TWI708793B - Polymer, composition for organic electroluminescent element, organic electroluminescent element, organic el display and organic el lighting - Google Patents

Abstract

The present invention provides a polymer having a higher hole injecting and transporting ability and a higher durability, a composition for organic electroluminescent element comprising the polymer, an organic electroluminescent element having a higher luminescent efficiency and produced by using the composition, and a display and lighting using the organic electroluminescent element. The polymer of the present invention comprises a unit represented by the following formula (1) as a repeating unit:

(In the formula, each of Ar¹, R¹ and T¹ has the same definition as in the present specification.)

Description

Polymers, compositions for organic electroluminescence devices, organic electroluminescence devices, organic EL display devices, and organic EL lighting

The present invention relates to a polymer, and more specifically, to a polymer that can be effectively used as a charge transporting material for an organic electroluminescence element, a composition for an organic electroluminescence element containing the polymer, and a composition containing the The organic electroluminescence element of the layer formed by the composition, the organic EL (Electro Luminescence) display device provided with the organic electroluminescence element, and the organic EL illumination.

Examples of methods for forming the organic layer of the organic electroluminescence element include a vacuum vapor deposition method and a wet film formation method. Because the vacuum evaporation method is easier to layer, it has the advantage of improving the charge injection from the anode and/or cathode, and the light-emitting layer is easier to block excitons. On the other hand, the wet film forming method does not require a vacuum process and can be easily enlarged. By using a coating solution mixed with multiple materials with various functions, a layer containing multiple materials with various functions can be easily formed Etc.

However, because the wet film forming method is more difficult to layer, compared with the components made by the vacuum evaporation method, the current situation shows that the driving stability is poor, and most of them are not yet practical.

Here, for the purpose of laminating by a wet film forming method, a charge transport polymer containing a crosslinkable group is expected, and development is underway. For example, patent documents 1~3 are disclosed Shows: An organic electroluminescent device that contains a polymer with a specific repeating unit and is laminated by a wet film forming method. In addition, in order to form an organic electroluminescence element with excellent hole transport properties, for example, Patent Documents 4 to 6 disclose an arylamine polymer used as a charge transport material and elements using the same.

[Prior Technical Literature] [Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2010-155985

Patent Document 2: Japanese Patent Laid-Open No. 2013-045986

Patent Document 3: Japanese Patent Laid-Open No. 2013-170228

Patent Document 4: Japanese Patent Laid-Open No. 2012-102286

Patent Document 5: Japanese Patent Special Form 2007-518842

Patent Document 6: International Publication No. 2013/114976

However, the devices described in Patent Documents 1 to 3 have problems of high driving voltage and short driving life. Therefore, it is expected that the charge injection and transport capability and durability of the charge transport material will be improved.

The reason is that the subject of the present invention is to provide a novel polymer with high hole injection and transport ability and high durability, and a composition for an organic electroluminescent device containing the polymer. In addition, the subject of the present invention is to provide an organic electroluminescence element with high brightness and long driving life.

After intensive research, the inventors found that polymers with specific repeating units are prone to generate cationic radicals. By efficiently transporting the cationic radicals, the above-mentioned problems can be solved, thus completing the present invention.

That is, the gist of the present invention is as follows [1] to [12].

[1] A polymer containing the unit represented by the following formula (1) as a repeating unit:

(In formula (1), Ar ¹ represents an aromatic hydrocarbon group or aromatic heterocyclic group that is independently or may have substituents and is condensed from 3 or more rings. R ¹ represents each independently or may have substituents The alkyl group. T ¹ represents an aromatic hydrocarbon group or an aromatic heterocyclic group having a crosslinkable group as a substituent.)

[2] The polymer as described in [1] above, which further contains a unit represented by the following formula (2) as a repeating unit:

(In formula (2), Ar ¹ represents an aromatic hydrocarbon group or aromatic heterocyclic group that is independently or may have substituents, and is condensed from 3 or more rings. R ¹ represents each independently or may have substituents The alkyl group. L ¹ represents an aromatic hydrocarbon group or an aromatic heterocyclic group.)

[3] The polymer as described in [2] above, wherein the total of the unit represented by the above formula (1) and the unit represented by the above formula (2) in the polymer is 100 mol% relative to the total monomer units contain More than 50 mol%.

[4] The polymer as described in any one of [1] to [3] above, wherein the Ar ¹ system may have a substituted 2-phosphonium group.

[5] The polymer as described in any one of [2] to [4] above, wherein the L ¹ is 4,4'-biphenylene, that is, it contains a unit represented by the following formula (3) as Repeating unit:

(In formula (3), Ar ¹ represents an aromatic hydrocarbon group or an aromatic heterocyclic group condensed from three or more rings, independently of each other, and may have substituents. R ¹ represents each independently or may have substituents的alkyl.)

[6] The polymer according to any one of [1] to [5] above, wherein the weight average molecular weight (Mw) is 20,000 or more, and the degree of dispersion (Mw/Mn) is 2.5 or less.

[7] A composition for an organic electroluminescence element, which contains the polymer described in any one of [1] to [6].

[8] An organic electroluminescence element comprising an anode, a cathode, and an organic layer provided between the anode and the cathode on a substrate; wherein the organic layer contains the above [7] The composition for an organic electroluminescence device as described in a layer formed by a wet film forming method.

[9] The organic electroluminescence device according to the above [8], wherein at least one of a hole injection layer and a hole transport layer is formed by the wet film forming method.

[10] The organic electroluminescent device as described in [8] or [9] above, wherein the anode A hole injection layer, a hole transport layer, and a light-emitting layer are contained between the cathode and the cathode; the hole injection layer, the hole transport layer, and the light-emitting layer are all formed by a wet film forming method.

[11] An organic EL display device provided with the organic electroluminescence element described in any one of [8] to [10] above.

[12] An organic EL lighting provided with the organic electroluminescence element described in any one of [8] to [10] above.

Because the N,N-bis(4-alkylphenyl)benzidine structure contained in the main chain of the polymer of the present invention is composed of a phenyl group having an alkyl group belonging to the electron-donating group at the para position, replacing the N atom of benzidine Therefore, it is easy to become cationic radicals, and the hole injection from the anode is excellent.

Furthermore, the above-mentioned N,N-bis(4-alkylphenyl)benzidine structure is substituted with an aromatic hydrocarbon group or an aromatic heterocyclic group condensed with three or more rings via the N atom present in the phenylene group. The orbits of condensed rings with three or more rings are easy to be non-localized, and hole transport between polymer chains is excellent.

Furthermore, since the polymer of the present invention contains a crosslinkable group, it becomes insoluble by crosslinking after coating.

By using the polymer-containing organic electroluminescent device composition of the present invention, the layer obtained by wet film formation does not generate cracks and the like, and has a flat surface. According to the organic electroluminescence element of the present invention, high brightness and long driving life can be achieved.

Furthermore, because the polymer of the present invention has excellent electrochemical stability, it contains elements using the layer formed by the polymer, and can be considered for applications such as flat-panel displays (for example, OA computers, wall-mounted televisions), and automotive displays. Components, mobile phone displays, light sources that utilize the characteristics of surface illuminators (such as photocopier light sources, liquid crystal displays and backlights for measuring instruments), display panels, and signal lights have great technical value.

1‧‧‧Substrate (glass substrate)

2‧‧‧Anode

3‧‧‧Electric hole injection layer

4‧‧‧Electric tunnel transport layer

5‧‧‧Light-emitting layer

6‧‧‧Electric hole barrier layer

7‧‧‧Electron transport layer

8‧‧‧Electron injection layer

9‧‧‧Cathode

10‧‧‧Organic electroluminescent element

FIG. 1 is a schematic cross-sectional view of an example of the structure of the organic electroluminescent device of the present invention.

The following is a detailed description of the embodiments of the present invention. The description of the constituent elements described below is only an example (representative example) of the embodiments of the present invention. The present invention is not limited to these contents without going beyond the gist.

Furthermore, in this manual, all "percentages" or "parts" shown by mass are the same as "percentages" and "parts" shown by weight.

<polymer>

The polymerization system of the present invention has the repeating unit represented by the following formula (1), that is, the repeating unit system contains the unit represented by the following formula (1):

(In formula (1), Ar ¹ represents an aromatic hydrocarbon group or aromatic heterocyclic group that is independently or may have substituents and is condensed from 3 or more rings. R ¹ represents each independently or may have substituents The alkyl group. T ¹ represents an aromatic hydrocarbon group or an aromatic heterocyclic group having a crosslinkable group as a substituent.)

[Substituents of Repeating Units]

環(chrysene ring)、聯伸三苯環、苊環、1,2-苯并苊環、茀環、茚并茀環等由五或六元環之3環以上縮環的基。 Ar ¹ in the unit represented by the above formula (1), the aromatic hydrocarbon group may include, for example: anthracene ring, phenanthrene ring, perylene ring, fused tetraphenyl ring, pyrene ring, benzopyrene ring,

Ring (chrysene ring), extended triphenyl ring, acenaphthene ring, 1,2-benzoacenaphthene ring, stilbene ring, indeno pyrene ring, etc. are groups condensed from three or more rings of five or six members.

Examples of aromatic heterocyclic groups include: carbazole ring, indenocarbazole ring, indolocarbazole ring, dibenzofuran ring, dibenzothiophene ring, etc., which are condensed from three or more five- or six-membered rings. The base of the ring.

From the viewpoint of excellent charge transportability and durability, Ar ¹ is preferably an aromatic hydrocarbon group, and more preferably is a monovalent group of a phenyl group or a stilbene ring, that is, a stilbene group, particularly preferably a stilbene group, and the most preferred is 2-茀基. In addition, the Ar ¹ systems in the unit represented by formula (1) may be the same or different, and are preferably the same.

For R ¹ in the unit represented by the above formula (1), the alkyl system may include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tertiary butyl A straight-chain, branched, or cyclic alkyl group having a carbon number of usually 1 or more and usually 24 or less, such as oxy, n-hexyl, n-octyl, cyclohexyl, and dodecyl.

Among them, preferred are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-hexyl, cyclohexyl, etc., with carbon numbers of 1 or more and 6 or less The straight-chain, branched, or cyclic alkyl group is more preferably a straight-chain or branched alkyl group having 1 or more and 4 or less carbon atoms. In addition, the R ¹ systems in the unit represented by formula (1) may be the same or different, and are preferably the same.

The aromatic hydrocarbon group and aromatic heterocyclic group of Ar ¹ and the substituents that the alkyl group of R ¹ may have are mentioned before the properties of the polymer are significantly reduced. The rest is not particularly limited, such as The group selected from the following substituent group Z is preferably an alkyl group, an alkoxy group, an aromatic hydrocarbon group, and an aromatic heterocyclic group, and more preferably an alkyl group.

[Substituent Group Z]

For example: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, second butyl, tertiary butyl, n-hexyl, cyclohexyl, dodecyl, etc. The carbon number is usually 1 or more , And usually 24 or less, preferably 12 or less linear, branched or cyclic alkyl; for example: vinyl and other carbon number is usually 2 or more and usually 24 or less, preferably 12 or less alkenyl; for example: acetylene The carbon number of the group is usually 2 or more, and usually 24 or less, preferably 12 or less; for example: methoxy, ethoxy, etc. The carbon number is usually 1 or more and usually 24 or less, preferably 12 or less. Oxy; for example: phenoxy, naphthyloxy, pyridyloxy and other aryloxy groups with carbon number usually 4 or more, preferably 5 or more, and usually 36 or less, preferably 24 or less; for example: methoxycarbonyl, ethoxy Carbon number such as carbonyl group is usually 2 or more, and usually 24 or less, preferably 12 or less alkoxycarbonyl groups; for example: dimethylamino group, diethylamino group and other carbon number usually 2 or more, usually 24 or less, preferably 12 or less Dialkylamino groups; for example: diphenylamino groups, xylamino groups, N-carbazolyl groups and other diarylamino groups with carbon numbers of usually 10 or more, preferably 12 or more, and usually 36 or less, preferably 24 or less; for example: Arylalkylamino groups with carbon numbers such as phenylmethylamino groups are usually 7 or more, and usually 36 or less, preferably 24 or less; for example: acetyl, benzyl and other carbon numbers are usually 2 or more and usually 24 or less, Preferably, an acyl group of 12 or less; for example, halogen atoms such as fluorine atom and chlorine atom; For example: trifluoromethyl and other haloalkyl groups with carbon number usually 1 or more, and usually 12 or less, preferably 6 or less; for example: methylthio, ethylthio and the like, usually having 1 or more carbon atoms and usually 24 or less, preferably Alkylthio groups of 12 or less; for example: phenylthio, naphthylthio, pyridinethio and other arylthio groups with carbon number usually 4 or more, preferably 5 or more, and usually 36 or less, preferably 24 or less; for example: trimethyl A silyl group with a carbon number of usually 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less; for example: trimethylsiloxy group, triphenylsiloxy group, etc. A siloxyalkyl group with a carbon number such as 2 or more, preferably 3 or more, and usually 36 or less, preferably 24 or less; cyano; for example: phenyl, naphthyl, etc. The carbon number is usually 6 or more and usually 36 or less, An aromatic hydrocarbon group of 24 or less is preferable; for example, an aromatic heterocyclic group having a carbon number of usually 3 or more, preferably 4 or more, and usually 36 or less, preferably 24 or less, such as thienyl and pyridyl.

