]

In the formula, R ¹¹And R ¹²Respectively independent be Wasserstoffatoms, alkyl, can substituted aryl, replacement is silica-based, can substituted nitrogenous heterocyclic radical or at least one of cyanic acid, R ¹³～R ¹⁶Respectively independent is can substituted alkyl or can substituted aryl, X ¹Be substituted carbon number to be the arylidene below 20, and n independently is respectively 0～3 integer.

[changing 32]

In the formula, R ³¹～R ³⁴Difference independently is any of methyl, sec.-propyl or phenyl, and, R ³⁵And R ³⁶Difference independently is any of hydrogen, methyl, sec.-propyl or phenyl.

Among the represented compound of said general formula (E-4), preferably by the represented compound of formula (E-4-3), more preferably by formula (E-4-3-1) or the represented compound of general formula (E-4-3-2).

[changing 33]

In the formula, R ¹¹And R ¹²Respectively independent be Wasserstoffatoms, alkyl, can substituted aryl, replacement is silica-based, can substituted nitrogenous heterocyclic radical or at least one of cyanic acid, R ¹³～R ¹⁶Respectively independent is can substituted alkyl or can substituted aryl, X ¹Be substituted carbon number to be the arylidene below 10, Y ¹Be substituted carbon number to be the aryl below 14, and n independently is respectively 0～3 integer.

[changing 34]

Benzimidizole derivatives is by the represented compound of formula (E-5).

[changing 35]

In the formula, Ar ¹～Ar ³Independent respectively for hydrogen or can substituted carbon number be 6～30 aryl.Especially, preferred Ar ¹Be benzimidizole derivatives that can substituted anthryl.

Carbon number is that the concrete example of 6～30 aryl is phenyl, 1-naphthyl, 2-naphthyl, acenaphthene-1-base, acenaphthene-3-base, acenaphthene-4-base, acenaphthene-5-base, fluorenes-1-base, fluorenes-2-base, fluorenes-3-base, fluorenes-4-base, fluorenes-9-Ji 、 Fu-1-Ji 、 Fu-2-base, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl; 9-phenanthryl, 1-anthryl, 2-anthryl, 9-anthryl, fluoranthene-1-base, fluoranthene-2-base, fluoranthene-3-base, fluoranthene-7-base, fluoranthene-8-base, triphenylene-1-base, triphenylene-2-base, pyrene-1-base, pyrene-2-base, pyrene-4-base, 1; 2-benzophenanthrene-1-base, 1; 2-benzophenanthrene-2-base, 1; 2-benzophenanthrene-3-base, 1; 2-benzophenanthrene-4-base, 1; 2-benzophenanthrene-5-base, 1,2-benzophenanthrene-6-base, tetracene-1-base, tetracene-2-base, tetracene-5-Ji 、 perylene-1-Ji 、 perylene-2-Ji 、 perylene-3-base, pentacene-1-base, pentacene-2-base, pentacene-5-base, pentacene-6-base.

The concrete example of benzimidizole derivatives is 1-phenyl-2-(4-(10-phenylanthracene-9-yl) phenyl)-1H-benzo [d] imidazoles, 2-(4-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1-phenyl-1H-benzo [d] imidazoles, 2-(3-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-1-phenyl-1H-benzo [d] imidazoles, 5-(10-(naphthalene-2-yl) anthracene-9-yl)-1; 2-phenylbenzene-1H-benzo [d] imidazoles, 1-(4-(10-(naphthalene-2-yl) anthracene-9-yl) phenyl)-2-phenyl-1H-benzo [d] imidazoles, (4-(9 for 2-; 10-two (naphthalene-2-yl) anthracene-2-yl) phenyl)-1-phenyl-1H-benzo [d] imidazoles, (4-(9 for 1-; 10-two (naphthalene-2-yl) anthracene-2-yl) phenyl)-2-phenyl-1H-benzo [d] imidazoles, 5-(9; 10-two (naphthalene-2-yl) anthracene-2-yl)-1,2-phenylbenzene-1H-benzo [d] imidazoles.

In electron transfer layer or electron injecting layer, and then can comprise can be with the material reductive material that forms electron transfer layer or electron injecting layer.This reducing substances is so long as have the material of certain reductibility; Then can use various materials, for example can preferably use at least one that is selected from the cohort of being formed by organic misfit thing of organic misfit thing of the oxide compound of basic metal, earth alkali metal, rare earth metal, alkali-metal oxide compound, alkali-metal halogenide, earth alkali metal, the halogenide of earth alkali metal, the oxide compound of rare earth metal, the halogenide of rare earth metal, alkali-metal organic misfit thing, earth alkali metal and rare earth metal.

As preferred reducing substances; Can enumerate Na (work function is 2.36eV), K (work function is 2.28eV), Rb (work function is 2.16eV) or Cs basic metal such as (work function are 1.95eV); Perhaps (work function is 2.0eV～2.5eV) or Ba earth alkali metal such as (work function are 2.52eV), and special preferred work function is the reducing substances below the 2.9eV for Ca (work function is 2.9eV), Sr.Among these reducing substanceses, preferred reducing substances is the basic metal of K, Rb or Cs, and then more preferably Rb or Cs, most preferably Cs.These alkali-metal reducing powers are high especially, through in the material that forms electron transfer layer or electron injecting layer, adding these basic metal more slightly, can seek the lifting or the long lifetime of light emission luminance.In addition, be the reducing substances below the 2.9eV as work function, also preferred two or more said alkali-metal combination, the special combination that preferably comprises Cs, the for example combination of Cs and Na, Cs and K, Cs and Rb or Cs and Na and K.Through comprising Cs, can bring into play reducing power efficiently, through in the material that forms electron transfer layer or electron injecting layer, adding, can seek the lifting or the long lifetime of the luminosity in the organic EL.

< negative electrode in the organic electroluminescent device >

Negative electrode 108 is effects that performance is injected into electronics via electron injecting layer 107 and electron transfer layer 106 luminescent layer 105.

As the material that forms negative electrode 108, if can with electronic high-effective be injected into the material of organic layer, then do not have special qualification, can use and form the material identical materials of anode 102.Wherein, metal such as preferred tin, indium, calcium, aluminium, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, caesium and magnesium or their alloy (aluminium-lithium alloy such as magnesium-silver alloys, magnesium-indium alloy, lithium fluoride/aluminium etc.) etc.Come the lift elements characteristic in order to improve electron injection efficiency, effectively lithium, sodium, potassium, caesium, calcium, magnesium or comprise the alloy of these low workfunction metal.But, these low workfunction metal generally in atmosphere unsettled situation more.In order to improve this point, known lithium, caesium or the magnesium that the trace that for example in organic layer, mixes is arranged, and the method for the high electrode of stability in use.As other hotchpotchs, also can use inorganic salt like lithium fluoride, cesium fluoride, Lithium Oxide 98min and Cs2O and so on.But, be not limited to these.

