CN105683255B

CN105683255B - Polymer, organic electroluminescent device composition, organic electroluminescent device, organic EL display and organic EL illuminating

Info

Publication number: CN105683255B
Application number: CN201480054297.8A
Authority: CN
Inventors: 饭田宏朗; 饭田宏一朗; 李延军; 梅基友和
Original assignee: Mitsubishi Kasei Corp
Current assignee: Mitsubishi Rayon Co Ltd
Priority date: 2013-10-04
Filing date: 2014-10-02
Publication date: 2018-05-29
Anticipated expiration: 2034-10-02
Also published as: CN108530624B; KR102157997B1; WO2015050232A1; TW201518340A; KR20160067847A; JP6565678B2; JP6879342B2; CN105683255A; CN108530624A; TWI641630B; JPWO2015050232A1; JP2019218550A

Abstract

Polymer with the repetitive unit represented by following formula (1).In formula, Ar¹、Ar²And Ar³The aromatic hydrocarbyl or aromatic heterocycle with or without substituent group are each independently represented, n represents more than 4 integer.Above-mentioned aromatic hydrocarbyl and aromatic heterocycle can it is direct or by linking group and 2 or more link together.

Description

Polymer, organic electroluminescent device composition, have organic electroluminescent device Machine EL display devices and organic EL illuminating

Technical field

The present invention relates to polymer, more particularly to the hole injection layer and hole transport as organic electroluminescent device The useful polymer of layer, the organic electroluminescent device containing the polymer are with composition and with the organic electroluminescent The organic el display panel and organic EL illuminating of element.

Background technology

As the forming method of the organic layer in organic electroluminescent device, vacuum vapour deposition and wet type film forming can be enumerated Method.The laminationization of vacuum vapour deposition is easy, thus with easily improving charge from the injecting of anode and/or cathode, will easily swash Son is enclosed in the advantages of luminescent layer.On the other hand, wet type membrane formation is not required vacuum technology, easy large area, by using The coating fluid that multiple material with various functions is mixed, with can easily be formed containing with a variety of of various functions The advantages that layer of material.

But wet type membrane formation is difficult to lamination, thus compared with the element with being obtained using vacuum vapour deposition, driving is stablized Property is poor, and present situation is that realistic scale has not yet been reached except for a part thereof.

Therefore, in order to utilize wet type membrane formation carry out lamination, it is desirable that a kind of charge-transporting with crosslinkable groups Polymer, and it is developed.For example, a kind of organic electroluminescent device is disclosed in Patent Documents 1 to 5, Containing the polymer with specific repetitive unit, formed by wet type membrane formation lamination.

Prior art literature

Patent document

Patent document 1：International Publication No. 2009/123269

Patent document 2：International Publication No. 2010/018813

Patent document 3：International Publication No. 2011/078387

Patent document 4：International Publication No. 2011/093428

Patent document 5：No. 5246386 publications of Japanese Patent No.

The content of the invention

The subject that the invention solves

But these elements described in Patent Documents 1 to 5 are with driving voltage is high, luminosity is low, driving short life The problem of.It is therefore desirable to the charge injection transmittability of charge transport materials and the raising of durability.

Then, problem of the invention be to provide a kind of hole injection transmittability is high, durability is high polymer and Organic electroluminescent device composition comprising the polymer.In addition, the problem of the present invention is to provide brightness height, driving longevity Order long organic electroluminescent device.

Solution for solving the problem

Present inventor has performed further investigation, it turns out that, it, can be with by using the polymer with specific repetitive unit The above subject is solved, is had thus completed the present invention.

That is, the present invention relates to following technical proposals.

[1] a kind of polymer, with the repetitive unit represented by following formula (1).

(in formula, Ar¹、Ar²And Ar³Each independently represent the aromatic hydrocarbyl or aromatic series with or without substituent group Heterocycle, n represent more than 4 integer.Above-mentioned aromatic hydrocarbyl and aromatic heterocycle can be direct or by linking groups And 2 or more link together.)

[2]

Polymer as described in [1], wherein, Ar¹、Ar²And Ar³In at least more than 1 there is crosslinking as substituent group Property group.

[3]

Polymer as described in [2], wherein, crosslinkable groups are the group comprising benzocyclobutene ring.

[4]

Polymer as described in [2] or [3], with the repetitive unit represented by above-mentioned formula (1) of more than two kinds, at least 1 Kind repetitive unit includes crosslinkable groups, and at least one kind of repetitive unit does not include crosslinkable groups.

[5]

Such as the polymer any one of [1]~[4], wherein, Ar¹And Ar²At least one of be with or without The 2- fluorenyls of substituent group.

[6]

Such as the polymer any one of [1]~[5], wherein, Ar³For the group represented by following formula (2).

(in formula, m represents 1~3 integer.)

[7]

Such as the polymer any one of [1]~[5], wherein, Ar³For the linker represented by by following formula (3) Group and aromatic hydrocarbyl or aromatic heterocycle that 2 or more link together.

(in formula, p represents 1~10 integer.R¹、R²Each independently represent hydrogen atom or with or without substitution Alkyl, aromatic hydrocarbyl or the aromatic heterocycle of base.R¹、R²There are at 2 or more, can be the same or different.)

[8]

Such as the polymer any one of [1]~[7], weight average molecular weight (Mw) is 20, more than 000, dispersion degree (Mw/Mn) it is less than 2.5.

[9]

A kind of organic electroluminescent device composition contains the polymer any one of [1]~[8].

[10]

A kind of organic electroluminescent device is to have anode, cathode on substrate and positioned at the anode and the cathode Between organic layer organic electroluminescent device,

The organic layer, which includes, uses the organic electroluminescent device composition described in [9] to be formed by wet type membrane formation Layer.

[11]

Organic electroluminescent device as described in [10], wherein, the layer formed by above-mentioned wet type membrane formation is hole At least one of implanted layer and hole transmission layer.

[12]

Organic electroluminescent device as described in [10] or [11], wherein, it is injected between the anode and the cathode comprising hole Layer, hole transmission layer and luminescent layer, above-mentioned hole injection layer, hole transmission layer and luminescent layer are all through wet type membrane formation shape Into.

[13]

A kind of organic EL display has the organic electroluminescent device any one of [10]~[12].

[14]

A kind of organic EL illuminating has the organic electroluminescent device any one of [10]~[12].

The effect of invention

The polymer of the present invention is continuous with 4 or more between the nitrogen-atoms and nitrogen-atoms with lone pair To phenylene, highest occupied orbital (HOMO) delocalization, therefore cavity transmission ability is excellent extensively enough.If to phenylene With substituent group, then the dihedral angle each phenylene becomes larger due to steric hindrance, hampers the delocalization of track, thus nothing Method obtains high cavity transmission ability, but does not have substituent group to phenylene in the polymer of the present invention, therefore track is abundant Ground delocalization has high cavity transmission ability.

In addition, the polymer of the present invention between 2 nitrogen-atoms with 4 or more to phenylene, therefore with to sub- benzene Base is compared when being less than 3, and the interaction between nitrogen-atoms is small, and ionization potential becomes larger, and the hole injection to luminescent layer is excellent.If from Hole transmission layer is injected to the hole of luminescent layer to be improved, then the accumulation in hole of hole transmission layer, the interlayer that shines is suppressed, therefore The durability of organic electroluminescent device improves.

In addition, the polymer of the present invention has 4 or more continuously to phenylene, lowest unoccupied molecular orbital (LUMO) is enough extensively General and delocalization, therefore for the excellent in te pins of durability of electronics, exciton.At 4 or more continuously in phenylene, LUMO is distributed In 2 or more of the position for being located remotely from 2 nitrogen-atoms continuously to phenylene, relatively LUMO is not distributed in electricity as a result, Sub or weak exciton nitrogen-atoms periphery, thus excellent in te pins of durability.If having substituent group to phenylene, two each phenylene Face angle becomes larger due to steric hindrance, hampers the delocalization of track, thus can not obtain high-durability, but the polymerization of the present invention Do not have substituent group, therefore track fully delocalization to phenylene in object, there is high-durability.

In addition, wet type film forming gained is carried out with composition using the organic electroluminescent device of the polymer containing the present invention To layer will not crack, be flat.If using the organic electroluminescent device in the present invention, brightness is high, drives the longevity Life length.

In addition, the electrochemical stability of the polymer of the present invention is excellent, therefore, it may be considered that will include and use the polymer The element of the layer of formation is applied to flat-panel monitor (such as OA computers are used or wall hanging TV set), car-mounted display element, movement Phone shows or make use of the light source of the feature as planar illuminant (for example, the light source of duplicator, liquid crystal display or metering The backlight of table class), display board, in mark lamp, technological value is very high.

Description of the drawings

Fig. 1 is the schematic cross-section for the configuration example for showing the organic electroluminescent device of the present invention.

Specific embodiment

The following detailed description of embodiments of the present invention, but the explanation for the technical characteristic recorded below is only the reality of the present invention An example (typical example) of mode is applied, without departing from its main points, then the present invention is not particularly limited in these contents.

" quality % " is identical with " weight % " meaning in this specification.

The polymer of the present invention is the polymer for having the repetitive unit represented by following formula (1).

[on Ar¹、Ar²]

Ar¹、Ar²Represent the aromatic hydrocarbyl or aromatic heterocycle of 1 valency with or without substituent group.

As aromatic hydrocarbyl, for example, phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, perylene ring, aphthacene ring, pyrene 6 yuan of rings such as ring, benzoin ring, 1,2- benzos phenanthrene ring, benzo [9,10] phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring monocyclic or 2~5 1 valency group of the condensed ring of ring.

As aromatic heterocycle, for example, furan nucleus, benzofuran ring, thiphene ring, benzothiophene ring, pyrroles Ring, pyrazole ring, imidazole ring, oxadiazole rings, indole ring, carbazole ring, pyrrolo- imidazole ring, pyrrolo-pyrazole ring, pyrrolopyrrole Ring, Thienopyrroles ring, thienothiophene ring, furans and pyrrole ring, furans and furan nucleus, thienofuran ring, Ben Bing Yi Evil Azoles ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinolin 5 or 6 yuan of ring, cinnolines ring, quinoxaline ring, phenanthridines ring, perimidine ring, quinazoline ring, quinazolinone ring, azulenes etc. 1 valency group of monocyclic or 2~4 rings the condensed ring of ring.

From charge-transporting it is excellent in terms of, from the aspect of excellent in te pins of durability, Ar¹、Ar²Optimization aromatic alkyl, wherein More preferable phenyl ring, 1 valency group of fluorenes ring, i.e. phenyl, fluorenyl, further preferred fluorenyl, particularly preferred 2- fluorenyls.

As the substituent group that aromatic hydrocarbyl, aromatic heterocycle can have, as long as not significantly reducing this polymer Characteristic is not particularly limited, for example, the group in following substituent group Z, optimizing alkyl, alkoxy, Aromatic hydrocarbyl, aromatic heterocycle, more preferable alkyl.

[substituent group Z]

Such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tertiary butyl, n-hexyl, hexamethylene The carbon numbers such as base, dodecyl are usually more than 1, are usually less than 24, are preferably less than 12 straight chain, branch or cricoid Alkyl；

Such as the carbon numbers such as vinyl are usually more than 2, are usually less than 24, are preferably less than 12 alkenyl；

Such as the carbon numbers such as acetenyl are usually more than 2, are usually less than 24, are preferably less than 12 alkynyl；

Such as the carbon numbers such as methoxyl group, ethyoxyl are usually more than 1, are usually less than 24, are preferably less than 12 alkane Oxygroup；

Such as the carbon numbers such as phenoxy group, naphthoxy, pyridine oxygroup are usually more than 4, are preferably more than 5, are usually 36 Below, preferably less than 24 aryloxy group；

Such as the carbon numbers such as methoxycarbonyl, ethoxy carbonyl are usually more than 2, are usually less than 24, are preferably 12 Following alkoxy carbonyl group；

Such as the carbon numbers such as dimethylamino, diethylamino are usually more than 2, are usually less than 24, are preferably 12 Following dialkyl amido；

Such as the carbon numbers such as diphenyl amino, xylyl amino, N- carbazyls be usually more than 10, be preferably 12 with Above, it is usually less than 36, is preferably less than 24 ammonia diaryl base；

Such as the carbon numbers such as phenylmethyl amino are usually more than 7, are usually less than 36, are preferably less than 24 aralkyl Base amino；

Such as the carbon numbers such as acetyl group, benzoyl are usually more than 2, are usually less than 24, are preferably less than 12 Acyl group；

Such as the halogen atoms such as fluorine atom, chlorine atom；

Such as the carbon numbers such as trifluoromethyl are usually more than 1, are usually less than 12, are preferably less than 6 alkylhalide group；

Such as the carbon numbers such as methyl mercapto, ethylmercapto group are usually more than 1, are usually less than 24, are preferably less than 12 alkane Sulfenyl；

Such as the carbon numbers such as thiophenyl, naphthalene sulfenyl, pyridine thio are usually more than 4, are preferably more than 5, are usually 36 Below, preferably less than 24 arylthio；

Such as the carbon numbers such as trimethyl silyl, triphenyl-silyl are usually more than 2, are preferably more than 3, are logical Often it is less than 36, is preferably less than 24 silicyl；

Such as the carbon numbers such as trimethylsiloxy, triphenylsiloxy group be usually more than 2, be preferably 3 with Above, it is usually less than 36, is preferably less than 24 siloxy；

Cyano；

Such as the carbon numbers such as phenyl, naphthalene are usually more than 6, are usually less than 36, are preferably less than 24 aromatic series Alkyl；

Such as the carbon numbers such as thienyl, pyridyl group are usually more than 3, are preferably more than 4, are usually less than 36, preferably For less than 24 aromatic heterocycle.

In these substituent groups, from the aspect of deliquescent, preferably carbon number is 1~12 alkyl and carbon number For 1~12 alkoxy.

In addition, above-mentioned each substituent group can further have substituent group, it, can be from above-mentioned (substituent group as its example Z selected in the group illustrated in item).

[on Ar³]

Ar³Represent the aromatic hydrocarbyl or aromatic heterocycle of the divalent with or without substituent group.Above-mentioned aromatic hydrocarbon Base and aromatic heterocycle can be 2 or more and be bonded together.

As aromatic hydrocarbyl, for example, phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, perylene ring, aphthacene ring, pyrene 6 yuan of rings such as ring, benzoin ring, 1,2- benzos phenanthrene ring, benzo [9,10] phenanthrene ring, acenaphthene ring, fluoranthene ring, fluorenes ring monocyclic or 2~5 The divalent group of the condensed ring of ring.

As aromatic heterocycle, for example, furan nucleus, benzofuran ring, thiphene ring, benzothiophene ring, pyrroles Ring, pyrazole ring, imidazole ring, oxadiazole rings, indole ring, carbazole ring, pyrrolo- imidazole ring, pyrrolo-pyrazole ring, pyrrolopyrrole Ring, Thienopyrroles ring, thienothiophene ring, furans and pyrrole ring, furans and furan nucleus, thienofuran ring, Ben Bing Yi Evil Azoles ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinolin 5 or 6 yuan of ring, cinnolines ring, quinoxaline ring, phenanthridines ring, perimidine ring, quinazoline ring, quinazolinone ring, azulenes etc. The divalent group of monocyclic or 2~4 rings the condensed ring of ring.

From charge-transporting it is excellent in terms of, from the aspect of excellent in te pins of durability, Ar³Optimization aromatic alkyl, wherein more It is preferred that the divalent group of phenyl ring, fluorenes ring, i.e. phenylene, fluorenylidene, further preferred 1,3- phenylenes, Isosorbide-5-Nitrae-phenylene, 2,7- are sub- Fluorenyl.