In addition, each of the above-mentioned substituents may further have a substituent, and examples of these substituents may be, for example, the same as the above-mentioned substituents (substituent group Z).

T ¹ in the unit represented by the above formula (1), the aromatic hydrocarbon group and the aromatic heterocyclic group may also be bonded by a plurality of bonds.

環、聯伸三苯環、苊環、1,2-苯并苊環、茀環等六元環單環或2~5縮合環之2價基。 Examples of aromatic hydrocarbon groups include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetraphenyl ring, pyrene ring, benzopyrene ring,

A six-membered monocyclic ring or a divalent group of 2 to 5 condensed rings such as ring, triphenyl ring, acenaphthene ring, 1,2-benzo acenaphthene ring, and stilbene ring.

二唑環、 吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、氟化吡咯環、氟化呋喃環、噻吩并呋喃環、苯并異

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、噠

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環(sinoline ring)、喹

啉環、菲啶環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等五或六元環單環或2~4縮合環之2價基。 Examples of aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,

Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, fluorinated pyrrole ring, fluorinated furan ring, thieno Furan ring, benziso

Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring

Ring, da

Ring, pyrimidine ring, three

Ring, quinoline ring, isoquinoline ring,

Sinoline ring, quine

Divalent groups of five- or six-membered monocyclic rings or 2~4 condensed rings such as phyllidine ring, phenanthridine ring, piperidine ring, quinazoline ring, quinazolinone ring, and azulene ring.

There are no particular restrictions on the substituents that the aromatic hydrocarbon group and the aromatic heterocyclic group may have. For example, a group selected from the above-mentioned substituent group Z is preferably an alkyl group, an alkoxy group, an aromatic hydrocarbon group, The aromatic heterocyclic group is more preferably an alkyl group.

When T ¹ is a group bonded to a plurality of the above-mentioned aromatic hydrocarbon group and aromatic heterocyclic group, from the viewpoint of excellent charge transportability and excellent durability, it is preferable that 2 to 6 of these groups are connected. The aromatic hydrocarbon group and the aromatic heterocyclic group to be connected may be one type or plural types.

In addition, when T ¹ is a group bonded by a plurality of the above-mentioned aromatic hydrocarbon group and aromatic heterocyclic group, it may be bonded via a linking group. In this case, the linking group is preferably a group selected from the group consisting of -CR ¹ R ² -, -O-, -CO-, -NR ³ -, and -S-, and those 2~ 10 connected bases. In addition, when two or more are connected, the connection base system may be one type or plural types. Among them, R ¹ to R ³ each represent an independent hydrogen atom, or an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and an aromatic heterocyclic group which may have a substituent. The linking base is more preferably -CR ¹ R ² -and a group linked by 2 to 6 -CR ¹ R ² -, particularly preferably -CR ¹ R ² -.

[Related crosslinking group]

The T ^{1 type} substituent contains a crosslinkable group. By containing the crosslinkable group, the solubility to the organic solvent can be greatly different before and after the reaction (insolubilization reaction) is initiated by heat and/or active energy ray irradiation.

The so-called "crosslinkable group" refers to a group that reacts with groups constituting other molecules located in the vicinity of the crosslinkable group by irradiation of heat and/or active energy rays to form a novel chemical bond. In this case, the reaction group may be the same group as the crosslinkable group, or may be a different group. Examples of the crosslinkable group system include groups shown in the following crosslinkable group T.

<Crosslinkable group T>

(In the above formula, R ⁷ to R ⁹ represent a hydrogen atom or an alkyl group. R ¹⁰ to R ¹² represent a hydrogen atom, an alkyl group or an alkoxy group. Ar ⁴ represents an aromatic hydrocarbon group that may have a substituent, or An aromatic heterocyclic group that may have a substituent.)

The alkyl group of R ⁷ to R ¹² is usually a straight or branched chain alkyl group with a carbon number of 6 or less, for example: methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl Wait. More preferably, it is methyl or ethyl. If the carbon number of the alkyl group of R ⁷ to R ¹² is 6 or less, the crosslinking reaction will not be suppressed stereoscopically, and the film tends to be insolubilized easily.

The alkoxy group of R ¹⁰ to R ¹² is usually a straight or branched chain alkoxy group with a carbon number of 6 or less, for example: methoxy, ethoxy, n-propoxy, 2-propoxy, n Butoxy and so on. More preferred are methoxy and ethoxy. If the alkoxy carbon number of R ¹⁰ to R ¹² is 6 or less, the cross-linking reaction will not be suppressed stereoscopically, and the insolubilization of the film tends to be easily caused.

In addition, the aromatic hydrocarbon group that may have a substituent of Ar ⁴ includes, for example, a six-membered monocyclic ring such as a benzene ring and a naphthalene ring having one free valence, or a 2 to 5 condensed ring. Particularly preferred is a benzene ring having 1 free valence. In addition, Ar ⁴ may be a group formed by bonding two or more of these aromatic hydrocarbons which may have a substituent. Examples of such groups include biphenylene, triphenylene, etc., and 4,4'-biphenylene is preferred.

Among them, from the viewpoint of high reactivity and easier cross-linking to form insolubilization, cyclic ether groups such as epoxy groups and oxetane groups, vinyl ether groups and the like are preferably cross-linked by cationic polymerization.的基。 The base. Among them, from the viewpoint of easy control of the cationic polymerization rate, the oxocyclobutane group is more preferable, and the vinyl ether group is preferable from the viewpoint that the hydroxyl group which may cause element deterioration is not easily generated during cationic polymerization.

Furthermore, from the viewpoint of further improving the electrochemical stability of the device, it is preferable to use a cyclization addition reaction of an arylvinyl carbonyl group such as a cinnamyl group, a benzocyclobutene ring having a monovalent free atom, etc. .

Furthermore, among the crosslinkable groups, from the viewpoint that the structure after crosslinking is particularly stable, a benzocyclobutene ring having a monovalent free valence is particularly preferred.

The aromatic heterocyclic group that may have a substituent for Ar ⁴ includes, for example, an aromatic heterocyclic ring having a carbon number of usually 3 or more, preferably 4 or more, and usually 36 or less, preferably 24 or less, such as thienyl and pyridyl. base. Especially preferred are thienyl and pyridyl.

[Other repeating units]

The polymer of the present invention can increase the N,N-bis(4-alkylphenyl)benzidine structure in the polymer, and is substituted by an aromatic hydrocarbon group or aromatic heterocyclic group condensed with three or more rings The ratio of N atoms, and the viewpoint of improving hole injection and hole transport, preferably The system further contains the repeating unit represented by the following formula (2), that is, it contains the unit represented by the following formula (2) as a repeating unit.

(In formula (2), Ar ¹ represents an aromatic hydrocarbon group or aromatic heterocyclic group that is independently or may have substituents, and is condensed from 3 or more rings. R ¹ represents each independently or may have substituents The alkyl group. L ¹ represents an aromatic hydrocarbon group or an aromatic heterocyclic group.)

Furthermore, by adjusting the ratio of the unit of formula (1) to the unit of formula (2), the number of crosslinkable groups in the polymer described later can be adjusted.

The aromatic hydrocarbon group and aromatic heterocyclic group of L ¹ in the unit represented by the above formula (2) may be bonded in plural.

環、聯伸三苯環、苊環、1,2-苯并苊環、茀環等六元環單環、或2~5縮合環的2價基。 Examples of aromatic hydrocarbon groups include benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetraphenyl ring, pyrene ring, benzopyrene ring,

A six-membered monocyclic ring such as a ring, a triphenylene ring, an acenaphthylene ring, a 1,2-benzoacenaphthene ring, and a stilbene ring, or a divalent group of 2 to 5 condensed rings.

二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、氟化吡咯環、氟化呋喃環、噻吩并呋喃環、苯并異

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、噠

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

啉環、菲啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等五 或六元環單環、或2~4縮合環之2價基。 Examples of aromatic heterocyclic groups include furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring,

Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, fluorinated pyrrole ring, fluorinated furan ring, thieno Furan ring, benziso

Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring

Ring, da

Ring, pyrimidine ring, three

Ring, quinoline ring, isoquinoline ring,

Quinoline ring

A five- or six-membered monocyclic ring such as a phyllidine ring, a phenanthridine ring, a benzimidazole ring, a piperidine ring, a quinazoline ring, a quinazolinone ring, and a azulene ring, or a divalent group of 2 to 4 condensed rings.

The substituents that the aromatic hydrocarbon group and the aromatic heterocyclic group may have are not particularly limited. For example, a group selected from the above-mentioned substituent group Z is preferably an alkyl group, an alkoxy group, an aromatic hydrocarbon group, and an aromatic group. A heterocyclic group, more preferably an alkyl group.

When L ¹ is a group bonded by a plurality of the above-mentioned aromatic hydrocarbon group and aromatic heterocyclic group, from the viewpoint of excellent charge transportability and excellent durability, it is preferable to connect 2 to 6 such groups. The connected aromatic hydrocarbon group and aromatic heterocyclic group system may be one type or plural types.

In addition, when L ¹ is a group bonded by a plurality of the above-mentioned aromatic hydrocarbon group and aromatic heterocyclic group, it may be bonded via a linking group. In this case, the linking group is preferably a group selected from the group consisting of -CR ¹ R ² -, -O-, -CO-, -NR ³ -, and -S-, and a group consisting of these 2-10 Linked base. In addition, when two or more are connected, the connection base system may be one type or plural types. Among them, R ¹ to R ³ each represent an independent hydrogen atom, or an alkyl group which may have a substituent, an aromatic hydrocarbon group which may have a substituent, and an aromatic heterocyclic group which may have a substituent. The linking base is more preferably -CR ¹ R ² -and 2~6 -CR ¹ R ² -linked groups, and particularly preferred is -CR ¹ R ² -.

From the viewpoint of excellent hole injection and transportability, L ^{1 is} preferably any one of 1,4-phenylene, 4,4'-biphenylene, and 4,4"-p-terphenylene.

It is particularly preferable that L ¹ is 4,4'-biphenylene, that is, it contains the unit represented by the following formula (3) as a repeating unit.

[化7]

(In formula (3), Ar ¹ represents an aromatic hydrocarbon group or an aromatic heterocyclic group condensed from three or more rings, independently of each other, and may have substituents. R ¹ represents each independently or may have substituents的alkyl.)

[Proportion of Repeating Units]

From the viewpoint of improving hole injection and hole transport, the polymer of the present invention is preferably 50 mol% of the units represented by the above formula (1) and the above formula (2) relative to 100 mol% of the total monomer unit. Ear% or more, more preferably 80 mol% or more, particularly preferably 100 mol% (that is, except for the units shown in the above formula (1) and the above formula (2), the rest are not contained).

[Number of crosslinkable groups]

The crosslinkable groups possessed by the polymer of the present invention are sufficiently insolubilized by crosslinking, and other layers can be easily formed by a wet film forming method, the more the better. On the other hand, from the viewpoints that the formed layer is less likely to crack, unreacted crosslinkable groups are less likely to remain, and the organic electroluminescent element is likely to prolong the life, the smaller the number of crosslinkable groups, the better.

