JP2006316224A - Macromolecular compound comprising thiophene in main chain and organic electroluminescent element comprising the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a macromolecular compound suitably used in an organic electrolluminescent element, method for producing the compound, and to provide an organic electrolluminescent element using the compound, drivable at a low voltage and is excellent in durability. <P>SOLUTION: The organic electroluminescent element comprises at least a layer comprising at least one macromolecular compound composed of a repeating unit expressed by general formula (1), between a pair of electrodes. In the formula, Z<SP>1</SP>-Z<SP>4</SP>are each a substituent, p1 and p2 are each an integer of 0-5, p3 and p4 are each an integer of 0-4, Ar<SP>1</SP>and Ar<SP>2</SP>are each a monovalent aromatic group, and Y is a divalent aromatic group. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a novel polymer compound containing thiophene in the main chain and a method for producing the same. Furthermore, this invention relates to the organic electroluminescent element containing this compound.

  In recent years, research and development of functional materials using organic compounds has been actively conducted. Recently, development of an organic electroluminescence element (organic electroluminescence element: organic EL element) using an organic compound as a constituent material of the element has been vigorously advanced (for example, Non-Patent Document 1).

  An organic electroluminescent device has a structure in which a thin film containing a fluorescent organic compound is sandwiched between an anode and a cathode. By injecting electrons and holes into the thin film and recombining them, an exciton (Exington) ) And emits light using light emitted when the exciton is deactivated. The organic electroluminescent element can emit light at a low direct current voltage of several volts to several tens of volts, and various colors (for example, red, blue, green) can be selected by selecting the type of the fluorescent organic compound. ) Can be emitted. The organic electroluminescent device having such characteristics is expected to be applied to various light emitting devices and display devices. In general, however, organic electroluminescent elements have drawbacks such as poor heat resistance and durability.

  For the purpose of efficiently injecting and transporting holes to a thin film containing a fluorescent organic compound of an organic electroluminescent device, an organic electroluminescent device having a hole injection layer disposed therein has also been reported. The material for the hole injection layer preferably has an energy level (ionization potential) equivalent to that of ITO in order to efficiently inject holes from ITO (indium-tin-oxide) as an anode. . Examples of such materials include starburst amine derivatives such as copper phthalocyanine, 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (for example, non-patent Document 2, Non-Patent Document 3) and the like are used, but copper phthalocyanine has a problem in that it absorbs light emitted from an electroluminescent element because its absorption wavelength is in the visible light region. Starburst polyamine compounds are also used as materials for the hole injection layer, but organic electroluminescence devices using these materials also have organic electroluminescence that combines the essential properties of high efficiency and long life. The present condition is that the element is not obtained.

The use of polymer compounds in organic electroluminescent devices has also been recently proposed. For example, an example using a polythiophene-based conductive polymer compound as a hole injection layer is known (Patent Document 1). However, organic electroluminescent devices using these materials have not been put into practical use.
Appl. Phys. Lett., 51, 913 (1987). Appl. Phys. Lett., 65, 807 (1994). Jpn. J. Appl. Phys., 34, L824 (1995). JP 2000-91081 A

  The subject of this invention is providing the high molecular compound which contains a novel thiophene in a principal chain, the manufacturing method of this compound, and the organic electroluminescent element containing this compound. More specifically, it is suitable for a hole injecting and transporting material of an organic electroluminescence device, etc., a polymer compound containing thiophene in the main chain, which has excellent heat resistance and can be applied, and can be driven at a low voltage and is durable using the compound. It is to provide an organic electroluminescent device excellent in.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have found polymer compounds containing thiophene in the main chain, methods for producing the same, and organic electroluminescent devices using the compounds, thereby completing the present invention. It came to.

  That is, according to the present invention, the general formula (1):

^(Wherein, Z 1 to Z ⁴ represents a substituent, p1 and p2 represents an integer of 0 to 5, p3 and p4 is an integer of 0 to 4, Ar ¹ and Ar ² are monovalent aromatic And Y represents a divalent aromatic group.)
The polymer compound which consists of a repeating unit represented by these is provided.

  According to the invention, at least one layer containing at least one polymer compound composed of the repeating unit represented by the general formula (1) according to claim 1 or 2 is sandwiched between a pair of electrodes. An organic electroluminescent device is provided. This organic electroluminescent element also includes an element having a light emitting layer and / or an electron injecting and transporting layer between a pair of electrodes.