As the substituent group that aromatic hydrocarbyl, aromatic heterocycle can have, as long as not significantly reducing this polymer Characteristic is not particularly limited, for example, the group in above-mentioned substituent group Z, optimizing alkyl, alkoxy, Aromatic hydrocarbyl, aromatic heterocycle, more preferable alkyl.

Ar³When being bonded the group formed for the above-mentioned aromatic hydrocarbyls and aromatic heterocycle of 2 or more, transmitted from charge From the aspect of the excellent aspect of property, excellent in te pins of durability, preferably 2~6 these groups link together.The aromatic series linked Alkyl and aromatic heterocycle can be a kind, or two or more.

Excellent aspect, Ar are injected from charge-transporting, durability and from the hole of anode-side³Particularly preferably For the group formed to phenylene bonding represented by 1~3 following formula (2).

(in formula, m represents 1~3 integer.)

In addition, Ar³It, can be with during the group formed for above-mentioned aromatic hydrocarbyls and the aromatic heterocycle bondings of 2 or more It is bonded by linking group.In this case, as linking group, it is preferably selected from by-CR¹R²―、―O―、― CO―、―NR³- and the group of-S-composition in group；And they are linked into 2~10 groups formed.In addition, even In the case of knot 2 or more, linking group can be a kind, or two or more.Herein, R¹~R³It each independently represents Hydrogen atom or the alkyl with or without substituent group, the aromatic hydrocarbyl with or without substituent group have or do not have The aromatic heterocycle of substituted base.As alkyl, aromatic hydrocarbyl or aromatic heterocycle, preferably with above-mentioned substituent group Z Described in the same group of group.As linking group, from the aspect of durability, particularly preferred-CR¹R²- and 2 ~6-CR to link together¹R²-, more preferable-CR¹R²―。

From the aspect of durability, Ar³Particularly preferably by the linking group represented by following formula (3) 2 with On the aromatic hydrocarbyl and aromatic heterocycle that link together.

(in formula, p represents 1~10 integer.R¹、R²Each independently represent hydrogen atom or with or without substitution Alkyl, aromatic hydrocarbyl or the aromatic heterocycle of base.As alkyl, aromatic hydrocarbyl or aromatic heterocycle, preferably with it is upper State the same group of group described in substituent group Z.R¹、R²In the case of there are 2 or more, can it is identical can not also Together.)

[on n]

N represents more than 4 integer.Excellent aspect, n are injected from cavity transmission ability height, by the hole of anode-side Preferably 4.From cavity transmission ability height, excellent aspect is injected to the hole of luminescent layer, n is preferably 5.

[on crosslinkable groups]

The preferred Ar of polymer of the present invention¹、Ar²And Ar³In at least more than 1 there is 5 base of bridging property as substituent group Group.By with crosslinkable groups, reacting (indissolubleization reaction) caused by the irradiation by heat and/or active energy beam It is front and rear, dissolubility in organic solvent can generate significant differences.From the aspect of durability, further preferably have Crosslinkable groups are as Ar³Substituent group.

Crosslinkable groups refer to following radicals：The friendship is located at forming by the irradiation of heat and/or active energy beam The radical reaction of other molecules near connection property group generates the group of new chemical bond.In this case, the group reacted It can be the group identical with crosslinkable groups, or different groups.As crosslinkable groups, for example, with Under crosslinkable groups group T shown in group.

＜ crosslinkable groups group T ＞

(in formula, R¹¹~R¹³Represent hydrogen atom or alkyl.R⁴、R⁵Represent hydrogen atom, alkyl or alkoxy.Ar⁷Expression has Or the aromatic hydrocarbyl without substituent group or the aromatic heterocycle with or without substituent group.)

As R¹¹~R¹³、R⁴、R⁵Alkyl, it is usually preferred to carbon number be less than 6 linear chain or branch chain chain-like alkyl, For example, methyl, ethyl, n-propyl, 2- propyl, normal-butyl, isobutyl group etc..More preferably methyl or ethyl.If R¹¹~R¹³、R⁴、 R⁵Carbon number for less than 6, will not spatially hinder cross-linking reaction, the insoluble tendency easy to perform with film.

As R⁴、R⁵Alkoxy, it is usually preferred to carbon number be less than 6 linear chain or branch chain chain alkoxy, such as For methoxyl group, ethyoxyl, positive propoxy, 2- propoxyl group, n-butoxy etc..More preferably methoxyl group, ethyoxyl.If R⁴、R⁵Carbon Atomicity is less than 6, will not spatially hinder cross-linking reaction, has the insoluble tendency easy to perform of film.

In addition, as Ar⁷The aromatic hydrocarbyl with or without substituent group, for example, with 1 freedom Monocyclic or 2~5 rings the condensed ring of 6 yuan of rings such as phenyl ring, naphthalene nucleus of valence.Particularly preferably there is 1 free atom valency Phenyl ring.In addition, Ar⁷It can also be the base that 2 the above is made to be formed with or without the aromatic hydrocarbyl bonding of substituent group Group.As such group, biphenylene, sub- terphenyl etc. can be enumerated, is preferably 4,4 '-biphenylene.

Among these, from it is reactive high, be easy to using crosslinking progress it is thawless from the aspect of, preferably epoxy group, oxa- The cyclic ether groups such as cyclobutane base；Vinyl ether group；Deng the group by cationic polymerization progress cross-linking reaction.Wherein, from easy Control cationic polymerization speed from the aspect of, more preferable oxetanyl, from be not easy generation in cationic polymerization sometimes From the aspect of the hydroxyl that can cause element deterioration, preferred vinyl ether.

In addition, from the aspect of the electrochemical stability for further improving element, preferred aryl vinyls such as cinnamoyl Carbonyl, the benzocyclobutene ring with 1 free atom valency etc. can carry out the group of cycloaddition reaction.

In addition, in crosslinkable groups, from the aspect of the structure after crosslinking is particularly stable, particularly preferably there is 1 The benzocyclobutene ring of free atom valency.

In the polymer of the present invention, crosslinkable groups can be with aromatic hydrocarbyl, aromatic heterocycle, and/or linker Group Direct Bonding, can also with the group Direct Bonding beyond aromatic hydrocarbyl and/or aromatic heterocycle, can also by appoint The divalent group of meaning and be bonded on these groups.As arbitrary divalent group, will preferably be selected from-O- bases ,-C (=O)-bases and (with or without substituent group)-CH₂Group in-base links 1~30 group formed with random order.

From using crosslinking carry out fully it is insoluble, be easy to from the aspect of forming other layers with wet type membrane formation on it, Crosslinkable groups possessed by the polymer of the present invention are preferably more.But then, from the layer formed be not likely to produce crackle, Unreacted crosslinked group is difficult to remain, from the aspect of the easy long lifetime of organic electroluminescent device (organic EL element), hands over Connection property group is preferably less.

The usual average out to more than 1 of crosslinkable groups present in 1 polymer chain in the polymer of the present invention is preferably put down It is more than 2 and usually less than 200, is preferably less than 100.

In addition, the quantity for the crosslinkable groups that the polymer of the present invention has can be with compared with every 1000 polymer molecule The form of the quantity of amount represents.

The quantity of crosslinkable groups that the polymer of the present invention is had is with compared with the number of every 1000 polymer molecular weight When the form of amount is indicated, compared with every 1000 molecular weight, it is usually less than 3.0, is preferably less than 1.0, more preferably For less than 0.5, further preferably less than 0.2 and usually more than 0, preferably 0.01 or more, be more preferably 0.02 or more, further preferably 0.05 or more.

It if the quantity of crosslinkable groups is within the above range, is difficult to crack, is easy to get flat film.And Crosslink density appropriateness, thus remaining unreacted crosslinkable groups are few in layer after cross-linking reaction, therefore, it is difficult to influence gained The service life of the element arrived.

In addition, the slightly solubility after cross-linking reaction in organic solvent is enough, therefore it is easy to utilize wet type membrane formation shape Into multilayer laminated structure.

Herein, on every 1000 molecular weight of polymer crosslinkable groups quantity, in the polymer not include its end Base can be calculated according to the molar ratio and structural formula of the monomer that feeds intake when synthesizing.

If it for example, is illustrated with the situation of the subject polymer 1 synthesized in aftermentioned synthesis example 1, in target polymerization In object 1, the molar mass average of the repetitive unit in addition to end group is 1148.69, and crosslinkable groups are compared with every 1 Repetitive unit average out to 0.1156.If merely calculating its proportion of utilization, the crosslinking of every 1000 molecular weight is calculated Property group quantity be 0.10.

[molecular weight on polymer]

The weight average molecular weight of the polymer of the present invention is usually less than 3,000,000, is preferably less than 1,000,000, more Preferably 500, less than 000, be more preferably 200, less than 000, and usually 2, more than 500, be preferably 5,000 with Above, more preferably more than 10,000, further preferably more than 30,000.

If the weight average molecular weight of polymer is more than above-mentioned upper limit value, dissolubility in a solvent reduces, it is therefore possible to Damage film forming.If in addition, the weight average molecular weight of polymer be less than above-mentioned lower limiting value, the glass transition temperature of polymer, Fusing point and gasification temperature reduce, therefore heat resistance reduces sometimes.

In addition, the number-average molecular weight (Mn) in the polymer of the present invention is usually 2, less than 500,000, is preferably 750, Less than 000, be more preferably 400, less than 000, and usually 2, more than 000, be preferably 4, more than 000, more preferably 8,000 Above, it is more preferably more than 20,000.

In addition, the dispersion degree (Mw/Mn) in the polymer of the present invention is preferably less than 3.5, further preferably 2.5 with Under, particularly preferably less than 2.0.It should be noted that the value of dispersion degree is the smaller the better, therefore lower limiting value ideally is 1.If The dispersion degree of the polymer is then easy to purify below above-mentioned upper limit value, and dissolubility in a solvent and charge transmission energy Power is good.

In general, the weight average molecular weight of polymer measures to determine by SEC (size exclusion chromatography).During SEC is measured, high score The dissolution time of son amount ingredient is short, and the dissolution time of low molecular weight compositions is long, uses the polystyrene (mark according to known to molecular weight Quasi- sample) dissolution time calculate calibration curve, the dissolution time of sample is converted into molecular weight, thus calculates Weight-average molecular Amount.

[concrete example]

The concrete example of the polymer of the present invention is illustrated below, but the polymer of the present invention is not limited to these.It needs to illustrate , the molar ratio of the digital representation repetitive unit in chemical formula.

Number in chemical formula is related with the molar ratio of repetitive unit, for example, in above-mentioned formula (1), comprising with friendship In the case of the polymer of the repetitive unit of connection property group and the repetitive unit without crosslinkable groups, on molar ratio, phase For the repetitive unit with crosslinkable groups, the repetitive unit without crosslinkable groups is usually more than 0, be preferably 1 with It is upper, more preferably more than 2, further preferably more than 5, and usually less than 100, be preferably less than 50, more preferably 20 Below, it is more preferably less than 10.If the molar ratio of the repetitive unit with crosslinkable groups is too small, after cross-linking reaction Slightly solubility in organic solvent is insufficient, has and the tendency that wet type membrane formation forms multilayer laminated structure is difficult to be utilized；If mole It than excessive, then easily cracks, has and be difficult to obtain the tendency of flat film.

These polymer can be in random copolymer, alternate copolymer, block copolymer or graft copolymer etc. It is any, putting in order for monomer is not limited.

The manufacturing method of the polymer of the present invention is not particularly limited, as long as the polymer that can obtain the present invention is exactly to appoint Meaning.It such as can be by Suzuki (Suzuki) reaction, grignard (Grignard) reaction, Liv Ullmann (Ullmann) reaction, cloth The C-C keys such as conspicuous Grindelwald-Hartwig (Buchwald-Hartwig) reaction form reaction and C-N keys form reaction and carry out group It closes to manufacture.But 4 or more of the feature of the polymer as the present invention continuously dissolve the part of phenylene to lack The structure of property, therefore preferably carry out following study intensively：To Ar¹And/or Ar²It imports and improves deliquescent substituent group, build 4 afterwards Above continuously to the part of phenylene.Studying intensively in this way, can improve the purity of monomer (repetitive unit), be easy to get institute The polymer of the desired degree of polymerization and molecular weight distribution.

Specifically, the high primary amine of dissolubilities such as 9,9- dialkyl group -2- aminofluorenes is preferably made to be reacted with bromobenzene, are obtained Secondary amine, afterwards using N- bromo-succinimides etc. by the para-bromination of amino, and then with 4,4 '-biphenyl hypoboric acid, 4,4 "-right The reactions such as terphenyl hypoboric acid or their ester derivant build intermediate 1.Intermediate 1 is made to be reacted with dihalide, so as to To the polymer of the present invention.

Unilateral side carry out respectively 4,4 '-biphenyl hypoboric acid, 4,4 "-para-terpheny hypoboric acid or their ester derivant etc. with The reaction of bromide, so as to so that 2 Ar of intermediate 1¹Be formed as mutually different group.

Additionally, it is preferred that making 9, the high primary amine of dissolubilities and 4 such as 9- dialkyl group -2- aminofluorenes, 4 '-'-dibromobiphenyl carries out anti- Should, it obtains after there is single bromide of secondary amine sites, is converted into borate with double (pinacol combined) two boron etc. and obtains intermediate 2, and then the primary amine for making dissolubility high and 4,4 '-'-dibromobiphenyl, 4, the dihalide such as 4 "-two bromo- para-terpheny reacted and Intermediate 3 is obtained, intermediate 2 is made to be reacted with intermediate 3 and build intermediate 4.The intermediate 4 is made to be carried out with dihalide Reaction, so as to obtain the polymer of the present invention.

It should be noted that in general, the reaction process of primary amine or secondary amine compound and halide is for example in potassium carbonate, tertiary fourth It is carried out in the presence of the alkali such as sodium alkoxide, triethylamine.In addition, such as can also in copper or palladium complex in the presence of transition-metal catalyst It carries out.

It should be noted that in general, the reaction process of boron derivative and halide is for example in potassium carbonate, sodium tert-butoxide, three It is carried out in the presence of the alkali such as ethamine.In addition, as needed such as can also in copper or palladium complex transition-metal catalyst exist Lower progress.And then in the reaction process with boron derivative, such as can be in potassium carbonate, potassium phosphate, sodium tert-butoxide, triethylamine etc. It is carried out in the presence of the transition-metal catalysts such as alkali or palladium complex.

The polymer of the present invention is preferably as organic electroluminescent device materials'use.That is, polymer of the invention is preferred For organic electroluminescent device material.

The polymer of the present invention is in the case of as organic electroluminescent device material, preferably as formation organic electroluminescence Material, the i.e. charge transport materials of hole injection layer and at least one of hole transmission layer in light-emitting component use.

, can be containing a kind of polymer of the invention in the case where being used as charge transport materials, it can also be with arbitrary Combination and arbitrary ratio contain two or more.

It is formed using the polymer of the present invention in the hole injection layer and hole transmission layer of organic electroluminescent device extremely When few a kind of, the content of the polymer of the present invention in hole injection layer and/or hole transmission layer be usually 1~100 mass %, Preferably 5~100 mass %, further preferably 10~100 mass %.If above range, then hole injection layer and/or sky The charge-transporting of cave transport layer improves, and driving voltage reduces, and driving stability improves, therefore it is preferred that.

When the polymer of the present invention is not 100 mass % in above-mentioned hole injection layer and/or hole transmission layer, as structure Into hole injection layer and/or the ingredient of hole transmission layer, aftermentioned hole transport ability compound etc. can be enumerated.