In the polymer of the present invention, the crosslinkable group present in one polymer chain is preferably generally 1 or more on average, more preferably 2 or more on average, and generally preferably 200 or less, more preferably 100 or less.

Furthermore, the number of crosslinkable groups in the polymer of the present invention can be expressed in terms of the molecular weight of the polymer per 1,000.

When the number of crosslinkable groups possessed by the polymer of the present invention is expressed in terms of the molecular weight of the polymer per 1000, the molecular weight per 1000 is usually 3.0 or less, preferably 2.0 or less, more preferably 1.0 or less, and usually 0.01 More than one, preferably more than 0.05.

If the crosslinkability base number is within the above range, cracks are less likely to occur, and a flat film can be easily obtained. In addition, because the crosslinking density is moderate, there are few unreacted crosslinkable groups remaining in the layer after the crosslinking reaction, which is unlikely to affect the life of the device obtained.

Furthermore, since the insolubility in organic solvents is sufficient after the crosslinking reaction, the wet film forming method can be easily used to form a multilayer structure.

Here, the number of crosslinkable groups per 1000 molecular weight of the polymer can be calculated by subtracting the terminal groups from the polymer, and then from the molar ratio of the monomers loaded during synthesis and the structural formula.

For example, if the description is based on the case of the polymer 1 synthesized in Example 1 described later, the molecular weight of the repeating unit after deducting the terminal group of the polymer 1 is an average of 1688.46, and the crosslinking group is 0.676 per repeating unit. If the simple ratio is used for calculation, the number of crosslinkability bases per 1,000 molecular weight can be calculated as 0.40.

[Molecular weight of polymer]

The weight average molecular weight of the polymer of the present invention is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 500,000 or less, particularly preferably 200,000 or less, and usually 2,500 or more, preferably 5,000 or more, more preferably 20,000 or more. The best department is over 30,000.

If the weight average molecular weight of the polymer exceeds the above upper limit, the solubility to the solvent is reduced, which may impair film-forming properties. In addition, if the weight average molecular weight of the polymer is lower than the above lower limit, the glass transition temperature, melting point, and vaporization temperature of the polymer may decrease, which may reduce the heat resistance.

Furthermore, the number average molecular weight (Mn) of the polymer of the present invention is generally below 2,500,000, preferably below 750,000, more preferably below 400,000, and generally above 2,000, preferably above 4,000, more preferably above 8,000, The best department is over 20,000.

Furthermore, the dispersion degree (Mw/Mn) of the polymer of the present invention is preferably 3.5 or less, more preferably 2.5 or less, particularly preferably 2.0 or less. In addition, since the value of the dispersion degree is as small as possible, the lower limit value is ideally 1. If the degree of dispersion of the polymer is less than the above upper limit, purification is easy, and the solubility to the solvent and the charge transport ability are good.

Generally, the weight average molecular weight of the polymer is determined by SEC (size exclusion chromatography) measurement. In the SEC measurement, the higher the molecular weight component, the shorter the dissolution time, and the lower the molecular weight component, the longer the dissolution time. Using the calibration curve calculated from the dissolution time of polystyrene (standard sample) of known molecular weight, the sample Converting the dissolution time to molecular weight, the weight average molecular weight can be calculated.

[Specific example]

Specific examples of the polymer of the present invention are shown below, but the polymer of the present invention is not only Limited to these. In addition, the number in the chemical formula represents the molar ratio of the repeating unit.

These polymerization systems can be any one of random copolymers, interactive copolymers, block copolymers, or graft copolymers, and the sequence of monomers is not limited.

[Manufacturing method of polymer]

The method for producing the polymer of the present invention is not particularly limited, and it can be arbitrarily mentioned before the polymer of the present invention can be obtained. For example, it can be manufactured according to the polymerization method by Suzuki reaction, the polymerization method by Grignard reaction, the polymerization method by Yamamoto reaction, the polymerization method by Ullmann reaction, the polymerization method by Buchwald-Hartwig reaction, etc.

In the polymerization method using the Ullmann reaction and the polymerization method using the Buchwald-Hartwig reaction, for example, by making the dihalogenated aryl group represented by the formula (1a), formula (1b), and formula (2b) (X series represents I , Br, Cl, F and other halogen atoms), react with the primary amine aryl group represented by formula (1c) to synthesize the polymer of the present invention.

(In the above formula, X represents a halogen atom; Ar ¹ , R ¹ , T ¹ , and L ^{1 have} the same meaning as above.)

Furthermore, in the above-mentioned polymerization method, the reaction system for forming N-aryl bonds is usually carried out in the presence of a base such as potassium carbonate, sodium tert-butoxide, and triethylamine. In addition, it can also be implemented in the presence of a transition metal catalyst such as copper and palladium complexes.

<Organic Electroluminescence Element Material>

The polymer of the present invention is particularly suitable as an organic electroluminescence element material. That is, the hair The polymer is preferably an organic electroluminescent device material.

When the polymer of the present invention is used as an organic electroluminescent element material, it is best to use a material that forms at least one of the hole injection layer and the hole transport layer of the organic electroluminescent element, that is, it is preferably used as a charge transport Sexual material.

When used as a charge-transporting material, the polymerization system of the present invention may contain only one type, or two or more types in any combination and any ratio.

When the polymer of the present invention is used to form at least one of the hole injection layer and the hole transport layer of the organic electroluminescent device, the content of the polymer of the present invention in the hole injection layer and/or the hole transport layer is usually It is 1-100% by mass, preferably 5-100% by mass, more preferably 10-100% by mass. If it is within the above range, the charge transportability of the hole injection layer and/or the hole transport layer will be improved, the driving voltage will be reduced, and the driving stability will be improved, which is preferable.

When the polymer of the present invention is not 100% by mass in the hole injection layer and/or hole transport layer, the components constituting the hole injection layer and/or hole transport layer include, for example, the hole transport properties described below. Compound etc.

Furthermore, since the organic electroluminescence element can be easily manufactured, the polymer of the present invention is preferably used for an organic layer formed by a wet film formation method.

<Composition for Organic Electroluminescence Device>

The composition system for an organic electroluminescence element of the present invention contains the polymer of the present invention. In addition, the composition system for an organic electroluminescence element of the present invention may contain one type of the polymer of the present invention, or may contain two or more types in any combination and any ratio.

[Content of polymer]

The content of the polymer of the present invention in the composition for an organic electroluminescence element of the present invention is usually 0.01 to 70% by mass, preferably 0.1 to 60% by mass, and more preferably 0.5 to 50% by mass.

If it is in the above range, the formed organic layer is less likely to have defects and less likely to have uneven film thickness, which is preferable.

In addition to the polymer of the present invention, the composition system for an organic electroluminescence element of the present invention may contain a solvent or the like.

[Solvent]

The composition for an organic electroluminescence element of the present invention usually contains a solvent. The solvent is preferably capable of dissolving the polymer of the present invention. Specifically, it is preferable to dissolve the polymer of the present invention in a solvent of generally 0.05% by mass or more, preferably 0.5% by mass or more, and more preferably 1% by mass or more at room temperature.

Specific examples of the solvent include, for example, aromatic solvents such as toluene, xylene, mesitylene, and cyclohexylbenzene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene, and o-dichlorobenzene; Aliphatic ethers such as dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole , Phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and other aromatic ethers, etc. Ether solvents; aliphatic ester solvents such as ethyl acetate, n-butyl acetate, ethyl lactate, n-butyl lactate; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, isobenzoate Organic solvents such as ester solvents such as propyl ester, propyl benzoate, n-butyl benzoate, and other aromatic esters; and other compositions for forming hole injection layers and composition for forming hole transport layers described later Of organic solvents.

In addition, one type of solvent may be used, or two or more types may be used in any combination and any ratio.

Among them, the solvent contained in the composition for an organic electroluminescence device of the present invention is preferably a solvent having a surface tension of less than 40 dyn/cm at 20° C., preferably 36 dyn/cm or less, more preferably 33 dyn/cm or less.

When using the composition for an organic electroluminescence element of the present invention to form a coating film by a wet film forming method, and crosslink the polymer of the present invention to form an organic layer, it is preferable that the solvent has a high affinity with the substrate. The reason is that the uniformity of the film quality has a greater impact on the uniformity and stability of the light emission of the organic electroluminescence device. Therefore, for the organic electroluminescent device composition used in the wet film forming method, in order to form a uniform coating film with higher leveling properties, it is required to reduce the surface tension. Here, by using a solvent having a low surface tension as described above, a uniform layer containing the polymer of the present invention can be formed, and a uniform crosslinked layer can be formed, which is preferable.

Specific examples of low surface tension solvents include, for example, aromatic solvents such as toluene, xylene, mesitylene, and cyclohexylbenzene; ester solvents such as ethyl benzoate; ether solvents such as anisole; trifluoromethane Oxyanisole, pentafluoromethoxybenzene, 3-(trifluoromethyl)anisole, ethyl pentafluorobenzoate, etc.

Furthermore, on the other hand, the solvent contained in the composition for an organic electroluminescence element of the present invention has a vapor pressure of generally 10 mmHg or less at 25°C, preferably 5 mmHg or less, and usually 0.1 mmHg or more. By using such a solvent, the organic electroluminescence device is suitable for the manufacturing process by the wet film forming method, and the composition for the organic electroluminescence device suitable for the polymer properties of the present invention can be prepared.

Specific examples of such solvents include, for example, aromatic solvents such as the aforementioned toluene, xylene, and mesitylene, ether solvents, and ester solvents.

However, moisture may cause deterioration of the performance of the organic electroluminescence element, and may promote a decrease in luminance especially during continuous driving. Therefore, in order to reduce the residual moisture in the wet film formation as much as possible, among the above-mentioned solvents, the solubility of water at 25° C. is preferably 1% by mass or less, more preferably 0.1% by mass or less.

The content of the solvent contained in the composition for an organic electroluminescence element of the present invention is usually 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, particularly preferably 80% by mass or more. When the content of the solvent is at least the above lower limit, the flatness and uniformity of the formed layer can be both good.

[Electron acceptor compound]

When the composition system for an organic electroluminescence element of the present invention is used to form a hole injection layer, it is preferable to further contain an electron acceptor compound from the viewpoint of reducing resistance.

The electron-accepting compound is preferably a compound having oxidizing power and the ability to accept an electron from the polymer of the present invention. Specifically, a compound having an electron affinity of 4 eV or more is preferable, and a compound having an electron affinity of 5 eV or more is more preferable.

Such electron-accepting compounds include, for example, triaryl boron compounds, metal halides, Lewis acid, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acid. Select one or more compounds from the group.

Specific examples include onium salts substituted with organic groups such as 4-isopropyl-4'-methyldiphenyliodonium tetrakis(pentafluorophenyl) borate, triphenyltetrafluoroborate, etc. (International Publication No. 2005/089024); iron(III) chloride (Japanese Patent Laid-Open No. 11-251067), high valence inorganic compounds such as ammonium peroxodisulfate; cyano compounds such as tetracyanoethylene; tris(pentafluoro Aromatic boron compounds such as phenyl)borane (Japanese Patent Laid-Open No. 2003-31365); fullerene derivatives, iodine, etc.

This kind of compound preferably has a long-period periodic table (hereinafter referred to as the "periodic table" without special statement, refers to the long-period periodic table) on the elements belonging to groups 15-17, using carbon atoms to bond Ionic compounds with at least one organic group structure are particularly preferably compounds represented by the following formula (4):

(In formula (4), R ⁹ represents an organic group bonded to A ₁ by a carbon atom; R ¹⁰ represents an optional substituent. R ⁹ and R ¹⁰ may also be bonded to each other to form a ring.)

If R ⁹ is an organic group having a carbon atom at the bonding portion with A ₁ , it is mentioned without violating the gist of the present invention, and there is no particular limitation on the type. The molecular weight of R ⁹ is usually in the range of 1000 or less, preferably 500 or less, including the substituent.

Preferred examples of R ⁹ are from the viewpoint of making the positive charge non-localized, and examples include alkyl groups, alkenyl groups, alkynyl groups, aromatic hydrocarbon groups, and aromatic heterocyclic groups. In particular, from the viewpoint of making the positive charge non-localized and thermally stable, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferred.