  Further according to the present invention, the general formula (2):

^(Wherein, Z ¹ to Z 4, it is p1 to p4, ^Z 1 ^{to Z} 4 in the general formula (1) has the same meaning as p1 to p4, X is a halogen atom.)
A compound represented by formula (3):

H-N (Ar < ¹ >)-Y-N (Ar < ² >)-H (3)
^(Wherein, Ar 1 to Ar ² and Y are as defined ^Ar 1 to Ar ² and Y in the general formula (1).)
A method for producing a polymer compound comprising a repeating unit represented by the general formula (1) according to claim 1, wherein the compound represented by formula (1) is polymerized in the presence of a base.

  INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel polymer compound containing thiophene in the main chain, a method for producing the compound, and an organic electroluminescent device that can be driven at a low voltage and has excellent durability using the compound. .

Hereinafter, the present invention will be described in detail.
The polymer compound containing thiophene in the main chain of the present invention comprises a repeating unit represented by the general formula (1).

In the general formula (1), Z ^{1 to} Z ⁴ represent the same or different substituents. Z ^{1 to} Z ⁴ include a halogen atom, — (O) mZ ¹⁰ group (wherein Z ¹⁰ is an unsubstituted or substituted linear, branched or cyclic alkyl group having 1 to 50 carbon atoms. A group, an unsubstituted or substituted monovalent aromatic group having 3 to 50 carbon atoms, an unsubstituted or substituted aralkyl group having 4 to 50 carbon atoms, and m represents 0 or 1. it can.

Z ^{1 to} Z ⁴ are preferably a halogen atom or a — (O) m—Z ¹⁰ group in which Z ¹⁰ has 1 to 30 carbon atoms.

Specific examples of the halogen atoms represented by Z ^{1 to} Z ⁴ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

When Z ¹⁰ is an unsubstituted or substituted linear, branched or cyclic alkyl group, those having 1 to 16 carbon atoms are more preferred, and those having 1 to 8 carbon atoms are particularly preferred. Examples of the unsubstituted alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, Neopentyl group, tert-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 2-ethylbutyl group, n-heptyl group, 1-methylhexyl group, n-octyl group, 1 -Methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 2,6-dimethyl-4-heptyl group, 3,5,5-trimethylhexyl group, n-decyl group, cyclobutyl group, cyclopentyl group, 1-methylcyclopentyl group, cyclohexyl group, 4-methylcyclohexyl group, cycloheptyl group, etc. It can be mentioned. Examples of the substituted alkyl group include those in which the above group is substituted with an alkyloxy group having 1 to 8 carbon atoms such as a methoxymethyl group and an ethoxymethyl group; a methylthiomethyl group and the like. Those substituted with an alkylthio group having 1 to 8 carbon atoms; those substituted with a halogen atom such as a fluoromethyl group, and those substituted with a hydroxyl group such as a hydroxylmethyl group. it can.

When Z ¹⁰ is an unsubstituted or substituted monovalent aromatic group, the aromatic group includes an aromatic hydrocarbon group and an aromatic heterocyclic group. Those having 3 to 20 carbon atoms are more preferred, and those having 3 to 16 carbon atoms are particularly preferred. Examples of the unsubstituted or substituted aromatic hydrocarbon group and aromatic heterocyclic group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 2-anthracenyl group, a 9-anthracenyl group, and a 9-methyl-10. -Anthracenyl group, 9-phenyl-10-anthracenyl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, 9-methyl-10-phenanthryl group, 9-phenyl -10-phenanthryl group, 2-fluoro-9-phenanthryl group, 4-quinolinyl group, 1-pyrenyl group, 2-pyrenyl group, 4-pyridinyl group, 3-pyridinyl group, 2-pyridinyl group, 4-pyrimidinyl group, 3-pyrimidinyl group, 2-pyrimidinyl group, 3-furanyl group, 2-furanyl group, 3-thienyl group, -Thienyl group, 2-oxazolyl group, 2-thiazolyl group, 2-benzoxazolyl group, 2-benzothiazolyl group, 2-benzimidazolyl group, 4-methylphenyl group, 4-methoxyphenyl group, 4-fluorophenyl group, 4-chlorophenyl group, 4-bromophenyl group, etc. can be mentioned.