Further, since organic electroluminescent device can be easily manufactured, thus the polymer of the present invention is preferred for leading to Cross the organic layer of wet type membrane formation formation.

[organic electroluminescent device composition]

The organic electroluminescent device composition of the present invention contains the polymer of the present invention.It should be noted that this hair Bright organic electroluminescent device composition can containing a kind of polymer of the invention, can also in any combination and appoint The ratio of meaning contains two or more.

{ content of polymer }

The organic electroluminescent device of the present invention with the content of the polymer of the present invention in composition be usually 0.01~ 70 mass %, it is preferably 0.1~60 mass %, further preferably 0.5~50 mass %.

It is difficult to generate defect if the organic layer in above range, then formed, and is difficult to generate film thickness unevenness, thus it is excellent Choosing.

In addition to the polymer of the present invention, the organic electroluminescent device composition in the present invention can include solvent Deng.

{ solvent }

The organic electroluminescent device of the present invention usually contains solvent with composition.The solvent preferably dissolves the poly- of the present invention Close object.Specifically, more than 0.05 mass %, preferably more than 0.5 mass % is usually dissolved at room temperature, is more preferably The solvent of polymer of the invention more than 1 mass % is suitable.

As the concrete example of solvent, the aromatic systems solvent such as toluene, dimethylbenzene, trimethylbenzene, cyclohexylbenzene can be enumerated；1,2- Dichloroethanes, chlorobenzene, o-dichlorohenzene etc. contain halogen solvent；Glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol -1- monomethyl ethers The fatty ethers such as acetic acid esters (PGMEA), 1,2- dimethoxy benzenes, 1,3- dimethoxy benzenes, methyl phenyl ethers anisole, phenetole, 2- methoxyl groups Aromatic ethers such as toluene, 3- methoxy toluenes, 4- methoxy toluenes, 2,3- dimethylanisoles, 2,4- dimethylanisoles etc. Ether series solvent；The aliphatic esters such as ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate；Phenylacetate, propionic acid benzene The esters such as aromatic esters such as ester, methyl benzoate, ethyl benzoate, isopropyl benzoate, propyl benzoate, n-butylbenzoate system Solvent；Wait organic solvents and in aftermentioned hole injection layer formation composition or hole transmission layer formation composition The organic solvent used.

It should be noted that solvent can use a kind, can also be shared in any combination with arbitrary ratio 2 kinds with On.

Wherein, the surface as the solvent, preferably 20 DEG C contained in the organic electroluminescent device composition of the present invention Tension is usually less than the solvent of 40dyn/cm, preferably below 36dyn/cm, more preferably below 33dyn/cm.

Using the organic electroluminescent device composition of the present invention, film is formed by wet type membrane formation, and makes this hair Bright crosslinked polymer and in the case of forming organic layer, the compatibility of preferred solvent and substrate is high.This is because film quality is equal Even property can produce bigger effect the uniformity and stability that organic electroluminescent device shines.Therefore, for wet type membrane formation The middle organic electroluminescent device composition used, in order to form levelability higher, film evenly, it is desirable that surface tension It is low.Therefore, by using the solvent with low surface tension as described above, the equal of the polymer containing the present invention can be formed Even layer, and then uniform cross-linked layer can be formed, therefore it is preferred that.

The concrete example of solvent as low surface tension can enumerate above-mentioned toluene, dimethylbenzene, trimethylbenzene, cyclohexylbenzene Etc. ether series solvents, trifluoromethoxy methyl phenyl ethers anisole, the five fluorine first such as ester series solvents, the methyl phenyl ethers anisole such as aromatic systems solvent, ethyl benzoate Oxygroup benzene, 3- (trifluoromethyl) methyl phenyl ethers anisole, ethyl (pentafluoro benzoic acid ester) etc..

On the other hand, as the solvent that contains in the organic electroluminescent device composition of the present invention, preferably 25 DEG C Vapour pressure is usually below 10mmHg, is preferably below 5mmHg, is usually the solvent of more than 0.1mmHg.By using such Solvent, the technique for being suitable for use with wet type membrane formation manufacture organic electroluminescent device can prepare and be suitable for the poly- of the present invention Close the organic electroluminescent device composition of the property of object.

As the concrete example of such solvent, it is molten that the aromatic systems such as above-mentioned toluene, dimethylbenzene, trimethylbenzene can be enumerated Agent, ether series solvent and ester series solvent.

However, moisture is it is possible that cause the performance degradation of organic electroluminescent device, wherein being especially possible to promote to connect Luminance-reduction during continuous driving.Therefore, in order to reduce remaining moisture in wet type film forming as far as possible, in above-mentioned solvent, preferably The solubility of 25 DEG C of water is the solvent of the solvent of below 1 mass %, more preferably below 0.1 mass %.

The organic electroluminescent device of the present invention is usually more than 10 mass % with the content of the solvent contained in composition, Preferably more than 30 mass %, more preferably more than 50 mass %, particularly preferably more than 80 mass %.By making containing for solvent It measures that the flatness of formed layer more than above-mentioned lower limit, can be made and has good uniformity.

The organic electroluminescent device composition of the present invention is in the case of for forming hole injection layer, from low resistance It sets out in terms of change, preferably further containing electron acceptor compound.

As electron acceptor compound, preferably have oxidability, have from polymer one electronics of receiving of the invention Ability compound.Specifically, the compound that preferably electron affinity is more than 4eV, further preferred electron affinity For the compound of more than 5eV.

As such electron acceptor compound, for example, selected from by triarylboron, metal halide, road Lewis acid, organic acid, salt, arylamine and the salt and arylamine of metal halide and 1 in the group of lewis acidic salt composition Kind or compound of more than two kinds etc..

Specifically, 4- isopropyls -4 '-methyldiphenyl base iodine four (pentafluorophenyl group) borate, triphenyl can be enumerated Salt (International Publication No. 2005/089024) after the substitution of the organic groups such as sulfonium tetrafluoroborate；Iron chloride (III) (Japan Unexamined Patent 11-251067 publications), the high valence inorganic compound such as ammonium persulfate；The cyano compounds such as tetracyanoethylene；Three The aromatic series boron compounds such as (pentafluorophenyl group) borine (Japanese Unexamined Patent Publication 2003-31365 publications)；Fullerene derivate and iodine etc..

As such compound, it is however preferred to have belonging to long period type periodic table (below, as long as no special note It is bright, in the case where being known as " periodic table ", refer to long period type periodic table.) the 15th~17 race element on it is at least one The ionic compound for the structure that organic group is bonded with carbon atom, the particularly preferably chemical combination represented by following formula (4) Object.

In formula (4), R⁶Expression carbon atom and A₁The organic group of bonding, R⁷Represent arbitrary substituent group.R⁶And R⁷It can be with It is mutually bonded and forms ring.

As R⁶As long as with A₁Bonded portion have carbon atom organic group, without departing from the present invention master Its species is just not particularly limited in purport.On R⁶Molecular weight, in terms of the value comprising substituent group, be usually less than 1000, it is excellent Elect less than 500 scope as.

As R⁶Preference, from the aspect of positive charge delocalization is made, can enumerate alkyl, alkenyl, alkynyl, Aromatic hydrocarbyl, aromatic heterocycle.Wherein, due to going back thermostabilization, thus preferred virtue while positive charge delocalization is made Fragrant race's alkyl or aromatic heterocycle.

As aromatic hydrocarbyl, following radicals can be enumerated：It is 5 yuan of rings or 6 yuan of rings with 1 free atom valency Monocyclic or 2~5 rings condensed ring is the group for making positive charge further delocalization on the base.It, can as its concrete example To enumerate the phenyl ring with 1 free atom valency, naphthalene nucleus, anthracene nucleus, phenanthrene ring, perylene ring, aphthacene ring, pyrene ring, benzoin Ring, 1,2- benzos phenanthrene ring, benzo [9,10] phenanthrene ring, acenaphthene ring, fluorenes ring etc..

As aromatic heterocycle, following radicals can be enumerated：It is 5 yuan of rings or 6 yuan of rings with 1 free atom valency Monocyclic or 2~4 rings condensed ring, be the group for making positive charge further delocalization on the base.It, can as its concrete example To enumerate the furan nucleus with 1 free atom valency, benzofuran ring, thiphene ring, benzothiophene ring, pyrrole ring, pyrazole ring, three Azoles ring, imidazole ring, oxadiazole rings, indole ring, carbazole ring, pyrrolo- imidazole ring, pyrrolo-pyrazole ring, pyrrolopyrrole ring, thiophene Fen and pyrrole ring, thienothiophene ring, furans and pyrrole ring, furans and furan nucleus, thienofuran ring, benzoisoxazole ring, Benzisothiazole ring, benzimidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinolin ring, are scolded at pyridine ring Quinoline ring, quinoxaline ring, phenanthridines ring, perimidine ring, quinazoline ring, quinazolinone ring, azulenes etc..

As alkyl, straight-chain, branched or cricoid alkyl can be enumerated, carbon number be usually more than 1 and Usually less than 12, it is preferably less than 6.As concrete example, methyl, ethyl, n-propyl, 2- propyl, normal-butyl, different can be enumerated Butyl, tertiary butyl, cyclohexyl etc..

As alkenyl, carbon number can be enumerated and be usually more than 2, be usually less than 12, be preferably less than 6 alkene Base.As concrete example, vinyl, pi-allyl, 1- cyclobutenyls etc. can be enumerated.

As alkynyl, carbon number can be enumerated and be usually more than 2, be usually less than 12, be preferably less than 6 alkynyl. As concrete example, acetenyl, propargyl etc. can be enumerated.

Without departing from the purport of the present invention, then to R⁷It is not particularly limited.R⁷Molecular weight to include the value of substituent group Meter is usually less than 1000, is preferably less than 500 scope.

As R⁷Example, alkyl, alkenyl, alkynyl, aromatic hydrocarbyl, aromatic heterocycle, amino, alkane can be enumerated Oxygroup, aryloxy group, acyl group, alkoxy carbonyl group, aryloxycarbonyl, alkyl oxycarbonyl acyloxy, alkylthio group, arylthio, sulfonyl, alkyl sulphur Acyl group, aryl sulfonyl, cyano, hydroxyl, mercapto, silicyl etc..

Wherein, with R⁶Similarly, from the aspect of electron acceptor is big, preferably with A₁Bonded portion have carbon atom Organic group, by way of example, optimizing alkyl, alkenyl, alkynyl, aromatic hydrocarbyl, aromatic heterocycle.Especially since Electron acceptor is big and thermostabilization, thus optimization aromatic alkyl or aromatic heterocycle.

As R⁷Alkyl, alkenyl, alkynyl, aromatic hydrocarbyl, aromatic heterocycle, can enumerate with above to R⁶ The same substance of substance of explanation.

As amino, alkyl amino, arylamino, acylamino- etc. can be enumerated.

As alkyl amino, the carbon number that can be enumerated with 1 or more be usually more than 1 and usually 12 with Under, be preferably less than 6 alkyl alkyl amino.As concrete example, methylamino, dimethylamino, diethyl can be enumerated Amino, dibenzyl amino etc..

As arylamino, the carbon number that can be enumerated with 1 or more is usually more than 3, is preferably more than 4, simultaneously And usually less than 25, be preferably less than 15 aromatic hydrocarbyl or the arylamino of aromatic heterocycle.It, can as concrete example To enumerate phenyl amino, diphenyl amino, Tolylamino, pyridinylamino, thienyl amino etc..

As acylamino-, the carbon number that can be enumerated with 1 or more is usually more than 2 and usually less than 25, The acylamino- of preferably less than 15 acyl group.As concrete example, acetyl-amino, benzoyl-amido etc. can be enumerated.

As alkoxy, carbon number can be enumerated and be usually more than 1 and usually less than 12, be preferably less than 6 Alkoxy.As concrete example, methoxyl group, ethyoxyl, butoxy etc. can be enumerated.

As aryloxy group, can to enumerate with carbon number be usually more than 3, be preferably more than 4 and usually 25 with Under, be preferably less than 15 aromatic hydrocarbyl or aromatic heterocycle aryloxy group.As concrete example, phenyl oxygen can be enumerated Base, naphthalene oxygroup, pyridyl group oxygroup, thienyl oxygroup etc..

As acyl group, carbon number can be enumerated and be usually more than 1 and usually less than 25, be preferably less than 15 Acyl group.As concrete example, formoxyl, acetyl group, benzoyl etc. can be enumerated.

As alkoxy carbonyl group, carbon number can be enumerated and be usually more than 2 and usually less than 10, be preferably less than 7 Alkoxy carbonyl group.As concrete example, methoxycarbonyl, ethoxy carbonyl etc. can be enumerated.

As aryloxycarbonyl, can to enumerate with carbon number be usually more than 3, is preferably more than 4 and is usually Less than 25, the group of preferably less than 15 aromatic hydrocarbyl or aromatic heterocycle.As concrete example, phenoxy group can be enumerated Carbonyl, pyridine Epoxide carbonyl etc..

As alkyl oxycarbonyl acyloxy, carbon number can be enumerated and be usually more than 2 and usually less than 10, be preferably 7 Following alkyl oxycarbonyl acyloxy.As concrete example, acetoxyl group, trifluoroacetyl oxygroup etc. can be enumerated.

As alkylthio group, carbon number can be enumerated and be usually more than 1 and usually less than 12, be preferably less than 6 Alkylthio group.As concrete example, methyl mercapto, ethylmercapto group etc. can be enumerated.

As arylthio, can enumerate carbon number be usually more than 3, be preferably more than 4 and usually less than 25, Preferably less than 14 arylthio.As concrete example, thiophenyl, naphthalene sulfenyl, pyridine thio etc. can be enumerated.

As alkyl sulphonyl and the concrete example of aryl sulfonyl, mesyl, tosyl etc. can be enumerated.

As the concrete example of sulfonyloxy, mesyl oxygroup, tosyl oxygroup etc. can be enumerated.

As the concrete example of silicyl, trimethyl silyl, triphenyl-silyl etc. can be enumerated.

More than, on as R⁶And R⁷Illustrated group, without departing from the present invention purport, it is possible to further by Other substituent groups are substituted.The species of substituent group is not particularly limited, by way of example, except as above-mentioned R⁶And R⁷Example respectively Beyond the group shown, halogen atom, cyano, thiocyanogen, nitro etc. can also be enumerated.Wherein, ionic compound is never interfered (by electricity Sub- property compound) heat resistance and electron acceptor from the aspect of, optimizing alkyl, alkenyl, alkynyl, alkoxy, aryloxy group, virtue Fragrant race's alkyl, aromatic heterocycle.

In formula (4), A₁The element of the 17th race of periodic table is preferably belonging to, in terms of electron acceptor and easiness in obtaining It sets out, the element in (the 3rd~the 5th cycle) before the 5th cycle of preferred cycle table.That is, as A₁, preferably iodine atom, bromine atoms, Any one of chlorine atom.

Particularly, from the A in electron acceptor, compound stability aspect, preferred formula (4)₁For bromine atoms or iodine A in the ionic compound of atom, most preferably formula (4)₁For the ionic compound of iodine atom.

In formula (4), Z₁ ^n1-Represent counter anion.The species of counter anion is not particularly limited, can be single former Daughter ion, or complex ion.But the more big then negative electrical charge of the size of counter anion more delocalization, therewith together, just Charge also delocalization, is increased by electronic capability, thus the more preferable complex ion compared with monatomic ion.

n₁It is and counter anion Z₁ ^n1-The comparable arbitrary positive integer of ioni valence.To n₁Value be not particularly limited, it is excellent It elects 1 or 2 as, is most preferably 1.