The alkyl group may be, for example, a linear, branched or cyclic alkyl group, and the carbon number is usually 1 or more, and usually 12 or less, preferably 6 or less. Specific examples include methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, tertiary butyl, cyclohexyl and the like.

As the alkenyl group, for example, the carbon number is usually 2 or more, and usually 12 or less, preferably 6 or less. Specific examples include vinyl, allyl, 1-butenyl and the like.

As the alkynyl system, for example, the carbon number is usually 2 or more, and usually 12 or less, and more Best below 6. Specific examples include, for example, ethynyl and propargyl.

環、聯伸三苯環、苊環、茀環等。 As the aromatic hydrocarbon group, for example, a five-membered ring or a six-membered monocyclic ring having one free valence, or a 2 to 5 condensed ring, and a group in which the positive charge is non-localized by this group. Specific examples include, for example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, fused tetrabenzene ring, pyrene ring, benzopyrene ring,

Ring, extended triphenyl ring, acenaphthene ring, stilbene ring, etc.

二唑環、吲哚環、咔唑環、吡咯并咪唑環、吡咯并吡唑環、吡咯并吡咯環、噻吩并吡咯環、噻吩并噻吩環、氟化吡咯環、氟化呋喃環、噻吩并呋喃環、苯并異

唑環、苯并異噻唑環、苯并咪唑環、吡啶環、吡

環、噠

環、嘧啶環、三

環、喹啉環、異喹啉環、

啉環、喹

啉環、菲啶環、苯并咪唑環、呸啶環、喹唑啉環、喹唑啉酮環、薁環等。 As the aromatic heterocyclic group, for example, a five-membered ring or a six-membered ring monocyclic ring or a 2 to 4 condensed ring having one free valence may be used, and the positive charge is non-localized by this group. Specific examples include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, triazole ring, imidazole ring,

Diazole ring, indole ring, carbazole ring, pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, fluorinated pyrrole ring, fluorinated furan ring, thieno Furan ring, benziso

Azole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyridine ring

Ring, da

Ring, pyrimidine ring, three

Ring, quinoline ring, isoquinoline ring,

Quinoline ring

Phytoline ring, phenanthridine ring, benzimidazole ring, pyridine ring, quinazoline ring, quinazolinone ring, azulene ring, etc.

R ¹⁰ is on the premise that it does not violate the gist of the present invention, and the rest is not particularly limited. The molecular weight of R ¹⁰ is usually in the range of 1,000 or less, preferably 500 or less, including the substituent.

Examples of R ¹⁰ include alkyl, alkenyl, alkynyl, aromatic hydrocarbon, aromatic heterocyclic, amino, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, Alkylcarbonyloxy, alkylthio, arylthio, sulfonyl, alkanesulfonyl, arylsulfonyl, sulfonyloxy, cyano, hydroxyl, thiol, silyl and the like.

Among them, as with R ⁹ , from the viewpoint of greater electron acceptability, an organic group having a carbon atom at the bonding portion with A ₁ is preferable, and preferable examples include alkyl, alkenyl, Alkynyl, aromatic hydrocarbon group, aromatic heterocyclic group. In particular, from the viewpoint of high electron acceptor properties and thermal stability, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferred.

R an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, an aromatic heterocyclic group is ^10, previously associated with the line may for example be described by R ⁹ are the same.

Examples of the amino group include an alkylamino group, an arylamino group, and an amide group.

As the alkylamino group, for example, an alkylamino group having one or more carbon number is usually 1 or more, and usually 12 or less, preferably 6 or less alkyl. Specific examples include, for example, methylamino, dimethylamino, diethylamino, and dibenzylamino.

As the arylamino group, for example, an aromatic hydrocarbon group or an aromatic heterocyclic group having at least one carbon number is usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 15 or less aromatic hydrocarbon group or aromatic heterocyclic group. Specific examples include, for example, anilino group, diphenylamino group, toluino group, pyridylamino group, and thienylamino group.

As the amido group, for example, an amido group having at least one carbon number is usually 2 or more, and usually 25 or less, preferably 15 or less. Specific examples include, for example, acetamido and benzamido.

As the alkoxy group, for example, an alkoxy group having a carbon number of usually 1 or more, and usually 12 or less, preferably 6 or less. Specific examples include methoxy, ethoxy, butoxy and the like.

As the aryloxy group, for example, an aryloxy group having an aromatic hydrocarbon group or an aromatic heterocyclic group whose carbon number is usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 15 or less. Specific examples include, for example, phenoxy, naphthyloxy, pyridyloxy, and thienyloxy.

As the acyl system, for example: the carbon number is usually 1 or more, and usually A base of 25 or less, preferably 15 or less. Specific examples include, for example, formyl, acetyl, and benzyl.

As the alkoxycarbonyl group, for example, an alkoxycarbonyl group having a carbon number of usually 2 or more, and usually 10 or less, preferably 7 or less. Specific examples include methoxycarbonyl and ethoxycarbonyl.

The aryloxycarbonyl group may have, for example, an aromatic hydrocarbon group or an aromatic heterocyclic group whose carbon number is usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 15 or less. Specific examples include, for example, phenoxycarbonyl and pyridyloxycarbonyl.

As the alkylcarbonyloxy system, for example, an alkylcarbonyloxy group having a carbon number of usually 2 or more, and usually 10 or less, preferably 7 or less. Specific examples include, for example, acetoxy and trifluoroacetoxy.

As the alkylthio group, for example, an alkylthio group having a carbon number of usually 1 or more, and usually 12 or less, preferably 6 or less. Specific examples include methylthio, ethylthio and the like.

As the arylthio group, for example, an arylthio group having a carbon number of usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 14 or less. Specific examples include phenylthio, naphthylthio, pyridinethio and the like.

As specific examples of alkanesulfonyl and arylenesulfonyl groups, for example, methanesulfonyl, p-toluenesulfonyl and the like can be given.

As a specific example of a sulfonyloxy group, a methylsulfonyloxy group, a p-toluenesulfonyloxy group, etc. are mentioned, for example.

As a specific example of a silyl group, a trimethylsilyl group, a triphenylsilyl group, etc. are mentioned, for example.

Above, the exemplified groups of R ⁹ and R ¹⁰ of formula (4) can be further substituted with other substituents, provided that they do not violate the gist of the present invention. The types of substituents are not particularly limited. For example, in addition to the groups exemplified for R ⁹ and R ¹⁰ above, there may be halogen atoms, cyano groups, thiocyano groups, nitro groups, and the like. In particular, from the viewpoint of not hindering the heat resistance and electron acceptor properties of ionic compounds (electron acceptor compounds), alkyl groups, alkenyl groups, alkynyl groups, alkoxy groups, aryloxy groups, aromatic hydrocarbon groups, and aromatic groups are preferred. Group heterocyclic group.

In formula (4), A _{1 is} preferably an element belonging to group 17 of the periodic table. From the standpoint of electron acceptability and ease of acquisition, it is preferably before the fifth period (third to fifth periods) of the periodic table element. That is, A _{1 is} preferably any one of an iodine atom, a bromine atom, and a chlorine atom.

In particular, from the standpoint of electron acceptor properties and compound stability, an ionic compound in which A ₁ of the formula (4) is a bromine atom or an iodine atom is preferable, and an ionic compound in which an iodine atom is more preferable.

In the formula (4), Z ₁ ^n1- represents a conjugated anion. The type of conjugate anion is not particularly limited, and it may be a monoatomic ion or a complex ion. However, because the larger the size of the conjugated anion, the more non-localized the negative charge, and the more non-localized the positive charge, the greater the electron acceptor energy, so the complex ion is better than the monoatomic ion.

n ₁ is an arbitrary positive integer corresponding to the valence of the conjugated anion Z ₁ ^n1- . The value of n ₁ is not particularly limited, and is preferably 1 or 2, more preferably 1.

Specific examples of Z ₁ ^n1- include, for example, hydroxide ion, fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, nitrate ion, nitrite ion, and sulfate ion. , Sulfite ion, perchlorate ion, perbromide ion, periodate ion, chlorate ion, chlorite ion, hypochlorite ion, phosphate ion, phosphite ion, hypochlorite ion, Borate ion, isocyanate ion, hydrogen sulfide ion, tetrafluoroborate ion, hexafluorophosphate ion, hexachloroantimonate ion; carboxylate ion such as acetate ion, trifluoroacetate ion and benzoate ion; Sulfonate ions such as methanesulfonate ion and trifluoromethanesulfonate ion; Alkoxide ion such as methoxy ion and tertiary butoxy ion, etc. Among them, tetrafluoroborate ion and hexafluoroborate ion are preferred.

Furthermore, as a conjugated anion, Z ₁ ^n1- system, from the viewpoint of compound stability, solubility in solvents, and larger size, because the negative charge is not localized, and the positive charge is not localized. The acceptor can become larger, so the complex ion shown in the following formula (5) is particularly preferred:

(In formula (5), E ₃ represents the elements belonging to group 13 of the long-period periodic table; Ar ⁵ to Ar ⁸ represent independent aromatic hydrocarbon groups or aromatic heterocyclic groups.)

E _{3 is} preferably a boron atom, aluminum atom, or gallium atom. From the viewpoint of compound stability and ease of synthesis and purification, it is preferably a boron atom.

環、噠

環、嘧啶環、三

環、喹啉環、異喹啉環。 The aromatic hydrocarbon groups and aromatic heterocyclic groups of Ar ⁵ to Ar ⁸ can be, for example, a five-membered or six-membered monocyclic ring with one free valence as exemplified in R ^{9 of} the previous related formula (4), Or 2~4 condensed rings. In particular, from the standpoint of compound stability and heat resistance, benzene ring, naphthalene ring, pyridine ring, pyridine ring having a valence of 1 free atom are preferred.

Ring, da

Ring, pyrimidine ring, three

Ring, quinoline ring, isoquinoline ring.

The aromatic hydrocarbon groups and aromatic heterocyclic groups exemplified as Ar ⁵ to Ar ⁸ may be further substituted with other substituents, provided that they do not violate the gist of the present invention. The type of substituent is not particularly limited, and any substituent can be used, but it is preferably an electrophilic group.

Regarding the substituents that Ar ⁵ to Ar ⁸ may have, if preferred electrophilic groups are exemplified, examples include halogen atoms such as fluorine atom, chlorine atom, and bromine atom; cyano group; thiocyano group; nitro group. Alkylsulfonyl groups such as toluenesulfonyl group; Arylsulfonyl groups such as p-toluenesulfonyl group; Carbon number such as methylsulfonyl group, acetyl group, and benzyl group is usually 1 or more, and usually 12 or less, more Preferably 6 or less acyl; methoxycarbonyl, ethoxycarbonyl, etc. carbon number is usually 2 or more, and usually 10 or less, preferably 7 or less alkoxycarbonyl group; phenoxycarbonyl, pyridyloxycarbonyl, etc. have carbon number usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 15 or less aromatic hydrocarbon group or aromatic heterocyclic aryloxycarbonyl group; aminocarbonyl group; sulfamoyl group; trifluoromethyl, pentafluoroethyl A linear, branched, or cyclic alkyl group having a carbon number of usually 1 or more, usually 10 or less, preferably 6 or less, and a haloalkyl group substituted with a halogen atom such as a fluorine atom or a chlorine atom.

Among them, it is more preferable that at least one of Ar ⁵ to Ar ⁸ has a fluorine atom or a chlorine atom as a substituent and has one or more. Particularly, from the viewpoint of making the negative charge efficient non-localization and the viewpoint of having moderate sublimability, particularly preferred is the perfluoroaryl group in which all hydrogen atoms of Ar ⁵ to Ar ⁸ are replaced by fluorine atoms. Specific examples of perfluoroaryl groups include, for example, pentafluorophenyl, heptafluoro-2-naphthyl, and tetrafluoro-4-pyridyl.

The molecular weight of the electron acceptor compound of the present invention is usually 100-5000, preferably 300-3000, more preferably 400-2000.

If it is within the above-mentioned range, it is preferable from the viewpoint that the positive and negative charges are sufficiently nonlocalized, the electron acceptor is good, and the charge transport is not easily hindered.

Hereinafter, the preferred specific examples of the electron-accepting compound described in the following formula (4) of the present invention are shown in Table 1 below, but the present invention is not limited to these.