When Z ¹⁰ is an unsubstituted or substituted aralkyl group, those having 4 to 30 carbon atoms are more preferred, and those having 4 to 16 carbon atoms are particularly preferred. Examples of the unsubstituted or substituted aralkyl group include benzyl group, α-methylbenzyl group, α-ethylbenzyl group, phenethyl group, α-methylphenethyl group, β-methylphenethyl group, 4-methylbenzyl group, 4 Examples include -methoxybenzyl group, 4-hydroxybenzyl group, 4-fluorobenzyl group, 4-chlorobenzyl group, 2-furfuryl group, diphenylmethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group and the like.

  In General formula (1), p1 and p2 represent the integer of 0-5 independently, p3 and p4 represent the integer of 0-4. p1 to p4 are preferably independently an integer of 0 to 2, more preferably an integer of 0 to 1.

For Z ^{1 to} Z ⁴ and p 1 to p ⁴ , Z ¹ and Z ² , Z ³ and Z ⁴ are the same substituents, and p 1 and p 2, and p 3 and p 4 are the same integer values. It is particularly preferable to take

In the general formula (1), Ar ¹ and Ar ² independently represent a monovalent aromatic group, and include a monovalent aromatic hydrocarbon group or a monovalent aromatic heterocyclic group. These groups may be unsubstituted or substituted. When these groups are unsubstituted or substituted aromatic hydrocarbon groups, the group preferably has 6 to 30 carbon atoms, and more preferably 6 to 20 carbon atoms. On the other hand, when these groups are unsubstituted or substituted aromatic heterocyclic groups, the group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms. Ar ¹ and Ar ² are particularly preferably the same group, and more preferably the same aromatic hydrocarbon group.

Specific examples of the unsubstituted or substituted aromatic hydrocarbon group or the aromatic heterocyclic group represented by Ar ¹ and Ar ² include the aromatic hydrocarbon group or the aromatic heterocyclic group shown as examples of Z ^10. be able to.

In addition, the aromatic hydrocarbon group or the aromatic heterocyclic group of Ar ¹ and Ar ² may be substituted with an amino group, a monosubstituted amino group, or a disubstituted amino group. Examples of the substituent of the substituted amino group include an unsubstituted or substituted linear, branched or cyclic alkyl group having 1 to 16 carbon atoms and an unsubstituted or substituted aromatic hydrocarbon having 3 to 16 carbon atoms. a group or an aromatic heterocyclic group, and specific examples thereof include those shown as examples of Z ^10. Specific examples of the substituted amino group include, for example, N-methylamino group, N-ethylamino group, N-phenylamino group, N- (1-naphthyl) amino group, N- (2-naphthyl) amino group, N , N-dimethylamino group, N, N-diethylamino group, N, N-diphenylamino group. The substitution number of the unsubstituted or substituted amino group is preferably 1 to 2, more preferably 1.

  Y represents a divalent aromatic group and includes a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group. These groups may be unsubstituted or substituted. When the group is an unsubstituted or substituted aromatic hydrocarbon group, the group preferably has 6 to 30 carbon atoms, and more preferably 6 to 20 carbon atoms. On the other hand, when the group is an unsubstituted or substituted aromatic heterocyclic group, the group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms. As these groups, for example, 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 2,6-naphthalenediyl group, 9,10- Anthracenediyl group and the like can be mentioned.

  Examples of the substituent of the substituted divalent aromatic hydrocarbon group or aromatic heterocyclic group represented by Y include, for example, a halogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkyl group And an alkyloxy group having a monovalent aromatic group. Among these substituents, examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a linear, branched or cyclic alkyl group having 1 to 16 carbon atoms, and 1 to 16 carbon atoms. An alkyloxy group having a linear, branched or cyclic alkyl group, an unsubstituted or substituted aromatic hydrocarbon group having 3 to 16 carbon atoms and an aromatic heterocyclic group are preferred.

In addition, the divalent aromatic group of Y is represented by formula (4) as -Y-:
-A-B-A- (4)
(In the formula, A represents a divalent aromatic group, and —B— represents a direct bond, —O—, —S—, —CO—, —SO— or —SO ₂ —).
A substituent represented by formula (5):
-A-B-A-B-A- (5)
(In formula, A and B are synonymous with A and B in the said General formula (4).)
The substituent represented by these is also included.