As Z₁ ^n1-Concrete example, can enumerate hydroxide ion, fluorine ion, chlorion, bromide ion, iodide ion, cyanogen from Son, nitrate ion, nitrite ion, sulfate ion, sulfite ion, perchlorate, perbromate ion, It is periodate ion, chloranion, chlorition, hypochlorite ion, phosphate anion, orthophosphite ions, secondary Phosphate anion, borate ion, isocyano ion, hydrogen sulfide radical ion, tetrafluoroborate ion, hexafluoro-phosphate radical from Son, chlordene metaantimmonic acid radical ion；The carboxylic acid ions such as acetate ion, trifluoroacetic ions, benzoate anion ion；Methanesulfonate The sulfonate ions such as ion, trifluoromethane sulfonic acid radical ion；Alkoxide ions such as methoxyl group ion, tert-butoxy ion etc., it is excellent Select tetrafluoroborate ion and hexafluoro borate ion.

In addition, as counter anion Z₁ ^n1-, in terms of from the stability of compound, in a solvent deliquescent and ruler Very little big aspect is set out, and due to negative electrical charge delocalization, positive charge also delocalization together, is increased by electronic capability therewith, because And the complex ion particularly preferably represented by following formula (5).

In formula (5), E₃Each independently represent the element for the 13rd race for belonging to long period type periodic table.Wherein, preferred boron Atom, aluminium atom, gallium atom, from the aspect of compound stability, synthesis and the easiness of purifying, preferred boron atom.

In formula (5), Ar⁶~Ar⁹Each independently represent aromatic hydrocarbyl or aromatic heterocycle.As aromatic hydrocarbyl, The illustration of aromatic heterocycle can be enumerated and above to R⁶Illustrated substance is same, has 1 free atom valency Monocyclic or 2~4 rings the condensed ring of 5 yuan of rings or 6 yuan of rings.Wherein, the stability from compound, from the aspect of heat resistance, it is excellent Phenyl ring of the choosing with 1 free atom valency, naphthalene nucleus, pyridine ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline Quinoline ring.

Without departing from the purport of the present invention, then as Ar⁶~Ar⁹Illustrated aromatic hydrocarbyl, aromatic heterocycle Can further it be substituted by other substituent groups.The species of substituent group is not particularly limited, arbitrary substituent group can be applicable in, But it is preferred that electron-withdrawing group.

If it exemplifies as Ar⁶~Ar⁹The preferred electron-withdrawing group of substituent group institute that can have, can enumerate：Fluorine is former The halogen atoms such as son, chlorine atom, bromine atoms；Cyano；Thiocyanogen；Nitro；The alkyl sulphonyls such as mesyl；The virtues such as tosyl Base sulfonyl；The carbon numbers such as formoxyl, acetyl group, benzoyl are usually more than 1, are usually less than 12, are preferably less than 6 Acyl group；The carbon numbers such as methoxycarbonyl, ethoxy carbonyl are usually more than 2, are usually less than 10, are preferably less than 7 Alkoxy carbonyl group；It is usually more than 3 that phenyloxycarbonyl, pyridine Epoxide carbonyl etc., which have carbon number, is preferably more than 4, is usually Less than 25, the aryloxycarbonyl of preferably less than 15 aromatic hydrocarbyl or aromatic heterocycle；Amino carbonyl；Aminosulfonyl Base；Trifluoromethyl, pentafluoroethyl group etc. carbon number be usually more than 1, be usually less than 10, be preferably less than 6 straight-chain, Substitution has halogenated alkyl of the halogen atoms such as fluorine atom, chlorine atom etc. in branched or cricoid alkyl.

Wherein, more preferable Ar⁶~Ar⁹In at least one group there is 1 or 2 or more fluorine atom or chlorine atom as taking Dai Ji.Particularly, from by negative electrical charge effectively delocalization in terms of and with appropriateness sublimability from the aspect of, most It is preferred that Ar⁶~Ar⁹The perfiuoroaryl that is all substituted by fluorine atom of hydrogen atom.As the concrete example of perfiuoroaryl, can enumerate Pentafluorophenyl group, seven fluoro- 2- naphthalenes, four fluoro-4-pyridinyls etc..

The molecular weight of electron acceptor compound in the present invention is usually 100~5000, be preferably 300~3000, into one Step is preferably 400~2000.

If in above range, positive charge and negative electrical charge fully delocalization are good by electronic capability, and are difficult to hamper Charge is hindered to transmit, is preferred from this point.

The concrete example of currently preferred electron acceptor compound is illustrated below, but the present invention is not limited to these.

【Table 1】

【Table 2】

【Table 3】

【Table 4】

【Table 5】

【Table 6】

【Table 7】

【Table 8】

The organic electroluminescent device composition of the present invention can individually comprising a kind of above-mentioned electron acceptor compound or Person can also include two or more in any combination and ratio.

In the case that the organic electroluminescent device of the present invention includes electron acceptor compound with composition, of the invention has Electro-luminescence element is usually more than 0.0005 mass %, preferably with the content of the electron acceptor compound of composition More than 0.001 mass %, it is usually below 20 mass %, preferably below 10 mass %.In addition, organic electroluminescent device is used Electron acceptor compound in composition compared with the ratio of the polymer of the present invention is usually more than 0.5 mass %, is preferably 1 More than quality %, more preferably more than 3 mass %, it is usually below 80 mass %, preferably below 60 mass %, further excellent It elects as below 40 mass %.

If the content of the electron acceptor compound in organic electroluminescent device composition is more than above-mentioned lower limit, electronics Receptor receives electronics by polymer, the organic layer generation low resistance formed, therefore it is preferred that；If content is below the above-mentioned upper limit, The organic layer then formed is difficult to generate defect, and is difficult to happen film thickness unevenness, therefore it is preferred that.

The organic electroluminescent device composition of the present invention can also further contain radical cation compound.

As radical cation compound, preferably as obtained from as single electron is removed from hole transport ability compound The ionic compound that the radical cation of chemical seed is formed with counter anion.But radical cation is passed from hole In the case of the high-molecular compound of defeated property, radical cation, which becomes from the repetitive unit of high-molecular compound, removes single electron Obtained from structure.

As radical cation, preferably remove single electron from the above-claimed cpd as hole transport ability compound and Obtained chemical seed.From noncrystalline, transmission of visible light, heat resistance and dissolubility etc. consideration, passed from as hole Chemical seed obtained from the defeated preferred compound of property compound removes single electron is suitable.

Herein, radical cation compound can be by by above-mentioned hole transport ability compound and above-mentioned electron acceptor It closes object mixing and generates.That is, by the way that above-mentioned hole transport ability compound is mixed with above-mentioned electron acceptor compound, electronics From hole transport ability compound to electron acceptor compound move, generate by hole transport ability compound radical cation and The cationic compound that counter anion is formed.

In the case that the organic electroluminescent device of the present invention includes radical cation compound with composition, the present invention Organic electroluminescent device be usually more than 0.0005 mass % with the content of the radical cation compound of composition, be excellent It elects as more than 0.001 mass %, be usually below 40 mass %, be preferably below 20 mass %.If radical cation chemical combination For the organic layer that more than above-mentioned lower limit, is then formed low resistance occurs for the content of object, therefore it is preferred that；If content for the above-mentioned upper limit with Under, then the organic layer formed is difficult to generate defect, and is difficult to happen film thickness unevenness, therefore it is preferred that.

It should be noted that in addition to mentioned component, also may be used in organic electroluminescent device composition of the invention It is included with containing aftermentioned hole injection layer formation with aftermentioned content with composition or hole transmission layer formation in composition Ingredient.

[organic electroluminescent device]

The organic electroluminescent device of the present invention is that have anode and cathode on substrate and positioned at the anode and the moon The organic electroluminescent device of organic layer between pole, the organic electroluminescent device are characterized in that the organic layer, which includes, to be made It is formed with the organic electroluminescent device composition of the present invention of the polymer containing the present invention by wet type membrane formation Layer.

In the organic electroluminescent device of the present invention, the layer that is formed by wet type membrane formation be preferably hole injection layer and At least one of hole transmission layer, it is therefore particularly preferred that the organic layer possesses hole injection layer, hole transmission layer and shines Layer, the layer that these hole injection layers, hole transmission layer and luminescent layer are formed all through wet type membrane formation.

Wet type membrane formation refers to film build method in the present invention, i.e., uses such as spin-coating method, dip coating, mould as coating method It is coating, stick coating method, knife coating, rolling method, spraying process, capillary rubbing method, ink-jet method, nozzle print method, silk screen print method, recessed The method that version printing method, flexographic plate print process etc. are formed a film with wet type, the method for making the coated film dry and carrying out film formation. In these film build methods, preferably spun on method, spraying process, ink-jet method, nozzle print method etc..

In the following, being formed with reference to Fig. 1 to the layer of the organic electroluminescent device of the present invention and its general forming method etc. An example of embodiment illustrates.

Fig. 1 is the schematic cross-section for the configuration example for showing the organic electroluminescent device 10 of the present invention, and in Fig. 1,1 represents Substrate, 2 expression anodes, 3 expression hole injection layers, 4 expression hole transmission layers, 5 expression luminescent layers, 6 expression hole blocking layers, 7 Represent electron transfer layer, 8 represent electron injecting layer, and 9 represent cathode.

{ substrate }

Substrate 1 is the support of organic electroluminescent device, usually using quartz or plate, metallic plate or the metal of glass Paper tinsel, plastic foil or plastic sheet etc..Among these, preferably glass plate or polyester, polymethacrylates, makrolon, polysulfones etc. The plate of lucite.Due to being difficult to the deterioration because organic electroluminescent device occurs during extraneous gas, thus substrate is preferred For the high material of barrier properties for gases.Therefore, particularly when using plastic substrate when the low material of barrier properties for gases, It is preferred that at least single side in substrate sets fine and close silicon oxide layer etc. to improve barrier properties for gases.

{ anode }

Anode 2 is responsible for the function that hole is injected into the layer of 5 side of luminescent layer.

Anode 2 is usually made of materials described below：The metals such as aluminium, gold, silver, nickel, palladium, platinum；The gold such as the oxide of indium and/or tin Belong to oxide；The metal halides such as cupric iodide；Carbon black and the electroconductive polymers such as poly- (3 methyl thiophene), polypyrrole, polyaniline Deng.

The formation of anode 2 is usually mostly carried out using dry processes such as sputtering method, vacuum vapour depositions.In addition, using silver etc. The particles such as metal particle, cupric iodide, carbon black, conductive metal oxide particle, electroconductive polymer micropowder etc. form sun It, also can be by being dispersed in appropriate binder resin solution and being coated on substrate to form anode in the case of pole. And then in the case of for electroconductive polymer, also film can be directly formed on substrate by electrolysis polymerization or on substrate Applying conductive macromolecule forms anode (Appl.Phys.Lett., volume 60, page 2711,1992).

Anode 2 is usually single layer structure, but can also be suitably laminated structure.Anode 2 is the situation of laminated structure Under, can on the 1st layer of anode the different conductive material of lamination.

The thickness of anode 2 is determined according to the required transparency and material etc..Particularly needing high transparency In the case of, the transmissivity of preferably visible ray reaches more than 60% thickness, further preferably reaches more than 80% thickness.Sun The thickness of pole 2 be usually more than 5nm, be preferably more than 10nm and usually below 1000nm, be preferably below 500nm.Separately On the one hand, in the case where the transparency is not required, the thickness of anode 2 is any thickness according to required intensity etc., In this case, anode 2 can be same thickness with substrate.

In the case of the other layers of surface filming of anode 2, implement ultraviolet light/ozone, oxygen plasma preferably before film forming Thus the processing such as body, argon plasma remove the impurity on anode 2, and adjust its ionization potential and improve hole injection.

{ hole injection layer }

The layer being responsible for from the function of 2 lateral direction light emission layer of anode, 5 side transporting holes is commonly known as hole injection/transport layer Or hole transmission layer.Also, it is responsible for the situation for being 2 layers or more from the layer of the function of 2 lateral direction light emission layer of anode, 5 side transporting holes Under, it will be known as hole injection layer 3 closer to the layer of anode-side sometimes.From strengthening from anode 2 to the work(of 5 side transporting holes of luminescent layer The aspect of energy is set out, and is preferably formed as hole injection layer 3.In the case where forming hole injection layer 3, usual 3 shape of hole injection layer Into on anode 2.

The film thickness of hole injection layer 3 is usually more than 1nm, is preferably more than 5nm and usually below 1000nm, excellent Elect below 500nm as.

The forming method of hole injection layer can be vacuum vapour deposition, or wet type membrane formation.It is excellent from film forming Aspect set out, preferably formed by wet type membrane formation.

Hole injection layer 3 preferably comprises hole transport ability compound, more preferably comprising hole transport ability compound and by electricity Sub- property compound.And then radical cation compound is preferably comprised in hole injection layer, particularly preferably comprising cation certainly By based compound and hole transport ability compound.

In the following, the forming method of general hole injection layer is illustrated, in the organic electroluminescent member of the present invention In part, hole injection layer it is preferable to use the present invention organic electroluminescent device to be formed with composition by wet type membrane formation.

Hole injection layer formation usually contains the hole transport ability compound to form hole injection layer 3 with composition.In addition, In the case of wet type membrane formation, usually further also contain solvent.The preferred hole transport of hole injection layer formation composition Property it is high, can effectively transmit institute's injected holes.It is therefore preferable that hole mobility is big, during fabrication or using when etc. be difficult to The impurity of trap can be become by generating.Additionally, it is preferred that excellent in stability, ionization potential are small, high to the transparency of visible ray.Particularly, exist In the case that hole injection layer is contacted with luminescent layer, preferably its will not make to carry out the luminous delustring of light emitting layer, will not be with luminescent layer It forms exciplex and reduces luminous efficiency.

As hole transport ability compound, from the charge injection barrier by anode to hole injection layer (Electricity lotuses inject barrier) Aspect set out, preferably have the compound of 4.5eV~6.0eV ionization potentials.It, can be with as the example of hole transport ability compound Enumerate aromatic amine based compound, phthalocyanine based compound, porphyrin based compound, Oligopoly thiophene based compound, polythiophene system chemical combination Compound that object, benzyl phenyl based compound, tertiary amine link through fluorenyl, hydrazone based compound, silazane based compound, quinoline a word used for translation Pyridine ketone based compound etc..

In above-mentioned exemplary compounds, from the aspect of noncrystalline and visible light permeability, optimization aromatic amination Close object, particularly preferred aromatic uncle amine compound.Herein, aromatic uncle amine compound refers to the change with aromatic nitrile base structure Object is closed, is also included with the compound with the group from aromatic nitrile base.

The species of aromatic uncle amine compound is not particularly limited, is obtained uniformly from easily by surface smoothing effect Shine from the aspect of, it is preferable to use weight average molecular weight be more than 1000, less than 1000000 high-molecular compound (repeat The polymeric compounds that unit is formed by connecting).As the preference of aromatic nitrile base high-molecular compound, can enumerate under having State high-molecular compound of repetitive unit represented by formula (6) etc..

(in formula (6), Ar¹¹And Ar¹²Each independently represent with or without substituent group aromatic hydrocarbyl or have Or the aromatic heterocycle without substituent group.Ar¹³~Ar¹⁵Each independently represent the fragrance with or without substituent group Race's alkyl or the aromatic heterocycle with or without substituent group.Y expressions are selected from following shown linking group groups Linking group.In addition, in Ar¹¹~Ar¹⁵In, two groups being connected on same N atoms can be mutually bonded and form ring.)