[化13]

The composition system for an organic electroluminescence device of the present invention may contain one type alone, or two or more types in any combination and ratio, just like the above-mentioned electron-accepting compound.

When the composition for an organic electroluminescence device of the present invention contains an electron acceptor compound, the electron acceptor compound of the composition for an organic electroluminescence device of the present invention contains The amount is usually 0.0005 mass% or more, preferably 0.001 mass% or more, and usually 20 mass% or less, preferably 10 mass% or less. In addition, the ratio of the electron acceptor compound to the polymer of the present invention in the composition for an organic electroluminescence element is usually 0.5% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, and usually 80% by mass or less, preferably 60% by mass or less, more preferably 40% by mass or less.

If the content of the electron acceptor compound in the composition for organic electroluminescence devices exceeds the above lower limit, the electron acceptor will receive electrons from the polymer to make the formed organic layer low in resistance, which is preferable; Below the above upper limit, the formed organic layer is less likely to generate defects, and the film thickness is less likely to be uneven, which is preferable.

[Cation radical compound]

The composition for an organic electroluminescence element of the present invention may further contain a cationic radical compound.

The cationic radical compound is preferably an ionic compound formed by a cationic radical of a chemical species that removes one electron from the hole transporting compound and a conjugated anion. However, when the cationic radical is derived from a hole transporting polymer compound, the cationic radical becomes a structure in which one electron is removed from the repeating unit of the polymer compound.

Furthermore, the cationic radical is preferably a chemical species that removes one electron from the hole transporting compound described later. From the viewpoints of amorphousness, visible light transmittance, heat resistance, and solubility, the hole transporting compound is preferably a chemical species that removes an electron from a preferred compound.

Among them, the cationic radical compound can be produced by mixing the hole transporting compound described below and the electron accepting compound described above. That is, by Mixing the hole-transporting compound and the electron-accepting compound initiates the movement of electrons from the hole-transporting compound to the electron-accepting compound, and the formation of cation radicals and conjugated anions of the hole-transporting compound is generated的cationic ionic compound.

When the composition for an organic electroluminescence element of the present invention contains a cationic radical compound, the content of the cationic radical compound in the composition for an organic electroluminescence element of the present invention is usually 0.0005% by mass or more, preferably 0.001% by mass % Or more, and usually 40% by mass or less, preferably 20% by mass or less. If the content of the cationic radical compound exceeds the lower limit, the formed organic layer has a low resistance, which is preferable; if the content is less than the upper limit, the formed organic layer is less prone to defects and less uneven in film thickness. So it is better.

In addition, in addition to the above-mentioned components, the composition for organic electroluminescence devices of the present invention may also be contained in the composition for forming a hole injection layer or a composition for forming a hole transport layer described later in accordance with the content described later. Ingredients.

<Organic Electroluminescence Element>

The organic electroluminescence element of the present invention is an organic electroluminescence element having an anode and a cathode provided on a substrate, and an organic layer is provided between the anode and the cathode; it is characterized in that: the organic layer contains The composition for the organic electroluminescent element of the present invention of the polymer of the present invention uses a layer formed by a wet film forming method.

In the organic electroluminescent device of the present invention, the layer formed by the wet film formation method is preferably at least one of a hole injection layer and a hole transport layer, and it is particularly preferable that the organic layer is provided with holes The injection layer, the hole transport layer and the light emitting layer, and the hole injection layer, the hole transport layer and the light emitting layer are all formed by the wet film forming method Floor.

In the present invention, the "wet film forming method" refers to the film forming method (ie, coating method) using, for example, spin coating, dip coating, die coating, bar coating, knife coating, and roll coating. Coating method, spraying method, capillary coating method, inkjet method, nozzle printing method, screen printing method, gravure printing method, quick-drying printing method and other methods of forming a film by wet method, and then drying the coating film The method of film formation is implemented. Among these film forming methods, spin coating, spray coating, inkjet, nozzle printing, etc. are preferred.

An example of the structure of the organic electroluminescence device of the present invention is a schematic diagram (cross section) of the structure example of the organic electroluminescence device 10 shown in FIG. 1. In Fig. 1, series 1 represents the substrate, series 2 the anode, series 3 the hole injection layer, series 4 the hole transport layer, series 5 the light-emitting layer, series 6 the hole barrier layer, and series 7 the electron transport layer , Series 8 represents the electron injection layer, and Series 9 represents the cathode.

Hereinafter, an example of an embodiment of the organic electroluminescence element of the present invention, such as the layer structure and general forming method thereof, will be described with reference to FIG. 1.

[Substrate]

The substrate 1 serves as a support for the organic electroluminescence device, and usually uses a plate-like quartz, glass, or metal plate, metal foil, plastic film/sheet, etc., for example. Among these, a glass plate, or a plate made of transparent synthetic resin such as polyester, polymethacrylate, polycarbonate, and polycure is preferable. The substrate is never prone to deterioration of the organic electroluminescence element due to external air, and it is best to use a material with high gas barrier properties. Therefore, especially when using a low gas barrier material such as a synthetic resin substrate, it is best to provide a dense silicon oxide film on at least one surface of the substrate to improve gas barrier properties.

[anode]

The anode 2 is responsible for the function of injecting holes into the layer on the side of the light-emitting layer 5.

The anode 2 usually uses metals such as aluminum, gold, silver, nickel, palladium, platinum, etc.; metal oxides such as indium and/or tin oxides; halogenated metals such as copper iodide; carbon black and poly(3-methyl) Thiophene), polypyrrole, polyaniline and other conductive polymers.

The formation of the anode 2 is usually carried out by a dry method such as a sputtering method or a vacuum vapor deposition method. In addition, when metal particles such as silver, copper iodide particles, carbon black, conductive metal oxide particles, conductive polymer fine powder, etc. are used to form the anode, it can also be dispersed in a suitable binder resin solution. , It is formed by coating on the substrate. In addition, in the case of conductive polymers, electrolytic polymerization can be used to directly form a thin film on the substrate, or a conductive polymer can be coated on the substrate to form an anode (Appl. Phys. Lett., Vol. 60, Page 2711, 1992).

The anode 2 usually has a single-layer structure, but a multilayer structure may be appropriately formed. When the anode 2 has a laminated structure, different conductive materials may be laminated on the first anode.

The thickness of the anode 2 may be determined according to the required transparency and material. Especially when high transparency is required, a thickness with a visible light transmittance of 60% or more is preferable, and a thickness of 80% or more is more preferable. The thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and usually 1000 nm or less, preferably 500 nm or less. On the other hand, when transparency is not required, the thickness of the anode 2 may be arbitrarily set according to the required strength, etc. In this case, the anode 2 may be the same thickness as the substrate.

When other layers are formed on the surface of the anode 2, the anode 2 can be removed by applying ultraviolet/ozone, oxygen plasma, argon plasma and other treatments before film formation. It is better to adjust its free potential to improve hole injection.

[Hole injection layer]

The layer responsible for the function of transporting holes from the anode 2 side to the light emitting layer 5 side is usually called the "hole injection transport layer" or the "hole transport layer". However, when the layer system responsible for the function of transporting holes from the anode 2 side to the light emitting layer 5 side reaches two or more layers, the layer closest to the anode side is referred to as the "hole injection layer 3". From the viewpoint of enhancing the function of transporting holes from the anode 2 to the light-emitting layer 5 side, it is preferable to form the hole injection layer 3. When the hole injection layer 3 is formed, the hole injection layer 3 is usually formed on the anode 2.

The thickness of the hole injection layer 3 is usually 1 nm or more, preferably 5 nm or more, and usually 1000 nm or less, preferably 500 nm or less.

The method of forming the hole injection layer may be a vacuum evaporation method or a wet film forming method. From the viewpoint of excellent film-forming properties, it is preferable to use a wet film-forming method.

The hole injection layer 3 preferably contains a hole transport compound, more preferably contains a hole transport compound and an electron acceptor compound. It is particularly preferred that the hole injection layer contains a cationic radical compound, and the most preferred system contains a cationic radical compound and a hole transporting compound.

The method for forming a general hole injection layer will be described below. However, in the organic electroluminescence device of the present invention, the hole injection layer is preferably formed by using the composition for the organic electroluminescence device of the present invention and formed by a wet film formation method. .

[Hole transporting compound]

The composition for forming a hole injection layer usually contains a hole transporting compound that becomes the hole injection layer 3. Moreover, in the case of the wet film forming method, a solvent is usually further contained. The composition for forming the hole injection layer is preferably one that has high hole transport properties and can efficiently transport the injected holes. Therefore, it is preferable that the hole mobility is relatively large, and impurities that may become traps are not easily generated during manufacturing or use. Moreover, it is preferable to have excellent stability, low free potential, and high transparency to visible light. In particular, it is preferable that when the hole injection layer is in contact with the light-emitting layer, it does not reduce the light emission from the light-emitting layer, and does not form excimer complexes with the light-emitting layer to reduce the light emission efficiency.

From the viewpoint of the charge injection barrier from the anode to the hole injection layer, the hole transporting compound is preferably a compound having a free potential of 4.5 eV to 6.0 eV. Examples of hole-transporting compounds include, for example, aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylbenzene compounds, and tertiary amines connected with stilbene groups. Compounds, hydrazone compounds, silazane compounds, quinacridone compounds, etc.

Among the exemplified compounds described above, from the viewpoint of amorphousness and visible light transmittance, aromatic amine compounds are preferred, and aromatic tertiary amine compounds are more preferred. Here, the "aromatic tertiary amine compound" refers to a compound having an aromatic tertiary amine structure, and also encompasses a compound having a group derived from an aromatic tertiary amine.

The type of aromatic tertiary amine compound is not particularly limited. From the standpoint of making it easier to use the surface smoothing effect to obtain uniform light emission, it is preferable to use a polymer compound with a weight average molecular weight of 1,000 or more and 1,000,000 or less (from the repeating unit phase Linked polymeric compound). Preferred examples of the aromatic tertiary amine polymer compound are in addition to the polymer of the present invention, for example: a polymer compound having a repeating unit represented by the following formula (6), that is, containing a unit represented by the following formula (6) A polymer compound that is a repeating unit, etc.

[化14]

(In formula (6), Ar ¹¹ and Ar ¹² represent an aromatic hydrocarbon group that may be independently substituted, or an aromatic heterocyclic group that may optionally have a substituent. Ar ¹³ to Ar ¹⁵ represent each independently, An aromatic hydrocarbon group that may have a substituent, or an aromatic heterocyclic group that may also have a substituent. Y represents a linking group selected from the linking group group shown below. In addition, in Ar ¹¹ to Ar ¹⁵ , also Two groups bonded on the same N atom can be bonded to each other to form a ring.)

<Link Group>

(In the above formula, Ar ¹⁶ to Ar ²⁶ represent an aromatic hydrocarbon group that may be independently substituted, or an aromatic heterocyclic group that may optionally have a substituent. R ¹¹ and R ¹² are independently hydrogen atoms Or any substituent.)

The aromatic hydrocarbon groups and aromatic heterocyclic groups of Ar ¹⁶ to Ar ²⁶ are preferably benzene with 1 or 2 free valences from the viewpoint of the solubility, heat resistance, and hole injection and transport properties of polymer compounds Ring, naphthalene ring, phenanthrene ring, thiophene ring, pyridine ring, more preferably benzene ring or naphthalene ring having 1 or 2 free valences.

Aromatic tertiary amine containing the unit represented by formula (6) as a repeating unit Specific examples of molecular compounds include those described in International Publication No. 2005/089024.

In the hole injection layer 3, in order to use the oxidation of the hole transporting compound to increase the conductivity of the hole injection layer, it is preferable to contain the electron acceptor compound or the cationic radical compound.

PEDOT/PSS (Adv. Mater., 2000, vol. 12, p. 481), or aniline green hydrochloride (J. Phys. Chem., 1990, vol. 94, p. 7716), etc. The cation radical compound of the molecular compound can also be generated by oxidative polymerization (dehydrogenation polymerization).

The term "oxidative polymerization" herein refers to chemically or electrochemically oxidizing monomers in an acid solution using peroxodisulfate or the like. In the case of this oxidative polymerization (dehydrogenation polymerization), the monomer is oxidized to form a polymer, and an anion derived from an acidic solution is used as a conjugated anion to generate a cation that removes one electron from the repeating unit of the polymer. base.