  In the formulas (4) and (5), the divalent aromatic group represented by A includes a divalent aromatic hydrocarbon group or a divalent aromatic heterocyclic group. These groups may be unsubstituted or substituted. When the group is an unsubstituted or substituted aromatic hydrocarbon group, the group preferably has 6 to 30 carbon atoms, and more preferably 6 to 20 carbon atoms. On the other hand, when the group is an unsubstituted or substituted aromatic heterocyclic group, the group preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms. As these groups, for example, 1,4-phenylene group, 1,3-phenylene group, 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 2,6-naphthalenediyl group, 9,10- Anthracenediyl group and the like can be mentioned. In the case of a substituted aromatic group, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and a linear, branched or cyclic alkyl having 1 to 8 carbon atoms. Group, an alkyloxy group having a linear, branched or cyclic alkyl group having 1 to 8 carbon atoms, and a monovalent aromatic group having 3 to 16 carbon atoms.

Y is preferably a divalent aromatic hydrocarbon group (a divalent group comprising an aromatic hydrocarbon group), and particularly preferable groups include 1,4-phenylene group, 1,4-naphthalenediyl group, and biphenylene group. _{(-C 6 H 4 -C 6 H} 4 -), triphenylene group _{(-C 6 H 4 -C 6 H} 4 -C 6 H 4 -) and the like.

  Although the number average molecular weight of the high molecular compound which consists of a repeating unit represented by General formula (1) is not specifically limited, It is 3000-1 million in polystyrene conversion, Preferably it is 3000-500000. More preferably, it is 4000-200000.

  Next, the manufacturing method of the high molecular compound which consists of a repeating unit represented by General formula (1) of this invention is demonstrated.

  The polymer compound of the present invention may be produced by any method and is not particularly limited. For example, a compound represented by the general formula (2) and a compound represented by the general formula (3) It can be produced by polymerizing in the presence of a base.

In General Formula (2) and General Formula (3), Z ^{1 to} Z ⁴ , p ^{1 to} p ⁴ , Ar ^{1 to} Ar ² and Y are Z ^{1 to} Z ⁴ , p ^{1 to} p ⁴ in General Formula (1), It is synonymous with Ar < ¹ > -Ar < ² > and Y. X represents a halogen atom, and examples thereof include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The charging ratio (molar ratio) of the compound represented by the general formula (2) and the compound represented by the general formula (3) may be in the range of 1: 3 to 3: 1 and is not particularly limited. In order to obtain a high molecular weight body, the range of 9:10 to 11:10 is preferable.

  Examples of the base used in the production method of the present invention include, but are not particularly limited to, carbonates such as sodium carbonate and potassium carbonate, inorganic bases such as alkali metal alkoxides, and organic bases such as tertiary amines. . Among these, alkali metal alkoxides such as sodium methoxide, sodium ethoxide, potassium methoxide, potassium ethoxide, lithium tert-butoxide, sodium tert-butoxide, potassium tert-butoxide are preferable, and these may be used as they are, or You may prepare and use in the reaction system from an alkali metal, an alkali metal hydride or an alkali metal hydroxide, and alcohol.

  The amount of the base used is not particularly limited, but is 0.5 to 10 moles, preferably 1.0 moles per mole of halogen atoms of the compound represented by the general formula (2) as a reaction raw material. It is the range of -5 times mole.

  In the production method of the present invention, a catalyst is appropriately used. As the catalyst, a copper catalyst such as copper powder or copper chloride, or a palladium catalyst is used. Examples of the palladium catalyst include tetravalent palladium compounds such as sodium hexachloropalladium (IV) tetrahydrate and potassium hexachloropalladium (IV); palladium (II) chloride, palladium (II) bromide, palladium acetate ( II), palladium acetylacetonate (II), dichlorobis (benzonitrile) palladium (II), dichlorobis (acetonitrile) palladium (II), dichlorobis (triphenylphosphine) palladium (II), dichlorotetraamminepalladium (II), dichloro ( Divalent palladium compounds such as cycloocta-1,5-diene) palladium (II) and palladium trifluoroacetate (II); tris (dibenzylideneacetone) dipalladium (0), tris (dibenzylide) Acetone) dipalladium chloroform complex (0), zero-valent palladium compounds such as tetrakis (triphenylphosphine) palladium (0) and the like. The amount of the palladium catalyst used is not particularly limited, but is preferably in the range of 0.0001 to 10 mol% in terms of palladium per mol of the halogen atom of the compound represented by the general formula (2) of the raw material. .