And then, can enumerate for guard electrode metals such as platinum, gold and silver, copper, iron, tin, aluminium and indiums, or use the alloy of these metals; And inorganicss such as silicon-dioxide, titanium oxide and silicon nitride; Z 150PH, vinylchlorid, hydrocarbon system macromolecular compound etc. carries out lamination and is used as preference.The manufacture method of these electrodes does not have special restriction so long as resistive heating, electron beam irradiation, sputter, ion plating and coating etc. can obtain the method for conducting yet.

< tackiness agent that can be used for each layer >

The material that is used for above electric hole input horizon, electric hole transport layer, luminescent layer, electron transfer layer and electron injecting layer can be individually formed each layer; Also can be dispersed in SE, polycarbonate, PS, gather (N-vinyl carbazole), polymethylmethacrylate, poly-n-butyl methacrylate, polyester, polysulfones, ppe, polyhutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polymeric amide, TKK 021, vinyl acetate resin, acrylonitrile-butadiene-styrene (ABS) (Acrylonitrile Butadiene Styrene as polymer binder; ABS) resin, urethane resin equal solvent soluble resin perhaps use in hardening resins such as phenol resins, xylene resin, petroleum resin, urea resin, melamine resin, unsaturated polyester resin, Synolac, epoxy resin, silicone resin etc.

< making method of organic electroluminescent device >

Each layer of formation organic electroluminescent device can be processed film through the material that utilizes vapour deposition method, resistive heating vapor deposition, electron beam evaporation plating, sputter, packing of molecules method, print process, spin-coating method or methods such as teeming practice, coating method should constitute each layer and form.The thickness of each layer that forms does not in this way have special qualification, can suit corresponding to the character of material to set, and is generally the scope of 2nm～5000nm.The common quartz oscillation formula determining film thickness device capable of using of thickness waits to be measured.When utilizing vapour deposition method to carry out film, its vapor deposition condition is according to the kind of material, as the crystalline texture of the target of film and associative structure etc. and different.The vapor deposition condition general preferred in boat Heating temperature+50 ℃～+ 400 ℃, vacuum tightness 10 ^-6Pa～10 ^-3Pa, evaporation rate 0.01nm/ the second～scope of 50nm/ second, substrate temperature-150 ℃～+ 300 ℃, thickness 2nm～5 μ m in suitable the setting.

Secondly; As an example of the method for making organic electroluminescent device, the manufacture method of the organic electroluminescent device of luminescent layer/electron transfer layer/electron injecting layer/negative electrode of comprising anode/electric hole input horizon/electric hole transport layer/comprise material of main part and dopant material is described.On suitable substrate, utilize the film of formation anode material such as vapour deposition method to make anode after, on this anode, form the film of electric hole input horizon and electric hole transport layer.Above that material of main part and dopant material are carried out common vapor deposition and form film being used as luminescent layer; On this luminescent layer, form electron transfer layer, electron injecting layer; And then utilize formation such as vapour deposition method to comprise negative electrode to be used as negative electrode with the film of material, to obtain organic electroluminescent device thus as target.Moreover, in the making of said organic electroluminescent device, also can make production order opposite, and with negative electrode, electron injecting layer, electron transfer layer, luminescent layer, electric hole transport layer, electric hole input horizon, anodic sequentially built.

When the organic electroluminescent device that is obtained is in this way applied volts DS; As long as with anode as+polarity apply; With negative electrode as-polarity apply and get final product; If apply the voltage about 2V～40V, then can be luminous from transparent or semitransparent electrode side (male or female, and both sides) observation.In addition, this organic electroluminescent device is also luminous under the situation that is applied with pulsed current or alternating current.Moreover the alternative waveform that applies can be any.

< application examples of organic electroluminescent device >

In addition, the present invention also can be applied to possess the display unit of organic electroluminescent device or possess means of illumination of organic electroluminescent device etc.

The display unit or the means of illumination that possess organic electroluminescent device can be through making the organic electroluminescent device of this example with known method such as known drive unit are connected, and can suit to use known driving methods such as direct drive, pulsed drive, AC driving to drive.

As display unit; For example can enumerate: flexible displays such as panel displays such as color flat panel display, flexible color organic electroluminescence (EL) indicating meter etc. (for example, with reference to japanese patent laid-open 10-335066 communique, Japanese Patent Laid open the 2003-321546 communique, Japanese Patent Laid is opened 2004-281086 communique etc.).In addition, as the display mode of indicating meter, for example can enumerate matrix and/or segmented mode etc.Moreover matrix shows with segmentation and shows and can in identical panel, coexist.

So-called matrix is meant that the pixel that is used to show is configured to reticulation or mosaic shape etc. two-dimentionally to form, and its set through pixel comes display text or image.The shape of pixel or size are to decide according to purposes.In the image and literal demonstration of Personal Computer, watch-dog, televisor, be the dimetric pixels below the 300 μ m for example Yi Bian use usually, in addition, under the situation of the giant display as display panel, Yi Bian use pixel as the mm level.Under the situation that monochrome shows,, under the situation that colour shows, the pixel of red, green, blue is shown side by side as long as arrange the pixel of same color.In the case, triangular form and stripe are more typically arranged.And, as the driving method of this matrix, can be any of line sequential driving method or active matrix.Line has driven this advantage simple in structure in proper order, but under the situation of having considered acting characteristic, active matrix is more excellent sometimes, so driving method also must be distinguished use according to purposes.

In segmented mode (type), form pattern with the mode that shows the information that is determined in advance, and make determined regional luminous.For example can enumerate: the operating state demonstration of the moment in digital dock or the TM or temperature demonstration, stereo set or electromagnetic oven etc. and the panel demonstration of automobile etc.

As means of illumination; For example can enumerate: the means of illumination of interior lighting etc., the backlight of liquid crystal indicator etc. (for example, open 2003-257621 communique, Japanese Patent Laid are opened the 2003-277741 communique, Japanese Patent Laid is opened 2004-119211 communique etc.) with reference to Japanese Patent Laid.Backlight mainly uses in order to promote the identification that does not carry out self light-emitting display device, and it is used for liquid crystal indicator, clock, PA-system, car panel, display panel and sign etc.Especially; Among liquid crystal indicator; Slimming is just becoming the backlight of the Personal Computer purposes of problem; If the backlight of considering previous mode then uses the backlight of the luminous element of this example to have characteristic slim, light weight because of comprising luminescent lamp or light guiding plate is difficult to slimming.