[Formation of hole injection layer by wet film forming method]

When the hole injection layer 3 is formed by a wet film formation method, it is usually mixed with a solvent (solvent for hole injection layer) that can dissolve the material to be the hole injection layer to prepare a film-forming composition (electric A composition for forming a hole injection layer), and then the composition for forming a hole injection layer is coated on a layer (usually an anode) belonging to the lower layer of the hole injection layer to form a film, which can be formed by drying.

The concentration of the hole-transporting compound in the composition for forming the hole injection layer may be arbitrary without impairing the effect of the present invention. From the viewpoint of film thickness uniformity, the lower the better; on the other hand, , From the hole injection layer is not prone to defects Viewpoint, the higher the better. Specifically, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, and particularly preferably 0.5% by mass or more; on the other hand, it is preferably 70% by mass or less, more preferably 60% by mass or less, Particularly good line is below 50% by mass.

Examples of the solvent system include ether solvents, ester solvents, aromatic hydrocarbon solvents, and amide solvents.

Examples of ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and propylene glycol-1-monomethyl ether acetate (PGMEA); and 1,2-dimethoxybenzene, 1,3-Dimethoxybenzene, anisole, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4 -Aromatic ethers such as dimethyl anisole, etc.

Examples of ester-based solvent systems include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.

Examples of aromatic hydrocarbon solvents include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene , Cyclohexylbenzene, methyl naphthalene, etc.

Examples of the amide-based solvent system include N,N-dimethylformamide, N,N-dimethylacetamide, and the like.

In addition to these, dimethyl sulfoxide and the like can also be used.

The hole injection layer 3 is formed by a wet film forming method, usually after preparing the composition for forming the hole injection layer, and then coating it on the layer belonging to the lower layer of the hole injection layer 3 (usually the anode 2) The film is formed on the top and dried and implemented.

The hole injection layer 3 is usually formed into a film, and then the coating film is dried by heating, drying under reduced pressure, or the like.

[Formation of hole injection layer by vacuum evaporation method]

When the hole injection layer 3 is formed by a vacuum evaporation method, usually one or more of the constituent materials (the aforementioned hole transporting compound, electron accepting compound, etc.) of the hole injection layer 3 are installed. Put it in a crucible set in a vacuum container (when using two or more materials, usually put them in separate crucibles), after the vacuum pump exhausts the vacuum container to about 10 ^-4 Pa, heat the crucible (use more than two materials) When the material is heated, the respective crucible is usually heated), while controlling the evaporation of the material in the crucible, evaporate it (when using more than two materials, usually evaporate while controlling the evaporation independently), then place it toward the crucible A hole injection layer is formed on the anode of the substrate. In addition, when two or more kinds of materials are used, the mixture is put into a crucible and heated and evaporated to form a hole injection layer.

The vacuum degree during vapor deposition is under the premise of not significantly impairing the effect of the present invention, and the rest is not limited, usually 0.1×10 ^-6 Torr (0.13×10 ^-4 Pa) or more, and 9.0×10 ^-6 Torr (12.0 ×10 ^-4 Pa) or less. The vapor deposition rate is increased before the effect of the present invention is significantly impaired, and the rest is not limited, and it is usually 0.10 Å/sec or more and 5.0 Å/sec or less. The film forming temperature during vapor deposition is set before the effect of the present invention is not significantly impaired, and the rest is not limited, and it is preferably carried out at 10°C or higher and 50°C or lower.

In addition, the hole injection layer 3 may be crosslinked in the same manner as the hole transport layer 4 described later.

[Hole transport layer]

The hole transport layer 4 is a layer responsible for transporting holes from the anode 2 side to the light emitting layer 5 side. The hole transport layer 4 is not an essential layer for the organic electroluminescent device of the present invention, but from the viewpoint of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5, it is preferable There is formation of this layer. When the hole transport layer 4 is formed, the hole transport layer 4 is usually formed between the anode 2 and the light emitting layer 5. In addition, when the hole injection layer 3 is formed, it is formed between the hole injection layer 3 and the light-emitting layer 5.

The film thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and on the other hand, it is usually 300 nm or less, preferably 100 nm or less.

The method of forming the hole transport layer 4 may be a vacuum evaporation method or a wet film formation method. From the viewpoint of excellent film-forming properties, it is preferable to form by a wet film-forming method.

The method for forming a general hole transport layer is described below.

The hole transport layer 4 usually contains a hole transport compound. The hole-transporting compound contained in the hole-transporting layer 4 can be, for example, the aforementioned compounds. More specifically, in addition to the polymer of the present invention, as a preferable example, for example: 4,4'-bis[ N-(1-naphthyl)-N-anilino]biphenyl represents an aromatic diamine containing two or more tertiary amines and having two or more condensed aromatic rings substituted for the nitrogen atom (Japanese Patent Laid-Open Hei 5- No. 234681); 4,4',4"-tris(1-naphthylanilino)triphenylamine and other aromatic amine compounds with starburst structure (J.Lumin., Volume 72-74, Page 985 , 1997); an aromatic amine compound formed by the tetramer of triphenylamine (Chem. Commun., p. 2175, 1996); 2,2',7,7'-tetra(diphenylamino)- Spiro compounds such as 9,9'-spirodistilbene (Synth.Metals, Volume 91, Page 209, 1997); 4,4'-N,N'-dicarbazole biphenyl and other carbazole derivatives, etc. In addition, it is also preferable to use, for example, polyvinylcarbazole, polyvinyltriphenylamine (Japanese Patent Laid-Open No. 7-53953), polyarylene ether containing tetraphenylbenzidine (Polym.Adv.Tech. , Volume 7, Page 33, 1996) etc.

[Formation of hole transport layer by wet film forming method]

When the hole transport layer is formed by the wet film forming method, it is usually the same as the wet film forming method. In the case of forming the hole injection layer by the same method, instead of the hole injection layer forming composition, the hole transport layer forming composition is used instead.

When the hole transport layer is formed by a wet film formation method, the composition system for forming the hole transport layer usually further contains a solvent. The solvent used in the composition for forming a hole transport layer may be the same as the solvent used in the composition for forming a hole injection layer.

The concentration of the hole transporting compound in the composition for forming a hole transport layer can be set to the same range as the concentration of the hole transporting compound in the composition for forming a hole injection layer.

When the hole transport layer is formed by a wet film forming method, it can be implemented in the same manner as the hole injection layer forming method described above.

[Formation of hole transport layer by vacuum evaporation method]

When the hole transport layer is formed by vacuum evaporation method, it is usually the same as the case of forming the hole injection layer by vacuum evaporation method. Instead of the composition for forming the hole injection layer, the hole transport layer is formed instead. The composition can be formed. The film formation conditions such as the degree of vacuum during the vapor deposition, the vapor deposition rate, and the temperature, etc., can be formed under the same conditions as when the hole injection layer is vacuum vapor deposited.

[Light-emitting layer]

The light-emitting layer 5 is a layer responsible for the function of exciting and emitting light by recombining the holes injected from the anode 2 and the electrons injected from the cathode 9 when an electric field is applied between the pair of electrodes. The light-emitting layer 5 is a layer formed between the anode 2 and the cathode 9. The light-emitting layer is formed between the hole injection layer and the cathode when a hole injection layer is formed on the anode. When a hole transport layer is provided on the anode, it is formed between the hole transport layer and the cathode.

The film thickness of the light-emitting layer 5 can be arbitrarily set before the effect of the present invention is significantly impaired. From the viewpoint that the film is not prone to defects, the thicker the better. On the other hand, from the viewpoint of easy formation of low driving voltage, The thinner the better. Therefore, it is preferably 3 nm or more, more preferably 5 nm or more, and on the other hand, it is generally preferably 200 nm or less, and more preferably 100 nm or less.

The light-emitting layer 5 contains at least a material with light-emitting properties (light-emitting material), and preferably contains a material with charge-transporting properties (charge-transporting material).

[Luminescent material]

The luminescent material emits light according to the required luminous wavelength, and it is mentioned before the effect of the present invention is not impaired. The rest is not particularly limited, and known luminescent materials can be used. The luminescent material may be a fluorescent luminescent material or a phosphorescent luminescent material, but it is preferably a material with good luminous efficiency. From the viewpoint of internal quantum efficiency, a phosphorescent luminescent material is preferred.

The fluorescent material system can be, for example, the following materials.

、對雙(2-苯基乙烯基)苯、及該等的衍生物等。 Examples of fluorescent materials (blue fluorescent materials) that provide blue light emission include naphthalene, perylene, pyrene, anthracene, coumarin,

, P-bis(2-phenylvinyl)benzene, and these derivatives, etc.

Examples of fluorescent materials that provide green light (green fluorescent materials) include: quinacridone derivatives, coumarin derivatives, aluminum complexes such as Al(C ₉ H ₆ NO) ₃ , etc. Wait.

Examples of the fluorescent material (yellow fluorescent material) that provides yellow light emission include rubrene and pyridone derivatives.

衍生物、氮雜苯并硫

等。 As a fluorescent material that provides red light (red fluorescent material), for example, DCM (4-(dicyanomethylene)-2-methyl-6-(p-dimethylaminostyryl) )-4H-pyran) compounds, benzopyran derivatives, rose bengal derivatives, benzooxysulfur

Derivatives, azabenzosulfur

Wait.

Furthermore, as the phosphorescent light-emitting material system, for example, an organometallic complex of a metal selected from Groups 7 to 11 of the long-period periodic table can be contained. Preferred metals selected from groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, gold and the like.

The ligands of organometallic complexes are preferably (hetero)arylpyridine ligands, (hetero)arylpyrazole ligands, etc., which are composed of (hetero)aryl, pyridine, pyrazole, phenanthroline, etc. The ligands to be linked are more preferably phenylpyridine ligands and phenylpyrazole ligands. The "(hetero)aryl group" used here means an aryl group or a heteroaryl group.

As a preferred specific system of phosphorescent luminescent materials, for example, tris(2-phenylpyridine)iridium, tris(2-phenylpyridine)ruthenium, tris(2-phenylpyridine)palladium, bis(2-phenylpyridine) Phenylpyridine complexes such as platinum, tris(2-phenylpyridine)osmium, tris(2-phenylpyridine)rhenium; and platinum octaethylporphyrin, platinum octaphenylporphyrin, and palladium octaethylporphyrin , Porphyrin complexes such as octaphenylporphyrin palladium, etc.

Examples of the polymer-based light-emitting material system include: poly(9,9-dioctyl -2,7-diyl), poly[(9,9-dioctyl -2,7-diyl)- co-(4,4'-(N-(4-second butylphenyl))diphenylamine)], poly[(9,9-dioctyl -2,7-diyl)-co-( 1,4-Benzo-2{2,1'-3}-triazole)] and other polytetrafluoroethylene materials; poly[2-methoxy-5-(2-ethylhexyloxy)-1,4 -Phenylene vinylene] and other polystyrene vinyl materials.

[Charge Transport Material]

Charge-transporting materials have positive charge (holes) or negative charge (electron) transport properties The materials are mentioned before the effect of the present invention is not impaired, and the rest is not particularly limited, and known luminescent materials can be used.

As the charge-transporting material, compounds used in the light-emitting layer of conventional organic electroluminescence devices and the like can be used, and compounds used as the host material of the light-emitting layer are particularly preferred.

二唑系化合物、矽諾魯系化合物等電子輸送性化合物等等。 Specific examples of charge-transporting materials include aromatic amine-based compounds, phthalocyanine-based compounds, porphyrin-based compounds, oligothiophene-based compounds, polythiophene-based compounds, benzylbenzene-based compounds, and use of the polymer of the present invention. Compounds with tertiary amine groups, hydrazone-based compounds, silazane-based compounds, silanamine-based compounds, phosphinoamine-based compounds, quinacridone-based compounds, etc. are exemplified as the hole transporting compound of the hole injection layer, etc., Other examples include: anthracene compounds, pyrene compounds, carbazole compounds, pyridine compounds, phenanthroline compounds,

Electron transporting compounds such as diazole-based compounds and silanolu-based compounds, etc.