(in the above formulas, Ar¹⁶~Ar²⁶Each independently represent the aromatic hydrocarbyl or tool with or without substituent group Have or the aromatic heterocycle without substituent group.R⁸And R⁹Each independently represent hydrogen atom or arbitrary substituent group.)

As Ar¹⁶~Ar²⁶Aromatic hydrocarbyl and aromatic heterocycle, it is dissolubility from high-molecular compound, heat-resisting Property, from the aspect of hole injection transporting, preferably have phenyl ring, naphthalene nucleus, phenanthrene ring, the thiophene of 1 or 2 free atom valency Ring, pyridine ring further preferably have phenyl ring, the naphthalene nucleus of 1 or 2 free atom valency.

As the concrete example of the aromatic nitrile base high-molecular compound with the repetitive unit represented by formula (6), Ke Yiju Go out the substance described in International Publication No. 2005/089024.

The electrical conductivity of hole injection layer can be improved by the oxidation of hole transport ability compound, thus, it is injected in hole Above-mentioned electron acceptor compound, above-mentioned radical cation compound are preferably comprised in layer 3.

PEDOT/PSS (Adv.Mater., 2000, volume 12, page 481) or emeraldine hydrochloride (J.Phys.Chem., Nineteen ninety, volume 94, page 7716) etc. the radical cation compound in high-molecular compounds source can also be poly- by carrying out oxidation It closes (dehydrogenation polymerization) and generates.

Oxidation polymerization described herein refers to using persulfate etc. in an acidic solution by monomer chemistries oxidation or electricity Chemical oxidation.In the case of the oxidation polymerization (dehydrogenation polymerization), producing high-molecular is occurred by oxidation for monomer, while since generation From the anion of acid solution as counter anion, remove single electron from high molecular repetitive unit obtained from cation Free radical.

By wet type membrane formation formed hole injection layer 3 in the case of, usually by as the material of hole injection layer with Soluble solvent (hole injection layer with solvent) mixing prepares the composition (hole injection layer formation composition) of film forming, The hole injection layer formation is coated on the layer (being usually anode) for be equivalent to hole injection layer lower floor to carry out with composition It forms a film and is dried, so as to form hole injection layer 3.

On the concentration of the hole transport ability compound in hole injection layer formation composition, as long as not damaging this significantly The effect of invention is exactly arbitrary, and from the aspect of film thickness uniformity, preferred concentration is low；And it on the other hand, is noted from hole Enter layer to be difficult to set out in terms of generating defect, preferred concentration is high.Specifically, it is preferably more than 0.01 mass %, further excellent It elects as more than 0.1 mass %, particularly preferably more than 0.5 mass %, and is on the other hand preferably below 70 mass %, into one Step is preferably below 60 mass %, particularly preferably below 50 mass %.

As solvent, for example, ether series solvent, ester series solvent, aromatic hydrocarbon series solvent, acid amides series solvent etc..

As ether series solvent, for example, glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol -1- monomethyl ether second The fatty ethers such as acid esters (PGMEA) and 1,2- dimethoxy benzenes, 1,3- dimethoxy benzenes, methyl phenyl ethers anisole, phenetole, 2- methoxy methyls Aromatic ethers such as benzene, 3- methoxy toluenes, 4- methoxy toluenes, 2,3- dimethylanisoles, 2,4- dimethylanisoles etc..

As ester series solvent, for example, phenylacetate, phenyl propionate, methyl benzoate, ethyl benzoate, benzene first Aromatic esters such as propyl propionate, n-butylbenzoate etc..

As aromatic hydrocarbon series solvent, for example, toluene, dimethylbenzene, cyclohexylbenzene, 3- isopropyl biphenyls, 1,2,3, 4- durols, 1,4- diisopropyl benzenes, methyl naphthalene etc..As acid amides series solvent, for example, N, N- dimethyl formyl Amine, DMAC N,N' dimethyl acetamide etc..

In addition, dimethyl sulfoxide (DMSO) etc. can also be used.

On the formation based on wet type membrane formation of hole injection layer 3, usually hole injection layer formation combination is being prepared After object, by its coating film forming and drying on the layer (be usually anode 2) for the lower floor for being equivalent to hole injection layer 3, thus come into Row.

For hole injection layer 3, dry coated film using heating or be dried under reduced pressure etc. usually after film forming.

In the case where forming hole injection layer 3 by vacuum vapour deposition, one kind or two or more hole can usually be noted The constituent material (above-mentioned hole transport ability compound, electron acceptor compound etc.) for entering layer 3 is put into vacuum tank It (in the case where using two or more material, is usually put into respective crucible) in crucible, it will be in vacuum tank with vacuum pump It is vented to 10^-4Pa or so afterwards heats crucible (in the case where using two or more material, usually to respective crucible Heated), control crucible in material evaporation capacity while make its evaporation (in the case where using two or more material, lead to Often control and be evaporated while evaporation capacity independently), formed on the anode on the substrate placed in opposite directions with crucible it is empty Cave implanted layer.It should be noted that in the case where using two or more material, their mixture can also be put into earthenware It in crucible, heated, evaporated, so as to form hole injection layer.

As long as not damaging the effect of the present invention significantly, then vacuum degree when being deposited simultaneously is not limited, and is usually 0.1 × 10^- ⁶Torr(0.13×10^-4Pa more than), 9.0 × 10^-6Torr(12.0×10^-4Pa) below.As long as do not damage the present invention's significantly Effect then evaporation rate and is not limited, and is usually/ more than the second,Below/the second.As long as do not damage the present invention's significantly Effect, then film-forming temperature when being deposited simultaneously are not limited, preferably in 10 DEG C or more, less than 50 DEG C progress.

It should be noted that hole injection layer 3 can be crosslinked in the same manner as aftermentioned hole transmission layer 4.

{ hole transmission layer }

Hole transmission layer 4 is the layer for being responsible for the function from 2 lateral direction light emission layer of anode, 5 side transporting holes.Hole transmission layer 4 are not required in that layer in the organic electroluminescent device of the present invention, but transmit sky from strengthening from anode 2 to luminescent layer 5 It sets out in terms of the function in cave, is preferably formed as the layer.In the case where forming hole transmission layer 4, usual hole transmission layer 4 is formed Between anode 2 and luminescent layer 5.In addition, in the case of with above-mentioned hole injection layer 3, hole injection layer 3 and hair are formed at Between photosphere 5.

The film thickness of hole transmission layer 4 is usually more than 5nm, is preferably more than 10nm, and is on the other hand usually 300nm Below, it is preferably below 100nm.

The forming method of hole transmission layer 4 can be vacuum vapour deposition, or wet type membrane formation.It is excellent from film forming Aspect set out, preferably formed by wet type membrane formation.

In the following, the forming method of general hole transmission layer is illustrated, in the organic electroluminescent member of the present invention In part, hole transmission layer it is preferable to use the present invention organic electroluminescent device to be formed with composition by wet type membrane formation.

Hole transmission layer 4 usually contains hole transport ability compound.As the hole transport ability included in hole transmission layer 4 Compound, can especially enumerate with 4,4 '-bis- [N- (1- naphthalenes)-N- phenyl aminos] biphenyl for representative, containing 2 or more uncles Amine and the condensation aromatic rings of 2 or more are substituted in the aromatic diamine (Japanese Unexamined Patent Publication 5-234681 publications) on nitrogen-atoms； 4,4 ', 4 "-three (1- naphthylphenyls amino) triphenylamines etc. have aromatic amines compound (J.Lumin., the 72-74 of star burst structure It rolls up, page 985,1997)；Formed by the tetramer of triphenylamine aromatic amines compound (Chem.Commun., page 2175, 1996)；The spiro-compounds such as 2,2 ', 7,7 '-four (diphenyl amino) -9,9 '-spiro-bisfluorenes (Synth.Metals, volume 91, Page 209,1997)；Carbazole derivates such as 4,4 '-N, the N carbazole biphenyl of '-two etc..Alternatively, it is also possible to which it is preferable to use for example poly- second Alkenyl carbazole, polyvinyl triphenylamine (Japanese Unexamined Patent Publication 7-53953 publications), the poly (arylene ether) containing tetraphenyl benzidine Sulfone (Polym.Adv.Tech., volume 7, page 33,1996) etc..

In the case where forming hole transmission layer by wet type membrane formation, usually with forming above-mentioned sky by wet type membrane formation The situation of cave implanted layer similarly, using hole transmission layer formation with composition replaces hole injection layer formation composition and shape Into.

In the case where forming hole transmission layer by wet type membrane formation, usual hole transmission layer formation composition is into one Step contains solvent.It can use and formed with above-mentioned hole injection layer with combining for the solvent of hole transmission layer formation composition The same solvent of solvent used in object.

The concentration of hole transport ability compound in hole transmission layer formation composition can be and hole injection layer shape Into the same scope of concentration with the hole transport ability compound in composition.

The formation based on wet type membrane formation of hole transmission layer can carry out in the same manner as above-mentioned hole injection layer membrane formation process.

By vacuum vapour deposition formed hole transmission layer in the case of, generally also with formed by vacuum vapour deposition it is above-mentioned The situation of hole injection layer with composition using hole transmission layer formation likewise it is possible to replace hole injection layer formation to combine Object and formed.Membrance casting conditions such as vacuum degree, evaporation rate and temperature during on vapor deposition etc., can with above-mentioned hole injection layer Vacuum evaporation when it is same under the conditions of form a film.

{ luminescent layer }

Luminescent layer 5 is following layers：When electric field is provided between a pair of electrodes, by 2 injected holes of anode with being injected by cathode 9 Electronics occur in conjunction with so as to be excited, being responsible for luminous function.Luminescent layer 5 is formed between anode 2 and cathode 9 Layer, on anode have hole injection layer in the case of, luminescent layer is formed between hole injection layer and cathode, on anode In the case of hole transmission layer, luminescent layer is formed between hole transmission layer and cathode.

As long as not damaging the effect of the present invention significantly, then the film thickness of luminescent layer 5 is arbitrary, but is difficult to from film to generate defect Aspect set out, preferably film thickness is thick；And on the other hand, from being easy to as low driving voltage aspect, preferably film thickness is thin.Cause This, be preferably more than 3nm, further preferably more than 5nm, and on the other hand, it is often preferred that below 200nm, further Preferably below 100nm.

Luminescent layer 5 at least contains the material (luminescent material) with luminosity, while preferably comprises and transmitted with charge The material (charge-transporting material) of property.

Luminescent material is shone with desired emission wavelength, is not limited especially as long as the effect not damaging the present invention System, can be applicable in well known luminescent material.Luminescent material can be fluorescence luminescent material, or phosphorescent light-emitting materials, it is excellent The good material of light efficiency is published, from internal quantum aspect, preferably phosphorescent light-emitting materials.

As fluorescence luminescent material, for example, following material.

As the fluorescence luminescent material (blue-fluorescence luminescent material) for providing blue-light-emitting, for example, naphthalene, dinaphthyl Embedding benzene, pyrene, anthracene, cumarin, 1,2- benzophenanthrenes, to double (2- phenyl vinyls) benzene and their derivative etc..

As the fluorescence luminescent material (green fluorescence luminescent material) for providing green emitting, for example, quinacridone Derivative, coumarin derivative, Al (C₉H₆NO)₃Wait aluminium complexs etc..

The fluorescence luminescent material (yellow fluorescence luminescent material) Yellow luminous as offer, for example, rubrene, Naphthalene pyrimidone derivatives etc..

As the fluorescence luminescent material (red fluorescence luminescent material) for providing emitting red light, for example, DCM (4- (dicyano methylene) -2- methyl -6- (4- dimethylaminostyryls) -4H- pyrans) based compound, chromene derive Object, rhodamine derivative, benzothioxanthene derivative, azepine benzothioxanthene etc..

In addition, as phosphorescent light-emitting materials, for example, comprising in the 7th~11 race selected from long period type periodic table The metal-organic complex of metal etc..As the metal in the 7th~11 race selected from periodic table, can preferably enumerate ruthenium, rhodium, Palladium, silver, rhenium, osmium, iridium, platinum, gold etc..

As the ligand of metal-organic complex, preferably (miscellaneous) arylpyridine ligand, (miscellaneous) arylpyrazole ligand etc. (miscellaneous) The ligand that aryl and pyridine, pyrazoles, phenanthroline etc. link, particularly preferred phenyl pyridine ligand, phenylpyrazole ligand.This Place, (miscellaneous) aryl represent aryl or heteroaryl.

As preferred phosphorescent light-emitting materials, specifically, for example, three (2- phenylpyridines) iridium, three (2- benzene Yl pyridines) ruthenium, three (2- phenylpyridines) palladiums, double (2- phenylpyridines) platinum, three (2- phenylpyridines) osmiums, three (2- phenylpyridines) rheniums Wait the porphyrins network such as phenylpyridines complex compound and octaethylporphyrin platinum, octaphenyl porphyrin platinum, octaethylporphyrin palladium, octaphenyl porphyrin palladium Close object etc..

As the luminescent material of macromolecular, poly- (9,9- dioctyl fluorene -2,7- diyl) can be enumerated, poly- [(9,9- bis- is pungent Base fluorenes -2,7- diyls)-co- (4,4 '-(N- (4- secondary butyl phenenyls)) diphenylamine)], poly- [(9,9- dioctyl fluorenes -2,7- two Base)-co- (1,4- benzos -2 { 2,1 ' -3 }-triazole)] etc. polyfluorenes based material, it is poly- [2- methoxyl groups -5- (2- ethyl hexyl oxies) -1, 4- phenylene vinylidenes] etc. polyphenylene vinylenes based material.

<Charge-transporting material>

Charge-transporting material is the material with positive charge (hole) or negative electrical charge (electronics) transporting, as long as not damaging The effect of the present invention is just not particularly limited, and can be applicable in well known luminescent material.

On charge-transporting material, chemical combination used in the luminescent layer of organic electroluminescent device can be used in the past Object etc., particularly preferable as the compound used in the material of main part of luminescent layer.

As charge-transporting material, specifically, aromatic amine based compound, phthalocyanine based compound, porphin can be enumerated Quinoline based compound, Oligopoly thiophene based compound, polythiophene based compound, benzyl phenyl based compound, tertiary amine through fluorenyl link and Into compound, hydrazone based compound, silazane based compound, silicon amine methane series compound, phosphinylidyne amine compound, quinacridone Compound etc. in addition, can enumerate anthracene as compound illustrated in the hole transport ability compound of hole injection layer etc. Based compound, pyrene based compound, carbazole based compound, pyridine based compound, phenanthroline based compound, oxadiazoles based compound, Thiophene coughs up electron-transportings compound such as based compound etc..

In addition, for example can also it is preferable to use with 4,4 '-bis- [N- (1- naphthalenes)-N- phenyl aminos] biphenyl for representative, Aromatic diamine (the Japanese Unexamined Patent Publication 5- being substituted in containing 2 or more tertiary amines and the condensation aromatic rings of 2 or more on nitrogen-atoms No. 234681 publications)；4,4 ', 4 "-three (1- naphthylphenyls amino) triphenylamines etc. have the aromatic series amine system chemical combination of star burst structure Object (J.Lumin., 72-74 volumes, page 985,1997)；The aromatic amine based compound formed by the tetramer of triphenylamine (Chem.Commun., page 2175,1996)；The fluorenes system chemical combination such as 2,2 ', 7,7 '-four-(diphenyl amino) -9,9 '-spiro-bisfluorenes Object (Synth.Metals, volume 91, page 209,1997)；Carbazoles based compounds such as 4,4 '-N, the N carbazole biphenyl of '-two etc. are as empty Compound illustrated in the hole transport ability compound of cave transport layer etc..In addition, in addition, 2- (4- biphenyl can also be enumerated Base) -5- (to tert-butyl-phenyl) -1,3,4- oxadiazoles (tBu-PBD), double (1- the naphthalenes) -1,3,4- oxadiazoles (BND) of 2,5- etc. Oxadiazole based compound；Double (6 '-(2 ', 2 "-bipyridyl)) -1,1- dimethyl -3,4- diphenyl thiophenes of 2,5- are coughed up (PyPySPyPy) Thiophenes is waited to cough up based compound；Bathophenanthroline (BPhen), 2,9- dimethyl -4,7- diphenyl -1,10- phenanthroline (BCP, bathocuproine) Wait phenanthroline based compound etc..