[instance]

At first, below employed synthetic example through the substituted anthracene compound of pyridyl phenyl in the instance is described.

[changing 36]

< synthesizing of 4-(4-bromophenyl) pyridine >

Under nitrogen environment, one side utilizes ice bath to cool off, stir, and one towards being added with 4-iodine pyridine (7.0g) and THF (Tetrahydrofuran, THF) dropping 2M isopropylmagnesium chloride THF solution (18.8ml) in the flask of (32ml).After dripping end, one side utilizes frozen water to cool off, stir, and one side is added zinc chloride Tetramethyl Ethylene Diamine misfit thing (9.1g)., at room temperature stir 0.5 hour, add 1,4-dibromobenzene (12.1g), Pd (PPh thereafter ₃) ₄(0.2g), stirred 2 hours with reflux temperature then.Till reaction solution is cooled to room temperature; In order to remove the metals ion of catalyst; Interpolation probably is equivalent to the solution that the tetrasodium salt of EDTA duohydrate is dissolved in form in an amount of water (below, slightly be designated as the EDTA4Na aqueous solution) of 2 times of moles with respect to target compound.And then add ETHYLE ACETATE and carry out the separatory operation.Utilize vaporizer that organic layer is concentrated, after making with extra care through silica gel chromatography (toluene/ethyl acetate=80/20 (volume ratio)), utilize heptane to clean, thereby obtain 4-(4-bromophenyl) pyridine (5.6g).

2,2 '-(2-([1,1 ': 3 ', 1 " terphenyl]-5 '-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) synthetic >

This boric acid ester is to open flow process 1-1～flow process 1-5 of being put down in writing in the 2009-275013 communique (with reference to 7 pages～10 pages of communique, paragraph [0014]～paragraph [0017]) according to Japanese Patent Laid to come synthetic.

With 2,2 '-(2-([1,1 ': 3 ', 1 " terphenyl]-5 '-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (67.0g), 4-(4-bromophenyl) pyridine (57.4g), Pd (PPh ₃) ₄(5.9g), Tripotassium phosphate (86.6g), 1 (350ml), the trimethyl carbinol (70ml) and water (14ml) is added in the flask, under nitrogen environment, stirred 2 hours with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, add water and heptane and filter.After utilizing water, solid that washed with methanol obtained, and then utilize toluene and chlorobenzene to clean.And then, from chlorobenzene carry out recrystallize and obtain by (1-1-10) represented compound " 4,4 '-((2-[1,1 ': 3 ', 1 " terphenyl]-5 '-yl) anthracene-9,10-two bases) two (4, the 1-phenylene) two pyridines " (22.1g).

Measure through NMR and to confirm the structure that obtained through the substituted anthracene compound of pyridyl phenyl.

¹H-NMR(CDCl ₃)：δ＝8.76(m，4H)，8.01(m，1H)，7.93(t，4H)，7.86(d，1H)，7.65-7.81(m，14H)，7.62(m，4H)，7.35～7.45(m，8H)。

[changing 37]

< synthesizing of 2-(naphthalene-2-yl) anthracene >

With 2-bromine anthracene (31.1g), 2-naphthalene boronic acids, two (dibenzalacetone) palladium (0) (0.35g), tricyclohexyl phosphine (0.34g), Tripotassium phosphate (77.1g), 1; 2; 4-Three methyl Benzene (311ml), the trimethyl carbinol (62ml) and water (12ml) are added in the flask; Under nitrogen environment, stirred 1 and a half hours with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, add water and heptane and filter.After utilizing water, solid that washed with heptane obtained, and then utilize methyl alcohol to clean, thereby obtain 2-(naphthalene-2-yl) anthracene (36.7g).

< 9,10-two bromo-2-(naphthalene-2-yl) anthracene synthetic >

Dripping bromine (40.0g) in the flask that is added with 2-(naphthalene-2-yl) anthracene (36.7g) and chloroform (600ml).After dripping end, at room temperature stirred 9 and a half hours stopped reaction behind interpolation water, sodium sulfite anhy 96 and the sodium hydrogencarbonate.Heat up in a steamer dechlorination from the decompression of this reaction soln and filter after imitative, the solid that is obtained is washed, and utilized heptane to clean, utilize methyl alcohol to clean then, and then utilize toluene to clean.From YLENE carry out recrystallize and obtain 9,10-two bromo-2-s (naphthalene-2-yl) anthracene (32.1g) thereafter.

2,2 '-(2-(naphthalene-2-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) synthetic >

Under nitrogen environment; With 130 ℃ to being added with 9,10-two bromo-2-(naphthalene-2-yl) anthracene (32.1g), two (tetramethyl ethylene ketone closes) two boron (44.2g), two (dibenzalacetone) palladium (0) are (2.0g), the flask of tricyclohexyl phosphine (2.0g), potassium acetate (27.3g), salt of wormwood (19.2g) and methyl-phenoxide (420ml) carries out 3 hours heated and stirred.After heating finishes, reaction solution is cooled to room temperature till, utilize to be paved with diatomaceous paulownia mountain funnel and to carry out suction filtration.With in filtrating, adding the crystallization filtering that heptane obtained, thus obtain 2,2 '-(2-(naphthalene-2-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) are (31.5g).

With 2,2 '-(2-(naphthalene-2-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (36.5g), 4-(4-bromophenyl) pyridine (36.9g), Pd (PPh ₃) ₄(3.8g), Tripotassium phosphate (55.7g), 1 (185ml), the trimethyl carbinol (37ml) and water (7.4ml) is added in the flask, under nitrogen environment, stirred 1 hour with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, add water and heptane and filter.After utilizing water, solid that washed with methanol obtained, carry out recrystallize from oil of mirbane and obtain (25.0g) by (1-1-7) represented compound " 4,4 '-((2-naphthalene-2-yl) anthracene-9,10-two bases) two (4, the 1-phenylene) two pyridines ".