Furthermore, it is preferable to use, for example, 4,4'-bis[N-(1-naphthyl)-N-anilino]biphenyl, which contains 2 or more tertiary amines and is condensed by 2 or more Aromatic diamines in which an aromatic ring replaces the nitrogen atom (Japanese Patent Laid-Open No. 5-234681); 4,4',4"-tris(1-naphthylanilino)triphenylamine and other aromatics with a starburst structure Family amine compounds (J. Lumin., vol. 72-74, p. 985, 1997); aromatic amine compounds formed by the tetramer of triphenylamine (Chem. Commun., p. 2175, 1996) ); 2,2',7,7'-tetrakis (diphenylamino)-9,9'-spirobifen and other spiro compounds (Synth.Metals, Volume 91, Page 209, 1997); 4,4 Carbazole compounds such as'-N,N'-dicarbazole biphenyl, etc. are exemplified compounds for hole transporting compounds in the hole transporting layer, etc.

二唑(tBu-PBD)、2,5-雙(1-萘基)-1,3,4-

二唑(BND)等

二唑系化合物；2,5-雙(6'-(2',2"-聯吡啶))-1,1-二甲基-3,4- 二苯基矽諾魯(PyPySPyPy)等矽諾魯系化合物；向紅菲咯啉(BPhen)、2,9-二甲基-4,7-二苯基-1,10-菲咯啉(BcP、浴銅靈)等菲咯啉系化合物等等。 Furthermore, other examples can also include: 2-(4-biphenylene)-5-(p-tert-butylphenyl)-1,3,4-

Diazole (tBu-PBD), 2,5-bis(1-naphthyl)-1,3,4-

Diazole (BND) etc.

Diazole compounds; 2,5-bis(6'-(2',2"-bipyridine))-1,1-dimethyl-3,4-diphenyl silanolu (PyPySPyPy) and other silanos Lu series compounds; phenanthroline series compounds such as red phenanthroline (BPhen), 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BcP, Yutongling), etc. Wait.

[Formation of light-emitting layer by wet film forming method]

The method of forming the light-emitting layer may be a vacuum deposition method or a wet film forming method. However, from the viewpoint of excellent film forming properties, the wet film forming method is preferred, the spin coating method and inkjet are more preferred law. In particular, if the composition for organic electroluminescence devices of the present invention is used to form a hole injection layer or a hole transport layer that will become the lower layer of the light emitting layer, it is easier to perform lamination by wet film formation, so it is preferable to use Wet film forming method. When the light-emitting layer is formed by the wet film formation method, it is usually the same as the above-mentioned wet film formation method for forming the hole injection layer. Instead of the composition for forming the hole injection layer, it is used instead of the composition for forming the hole injection layer. The solvent (solvent for the light-emitting layer) of the material of the light-emitting layer is mixed to form the prepared composition for forming the light-emitting layer.

In addition to the ether-based solvents, ester-based solvents, aromatic hydrocarbon-based solvents, and amine-based solvents exemplified for the formation of the hole injection layer, the solvent system may include: alkane-based solvents, halogenated aromatic hydrocarbon-based solvents, and fatty acids. Alcohol solvents, alicyclic alcohol solvents, aliphatic ketone solvents, alicyclic ketone solvents, etc. Specific examples of solvents are given below, but they are not limited to these as long as they do not impair the effects of the present invention.

For example: aliphatic ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethyl Oxybenzene, anisole, phenethyl ether, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole , Diphenyl ether and other aromatic ether solvents; phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, benzene Aromatic ester solvents such as propyl formate and n-butyl benzoate; toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3-isopropyl biphenyl, 1,2,3,4- Aromatic hydrocarbon solvents such as tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, methylnaphthalene; N,N-dimethylformamide, N,N-dimethylacetamide Isotamine-based solvents; alkane-based solvents such as n-decane, cyclohexane, ethylcyclohexane, decalin, and bicyclohexane; halogenated aromatic hydrocarbon-based solvents such as chlorobenzene, dichlorobenzene, and trichlorobenzene; Aliphatic alcohol solvents such as butanol and hexanol; alicyclic alcohol solvents such as cyclohexanol and cyclooctanol; aliphatic ketone solvents such as methyl ethyl ketone and dibutyl ketone; cyclohexanone and cyclooctanone Alicyclic ketone solvents such as fenchone, etc. Among these, more preferred are alkane-based solvents and aromatic hydrocarbon-based solvents.

[Electric hole barrier layer]

A hole blocking layer 6 may also be provided between the light-emitting layer 5 and the electron injection layer 8 described later. The hole blocking layer 6 is on the light-emitting layer 5, and is a layer laminated so as to contact the interface of the light-emitting layer 5 on the cathode 9 side.

The hole blocking layer 6 has the function of preventing the holes moved from the anode 2 from reaching the cathode 9 and the function of efficiently transporting electrons injected from the cathode 9 toward the light-emitting layer 5. The physical properties required for the material constituting the hole barrier layer 6 can be, for example, high electron mobility, low hole mobility, large energy gap (difference between HOMO and LUMO), and high excited triplet energy level (T1).

Examples of material systems for the hole barrier layer satisfying such conditions include bis(2-methyl-8-quinolinyl) (phenolic) aluminum, bis(2-methyl-8-quinolinyl) (triphenyl) Silanol group) aluminum and other mixed ligand complexes; bis(2-methyl-8-quinolinyl)aluminum-μ-oxy-bis-(2-methyl-8-quinolinyl)aluminum Metal complexes such as dinuclear metal complexes; Styrene compounds such as stilbene biphenyl derivatives (Japanese Patent Laid-Open No. 11-242996); 3-(4-Biphenyl)-4- Triazole derivatives such as phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (Japanese Patent Application Laid-Open No. 7-41759); phenanthroline derivatives such as Yutongling (Japanese Patent Laid-Open No. 10-79297) and so on. In addition, compounds described in International Publication No. 2005/022962 that have at least one pyridine ring substituted at positions 2, 4, and 6 are also preferable materials for the hole barrier layer.

The method of forming the hole barrier layer 6 is not limited. Therefore, it can be formed by a wet film forming method, an evaporation method, or other methods.

The film thickness of the hole barrier layer 6 can be any as long as it does not significantly impair the effect of the present invention, and is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less.

[Electron transport layer]

The electron transport layer 7 is arranged between the light emitting layer 5 and the electron injection layer 8 for the purpose of further improving the current efficiency of the device.

The electron transport layer 7 is formed by using a compound that can efficiently transport electrons injected from the cathode 9 toward the light emitting layer 5 between electrodes to which an electric field is applied. The electron transporting compound used in the electron transport layer 7 must be a compound that has a high electron injection efficiency from the cathode 9 or the electron injection layer 8, and has high electron mobility, and can efficiently transport the injected electrons.

二唑衍生物、二苯乙烯聯苯衍生物、矽諾魯衍生物、3-羥基黃酮金屬錯合物、5-羥基黃酮金屬錯合物、苯并

唑金屬錯合物、苯并噻唑金屬 錯合物、三苯并咪唑苯(美國專利第5645948號說明書)；喹

啉化合物(日本專利特開平6-207169號公報)；菲咯啉衍生物(日本專利特開平5-331459號公報)；2-第三丁基-9,10-N,N'-二氰基蒽醌二亞胺、n型氫化非晶質碳化矽、n型硫化鋅、n型硒化鋅等。 Specific examples of electron-transporting compounds used in the electron-transporting layer include metal complexes such as aluminum complexes of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393); 10-hydroxybenzene And [h]quinoline metal complexes,

Diazole Derivatives, Stilbene Biphenyl Derivatives, Sinulu Derivatives, 3-Hydroxyflavonoid Metal Complexes, 5-Hydroxyflavonoid Metal Complexes, Benzo

Azole metal complexes, benzothiazole metal complexes, tribenzimidazole benzene (U.S. Patent No. 5645948 specification); quine

Phenanthroline compounds (Japanese Patent Laid-Open No. Hei 6-207169); Phenanthroline derivatives (Japanese Patent Laid-Open No. 5-331459); 2-tert-butyl-9,10-N,N'-dicyano Anthraquinone diimide, n-type hydrogenated amorphous silicon carbide, n-type zinc sulfide, n-type zinc selenide, etc.

The thickness of the electron transport layer 7 is usually 1 nm or more, preferably 5 nm or more, and usually 300 nm or less, preferably 100 nm or less.

The electron transport layer 7 is the same as described above, and is formed by stacking on the hole barrier layer 6 by a wet film formation method or a vacuum evaporation method. Usually a vacuum evaporation method is used.

[Electron injection layer]

The electron injection layer 8 performs a function of efficiently injecting electrons injected from the cathode 9 to the electron transport layer 7 or the light emitting layer 5.

In order to perform electron injection efficiently, the material forming the electron injection layer 8 is preferably a metal with a low work function. For example, alkali metals such as sodium and cesium; alkaline earth metals such as barium and calcium can be used. The film thickness is usually preferably 0.1 nm or more and 5 nm or less.

Furthermore, for example, organic electron transport materials represented by nitrogen-containing heterocyclic compounds such as bathophenanthroline or metal complexes such as aluminum complexes of 8-hydroxyquinoline are doped with sodium, potassium, cesium, Alkali metals such as lithium and rubidium (described in Japanese Patent Laid-Open No. 10-270171, Japanese Patent Laid-Open No. 2002-100478, Japanese Patent Laid-Open No. 2002-100482, etc.), which can take into account electron injection and improve transportability, And excellent film quality, so it is better.

The thickness of the electron injection layer 8 is usually 5 nm or more, preferably 10 nm or more, and usually 200 nm or less, preferably 100 nm or less.

The electron injection layer 8 is laminated in the hair by using a wet film formation method or a vacuum evaporation method. The optical layer 5 or the hole blocking layer 6 or the electron transport layer 7 on it is formed.

The details of the wet film formation method are the same as those of the aforementioned light-emitting layer.

[cathode]

The cathode 9 has a function of injecting electrons toward a layer (electron injection layer, light emitting layer, etc.) on the light emitting layer 5 side.

The material of the cathode 9 can be the material used in the anode 2, but it is better to use a metal with a lower work function under the premise of efficient electron injection, such as tin, magnesium, indium, calcium, aluminum, silver Other metals or such alloys, etc. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.

From the standpoint of element stability, it is best to laminate a metal layer with a high work function and stable to the atmosphere on the cathode to protect the cathode made of a metal with a low work function. The deposited metal series can be, for example, metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum.

The thickness of the cathode is usually the same as that of the anode.

[Other layers]

The organic electroluminescent device of the present invention can be further provided with other layers under the premise of not significantly impairing the effect of the present invention. That is, any of the above-mentioned other layers may be provided between the anode and the cathode.

[Other components]

The organic electroluminescence element of the present invention may also have a structure that is reversed from the above description, that is, a cathode, an electron injection layer, an electron transport layer, Hole barrier layer, light emitting layer, hole transport layer, hole injection layer, anode.

When the organic electroluminescence element of the present invention is used in an organic electroluminescence device, it can be used as a single organic electroluminescence element, or as a configuration in which a plurality of organic electroluminescence elements are arranged in an array, and can also be used as The anode and cathode are arranged in an XY matrix.

<Organic EL display device>

The organic EL display device (organic electroluminescence element display device) of the present invention uses the above-mentioned organic electroluminescence element of the present invention. There are no special restrictions on the type and structure of the organic EL display device of the present invention, and the organic electroluminescent device of the present invention can be used to assemble according to a conventional method.

For example, the organic EL display device of the present invention can be formed in accordance with the method described in "Organic EL Display" (Ohm Corporation, published on August 20, Heisei, by Shishishi at the time, Chinami Adachi, Hideyuki Murata).

<Organic EL Lighting>

The organic EL lighting (organic electroluminescence element lighting) of the present invention uses the above-mentioned organic electroluminescence element of the present invention. There are no special restrictions on the type and structure of the organic EL lighting of the present invention, and the organic electroluminescent element of the present invention can be used to assemble according to conventional methods.

Example

Hereinafter, the present invention will be explained in more detail by exemplified examples. However, the present invention is not limited to the following embodiments, and the present invention can be implemented in any modification without going beyond the gist.

<Example 1> [Synthesis of Monomer (Compound 3)]

Compound 1 was synthesized as follows.