The forming method of luminescent layer can be vacuum vapour deposition, or wet type membrane formation, due to film forming it is excellent and It is preferred that wet type membrane formation, further preferred spin-coating method and ink-jet method.Particularly, if using organic electroluminescent device of the invention Form hole injection layer or hole transmission layer as the lower floor of luminescent layer by the use of composition, then easily using wet type membrane formation into Row lamination, thus preferably use wet type membrane formation.In the case where forming luminescent layer by wet type membrane formation, usually with passing through Wet type membrane formation forms the situation of above-mentioned hole injection layer similarly, uses the material and soluble solvent that will become luminescent layer The prepared luminescent layer formation of (luminescent layer with solvent) mixing with composition come instead of hole injection layer formation composition, thus Form luminescent layer.

As solvent, for example, for cited by the formation of hole injection layer ether series solvent, ester series solvent, virtue Fragrant race's hydrocarbon system solvent, acid amides series solvent and alkane hydrocarbon system solvent, halogenated aromatic hydrocarbon system solvent, aliphatic alcohol series solvent, fat Ring race alcohol series solvent, aliphatic ketone series solvent and alicyclic ketone series solvent etc..The concrete example of solvent is enumerated below, but as long as not damaging The effect of the evil present invention is just not limited to these.

For example, glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol -1- methyl ether acetates (PGMEA) etc. Fatty ether series solvent；1,2- dimethoxy benzenes, 1,3- dimethoxy benzenes, methyl phenyl ethers anisole, phenetole, 2- methoxy toluenes, 3- first The aromatic ether of oxygroup toluene, 4- methoxy toluenes, 2,3- dimethylanisoles, 2,4- dimethylanisoles, diphenyl ether etc. Series solvent；The fragrance such as phenylacetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, n-butylbenzoate Race's ester series solvent；Toluene, dimethylbenzene, trimethylbenzene, cyclohexylbenzene, tetrahydronaphthalene, 3- isopropyl biphenyls, 1,2,3,4- durols, The aromatic hydrocarbon series solvents such as 1,4- diisopropyl benzenes, methyl naphthalene；The amides such as N,N-dimethylformamide, DMAC N,N' dimethyl acetamide Series solvent；The alkanes hydrocarbon system solvent such as n-decane, hexamethylene, ethyl cyclohexane, decahydronaphthalenes, bicyclohexane；Chlorobenzene, dichloro-benzenes, The halogenated aromatics hydrocarbon system solvent such as trichloro-benzenes；The aliphatic alcohols series solvent such as butanol, hexanol；The alicyclic alcohols such as cyclohexanol, Lotka-Volterra circle system Series solvent；The aliphatic ketones series solvent such as methyl ethyl ketone, dibutyl ketone；The alicyclic ketone series solvent such as cyclohexanone, cyclooctanone, fenchone Deng.Among these, particularly preferred alkane hydrocarbon system solvent and aromatic hydrocarbon series solvent.

{ hole blocking layer }

Hole blocking layer 6 can be set between luminescent layer 5 and aftermentioned electron injecting layer 8.Hole blocking layer 6 is to connect The mode lamination at the interface of 9 side of cathode of photosphere 5 is triggered in the layer on luminescent layer 5.

The hole blocking layer 6, which plays an important role of to prevent to migrate the hole that comes from anode 2, reaches cathode 9 and will be from cathode 9 The effect that injected electrons is efficiently transmitted to the direction of luminescent layer 5.As required by the material to forming hole blocking layer 6 Physical property can enumerate electron mobility height and hole mobility is low, energy gap (difference of HOMO, LUMO) is big, excited triplet state energy level (T1) it is high.

As the material for the hole blocking layer for meeting above-mentioned condition, for example, double (2- methyl -8-hydroxyquinoline) (phenol) closes aluminium, double (2- methyl -8-hydroxyquinoline) (triphenyl silanols) closes mixed-ligand complexes, double (2- methyl -8- such as aluminium Oxyquinoline) close aluminium-μ-oxygen-it is bis--(2- methyl -8-hydroxyquinoline) close metal complexes, the hexichol such as aluminium PROCESS FOR PRODUCTION OF BINUCLEAR The compound of styryl such as vinyl biphenyl derivative (Japanese Unexamined Patent Publication 11-242996 publications), 3- (4- xenyls) -4- benzene The phenanthrene such as triazole derivatives (Japanese Unexamined Patent Publication 7-41759 publications), the bathocuproines such as base -5 (4- tert-butyl-phenyls) -1,2,4- triazoles Cough up quinoline derivant (Japanese Unexamined Patent Publication 10-79297 publications) etc..Further, International Publication No. 2005/022962 is recorded As the material of hole blocking layer it is also preferred at least one 2, the compound of 4,6 substituted pyridine rings.

To the forming method of hole blocking layer 6 there is no limit.It therefore, can be by wet type membrane formation, vapour deposition method or other sides Method is formed.

As long as not damaging the effect of the present invention significantly, then the film thickness of hole blocking layer 6 is arbitrary, but usually 0.3nm Above, it is preferably more than 0.5nm, and usually below 100nm, preferably below 50nm.

{ electron transfer layer }

For the purpose for the current efficiency for further improving element, electricity is provided between luminescent layer 5 and electron injecting layer 8 Sub- transport layer 7.

Electron supplying layer 7 from can between the electrode of electric field is applied with will from 9 injected electrons of cathode efficiently to shine The compound of the direction transmission of layer 5 is formed.As electron-transporting compound used in electron transfer layer 7, it is necessary to be following Compound, the compound is high by cathode 9 or the electron injection efficiency carried out by electron injecting layer 8, and with high electron mobility Rate can efficiently transmit institute's injected electrons.

As the electron-transporting compound for electron transfer layer, specifically, for example, 8-hydroxyquinoline Metal complexes (Japanese Unexamined Patent Application 59-194393 publications), the metal network of 10- hydroxy benzos [h] quinoline such as aluminium complex Close Wu, oxadiazole derivatives, distyrylbiphenyl derivatives, thiophene cough up derivative, 3-hydroxyflavone metal complex, 5- hydroxyls Flavones metal complex, benzoxazole metal complex, benzothiazole metal complex, three benzimidazolyl benzene (United States Patent (USP)s No. 5645948 specification), quinoxaline compounds (Japanese Unexamined Patent Publication 6-207169 publications), (Japan is special for phenanthroline derivative Open flat 5-331459 publications), 2- tertiary butyls -9,10-N, N '-dicyan anthraquinone diimine, the hydrogenated amorphous state carborundum of n-type, n Type zinc sulphide, n-type zinc selenide etc..

The film thickness of electron transfer layer 7 is usually more than 1nm, is preferably more than 5nm, and usually below 300nm, preferably For below 100nm.

Electron transfer layer 7 is as described above by using wet type membrane formation or vacuum vapour deposition lamination in hole blocking layer It is formed on 6.Usually using vacuum vapour deposition.

{ electron injecting layer }

Electron injecting layer 8, which has been given play to, to be efficiently injected into electron transfer layer 7 or luminescent layer 5 by 9 injected electrons of cathode In effect.

In order to efficiently carry out electron injection, the material for forming electron injecting layer 8 is preferably the low metal of work content.As showing Alkaline-earth metal such as the alkali metal such as sodium or caesium, barium or calcium etc. can be used in example.Its film thickness be usually more than 0.1nm, be preferably 5nm with Under.

Further, by with metals such as the aluminium complexs of the nitrogen-containing heterocycle compounds such as bathophenanthroline or 8-hydroxyquinoline Complex compound (is recorded in Japanese Unexamined Patent Publication for alkali metal such as sodium contaminated, potassium, caesium, lithium, rubidiums in the Organic Electron Transport Material of representative In 10-270171 publications, Japanese Unexamined Patent Publication 2002-100478 publications, Japanese Unexamined Patent Publication 2002-100482 publications etc.), also can The fact that enough to have both excellent film quality while electron injection transporting is improved, thus preferred.

The film thickness of electron injecting layer 8 is usually more than 5nm, is preferably more than 10nm and usually below 200nm, excellent Elect the scope of below 100nm as.

Electron injecting layer 8 can be by using the hole of wet type membrane formation or vacuum vapour deposition lamination in luminescent layer 5 or thereon It is formed on barrier layer 6 or electron transfer layer 7.

Details during wet type membrane formation is identical with the situation of above-mentioned luminescent layer.

{ cathode }

Cathode 9 has given play to the effect for the layer (electron injecting layer or luminescent layer etc.) for injecting electrons into 5 side of luminescent layer.

As the material of cathode 9, the material used in above-mentioned anode 2 can be used；In order to which electronics note is effectively performed Enter, it is preferable to use the low metal of work content, such as the metals or their alloy etc. such as tin, magnesium, indium, calcium, aluminium, silver can be used.As Concrete example, for example, low work content alloy electrode such as magnesium-silver alloy, magnesium-indium alloy, aluminum-copper-lithium alloys etc..

From the aspect of the stability of element, lamination work content is high and to the metal layer of atmospheric stability preferably on cathode, To protect the cathode being made of low work function metal.As the metal of lamination, for example, aluminium, silver, copper, nickel, chromium, gold, platinum Wait metals.

The film thickness of cathode is usually identical with anode.

{ other layers }

As long as not damaging the effect of the present invention significantly, then organic electroluminescent device of the invention can further have it Its layer.That is, there can be arbitrary layer other than the above between the anode and the cathode.

{ other element compositions }

The organic electroluminescent device or structure in contrast with the above description of the present invention, i.e. on substrate successively Lamination cathode, electron injecting layer, electron transfer layer, hole blocking layer, luminescent layer, hole transmission layer, hole injection layer, anode.

In the case that the organic electroluminescent device of the present invention is suitable for Organnic electroluminescent device, it can be used as single Organic electroluminescent device use, the composition that the organic electroluminescent device of 2 or more is configured to array-like can also be formed And use, anode can also be formed and used with cathode arrangement into composition rectangular X-Y.

[organic EL display]

The organic electroluminescent device display device (organic EL display) of the present invention is organic using the invention described above Electroluminescent cell.Model, the structure of the organic EL display of the present invention are not particularly limited, can use the present invention's Organic electroluminescent device is conventionally assembled.

For example, " organic el display " can be utilized, (Ohmsha, (Heisei 16 years) August in 2004 issue, are former quiet on the 20th Scholar, thousand wave vector of Anda, village Tian Yingxing write) described in method come formed the present invention organic EL display.

[organic EL illuminating]

The organic electroluminescent device illumination (organic EL illuminating) of the present invention uses the organic electroluminescent of the invention described above Element.Model, the structure of the organic EL illuminating of the present invention are not particularly limited, the organic electroluminescent of the present invention can be used Element is conventionally assembled.

Embodiment

Embodiment is illustrated below, more specific description is carried out to the present invention.But the present invention is not limited to following embodiment, Without departing from its main points, then the present invention can be changed arbitrarily and implemented.

Put into compound 1 (10.0g, 28.61mmol), bromobenzene (4.27g, 27.18mmol) and sodium tert-butoxide (7.4g, 77.25mmol), toluene (150ml) to carrying out nitrogen displacement in system, is heated to 60 DEG C (solution As).To three (dibenzylidenes third Ketone) two palladium chloroform complex compounds (0.089g, 0.086mmol) toluene 15ml solution in add in 1,1 '-bis- (diphenylphosphinos) two Luxuriant iron (0.19g, 0.344mmol), is heated to 60 DEG C (solution Bs).In nitrogen stream, solution B is added into solution A, is heated back Flow 3.0 it is small when.After cooled to room temperature, ethyl acetate (300ml) and saline solution (100ml) are added in reaction solution and is carried out Stirring, carries out liquid separation afterwards, extracts water layer with ethyl acetate (100ml × 2 time), merges organic layer, is dried with magnesium sulfate laggard Row concentration.In addition, being purified using silica gel column chromatography (n-hexane/dichloromethane=3/1), faint yellow oily is thus obtained Compound 2 (10.4g).

N,N-dimethylformamide (200ml) and dichloromethane are added in into compound 2 (10.4g, 24.43mmol) (200ml), is cooled down with ice bath.The N of N- bromo-succinimides (4.35g, 24.43mmol), N- diformazans are added dropwise thereto Base formamide (50ml) and dichloromethane (50ml) solution, under stiring with 3 it is small when be warming up to room temperature.It is added in into reaction solution Water is extracted with dichloromethane.Concentration of organic layers, with column chromatography (developping solution:Hexanes/ch=3/1) it is purified, Thus the compound 3 (10.8g) of faint yellow oily is obtained.

By compound 3 (15.95g, 31.61mmol), 4,4 '-biphenyl hypoboric acid (3.9g, 16.13mmol), potassium carbonate In (10.9g, 79.03mmol) and toluene (120ml), ethyl alcohol (60ml), water (40ml) input flask, to abundant in system Nitrogen displacement is carried out, is heated to 80 DEG C.Tetrakis triphenylphosphine palladium (1.8g, 1.58mmol) is added in, when 80 DEG C of stirrings 4 are small.To Water is added in reaction solution, is extracted with toluene.Concentration of organic layers utilizes column chromatography (developping solution:Hexane/toluene=2/1) into Row purifying.Then column chromatography (developping solution is reused:THF/ acetonitrile=1/2) it is purified.Obtain compound 4 (8.5g, yield 52.6%).The HPLC purity of compound 4 is 99.7 area %.

Mix 4- (3- aminophenyls) benzocyclobutene (8.77g, 45mmol) and N-Methyl pyrrolidone (60ml), cooling To -5 DEG C.Concentrated hydrochloric acid (8.59ml, 99mmol), deionized water (30ml) are added in, is stirred 30 minutes.Then, added in below 5 DEG C - 5 DEG C sodium nitrite (3.20g, 46.35mmol) aqueous solution (30ml) is cooled to, stirs 30 minutes, diazonium salt solution is made. Above-mentioned diazonium salt solution, stirring 2 are added dropwise in potassium iodide (the 2263g, 136.35mmol) aqueous solution (400ml) for being heated to 60 DEG C Hour.Dichloromethane is added in into reaction solution to extract, is washed, and after being cleaned with hypo solution, is added in Magnesium sulfate is filtered after stirring, concentrates filtrate.Utilize silica gel column chromatography (developing solvent:N-hexane) it is purified, obtain 4- (3- iodophenyls) benzocyclobutene (7.8g, yield 56.6%).

Under nitrogen flowing, by dimethyl sulfoxide (DMSO) (100ml), 4- (3- iodophenyls) benzocyclobutene (5.00g, 16.3mmol), in double (pinacol combined) two boron (5.39g, 21.2mmol), potassium acetate (4.00g, 40.8mmol) input flask, It is stirred 30 minutes at 60 DEG C.It is subsequently added into 1,1 '-bis- (diphenylphosphino) ferrocene-palladium chloride (II)-dichloromethane [PdCl₂(dppf)CH₂Cl₂] (0.33g, 0.41mmol), when 85 DEG C of heating stirrings 8 are small.Toluene is added in into reaction solution, into Row washing, adds in magnesium sulfate, is filtered after stirring.Atlapulgite is added in into filtrate, is filtered after stirring.Concentration filter Liquid obtains the compound 6 (4.71g, yield 94.2%) of colorless solid.