¹H-NMR(CDCl ₃)：δ＝8.78(m，4H)，8.03(m，1H)，8.00(m，1H)，7.95(d，4H)，7.65-7.90(m，16H)，7.37～7.50(m，4H)。

[changing 38]

< 2-([1,1 '-biphenyl]-3-yl) anthracene synthetic >

With 2-bromine anthracene (31.1g), 3-biphenyl boric acid (18.5g), two (dibenzalacetone) palladium (0) (0.22g), tricyclohexyl phosphine (0.22g), Tripotassium phosphate (49.5g), 1; 2; 4-Three methyl Benzene (200ml), the trimethyl carbinol (40ml) and water (8ml) are added in the flask; Under nitrogen environment, stirred 1 and a half hours with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, utilize to be paved with diatomaceous paulownia mountain funnel and to carry out suction filtration.After the filtrate decompression that is obtained heated up in a steamer, utilize heptane to clean, thereby obtain 2-([1,1 '-biphenyl]-3-yl) anthracene (32.0g).

< 2-([1,1 '-biphenyl]-3-yl)-9,10-dibromoanthracene synthetic >

Dripping bromine (25.0g) in the flask that is added with 2-([1,1 '-biphenyl]-3-yl) anthracene (32.0g) and chloroform (300ml).After dripping end, at room temperature stir a night, stopped reaction behind interpolation water, sodium sulfite anhy 96 and the sodium hydrogencarbonate.Heat up in a steamer dechlorination from the decompression of this reaction soln and filter after imitative, the solid that is obtained is washed, and utilized heptane to clean, utilize methyl alcohol to clean then, thereby obtain 2-([1,1 '-biphenyl]-3-yl)-9,10-dibromoanthracene (34.0g).

2,2 '-(2-([1,1 '-biphenyl]-3-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) synthetic >

Under nitrogen environment; With 130 ℃ to being added with 2-([1; 1 '-biphenyl]-the 3-yl)-9,10-dibromoanthracene (34.0g), two (tetramethyl ethylene ketone closes) two boron (44.2g), two (dibenzalacetone) palladium (0) are (2.0g), the flask of tricyclohexyl phosphine (2.0g), potassium acetate (27.4g), salt of wormwood (19.2g) and methyl-phenoxide (360ml) carries out 2 hours heated and stirred.After heating finishes, reaction solution is cooled to room temperature till, utilize to be paved with diatomaceous paulownia mountain funnel and to carry out suction filtration.With in filtrating, adding the crystallization filtering that heptane obtained, thus obtain 2,2 '-(2-([1,1 '-biphenyl]-3-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (31.0g).

With 2,2 '-(2-([1,1 '-biphenyl]-3-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (24.3g), 4-(4-bromophenyl) pyridine (23.4g), Pd (PPh ₃) ₄(2.4g), Tripotassium phosphate (35.4g), 1 (120ml), the trimethyl carbinol (24ml) and water (5ml) is added in the flask, under nitrogen environment, stirred 1 hour with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, add water and heptane and filter.After utilizing water, solid that washed with methanol obtained, carry out recrystallize from oil of mirbane and obtain (12.5g) by (1-1-2) represented compound " 4,4 '-((2-[1,1 '-biphenyl]-3-yl) anthracene-9,10-two bases) two (4, the 1-phenylene) two pyridines ".

¹H-NMR(CDCl ₃)：δ＝8.76(m，4H)，7.98(m，1H)，7.93(m，4H)，7.86(d，1H)，7.77(m，3H)，7.65～7.73(m，9H)，7.52～7.58(m，4H)，7.47(t，1H)，7.34-7.43(m，5H)。

[changing 39]

With 2,2 '-(2-([1,1 '-biphenyl]-4-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (58.2g), 4-(4-bromophenyl) pyridine (56.2g), Pd (PPh ₃) ₄(2.31g), Tripotassium phosphate (106.0g), 1 (320ml), the trimethyl carbinol (65ml) and water (65ml) is added in the flask, under nitrogen environment, stirred 2 hours with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, add water and extract solid through suction filtration.Utilize methyl alcohol, clean the solid that is obtained through the orthodichlorobenzene that heats.And then, carry out recrystallize from orthodichlorobenzene and obtain (48.0g) by the represented compound of formula (1-1-3) " 4,4 '-((2-([1,1 '-biphenyl]-4-yl) anthracene-9,10-two bases) two (4, the 1-phenylene)) two pyridines ".

¹H-NMR(CDCl ₃)：δ＝8.77(m，4H)，7.99(m，1H)，7.94(m，4H)，7.86(d，1H)，7.77(m，2H)，7.63-7.74(m，13H)，7.60(m，2H)，7.38-7.45(m，4H)，7.35(t，1H)。

[changing 40]

With 2,2 '-(2-(naphthalene-1-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (54.8g), 4-(4-bromophenyl) pyridine (55.3g), Pd (PPh ₃) ₄(5.69g), Tripotassium phosphate (83.6g), 1 (300ml), the trimethyl carbinol (60ml) and water (12ml) is added in the flask, under nitrogen environment, stirred 1 hour with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, add water and extract precipitate through suction filtration.The solid that utilizes washed with methanol to obtain utilizes ETHYLE ACETATE to clean then.And then utilize after the orthodichlorobenzene of heating cleans; Make with extra care through active carbon column chromatography (chlorobenzene), thereby obtain (8.19g) by the represented compound of formula (1-1-4) " 4,4 '-((2-naphthalene-1-yl) anthracene-9; 10-two bases) two (4, the 1-phenylene) two pyridines ".

¹H-NMR(CDCl ₃)：δ＝8.77(dd，2H)，8.70(dd，2H)，7.95(d，2H)，7.82-7.92(m，7H)，7.75-7.81(m，2H)，7.71(m，4H)，7.66(d，2H)，7.62(dd，2H)，7.57(dd，1H)，7.39-7.52(m，6H)。

[changing 41]

< synthesizing of 4-(3-bromophenyl) pyridine >

Under nitrogen environment, one side utilizes ice bath to cool off, stir, and one drips 2M isopropylmagnesium chloride THF solution (16.1ml) in the flask that is added with 4-iodine pyridine (6.0g) and THF (30ml).After dripping end, at room temperature stirred 0.5 hour, one side utilizes frozen water that flask is cooled off, stirs once more, and one side is added zinc chloride Tetramethyl Ethylene Diamine misfit thing (8.1g)., at room temperature stir 1 hour, add 1-bromo-3-iodobenzene (8.2g), Pd (PPh thereafter ₃) ₄(1.0g), stirred 2 hours with reflux temperature then.Till reaction solution is cooled to room temperature; In order to remove the metals ion of catalyst; Interpolation probably is equivalent to the solution that the tetrasodium salt of EDTA duohydrate is dissolved in form in an amount of water (below, slightly be designated as the EDTA4Na aqueous solution) of 2 times of moles with respect to target compound.And then add ETHYLE ACETATE and carry out the separatory operation.Utilize vaporizer that organic layer is concentrated, make with extra care, thereby obtain 4-(3-bromophenyl) pyridine (6.2g) through silica gel chromatography (toluene/ethyl acetate=80/20 (volume ratio)).