  When a palladium catalyst is used, phosphine may coexist as a catalyst component. Examples of the phosphine include trialkylphosphines such as triethylphosphine, tricyclohexylphosphine, triisopropylphosphine, tri-n-butylphosphine, triisobutylphosphine, trisec-butylphosphine, tri-tert-butylphosphine; Arylphosphines such as tri (o-tolyl) phosphine, tri (m-tolyl) phosphine, tri (p-tolyl) phosphine, BINAP, trimesitylphosphine, diphenylphosphinoethane, diphenylphosphinopropane, diphenylphosphinoferrocene, etc. Is mentioned. What is necessary is just to use the usage-amount of a phosphine in the range of 0.01-10 times mole with respect to a palladium compound.

  The palladium catalyst and phosphine may be added to the reaction system alone or may be prepared in the form of a complex and added in advance.

  The solvent used in the reaction is not particularly limited as long as it does not affect the reaction. For example, aromatic hydrocarbons such as benzene, toluene and xylene; ethers such as diethyl ether, tetrahydrofuran and 1,4-dioxane Nitriles such as acetonitrile, amides such as dimethylformamide, and sulfur-containing solvents such as dimethyl sulfoxide.

  These solvents are used alone or as a mixed solvent, and when used as a mixed solvent, they can be used in any ratio. The raw material, base and catalyst may be reacted after being completely dissolved in the reaction solvent, or may be reacted in a slurry state.

  The reaction is preferably performed under normal pressure and an inert gas atmosphere such as nitrogen or argon, but can be performed even under pressurized conditions.

  The reaction conditions are not particularly limited, but the reaction temperature may be selected from the range of 0 ° C. to the boiling point of the solvent, preferably from 20 ° C. to 150 ° C., and the reaction time is from several minutes to 72 hours.

  The method for isolating the polymer compound of the present invention is not particularly limited. If the product is precipitated from the reaction solvent, it can be isolated by filtration or centrifugation, and if dissolved in the reaction solvent, the solvent can be distilled off under reduced pressure or an appropriate solvent can be added. It is possible to adopt a method of precipitating and then filtering or centrifuging.

  When purification is required for the polymer compound of the present invention, a well-known method can be employed. For example, a recrystallization method, a reprecipitation method, a column chromatography method, washing with a solvent ( Sludge), activated carbon treatment and the like.

  When the polymer compound of the present invention is produced by the above production method or the like, the terminal portion of the polymer is represented by the general formula (21) derived from the compound represented by the general formula (2) as a raw material:

(In the formula, Z represents either Z ³ or Z ⁴ defined in the general formula (2), p represents either p3 or p4 defined in the general formula (2), and X represents the above general formula. (It is synonymous with X in Formula (2).)
And / or the general formula (31) derived from the compound represented by the general formula (3) which is the other raw material:

-N (Ar) -H (31)
(In the formula, Ar represents either Ar ¹ or Ar ^{2 in} the general formula (3).)
It is comprised by the substituent represented by these.

  In the polymer compound comprising the repeating unit represented by the general formula (1) of the present invention, the polymer terminal is represented by the substituent represented by the general formula (21) and / or the general formula (31). In addition, a polymer compound in which a substituent is converted is also included.

  Examples of the substituent obtained by converting the substituent represented by the general formula (21) include, for example, the general formula (22):

(In the formula, Z and p have the same meanings as Z and p in the general formula (21), and R ²¹ and R ²² each independently represent a hydrogen atom, a monovalent alkyl group, or a monovalent aromatic group. Show.)
The substituent represented by these can be mentioned.

  On the other hand, as a substituent obtained by converting the substituent represented by the general formula (31), for example, the general formula (32):

—N (Ar) —R ³¹ (32)
(In the formula, Ar has the same meaning as Ar in the general formula (31), and R ³¹ represents a monovalent alkyl group or a monovalent aromatic.)
The substituent represented by these can be mentioned.

The monovalent alkyl group for R ²¹ , R ²² and R ³¹ includes an unsubstituted or substituted linear, branched or cyclic alkyl group, preferably having 1 to 16 carbon atoms, particularly 1 ~ 8 is preferred.