Under nitrogen flowing, by toluene (100ml), ethyl alcohol (50ml), compound 6 (4.00g, 13.1mmol), 1,3,5- tri- Bromobenzene (4.11g, 13.1mmol), 2M aqueous sodium carbonate (50ml) input flask in, in 60 DEG C of heating stirrings 30 minutes.It connects Addition tetrakis triphenylphosphine palladium (0.30g, 0.26mmol), when reflux 2 is small.Water is added in into reaction solution, is carried with toluene It takes, adds in magnesium sulfate and atlapulgite, be filtered after stirring, concentrate filtrate.Utilize silica gel column chromatography (developing solvent:Just oneself Alkane:Toluene=5:1) purified, obtain the compound 7 (3.89g, yield 71.9%) of colorless oil.

Under nitrogen flowing, dimethyl sulfoxide (DMSO) (300ml), 4,4 "-two bromo- para-terpheny, 3.0g (7.73mmol), double is put into (pinacol combined) two boron 4.71g (18.55mmol), potassium acetate 4.55g (46.38mmol), to carrying out nitrogen displacement in system, 60 DEG C are stirred 30 minutes.It is subsequently added into 1,1 '-bis- (diphenylphosphino) ferrocene palladium chloride (II) dichloromethane adducts 0.32g (0.387mmol), when 83 DEG C of reactions 4 are small.Reaction solution is filtered under diminished pressure, water is added in into filtrate, with toluene into Row extraction.Anhydrous magnesium sulfate, atlapulgite are added in into organic layer, is filtered under diminished pressure after stirring, concentrates filtrate.It is hanged with methanol The solid that floating cleaning is precipitated, obtains the compound 7 (yield 2.8g, yield 75%) of colorless solid.

Put into compound 3 (4.95g, 9.95mmol), compound 7 (2.36g, 4.97mmol), potassium carbonate (5.53g, 40.0mmol) and toluene (60ml), ethyl alcohol (20ml), water (20ml), to fully carrying out nitrogen displacement in system, it is heated to 60℃.Tetrakis triphenylphosphine palladium (0.29g, 0.25mmol) is added in, when 80 DEG C of stirrings 4 are small.Water is added in into reaction solution, uses first Benzene extracts.Concentration of organic layers utilizes column chromatography (developping solution:Hexanes/ch=2/1) it is purified, obtain chemical combination Object 8 (2.77g, yield 51.7%).

Put into compound 4 (2.0g, 1.997mmol), compound 6 (0.095g, 0.2296mmol) and sodium tert-butoxide (1.48g, 15.38mmol), toluene (30ml) to carrying out nitrogen displacement in system, is heated to 60 DEG C (solution As).To three, (two is sub- Benzylacetone) two palladium chloroform complex compounds (0.042g, 0.0399mmol) toluene solution (5ml) in add in [4- (N, N- diformazan ammonia Base) phenyl] di-t-butyl phosphine (0.085g, 0.3195mmol), it is heated to 60 DEG C (solution Bs).In nitrogen stream, into solution A Add solution B, be heated to reflux 1.0 it is small when.Then 4,4 '-'-dibromobiphenyl (0.52g, 1.667mmol) is added.It is heated to reflux 1.0 After hour, additional 4,4 '-'-dibromobiphenyl (0.025g, 0.08mmol).By reaction solution natural cooling after 30 minutes, drop will be reacted It adds in ethyl alcohol 500ml, crystallizes crude polymer.

Obtained crude polymer is dissolved in toluene (90ml), input N, N- diphenylamines (0.068g, 0.403mmol), sodium tert-butoxide (0.74g, 7.7mmol) to carrying out nitrogen displacement in system, is heated to 60 DEG C (solution Cs).To Added in the toluene solution (3ml) of three (dibenzalacetone) two palladium chloroform complex compound (0.021g, 0.0203mmol) [4- (N, N- dimethylaminos) phenyl] di-t-butyl phosphine (0.043g, 0.1598mmol), it is heated to 60 DEG C (solution Ds).In nitrogen stream, to Solution D is added in solution C, be heated to reflux 3 it is small when.Bromobenzene (0.35g, 0.2229mmol) is added into the reaction solution.To three (two BENZYLIDENE ACETONE) two palladium chloroform complex compounds (0.021g, 0.0203mmol) toluene solution (3ml) in add in [4- (N, N- diformazans Amino) phenyl] di-t-butyl phosphine (0.043g, 0.1598mmol), it is heated to 60 DEG C (solution Es).In nitrogen stream, to reaction solution Middle addition solution E, be heated to reflux 3 it is small when.Reaction solution natural cooling is added dropwise in ethanol/water (1500ml/100ml) solution, The crude polymer blocked.

The crude polymer of the sealing end is dissolved in toluene, makes its reprecipitation with acetone, the polymer of precipitation is redissolved It in toluene, is cleaned with dilute hydrochloric acid, reprecipitation is carried out using containing cholamine.The polymer of leaching is purified using column chromatography, Obtain polymer 1 (1.0g).

Weight average molecular weight (Mw)=47100

Number-average molecular weight (Mn)=33400

Dispersion degree (Mw/Mn)=1.41

Put into compound 8 (2.155g, 2.00mmol), compound 6 (0.095g, 0.23mmol) and sodium tert-butoxide (1.48g, 15.4mmol), toluene (35ml) to carrying out nitrogen displacement in system, is heated to 60 DEG C (solution As).To three, (two is sub- Benzylacetone) two palladium chloroform complex compounds (0.041g, 0.041mmol) toluene solution (5ml) in add in [4- (N, N- diformazan ammonia Base) phenyl] di-t-butyl phosphine (0.085g, 0.32mmol), it is heated to 60 DEG C (solution Bs).In nitrogen stream, add into solution A Add solution B, be heated to reflux 1.0 it is small when.Then 4,4 '-'-dibromobiphenyl (0.493g, 1.58mmol) is added.It is small to be heated to reflux 1.0 Shi Hou by reaction solution natural cooling, reaction solution is added dropwise in ethyl alcohol 500ml, crystallizes crude polymer.

Obtained crude polymer is dissolved in toluene (150ml), input N, N- diphenylamines (0.068g, 0.040mmol), sodium tert-butoxide (0.74g, 7.7mmol) to carrying out nitrogen displacement in system, is heated to 60 DEG C (solution Cs).To Added in the toluene solution (3ml) of three (dibenzalacetone) two palladium chloroform complex compound (0.021g, 0.0203mmol) [4- (N, N- dimethylaminos) phenyl] di-t-butyl phosphine (0.043g, 0.16mmol), it is heated to 60 DEG C (solution Ds).In nitrogen stream, Xiang Rong Add solution D in liquid C, be heated to reflux 3 it is small when.Bromobenzene (0.35g, 0.223mmol) is added into the reaction solution.To three, (two is sub- Benzylacetone) two palladium chloroform complex compounds (0.021g, 0.0203mmol) toluene solution (3ml) in add in [4- (N, N- diformazan ammonia Base) phenyl] di-t-butyl phosphine (0.043g, 0.1598mmol), it is heated to 60 DEG C (solution Es).In nitrogen stream, into reaction solution Add solution E, be heated to reflux 3 it is small when.By reaction solution natural cooling, it is added dropwise in ethanol/water (1500ml/100ml) solution, obtains To the crude polymer of sealing end.

The crude polymer of the sealing end is dissolved in toluene, makes its reprecipitation with acetone, the polymer of precipitation is redissolved It in toluene, is cleaned with dilute hydrochloric acid, reprecipitation is carried out using containing cholamine.The polymer of leaching is purified using column chromatography, Obtain polymer 2 (1.2g).

Weight average molecular weight (Mw)=110000

Number-average molecular weight (Mn)=48200

Dispersion degree (Mw/Mn)=2.28

Put into compound 4 (9.0g, 8.99mmol), compound 9 (0.911g, 1.36mmol) and sodium tert-butoxide (6.66g, 69.3mmol), toluene (187ml) to fully carrying out nitrogen displacement in system, is heated to 60 DEG C (solution As).To three [4- (N, N- diformazans are added in the toluene 31ml solution of (dibenzalacetone) two palladium chloroform complex compound (0.186g, 1.8mmol) Amino) phenyl] di-t-butyl phosphine (0.382g, 1.4mmol), it is heated to 60 DEG C (solution Bs).In nitrogen stream, add into solution A Add solution B, when heating reflux reaction 1.0 is small.Then 4,4 "-two bromo- para-terpheny (2.546g, 6.56mmol) are added.Heating Flow back 1.0 it is small when.By reaction solution natural cooling, toluene (125ml) is added in, reaction solution is added dropwise in ethyl alcohol 1250ml, made thick Polymer crystallization.

Obtained crude polymer is dissolved in toluene 224ml, input N, N- diphenylamines (0.573g, 3.4mmol), Sodium tert-butoxide (3.125g, 32.5mmol) to fully carrying out nitrogen displacement in system, is heated to 60 DEG C (solution Cs).To three (two BENZYLIDENE ACETONE) two palladium chloroform complex compounds (0.088g, 0.1mmol) toluene 12.5ml solution in add in [4- (N, N- diformazan ammonia Base) phenyl] di-t-butyl phosphine (0.18g, 0.7mmol), it is heated to 60 DEG C (solution Ds).In nitrogen stream, added into solution C Solution D, when heating reflux reaction 3 is small.Bromobenzene (2.659g, 16.9mmol) is added into the reaction solution.To three (dibenzylidenes third Ketone) two palladium chloroform complex compounds (0.088g, 0.1mmol) toluene 12.5ml solution in add in [4- (N, N- dimethylamino) phenyl] Di-t-butyl phosphine (0.18g, 0.7mmol) is heated to 60 DEG C (solution Es).In nitrogen stream, solution E is added into reaction solution, is added When hot back flow reaction 3 is small.By reaction solution natural cooling, it is added dropwise in ethanol/water (1120ml/108ml) solution, is blocked Crude polymer.

The crude polymer of the sealing end is dissolved in toluene, makes its reprecipitation with acetone, the polymer of precipitation is redissolved It in toluene, is cleaned with dilute hydrochloric acid, reprecipitation is carried out using containing cholamine.The polymer of leaching is purified using column chromatography, Obtain polymer 3 (4.3g).

Weight average molecular weight (Mw)=35900

Number-average molecular weight (Mn)=27600

Dispersion degree (Mw/Mn)=1.30

Put into compound 4 (5.0g, 4.99mmol), compound 6 (0.313g, 0.756mmol) and sodium tert-butoxide (3.699g, 38.5mmol), toluene (104ml) to fully carrying out nitrogen displacement in system, is heated to 60 DEG C (solution As).To three [4- (N, N- diformazans are added in the toluene 17ml solution of (dibenzalacetone) two palladium chloroform complex compound (0.103g, 0.1mmol) Amino) phenyl] di-t-butyl phosphine (0.212g, 0.8mmol), it is heated to 60 DEG C (solution Bs).In nitrogen stream, add into solution A Add solution B, when heating reflux reaction 1.0 is small.It is subsequently added into compound 10 (2.053g, 3.74mmol).It is small to be heated to reflux 1.0 When.

Add in N, N- diphenylamines (0.338g, 2.0mmol), when heating reflux reaction 1 is small.Bromine is added into the reaction solution Benzene (1.568g, 10mmol).When heating reflux reaction 2 is small.By reaction solution natural cooling, ethanol/water (342ml/ is added dropwise to 100ml) in solution, the crude polymer that is blocked.

The crude polymer of the sealing end is dissolved in toluene, makes its reprecipitation with acetone, the polymer of precipitation is redissolved It in toluene, is cleaned with dilute hydrochloric acid, reprecipitation is carried out using containing cholamine.The polymer of leaching is purified using column chromatography, Obtain polymer 4 (2.1g).

Weight average molecular weight (Mw)=38800

Number-average molecular weight (Mn)=29800

Dispersion degree (Mw/Mn)=1.30

(embodiment 1)

Produce organic electroluminescent device shown in FIG. 1.

After accumulating indium tin oxide (ITO) transparent conductive film on glass substrate 1 by spatter film forming, common photograph is used Phase lithography technique and hydrochloric acid pattern dissolve the striped of 2mm wide, form the anode 2 that film thickness is 70nm.Scheme being formed After case ito substrate according to using aqueous surfactant solution ultrasonic cleaning, using ultra-pure water washing, utilize ultra-pure water After ultrasonic cleaning, the order cleaning using the washing of ultra-pure water, it is dried using compressed air, it is smelly finally carries out ultraviolet light Oxygen cleans.

Then, prepare different containing the aryl amine polymers shown in following structural formula (P1), the 4- shown in structural formula (A1) The hole injection layer formation coating fluid of propyl -4 '-four (pentafluorophenyl group) borate of methyldiphenyl base iodine and ethyl benzoate. The coating fluid with following conditions on anode 2 is formed a film by spin coating, has obtained the hole injection layer that film thickness is 31nm.

Solvent ethyl benzoate

Coating fluid concentration P1：2.5 weight %

A1：0.5 weight %

Then, the hole transmission layer formation containing the polymer 1 (P2) with following shown structural formulas is prepared to apply Cloth liquid is formed a film by spin coating with following conditions on hole injection layer 3, is heated and forms the hole that film thickness is 20nm and pass Defeated layer.

Solvent cyclohexyl benzene

1.5 weight % of coating fluid concentration

Then, the luminescent layer formation containing following structural formula compound represented (H1), (H2) and (D1) is prepared to apply Cloth liquid is formed a film with following conditions by spin coating, is heated, and is 50nm's so as to form film thickness on hole transmission layer 4 Luminescent layer.

Herein, the substrate to form a film until luminescent layer is moved into vacuum deposition apparatus, be exhausted until in device Vacuum degree reaches 2.0 × 10^-4Then below Pa, is controlled evaporation rate using vacuum vapour depositionThe model of/second It encloses, by organic compound (E1) lamination with following shown structures on luminescent layer 5, obtains the hole that film thickness is 10nm and hinder Barrier 6.

Then, evaporation rate is controlled using vacuum vapour depositionThe scope of/second will have following shown Structure organic compound (E2) lamination on hole blocking layer 6, obtain film thickness be 20nm electron transfer layer 7.

Herein, the element until electron transfer layer 7 will be deposited to move in other vacuum deposition apparatus, makes conduct The striated shadow mask of the 2mm wide of cathode evaporation mask is close according to the mode orthogonal with the ITO stripeds of anode 2 and element It closes, is exhausted until the vacuum degree in device reaches 3.1 × 10^-4Until below Pa.

As electron injecting layer 8, first using molybdenum boat, with evaporation rate/ the second is controlled, by lithium fluoride (LiF) formed a film with the film thickness of 0.5nm on electron transfer layer 7.Then, as cathode 9, similarly using molybdenum boat to aluminium It is heated, with evaporation rateThe scope of/second is controlled, and forms the aluminium layer that film thickness is 80nm.Above-mentioned 2 layers of steaming Substrate temperature during plating remains room temperature.

Next, element deteriorates in keeping due tos moisture in air etc. in order to prevent, in following recorded methods Encapsulation process is carried out.