With 2,2 '-(2-([1,1 ': 3 ', 1 " terphenyl]-5 '-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (35.0g), 4-(3-bromophenyl) pyridine (29.9g), Pd (PPh ₃) ₄(6.2g), Tripotassium phosphate (45.2g), 1 (175ml), the trimethyl carbinol (35ml) and water (7ml) is added in the flask, under nitrogen environment, stirred 1 hour with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, add water and toluene and also carry out the separatory operation.Heat up in a steamer from organic layer decompression and to desolvate; Make with extra care through silica gel column chromatography (toluene/ethyl acetate=80/20 (volume ratio)) then, thus acquisition by the represented compound of formula (1-2-10) " 4,4 '-((2-[and 1; 1 ': 3 '; 1 "-terphenyl]-5 '-yl) anthracene-9,10-two bases) two (3, the 1-phenylene) two pyridines " (14.2g).

¹H-NMR(CDCl ₃)：δ＝8.68(m，4H)，8.14(m，1H)，7.82-7.90(m，5H)，7.70-7.80(m，8H)，7.58-7.66(m，10H)，7.35～7.45(m，8H)。

[changing 42]

< synthesizing of 2-(naphthalene-1-yl) anthracene >

With 2-bromine anthracene (10.0g), 1-naphthalene boronic acids (12.5g), Pd (PPh ₃) ₄(1.1g), yellow soda ash (10.3g), toluene (100ml), ethanol (20ml) and water (20ml) is added in the flask, under nitrogen environment, stirred 6 hours with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, carry out the separatory operation.With the organic layer concentrating under reduced pressure, make with extra care through silica gel chromatography (toluene) then.From THF the solid that the dissolution fluid concentrating under reduced pressure is obtained is carried out recrystallize, thereby obtain 2-(naphthalene-1-yl) anthracene (11.6g).

< 9,10-two bromo-2-(naphthalene-1-yl) anthracene synthetic >

Utilize ice bath that the flask that is added with 2-(naphthalene-2-yl) anthracene (7.0g), iodine (30mg) and THF (120ml) is cooled off, add N-bromo-succinimide (9.8g) then.Utilize ice bath simultaneously cool off the one side stir 1 hour after, at room temperature stirred 3 and a half hours.Come the solid in the abstraction reaction liquid through suction filtration, utilize sodium thiosulfate solution to clean then.This solid is dissolved in the chlorobenzene, adds saturated aqueous common salt and carry out the separatory operation.Extract the solid that the organic layer concentrating under reduced pressure is separated out through suction filtration, thereby obtain 9,10-two bromo-2-(naphthalene-1-yl) anthracene (4.4g).

2,2 '-(2-(naphthalene-1-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) synthetic >

Under nitrogen environment; With 130 ℃ to being added with 9,10-two bromo-2-(naphthalene-1-yl) anthracene (3.2g), two (tetramethyl ethylene ketone closes) two boron (4.4g), two (dibenzalacetone) palladium (0) are (0.2g), the flask of tricyclohexyl phosphine (0.2g), potassium acetate (2.7g), salt of wormwood (1.9g) and methyl-phenoxide (15ml) carries out 7 hours heated and stirred.After heating finishes, reaction solution is cooled to room temperature till, utilize to be paved with diatomaceous paulownia mountain funnel and to carry out suction filtration.Extract through suction filtration and in filtrating, to add the crystallization that heptane obtained, thereby obtain 2,2 '-(2-(naphthalene-1-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) are (3.0g).

With 2,2 '-(2-(naphthalene-1-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (3.0g), 4-(3-bromophenyl) pyridine (3.2g), Pd (PPh ₃) ₄(320mg), Tripotassium phosphate (4.8g), 1 (10ml), the trimethyl carbinol (2ml) and water (0.5ml) is added in the flask, under nitrogen environment, stirred 4 hours with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, add water and toluene and also carry out the separatory operation.Heat up in a steamer from organic layer decompression and to desolvate; Make with extra care through silica gel column chromatography (toluene/ethyl acetate=80/20 (volume ratio)) then, thereby acquisition by the represented compound of formula (1-2-7) " 4,4 '-((2-naphthalene-1-yl) anthracene-9; 10-two bases) two (3, the 1-phenylene) two pyridines " (2.2g).

¹H-NMR(CDCl ₃)：δ＝8.69(dd，2H)，8.65(m，2H)，7.75-7.91(m，12H)，7.60-7.70(m，5H)，7.55(m，3H)，7.38～7.50(m，5H)，7.30(t，1H)。

[changing 43]

< 2-([1,1 '-biphenyl]-4-yl) anthracene synthetic >

With 2-bromine anthracene (100.0g), [1; 1 '-biphenyl]-4-ylboronic acid (92.4g), two (dibenzalacetone) palladium (0) (1.1g), tricyclohexyl phosphine (1.1g), Tripotassium phosphate (310.0g), 1; 2; 4-Three methyl Benzene (1000ml), the trimethyl carbinol (200ml) and water (40ml) are added in the flask, under nitrogen environment, stir 3 and a half hours with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, after adding water and stirring, extract solid through suction filtration.The solid that utilizes washed with methanol to obtain utilizes heptane to clean then, thereby acquisition 2-([1,1 '-biphenyl]-the 4-yl) anthracene (128.0g).

< 2-([1,1 '-biphenyl]-4-yl)-9,10-dibromoanthracene synthetic >

Under nitrogen environment, and dripping bromine (100.0g) in the flask that is added with 2-([1,1 '-biphenyl]-4-yl) anthracene (93.6g) and chloroform (2000ml) at room temperature.After at room temperature stirring a night, add chlorobenzene (500ml), stirred 4 hours down at 80 ℃ then.After reaction finishes, add sodium bicarbonate aqueous solution, add sodium sulfite aqueous solution then, extract solid through suction filtration.After utilizing the solid that washed with methanol obtains, it is dissolved in the chlorobenzene of heating, removes insolubles through decant.Till this solution is cooled to room temperature, extract the crystallization of being separated out, thereby obtain 2-([1,1 '-biphenyl]-4-yl)-9,10-dibromoanthracene (126.0g) through suction filtration.