The monovalent aromatic group of R ²¹ , R ²² , and R ³¹ includes unsubstituted and substituted aromatic groups, and the aromatic group includes aromatic hydrocarbon groups and aromatic heterocyclic groups. The 3-20 are preferable, and 3-16 are especially preferable.

Examples of R ²¹ , R ²² , and R ³¹ include the alkyl groups and aromatic groups exemplified for Z ¹⁰ . Of these groups, an aromatic hydrocarbon group is preferable, an unsubstituted aromatic hydrocarbon group is more preferable, and a phenyl group and a naphthyl group are particularly preferable.

  The polymer compound having the substituent represented by the general formula (22) at the polymer terminal is the polymer terminal portion represented by the general formula (21) and the general formula (23):

^{R 21 -NH-R 22 (23} )
^{(Wherein, R 21} and ^{R 22} has the same meaning as ^{R 21} and ^{R 22} in the general formula (22).)
It can manufacture by making it react with the compound represented by these.

  In addition, the polymer compound having a substituent represented by the general formula (32) at the polymer terminal is a polymer terminal portion represented by the general formula (31) and the general formula (33):

R ³¹ -X (33)
(In the formula, R ³¹ has the same meaning as R ³¹ in the general formula (32), and X has the same meaning as X in the general formula (2).)
It can manufacture by making it react with the compound represented by these.

  These reactions produce a polymer compound composed of the repeating unit represented by the general formula (1) of the present invention from the compound represented by the general formula (2) and the compound represented by the general formula (3). What is necessary is just to implement according to the reaction conditions at the time.

  Next, the organic electroluminescent element of the present invention will be described. The organic electroluminescent element of the present invention is formed by sandwiching at least one layer containing at least one polymer compound composed of a repeating unit represented by the general formula (1) between a pair of electrodes. An organic electroluminescent element is usually formed by sandwiching at least one light emitting layer containing at least one light emitting component between a pair of electrodes. A hole injection / transport layer and / or an electron injection containing a hole injection component as desired, considering the functional level of the hole injection and hole transport, electron injection and electron transport of the compound used in the light emitting layer. An electron injecting and transporting layer containing a transporting component can also be provided.

  For example, when the hole injection function, the hole transport function and / or the electron injection function, and the electron transport function of the compound used in the light emitting layer are good, the light emitting layer is a hole injection transport layer and / or an electron injection transport layer. As a type of element configuration that also serves as a single layer type element configuration. Further, when the light emitting layer is poor in the hole injection function and / or the hole transport function, a two-layer device configuration in which a hole injection transport layer is provided on the anode side of the light emitting layer, the light emitting layer has an electron injection function and / or Alternatively, when the electron transport function is poor, a two-layer device structure in which an electron injection transport layer is provided on the cathode side of the light emitting layer can be obtained. Furthermore, a three-layer device structure in which the light-emitting layer is sandwiched between a hole injecting and transporting layer and an electron injecting and transporting layer can be used.

  In addition, each of the hole injecting and transporting layer, the electron injecting and transporting layer, and the light emitting layer may have a single layer structure or a multilayer structure, and the hole injecting and transporting layer and the electron injecting and transporting layer The layer having an injection function and the layer having a transport function can be separately provided.

  In the organic electroluminescence device of the present invention, the polymer compound composed of the repeating unit represented by the general formula (1) is preferably used as a component of the hole injection transport layer and / or the light emitting layer. More preferably, it is used as a constituent of the transport layer.

  In the organic electroluminescent element of the present invention, the polymer compound composed of the repeating unit represented by the general formula (1) may be used alone or in combination.

  The configuration of the organic electroluminescent device of the present invention is not particularly limited. For example, (EL-1) anode / hole injection transport layer / light emitting layer / electron injection transport layer / cathode type device (FIG. 1). ), (EL-2) anode / hole injection transport layer / light emitting layer / cathode type device (FIG. 2), (EL-3) anode / light emitting layer / electron injection transport layer / cathode type device (FIG. 3), EL-4) Anode / light emitting layer / cathode type element (FIG. 4), and the like. Further, an EL (EL-5) anode / hole injection / transport layer / electron injection / transport layer / light-emitting layer / electron injection / transport layer / cathode-type device (FIG. 5) in which the light-emitting layer is sandwiched between electron injection / transport layers. You can also. The (EL-4) type element structure includes an element of a type in which a light emitting component is sandwiched between a pair of electrodes as a light emitting layer, (EL-6) a hole injection transport component as a light emitting layer, A device of a type in which a light emitting component and an electron injection component are mixed and sandwiched between a pair of electrodes (FIG. 6), (EL-7) a layer in which a hole injection transport component and a light emitting component are mixed as a light emitting layer Type element sandwiched between a pair of electrodes in a form (FIG. 7), (EL-8) type element sandwiched between a pair of electrodes in a single layer form in which a light emitting component and an electron injection component are mixed as a light emitting layer Any of (FIG. 8) may be sufficient.