Synthesis of monomer

Fill the flask with 4-second butylaniline (37.36g, 250.34mmol), bromobenzene (38.52g, 245.33mmol), tertiary butoxy sodium (57.77g, 601.05mmol), and toluene (500ml), The system is fully replaced with nitrogen and heated to 60°C (solution A). In another flask filled with tris(benzylideneacetone)dipalladium chloroform complex compound (0.52g, 0.491mmol) in 25ml of toluene solution, add 1,1'-bis(diphenylphosphine)ferrocene (1.09 g, 1.96 mmol) and heated to 60°C (solution B). In a nitrogen stream, solution B was added to solution A, and stirred at 100°C for 4.0 hours. After being allowed to cool to room temperature, ethyl acetate (300ml) and brine (100ml) were added to the reaction solution and stirred, then liquid separation was performed. The aqueous layer was extracted with ethyl acetate (100ml×2 times), and The organic layer was dried with magnesium sulfate and then concentrated. In addition, purification was performed with a silica gel column chromatography (n-hexane/dichloromethane=9/1) to obtain compound 1 (40.2 g) in the form of a pale yellow oil.

[化17]

Compound 1 (40.0g, 177.5mmol), 4,4'-dibromobiphenyl (27.15g, 87.02mmol), tertiary butoxy sodium (42.6g, 443.8mmol), and toluene (500ml) were filled in the flask In the middle, the system is fully replaced with nitrogen, and the temperature is raised to 60°C (solution C). In another flask, add three (dibenzylideneacetone) two palladium chloroform complex (0.92g, 0.89mmol), toluene (25ml), 4-(N,N-dimethylamino)phenyl) two Tertiary butyl phosphine (1.9 g, 7.12 mmol), heated to 60°C (solution D). In a nitrogen stream, solution D was added to solution C, and reacted at 100°C for 5.5 hours. After cooling to room temperature, toluene (300ml) and brine (100ml) were added to the reaction solution and stirred, then liquid separation was carried out. The aqueous layer was extracted with toluene (100ml×2 times) and used together with the organic layer. After the magnesium sulfate is dried, it is treated with activated clay and then concentrated. In addition, purification was performed with a silica gel column chromatography analyzer (n-hexane/ethyl acetate=9/1) to obtain a pale yellow oily compound 2 (52.2 g).

N,N-dimethylformamide (300 ml) and dichloromethane (300 ml) were added to compound 2 (52.1 g, 86.71 mmol), and the mixture was cooled in an ice bath. Dropped N-bromosuccinimide (38.87g, 173.42mmol) of N,N-dimethylformamide (100ml) and two The methyl chloride (100 ml) solution was heated to room temperature over 4.5 hours while stirring. Water was added to the reaction solution, extraction was performed with dichloromethane, the organic layer was concentrated, and purified by column chromatography (developing solution: hexane/dichloromethane = 4/1) to obtain a colorless solid compound 3 (23.2 g).

[Synthesis of Polymer 1]

Polymer 1 was synthesized according to the following reaction formula.

Fill compound 3 (5.00g, 6.6mmol), 2-amino-9,9-dihexylpyridine (4.6lg, 13.2mmol), tertiary butoxy sodium (4.88g, 50.8mmol) and toluene (100g) Put it in a flask and fully replace the system with nitrogen, and heat to 90°C (solution E). In another flask, add tris(benzylideneacetone) dipalladium complex (0.12g, 1.1mmol), toluene (7.8ml) and [4-(N,N-dimethylamino)phenyl] Di-tertiary butyl phosphine (0.28 g, 0.11 mmol) was heated to 60°C (solution F). In a nitrogen stream, solution F was added to solution E, and heating and refluxing reaction was performed for 1 hour. When it was confirmed that the raw material disappeared, 4,4'-dibromobiphenyl (0.60 g, 1.92 mmol) was added, and heating and refluxing were performed for 1 hour. Add 4-(4-{1,1-bis[4-(4-bromophenyl)phenyl]ethyl}phenyl)benzocyclobutene (2.69g, 4.01 mmol), after heating and refluxing for 1 hour, bromobenzene (1.04 g, 6.6 mmol) was added, and heating and refluxing reaction was performed for 1.5 hours. After the reaction liquid was allowed to cool, toluene (100 g) was added and dropped into ethanol (5000 g) to obtain a crude polymer.

The crude polymer was dissolved in toluene, re-precipitated in acetone, and the precipitated polymer was filtered out. The obtained polymer was dissolved in toluene, washed with dilute hydrochloric acid, and re-precipitated in ethanol containing ammonia. The filtered polymer was purified with a column chromatography analyzer to obtain polymer 1 (3.7 g).

Weight average molecular weight (Mw)=45200

Number average molecular weight (Mn)=32700

Dispersion (Mw/Mn)=1.38

(Organic electroluminescence element) <Example 2>

The organic electroluminescence device shown in Fig. 1 was produced.

After depositing a transparent conductive film of indium tin oxide (ITO) on the glass substrate 1 by sputtering, the usual lithography technique and hydrochloric acid etching are used to form a stripe pattern with a width of 2 mm, and an anode 2 with a film thickness of 70 nm is formed. . The patterned ITO substrate is washed sequentially with a surfactant aqueous solution, washed with ultra-pure water, washed with ultra-pure water, washed with ultra-sonic, washed with ultra-pure water, and then compressed. The air is dried and finally washed with ultraviolet ozone.

Next, prepare containing: polymer 1 (P1) synthesized in Example 1, 4-isopropyl-4'-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate represented by structural formula (A1) and A coating solution for forming a hole injection layer of ethyl benzoate. The coating solution was spin-coated to form a film on the anode 2 and heated according to the following conditions to obtain a hole injection with a thickness of 35 nm. Into the layer.

<Coating Solution for Hole Injection Layer Formation>

<Film formation conditions of hole injection layer 3>

Next, a coating solution for forming a hole transport layer containing the following (P2) was prepared, a film was formed by spin coating on the hole injection layer 3 according to the following conditions, and heated to form a hole transport with a thickness of 40 nm Floor.

[化21]

<Coating Liquid for Hole Transport Layer Formation>

<Film forming conditions for hole transport layer 4>

Next, a coating solution for forming a light-emitting layer containing the compounds (H1), (H2) and (D1) represented by the following structural formulas was prepared, and a film was formed by spin coating according to the following conditions. After heating, the hole transport layer A light-emitting layer with a thickness of 56 nm is formed on 4.

[化22]

<Coating Liquid for Light-Emitting Layer Formation>

<Film-forming conditions of luminescent layer 5>

Here, the substrate that has been formed into the light-emitting layer is moved into a vacuum evaporation device, and the organic compound (E1) with the structure shown below is laminated on the light-emitting layer 5 by vacuum evaporation to form a film thickness of 10nm The hole barrier layer 6.

[化23]

Next, an organic compound (E2) having the structure shown below is laminated on the hole barrier layer 6 by a vacuum vapor deposition method to form an electron transport layer 7 with a thickness of 10 nm.

Here, the component that has been vapor-deposited to the electron transport layer 7 is moved into another vacuum vapor deposition device, and a stripe-shaped shadow mask with a width of 2 mm, which is used as a cathode vapor deposition mask, is perpendicular to the ITO stripe of the anode 2 The state is closely connected to the component. As the electron injection layer 8, lithium fluoride (LiF) was first formed on the electron transport layer 7 with a thickness of 0.5 nm by a vacuum evaporation method using a molybdenum bottle. Next, as the cathode 9 system, aluminum was heated in a molybdenum bottle in the same manner, and then an aluminum layer with a film thickness of 80 nm was formed by a vacuum vapor deposition method. The substrate temperature during vapor deposition of the above two layers is kept at room temperature.

Next, in order to prevent the components from being degraded due to moisture in the atmosphere during storage, the sealing process was performed according to the method described below.

In a nitrogen glove box, a light-curing resin (30Y-437 made by ThreeBond Refinery Co., Ltd.) is coated on the outer circumference of a 23mm×23mm glass plate with a width of about 1mm, and a moisture trap is set in the center. Film (manufactured by Dynaic Co., Ltd.). On top of it, the substrate with the cathode formed is opposed to the desiccant sheet according to the vapor-deposited surface The way fits. Then, only the area coated with the photocurable resin is irradiated with ultraviolet light to harden the resin.

According to the above, an organic electroluminescence device having a light-emitting area of 2 mm×2 mm was obtained. The characteristics of this component are shown in Table 2.

<Comparative Example 1>

Except that the polymer used in the coating liquid for forming the hole injection layer was changed from the polymer 1 (P1) to the polymer (P3) shown in the following formula, the rest was the same as in Example 2 to produce an organic electric Luminescent element. The characteristics of this component are shown in Table 2.

<Comparative Example 2>

Except that the polymer used in the coating solution for forming the hole injection layer was changed from the polymer 1 (P1) to the polymer (P4) shown in the following formula, the rest was the same as in Example 2 to prepare an organic electric Luminescent element. The characteristics of this component are shown in Table 2.

<Comparative Example 3>

Except that the polymer used in the coating liquid for forming the hole injection layer was changed from the polymer 1 (P1) to the polymer (P5) shown in the following formula, the rest was the same as in Example 2 to prepare an organic electric Luminescent element. The characteristics of this component are shown in Table 2.

It can be seen from Table 2 that the organic electroluminescence element using the polymer of the present invention has a lower voltage.

The present invention will be described with reference to detailed descriptions and specific embodiments. However, various changes and modifications can be made without departing from the spirit and scope of the present invention, which can be easily thought of by those familiar with this technology. This application is based on the Japanese patent application (Japanese Patent Application 2015-035607) filed on February 25, 2015, and the content is referred to and cited in this application.

1‧‧‧Substrate (glass substrate)

2‧‧‧Anode

3‧‧‧Electric hole injection layer

4‧‧‧Electric tunnel transport layer

5‧‧‧Light-emitting layer

6‧‧‧Electric hole barrier layer

7‧‧‧Electron transport layer

8‧‧‧Electron injection layer

9‧‧‧Cathode

10‧‧‧Organic electroluminescent element

Claims (11)

A polymer containing the unit represented by the following formula (1) as a repeating unit:

(In formula (1), Ar ¹ represents each independently and optionally substituted 2-phosphonium group; R ¹ represents each independent linear or branched alkyl having ^{1 to} 4 carbon atoms; T ¹ It represents an aromatic hydrocarbon group having a crosslinkable group as a substituent). Such as the polymer of claim 1, which further contains a unit represented by the following formula (2) as a repeating unit:

(In formula (2), Ar ¹ represents each independently and optionally substituted 2-phosphonium group; R ¹ represents each independent linear or branched alkyl having ^{1 to} 4 carbon atoms; L ¹ It represents any of 1,4-phenylene, 4,4'-biphenylene, 4,4"-p-terphenylene). Such as the polymer of claim 2, wherein in the polymer, relative to 100 mol% of the total monomer units, the unit represented by the above formula (1) and the unit represented by the above formula (2) together contain 50 mol% or more . The polymer of claim 2 or 3, wherein the above L ¹ is 4,4'-biphenylene, that is, contains the unit represented by the following formula (3) as a repeating unit:

(In formula (3), Ar ¹ represents each independently and optionally substituted 2-phosphonium group; R ¹ represents each independent linear or branched alkyl group having 1 to 4 carbon atoms). The polymer according to any one of claims 1 to 3, wherein the weight average molecular weight (Mw) is 20,000 or more, and the dispersion degree (Mw/Mn) is 2.5 or less. A composition for an organic electroluminescence element, which is a polymer containing any one of claims 1 to 5. An organic electroluminescent element, which is provided on a substrate, is provided with an anode, a cathode, and an organic electroluminescent element with an organic layer between the anode and the cathode; wherein, the organic layer contains the use claim 6 The composition for organic electroluminescence devices is a layer formed by a wet film forming method. An organic electroluminescent device according to claim 7, wherein the layer formed by the wet film forming method is at least one of a hole injection layer and a hole transport layer. The organic electroluminescence element of claim 7 or 8, wherein a hole injection layer, a hole transport layer and a light emitting layer are contained between the anode and the cathode; all of the above hole injection layer, hole transport layer and light emitting layer It is formed by a wet film forming method. An organic EL display device is provided with an organic electroluminescence element according to any one of claims 7 to 9. An organic EL lighting is provided with an organic electroluminescence element according to any one of claims 7 to 9.

Images