2,2 '-(2-([1,1 '-biphenyl]-4-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) synthetic >

Under nitrogen environment; With 150 ℃ to being added with 2-([1; 1 '-biphenyl]-the 4-yl)-9,10-dibromoanthracene (62.0g), two (tetramethyl ethylene ketone closes) two boron (77.5g), two (dibenzalacetone) palladium (0) are (7.30g), the flask of tricyclohexyl phosphine (8.55g), potassium acetate (49.9g), salt of wormwood (35.1g) and methyl-phenoxide (760ml) carries out 2.5 hours heated and stirred.After heating finishes, reaction solution is cooled to room temperature till, add YLENE (1000ml), utilize to be paved with diatomaceous paulownia mountain funnel and to carry out suction filtration.After filtrate decompression heated up in a steamer, extract through suction filtration and to add the crystallization that heptane obtained, thereby obtain 2,2 '-(2-([1,1 '-biphenyl]-4-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (51.8g).

With 2,2 '-(2-([1,1 '-biphenyl]-4-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (46.3g), 4-(3-bromophenyl) pyridine (44.7g), Pd (PPh ₃) ₄(1.84g), Tripotassium phosphate (84.4g), 1 (260ml), the trimethyl carbinol (52ml) and water (10ml) is added in the flask, under nitrogen environment, stirred 2 hours with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, add water and extract solid through suction filtration.Utilize methyl alcohol, clean the solid that is obtained through the chlorobenzene that heats.And then, carry out recrystallize from orthodichlorobenzene after, make with extra care through active carbon column chromatography (chlorobenzene); Thereby obtain (29.6g) by the represented compound of formula (1-2-1) " 4,4 '-((2-([1,1 '-biphenyl]-4-yl) anthracene-9; 10-two bases) two (3, the 1-phenylene)) two pyridines ".

¹H-NMR(CDCl ₃)：δ＝8.69(m，4H)，7.98(m，1H)，7.89(d，2H)，7.84(m，3H)，7.69-7.81(m，5H)，7.58～7.67(m，12H)，7.32-7.46(m，5H)。

[changing 44]

With 2,2 '-(2-([1,1 '-biphenyl]-3-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (67.6g), 4-(3-bromophenyl) pyridine (65.2g), Pd (PPh ₃) ₄(6.7g), Tripotassium phosphate (98.5g), 1 (350ml), the trimethyl carbinol (70ml) and water (14ml) is added in the flask, under nitrogen environment, stirred 1 hour with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, utilize to be paved with diatomaceous paulownia mountain funnel and to carry out suction filtration.After filtrate decompression heated up in a steamer, add methyl alcohol and Shen Dian is separated out.Utilization is made with extra care by carbon column chromatography (toluene) after the ethyl acetate of heating cleans by the Shen Dian that suction filtration extracted.And then, make with extra care through silica gel column chromatography (toluene/ethyl acetate mixed solvent).At this moment, the method for being put down in writing in the 94th page of " (the 1)-mass treatment method of crossing the threshold of Experiment of Organic Chemistry and the separation and purification method-" of publishing with people limited-liability company with reference to chemistry, the ratio that increases the ETHYLE ACETATE in the developping agent lentamente makes the target compound stripping.Solvent decompression is heated up in a steamer, thereby obtain (21.3g) by the represented compound of formula (1-2-2) " 4,4 '-((2-([1,1 '-biphenyl]-3-yl) anthracene-9,10-two bases) two (3, the 1-phenylene)) two pyridines ".

¹H-NMR(CDCl ₃)：δ＝8.68(m，4H)，7.99(m，1H)，7.82-7.91(m，5H)，7.74-7.80(m，5H)，7.70(dd，1H)，7.59-7.66(m，6H)，7.50-7.57(m，4H)，7.47(t，1H)，7.32-7.43(m，5H)。

[changing 45]

With 2,2 '-(2-(naphthalene-2-yl) anthracene-9,10-two bases) two (4,4,5,5-tetramethyl--1,3,2-dioxa borine) (68.1g), 4-(3-bromophenyl) pyridine (68.8g), Pd (PPh ₃) ₄(7.05g), Tripotassium phosphate (104g), 1 (350ml), the trimethyl carbinol (70ml) and water (14ml) is added in the flask, under nitrogen environment, stirred 1 hour with reflux temperature.After heating finishes, reaction solution is cooled to room temperature till, add water and heptane and filter.Utilize water, solid that washed with methanol obtained, utilize ETHYLE ACETATE to clean then.And then utilize after the chlorobenzene that heats cleans, carry out recrystallize and obtain (36.2g) from orthodichlorobenzene by the represented compound of formula (1-2-4) " 4,4 '-((2-naphthalene-2-yl) anthracene-9,10-two bases) two (3, the 1-phenylene) two pyridines ".

¹H-NMR(CDCl ₃)：δ＝8.68(m，4H)，8.05(m，1H)，8.00(m，1H)，7.74-7.92(m，13H)，7.61-7.70(m，7H)，7.47(m，2H)，7.40(m，2H)。

Through the compound of suitable change raw material, can with according to the method for said synthetic example synthetic of the present invention other through the substituted anthracene compound of pyridyl phenyl.

Below, for further explain the present invention, disclose the instance of the organic EL that uses compound of the present invention, but the present invention is not limited to these instances.

< about by the represented examples for compounds of general formula (1-1) >

The organic EL of example of making 1～instance 5 and comparative example 1, and carry out respectively in the constant current driven test driving starting voltage (V), keep the mensuration of time (hr) of the brightness more than 90% of initial value.Below, instance and comparative example are elaborated.

The material of each layer in the organic EL of the instance 1～instance 5 of made and comparative example 1 constituted be shown in below table 1.Moreover, in all examples, constitute negative electrode by hydroxyquinoline lithium (Liq)/(magnesium+silver).

[table 1]

In the table 1, " HI " is N4, N4 '-phenylbenzene-N4; N4 '-two (9-phenyl-9H-carbazole-3-yl)-[1,1 '-biphenyl]-4,4 '-diamines; " NPD " is N, N '-phenylbenzene-N, N '-dinaphthyl-4; 4 '-benzidine, compound (A) is 9-phenyl-10-(4-phenylnaphthalene-1-yl) anthracene, compound (B) is N ⁵, N ⁵, N ⁹, N ⁹-7,7-hexaphenyl-7H-benzo [C] fluorenes-5,9-diamines, compound (C) be 4,4 '-((2-phenylanthracene-9,10-two bases) two (4, the 1-phenylene)) two pyridines, and " Liq " is the oxine lithium.Below represent chemical structure.