In nitrogen glove box, photocuring is coated with the width of about 1mm in the peripheral part of the glass plate of 23mm × 23mm sizes Property resin (Three Bond Fine Chemical Co., Ltd. manufacture 30Y-437), in central portion, moisture absorption piece (dynic is set Co., Ltd. manufactures).Fitting forms the substrate until cathode on it, makes vapor deposition face opposite with drying agent chip.Thereafter, it is only right The area illumination ultraviolet light of light-cured resin is coated with, makes resin solidification.

As above the organic electroluminescent device of the light-emitting area part with 2mm × 2mm sizes has been obtained.By the element Characteristic is shown in table 9.

(comparative example 1)

For hole transmission layer 4, the hole transmission layer shape containing (P3) represented by following shown structural formulas is prepared It into coating fluid, is formed a film by spin coating with following conditions on hole injection layer 3, is heated and form the sky that film thickness is 19nm Cave transport layer in addition, produces organic electroluminescent device similarly to Example 1.By the characteristic of obtained element It is shown in table 9.

Solvent cyclohexylbenzene

1.5 weight % of coating fluid concentration

【Table 9】

	Hole transmission layer 4	10mA/cm²Voltage/V during energization
			Embodiment 1	P2	6.6
Comparative example 1	P3	6.9

As shown in Table 9, the voltage for having used the organic electroluminescent device of the polymer of the present invention is low.

(embodiment 2)

For hole transmission layer 4, the hole containing the polymer 2 (P4) represented by following shown structural formulas is prepared Transport layer formation coating fluid is formed a film by spin coating with following conditions on hole injection layer 3, is heated and forms film thickness and is The hole transmission layer of 20nm.

Solvent cyclohexylbenzene

1.5 weight % of coating fluid concentration

For luminescent layer 5, prepare to be formed containing the luminescent layer of following structural formula compound represented (H3) and (D2) and use Coating fluid is formed a film with following conditions by spin coating, is heated, and it is 41nm that film thickness is thus formed on hole transmission layer 4 Luminescent layer.

In addition, organic electroluminescent device is produced similarly to Example 1.The characteristic of obtained element is shown In table 10.

Solvent cyclohexylbenzene

Coating fluid concentration H3：3.5 weight %

D2：0.35 weight %

(comparative example 2)

It, will the hole transmission layer shape containing the compound of structural formula (P3) in the same manner as comparative example 1 for hole transmission layer 4 It forms a film, is heated into coating fluid, form the hole transmission layer that film thickness is 19nm, make similarly to Example 2 in addition Make organic electroluminescent device.The characteristic of obtained element is shown in table 10.

(comparative example 3)

For hole transmission layer 4, the hole transmission layer shape containing (P5) represented by following shown structural formulas is prepared It into coating fluid, is formed a film, is heated on hole injection layer 3 with following conditions by spin coating, form the sky that film thickness is 20nm Cave transport layer, produces organic electroluminescent device similarly to Example 2 in addition.The characteristic of obtained element is shown In table 10.

Solvent cyclohexylbenzene

1.5 weight % of coating fluid concentration

【Table 10】

	Hole transmission layer 4	1000cd/m²When voltage/V	1000cd/m²When current efficiency/cd/A
				Embodiment 2	P4	7.3	4.3
Comparative example 2	P3	7.7	1.7
				Comparative example 3	P5	7.6	1.5

As shown in Table 10, the voltage for having used the organic electroluminescent device of the polymer of the present invention is low, efficient.

(embodiment 3)

Using flight time (TOF) method, measured in the same manner as the method described in Japanese Unexamined Patent Publication 2014-51667 publications The hole mobility of polymer 3 (P6).

First, on the glass substrate with the thickness accumulation ITO nesa coating (ITO stripeds) of 70nm, for obtained Substrate (manufacture of GEOMATEC societies), according to using aqueous surfactant solution ultrasonic cleaning, utilize the washing of ultra-pure water, profit With the ultrasonic cleaning of ultra-pure water, cleaned using the order of the washing of ultra-pure water after, be dried using compressed air, Ran Houshi Ultraviolet and ozone cleaning is applied.

By toluene and silicone oil, (Shin-Etsu Silicones societies manufacture：KF-96 with 10 matter in the solvent) mixed The concentration of amount % dissolves (P6) and produces solution, is formed a film using spin-coating method on the substrate after the cleaning.It needs to illustrate , form a film and all carried out in nitrogen atmosphere.Thus the film for the subject polymer 1 that film thickness is 2 μm is obtained.Then, by sample It is sent in the vacuum chamber of vacuum deposition apparatus.Make striated shadow mask as the 2mm wide of cathode evaporation mask by It is closely sealed according to the mode orthogonal with ITO stripeds and element, so as to be configured.Afterwards, the vacuum degree until in device is exhausted Reach 8.0 × 10^-4Below Pa afterwards heats aluminium using molybdenum boat, and the electricity that thickness is 80nm is thus formed on sample Pole.It should be noted that in the film forming of aluminium, the indoor vacuum degree of chamber is remained 2.0 × 10^-3Below Pa, and will vapor deposition Speed remains/ the second.

For the sample, apply electric field strength in a manner that ito film is anode, aluminium electrode is cathode, in this state, " VSL-337ND-S (nitrogen laser) " (excitation wavelength 337nm, the pulse width manufactured using Spectra-Physics societies< 4ns) carry out the measure of transient photocurrents.It should be noted that on light irradiation energy, it will using the ND optical filters of reflection-type The light quantity of every 1 pulse is adjusted to 10 μ J, is irradiated from ITO electrode side.Transient photocurrents waveform utilizes oscillograph (" TDS2022 " of the manufacture of Tektronix societies) is measured, and charge mobility is calculated by inflection point.The measure is to be applied with It is carried out in the state of electric field strength 160kV/cm.

The result of calculation of hole mobility is with by the result of calculation of the hole mobility of the compound of aftermentioned structural formula (P7) Relative value (standardization hole mobility) when being set to " 1.0 " represents.The results are shown in tables 11.

(comparative example 4)

The compound of structural formula (P6) is changed to the compound of structural formula (P7), in addition similarly to Example 3 The measure of (P7) is carried out, the hole mobility calculated is made to be set to 1.0.

【Table 11】

	Sample	Standardize hole mobility
			Embodiment 3	P6	1.4
Comparative example 4	P7	1.0

As shown in Table 11, the hole mobility of polymer of the invention is big.

The present invention is described in detail with reference to particular implementation, but is not departing from the feelings of the spirit and scope of the present invention It can be made various changes and modifications under condition, this will be readily apparent to one having ordinary skill.The application is based on 2013 The Japanese patent application (Japanese Patent Application 2013-209111) and the Japan Patent submitted on January 28th, 2014 that October 4 submitted Apply (Japanese Patent Application 2014-013358), its content is introduced into this specification in reference form.

Symbol description

1. substrate

2. anode

3. hole injection layer

4. hole transmission layer

5. luminescent layer

6. hole blocking layer

7. electron transfer layer

8. electron injecting layer

9. cathode

Claims

1. a kind of polymer, with the repetitive unit represented by following formula (1),

In formula, Ar¹And Ar²It is the 2- fluorenyls with or without substituent group；Or Ar¹And Ar²One of to have or not 2- fluorenyls with substituent group, another one are as the thick of 6 yuan of rings monocyclic or 2~5 rings with or without substituent group The aromatic hydrocarbyl of 1 valency group of ring or with or without substituent group as 5 or 6 yuan of rings monocyclic or 2~4 rings The aromatic heterocycle of 1 valency group of condensed ring；

Ar³Each independently represent the divalent of monocyclic or 2~5 rings the condensed ring as 6 yuan of rings with or without substituent group The 2 of the aromatic hydrocarbyl of group or monocyclic or 2~4 rings the condensed ring as 5 or 6 yuan of rings with or without substituent group The aromatic heterocycle of valency group, the aromatic hydrocarbyl and the aromatic heterocycle can be direct or by linking groups And 2 or more link together,

N represents more than 4 integer,

The substituent group that the aromatic hydrocarbyl and aromatic heterocycle can have in following substituent group Z group and Crosslinkable groups,

The substituent group Z is：

Carbon number is more than 1, less than 24 straight chain, branch or cricoid alkyl,

Carbon number is more than 2, less than 24 alkenyl,

Carbon number is more than 2, less than 24 alkynyl,

Carbon number is more than 1, less than 24 alkoxy,

Carbon number is more than 4, less than 36 aryloxy group,

Carbon number is more than 2, less than 24 alkoxy carbonyl group,

Carbon number is more than 2, less than 24 dialkyl amido,

Carbon number is more than 10, less than 36 ammonia diaryl base,

Carbon number is more than 7, less than 36 aryl alkyl amino,

Carbon number is more than 2, less than 24 acyl group,

Halogen atom,

Carbon number is more than 1, less than 12 alkylhalide group,

Carbon number is more than 1, less than 24 alkylthio group,

Carbon number is more than 4, less than 36 arylthio,

Carbon number is more than 2, less than 36 silicyl,

Carbon number is more than 2, less than 36 siloxy,

Cyano,

Carbon number be more than 6, less than 36 aromatic hydrocarbyl and

Carbon number is more than 3, less than 36 aromatic heterocycle；

Group in substituent group Z can be further substituted with the group in substituent group Z.

2. polymer as described in claim 1, wherein, the substituent group Z is：

Carbon number is more than 1, less than 24 alkoxy,

Carbon number be more than 6, less than 36 aromatic hydrocarbyl and

Carbon number is more than 3, less than 36 aromatic heterocycle.

3. polymer as described in claim 1, wherein, work as Ar¹And Ar²One of be with or without the substituent group 2- fluorenyls when, another one be with or without the aromatic hydrocarbyl of the substituent group or with or without the substitution The aromatic heterocycle of base, the aromatic hydrocarbyl is phenyl ring, naphthalene nucleus, anthracene nucleus, phenanthrene ring, perylene ring, aphthacene ring, pyrene Ring, benzoin ring, 1,2- benzos phenanthrene ring, benzo [9,10] phenanthrene ring, acenaphthene ring, 1 valency group of fluoranthene ring or fluorenes ring；The aromatic series Heterocycle is furan nucleus, benzofuran ring, thiphene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole rings, Yin Diindyl ring, carbazole ring, pyrrolo- imidazole ring, pyrrolo-pyrazole ring, pyrrolopyrrole ring, Thienopyrroles ring, thienothiophene ring, Furans and pyrrole ring, furans and furan nucleus, thienofuran ring, benzoisoxazole ring, benzisothiazole ring, benzimidazole ring, Pyridine ring, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinolin ring, cinnolines ring, quinoxaline ring, phenanthridines ring, naphthalene Embedding metadiazine ring, quinazoline ring, 1 valency group of quinazolinone ring or azulenes,

The aromatic hydrocarbyl and the aromatic heterocycle can be direct or by linking group and 2 or more are attached at one It rises.

4. polymer as claimed in claim 3, wherein, the another one be with or without the substituent group phenyl, Fluorenyl.

5. polymer as described in claim 1, wherein, the Ar¹、Ar²And Ar³In at least more than 1 have as substitution The crosslinkable groups of base.

6. polymer as described in claim 1, wherein, the crosslinkable groups is shown in following crosslinkable groups group T Group,

Crosslinkable groups group T：

In formula, R¹¹~R¹³Represent the chain-like alkyl of hydrogen atom or carbon number for less than 6 linear chain or branch chain,

R⁴、R⁵Represent the chain-like alkyl for the linear chain or branch chain that hydrogen atom, carbon number are less than 6 or carbon number be less than 6 it is straight The chain alkoxy of chain or branch,

Ar⁷Represent the aromatic hydrocarbyl with or without substituent group or the aromatic heterocycle with or without substituent group, Ar⁷The aromatic hydrocarbyl with or without substituent group be 6 yuan of rings monocyclic or 2~5 rings condensed ring, these have or not Aromatic hydrocarbyl with substituent group can be 2 or more and carry out the group that bonding forms.

7. polymer as described in claim 1, wherein, the crosslinkable groups are following bases comprising benzocyclobutene ring Group,

R⁴、R⁵Represent the chain-like alkyl for the linear chain or branch chain that hydrogen atom, carbon number are less than 6 or carbon number be less than 6 it is straight The chain alkoxy of chain or branch.

8. such as polymer according to any one of claims 1 to 7, wherein, the polymer has of more than two kinds by above-mentioned formula (1) repetitive unit represented by, at least one kind of repetitive unit include crosslinkable groups, and at least one kind of repetitive unit does not include bridging property Group.

9. such as polymer according to any one of claims 1 to 7, wherein, Ar³For the group represented by following formula (2),

In formula, m represents 1~3 integer.

10. such as polymer according to any one of claims 1 to 7, wherein, the Ar³In, the aromatic hydrocarbon of 2 or more When the aromatic heterocycle bonding of base and 2 or more, linking group that can be between be selected from by- CR¹R²―、―O―、―CO―、―NR³- and group in the group of-S-composition and by 2~10 companies of these groups The group formed is tied, in the case of connection 2 or more, linking group can be a kind, or two or more,

The R¹~R³It is less than more than 1 24 to each independently represent hydrogen atom or the carbon number with or without substituent group Straight chain, branch or cricoid alkyl, with or without substituent group carbon number be less than more than 6 36 aromatic hydrocarbon Base or with or without substituent group carbon number be less than more than 3 36 aromatic heterocycle.

11. such as polymer according to any one of claims 1 to 7, wherein, the Ar³In, the aromatic hydrocarbon of 2 or more When base and the bonding of the aromatic heterocycle of 2 or more, linking group that can be between is selected from-CR¹R²-, with And 2~6-CR to link together¹R²- in group,

The R¹~R²It is less than more than 1 24 to each independently represent hydrogen atom or the carbon number with or without substituent group Straight chain, branch or cricoid alkyl, with or without substituent group carbon number be less than more than 6 36 aromatic hydrocarbon Base or with or without substituent group carbon number be less than more than 3 36 aromatic heterocycle.

12. such as polymer according to any one of claims 1 to 7, wherein, Ar³For the connection represented by by following formula (3) Group and aromatic hydrocarbyl or aromatic heterocycle that 2 or more link together,

In formula, p represents 1~10 integer, R¹、R²Each independently represent hydrogen atom or the carbon with or without substituent group Straight chain that atomicity is less than more than 1 24, branch or aromatic hydrocarbyl that cricoid alkyl, carbon number are less than more than 6 36 Or the aromatic heterocycle that carbon number is less than more than 3 36；R¹、R²There are at 2 or more, can be the same or different.

13. such as polymer according to any one of claims 1 to 7, wherein, the weight average molecular weight Mw of the polymer is 20, More than 000, dispersion degree Mw/Mn are less than 2.5.

14. a kind of organic electroluminescent device composition, said composition contains poly- any one of claim 1~13 Close object.

15. a kind of organic electroluminescent device, be have on substrate anode, cathode and positioned at the anode and the cathode it Between organic layer organic electroluminescent device,

The organic electroluminescent device composition that the organic layer includes described in usage right requirement 14 passes through wet type membrane formation institute The layer of formation.

16. organic electroluminescent device as claimed in claim 15, wherein, the layer formed by the wet type membrane formation is At least one of hole injection layer and hole transmission layer.

17. the organic electroluminescent device as described in claim 15 or 16, wherein, it is noted between the anode and the cathode comprising hole Enter layer, hole transmission layer and luminescent layer, the hole injection layer, hole transmission layer and luminescent layer are all through wet type membrane formation It is formed.

18. a kind of organic EL display, with the organic electroluminescent device any one of claim 15~17.

19. a kind of organic EL illuminating, with the organic electroluminescent device any one of claim 15~17.