[changing 46]

< instance 1 >

< element that compound (1-1-10) is used for electron transfer layer >

To will make glass substrate (Ao Putuo science and technology (Optoscience) (share) made) that ITO that film becomes the thickness of 180nm is ground to the 26mm * 28mm * 0.7mm till the 150nm as the transparent support substrate through sputter.This transparent support substrate is fixed on the substrate holder of commercially available evaporation coating device (vacuum machine worker (share) manufacturing); The molybdenum system vapor deposition be added with HI is installed is then used boat, the molybdenum system vapor deposition that is added with NPD with boat, be added with compound (A) molybdenum system vapor deposition with boat, be added with compound (B) molybdenum system vapor deposition with boat, be added with compound of the present invention (1-1-10) molybdenum system vapor deposition with boat, be added with hydroxyquinoline lithium (Liq) molybdenum system vapor deposition with boat, be added with the molybdenum boat of magnesium and be added with silver-colored tungsten system vapor deposition and use boat.

On the ITO of transparent support substrate film, form following each layer successively.Vacuum tank is decompressed to 5 * 10 ^-4Till the Pa; At first; The vapor deposition that is added with HI is heated with boat and so that thickness becomes the mode of 40nm carries out vapor deposition and form electric hole input horizon; Then, the vapor deposition that is added with NPD is heated with boat and so that thickness becomes the mode of 30nm carries out vapor deposition and form electric hole transport layer.Secondly, the vapor deposition that is added with compound (A) is heated with boat with boat and the vapor deposition that is added with compound (B) simultaneously and so that thickness becomes the mode of 35nm carries out vapor deposition and form luminescent layer.So that roughly becoming 95 pairs 5 mode, the weight ratio of compound (A) and compound (B) regulates evaporation rate.Secondly, the vapor deposition that is added with compound (1-1-10) is heated with boat and so that thickness becomes the mode of 15nm carries out vapor deposition and form electron transfer layer.The evaporation rate of each layer is second 0.01nm/ second～1nm/.

The vapor deposition that be added with hydroxyquinoline lithium (Liq) with boat heated and so that the mode that thickness becomes 1nm is carried out vapor deposition with the evaporation rate of second 0.01nm/ second～0.1nm/ thereafter.Then, the boat that is added with magnesium and the boat that is added with silver are heated simultaneously and so that thickness becomes the mode of 100nm carries out vapor deposition and form negative electrode.At this moment so that magnesium is regulated evaporation rate with the atomicity of silver than the mode that becomes 10 pairs 1, and so that evaporation rate form negative electrode and obtain organic electroluminescent device from the mode that 0.1nm/ becomes 10nm/ second second.

The ITO electrode as anode, as negative electrode, if apply volts DS, then can be obtained the blue-light-emitting of the about 460nm of wavelength with magnesium/silver electrode.In addition, be used to obtain 2000cd/m ²The current density of original intensity implement the constant current driven test.Its result, driving the test starting voltage is 4.89V, keeps 90% (1800cd/m of initial value ²) time of above brightness is 206 hours.

< instance 2 >

< element that compound (1-1-7) is used for electron transfer layer >

Except that compound (1-1-10) is replaced to the compound (1-1-7), obtain organic EL with method according to instance 1.The ITO electrode as anode, as negative electrode, is used to obtain 2000cd/m with magnesium/silver electrode ²The current density of original intensity implement the constant current driven test.Its result, driving the test starting voltage is 5.31V, keeping the time of the brightness more than 90% of initial value is 158 hours.

< instance 3 >

< element that compound (1-1-2) is used for electron transfer layer >

Except that compound (1-1-10) is replaced to the compound (1-1-2), obtain organic EL with method according to instance 1.The ITO electrode as anode, as negative electrode, is used to obtain 2000cd/m with magnesium/silver electrode ²The current density of original intensity implement the constant current driven test.Its result, driving the test starting voltage is 5.24V, keeping the time of the brightness more than 90% of initial value is 104 hours.

< instance 4 >

< element that compound (1-1-3) is used for electron transfer layer >

Except that compound (1-1-10) is replaced to the compound (1-1-3), obtain organic EL with method according to instance 1.The ITO electrode as anode, as negative electrode, is used to obtain 2000cd/m with magnesium/silver electrode ²The current density of original intensity implement the constant current driven test.Its result, driving the test starting voltage is 5.26V, keeping the time of the brightness more than 90% of initial value is 103 hours.

< instance 5 >

< element that compound (1-1-4) is used for electron transfer layer >

Except that compound (1-1-10) is replaced to the compound (1-1-4), obtain organic EL with method according to instance 1.The ITO electrode as anode, as negative electrode, is used to obtain 2000cd/m with magnesium/silver electrode ²The current density of original intensity implement the constant current driven test.Its result, driving the test starting voltage is 5.48V, keeping the time of the brightness more than 90% of initial value is 148 hours.

< comparative example 1 >

Except that compound (1-10) is replaced to the compound (C), obtain organic EL with method according to instance 1.The ITO electrode as anode, as negative electrode, is used to obtain 2000cd/m with magnesium/silver electrode ²The current density of original intensity implement the constant current driven test.Its result, driving the test starting voltage is 5.13V, keeping the time of the brightness more than 90% of initial value is 66 hours.

Above result is summarized in table 2.

[table 2]

< about by the represented examples for compounds of general formula (1-2) >

The organic EL of example of making 6, instance 7 and comparative example 2, and carry out respectively in the constant current driven test driving starting voltage (V), keep the mensuration of time (hr) of the brightness more than 90% of initial value.Below, instance and comparative example are elaborated.

The material of each layer in the organic EL of instance 6, instance 7 and the comparative example 2 of made constituted be shown in below table 3.Moreover, in all examples, constitute negative electrode by hydroxyquinoline lithium (Liq)/(magnesium+silver).

[table 3]

In the table 3, " HI " is N ⁴, N ⁴'-phenylbenzene-N ⁴, N ⁴'-two (9-phenyl-9H-carbazole-3-yl)-[1,1 '-biphenyl]-4,4 '-diamines, " NPD " is N ⁴, N ⁴'-two (naphthalene-1-yl)-N ⁴, N ⁴'-phenylbenzene-[1,1 '-biphenyl]-4,4 '-amine, compound (A) is 9-phenyl-10-(4-phenylnaphthalene-1-yl) anthracene, compound (B) is N ⁵, N ⁵, N ⁹, N ⁹-7,7-hexaphenyl-7H-benzo [C] fluorenes-5,9-diamines, compound (D) be 4,4 '-((2-phenylanthracene-9,10-two bases) two (3, the 1-phenylene)) two pyridines, and " Liq " is the oxine lithium.Below represent chemical structure.

[changing 47]

< instance 6 >

< element that compound (1-2-10) is used for electron transfer layer >

To will make glass substrate (photoelectricity science and technology (Optoscience) (share) made) that ITO that film becomes the thickness of 180nm is ground to the 26mm * 28mm * 0.7mm till the 150nm as the transparent support substrate through sputter.This transparent support substrate is fixed on the substrate holder of commercially available evaporation coating device (vacuum machine worker (share) manufacturing); The molybdenum system vapor deposition be added with HI is installed is then used boat, the molybdenum system vapor deposition that is added with NPD with boat, be added with compound (A) molybdenum system vapor deposition with boat, be added with compound (B) molybdenum system vapor deposition with boat, be added with compound of the present invention (1-2-10) molybdenum system vapor deposition with boat, be added with hydroxyquinoline lithium (Liq) molybdenum system vapor deposition with boat, be added with the molybdenum boat of magnesium and be added with silver-colored tungsten system vapor deposition and use boat.

On the ITO of transparent support substrate film, form following each layer successively.Vacuum tank is decompressed to 5 * 10 ^-4Till the Pa; At first; The vapor deposition that is added with HI is heated with boat and so that thickness becomes the mode of 40nm carries out vapor deposition and form electric hole input horizon; Then, the vapor deposition that is added with NPD is heated with boat and so that thickness becomes the mode of 30nm carries out vapor deposition and form electric hole transport layer.Secondly, the vapor deposition that is added with compound (A) is heated with boat with boat and the vapor deposition that is added with compound (B) simultaneously and so that thickness becomes the mode of 35nm carries out vapor deposition and form luminescent layer.So that roughly becoming 95 pairs 5 mode, the weight ratio of compound (A) and compound (B) regulates evaporation rate.Secondly, the vapor deposition that is added with compound (1-2-10) is heated with boat and so that thickness becomes the mode of 15nm carries out vapor deposition and form electron transfer layer.The evaporation rate of each layer is second 0.01nm/ second～1nm/.

The vapor deposition that be added with hydroxyquinoline lithium (Liq) with boat heated and so that the mode that thickness becomes 1nm is carried out vapor deposition with the evaporation rate of second 0.01nm/ second～0.1nm/ thereafter.Then, the boat that is added with magnesium and the boat that is added with silver are heated simultaneously and so that thickness becomes the mode of 100nm carries out vapor deposition and form negative electrode.At this moment, so that magnesium is regulated evaporation rate with the atomicity of silver than the mode that becomes 10 pairs 1, and so that evaporation rate becomes the mode of second 0.1nm/ second～10nm/ forms negative electrode and obtain organic electroluminescent device.

The ITO electrode as anode, as negative electrode, if apply volts DS, then can be obtained the blue-light-emitting of the about 460nm of wavelength with magnesium/silver electrode.In addition, be used to obtain 2000cd/m ²The current density of original intensity implement the constant current driven test.Its result, driving the test starting voltage is 5.31V, keeps 90% (1800cd/m of initial value ²) time of above brightness is 140 hours.

< instance 7 >

< element that compound (1-2-2) is used for electron transfer layer >

Except that compound (1-2-10) is replaced to the compound (1-2-2), obtain organic EL with method according to instance 6.The ITO electrode as anode, as negative electrode, is used to obtain 2000cd/m with magnesium/silver electrode ²The current density of original intensity implement the constant current driven test.Its result, driving the test starting voltage is 5.65V, keeping the time of the brightness more than 90% of initial value is 216 hours.

< comparative example 2 >

Except that compound (1-2-10) is replaced to the compound (D), obtain organic EL with method according to instance 6.The ITO electrode as anode, as negative electrode, is used to obtain 2000cd/m with magnesium/silver electrode ²The current density of original intensity implement the constant current driven test.Its result, driving the test starting voltage is 5.15V, keeping the time of the brightness more than 90% of initial value is 68 hours.

Above result is summarized in table 4.

[table 4]

Utilizability on the industry

According to preferred form of the present invention; Especially the life-span upgrading that makes luminous element can be provided; With the also excellent organic electroluminescent device of the balance of driving voltage, possess the display unit of this organic electroluminescent device and possess the means of illumination etc. of this organic electroluminescent device.

Claims

1. electron transport material, it contains by the represented compound of formula (1):

[changing 1]

In the formula (1); Ar is that carbon number is 10～24 aryl; This aryl can be that 1～12 alkyl, carbon number are that 3～12 naphthenic base or carbon number are that 6～20 aryl replaces by carbon number; 4-pyridyl and phenyl 3 or 4 all link, and in addition, can be replaced by deuterium by at least one hydrogen in the represented compound of formula (1).

2. electron transport material, it contains by the represented compound of formula (1-1):

[changing 2]

3. electron transport material, it contains by the represented compound of formula (1-2):

[changing 3]

4. according to each the described electron transport material in the claim 1 to 3, wherein Ar is xenyl, terphenylyl or naphthyl, and this naphthyl can be replaced by phenyl.

5. according to each the described electron transport material in the claim 1 to 3, wherein Ar be 3-xenyl, 4-xenyl, meta-terphenyl-5 '-Ji, 1-naphthyl or 2-naphthyl.

6. organic electroluminescent device; It comprises: the pair of electrodes that comprises anode and negative electrode; Be configured in this pair of electrical interpolar luminescent layer, and be configured between said negative electrode and this luminescent layer and contain the electron transfer layer and/or the electron injecting layer of each the described electron transport material in the with good grounds claim 1 to 5.

7. organic electroluminescent device according to claim 6, one deck at least of wherein said electron transfer layer and electron injecting layer comprise also that to be selected from by hydroxyquinoline be at least a in the cohort formed of metal misfit thing, dipyridyl derivatives, phenanthroline derivative, borane derivative and benzimidizole derivatives.

8. according to claim 6 or 7 described organic electroluminescent devices, one deck at least of wherein said electron transfer layer and electron injecting layer also comprises and is selected from least a in the cohort of being made up of organic misfit thing of organic misfit thing of the oxide compound of basic metal, earth alkali metal, rare earth metal, alkali-metal oxide compound, alkali-metal halogenide, earth alkali metal, the halogenide of earth alkali metal, the oxide compound of rare earth metal, the halogenide of rare earth metal, alkali-metal organic misfit thing, earth alkali metal and rare earth metal.

9. display unit, it possesses according to each the described organic electroluminescent device in the claim 6 to 8.

10. means of illumination, it possesses according to each the described organic electroluminescent device in the claim 6 to 8.