  The organic electroluminescent device of the present invention is not limited to these device configurations, and each type of device can be provided with a plurality of hole injection / transport layers, light emitting layers, and electron injection / transport layers. Further, in each type of device, the hole injection / transport layer is disposed between the light emitting layer, the hole injection / transport component and the light emitting component mixed layer and / or the light emitting layer and the electron injection / transport layer between the light emitting component and the light emitting component. And a mixed layer of electron injecting and transporting components can be provided.

  A preferred organic electroluminescent element is an (EL-1) type element, an (EL-2) type element, an (EL-5) type element, an (EL-6) type element or an (EL-7) type element. More preferably, it is an (EL-1) type element, an (EL-2) type element or an (EL-7) type element.

  Hereinafter, the components of the organic electroluminescence device of the present invention will be described in detail. As an example, (EL-1) anode / hole injection / transport layer / light emitting layer / electron injection / transport layer / cathode type device shown in FIG. 1 will be described.

  In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injecting and transporting layer, 4 is a light emitting layer, 5 is an electron injecting and transporting layer, 6 is a cathode, and 7 is a power source.

  The organic electroluminescent element of the present invention is preferably supported by the substrate 1, and the substrate is not particularly limited, but a transparent or translucent substrate is preferable, and the material is soda lime glass, Examples thereof include glass such as borosilicate glass and transparent polymers such as polyester, polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethyl methacrylate, polypropylene, and polyethylene. Further, a substrate made of a translucent plastic sheet, quartz, transparent ceramics, or a composite sheet in which these are combined can also be used. Furthermore, for example, a color filter film, a color conversion film, and a dielectric reflection film can be combined with the substrate to control the emission color.

  As the anode 2, it is preferable to use a metal, an alloy or a conductive compound having a relatively large work function as an electrode material. Examples of the electrode material used for the anode include gold, platinum, silver, copper, cobalt, nickel, palladium, vanadium, tungsten, indium oxide (In 2 O 3), tin oxide (SnO 2), zinc oxide, and ITO (indium / tin / tin). Examples thereof include oxide (Indium Tin Oxide), polythiophene, and polypyrrole. These electrode materials may be used alone or in combination. For the anode, these electrode materials can be formed on the substrate by a method such as vapor deposition or sputtering. Further, the anode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the anode is preferably set to several hundred Ω or less, more preferably about 5 to 50 Ω. The thickness of the anode is generally about 5 to 1000 nm, more preferably about 10 to 500 nm, although it depends on the material of the electrode material used.

  The hole injection transport layer 3 is a layer containing a compound having a function of facilitating the injection of holes from the anode and a function of transporting the injected holes.

  The hole injecting and transporting layer of the electroluminescent device of the present invention comprises a polymer compound comprising a repeating unit represented by the general formula (1) and / or other compounds having a hole injecting and transporting function (for example, phthalocyanine derivatives, tria At least one kind of reelamine derivative, triarylmethane derivative, oxazole derivative, hydrazone derivative, stilbene derivative, pyrazoline derivative, polysilane derivative, polyphenylenevinylene and its derivative, polythiophene and its derivative, poly-N-vinylcarbazole, etc.) Can be formed. The compounds having a hole injecting and transporting function may be used alone or in combination.

  The organic electroluminescent element of the present invention preferably contains a polymer compound composed of a repeating unit represented by the general formula (1) in the hole injection transport layer. Examples of the compound having a hole injecting and transporting function other than the polymer compound composed of the repeating unit represented by the general formula (1) of the present invention that can be used in the organic electroluminescent device of the present invention include triarylamine derivatives. (For example, 4,4′-bis [N-phenyl-N- (4 ″ -methylphenyl) amino] -1,1′-biphenyl, 4,4′-bis [N-phenyl-N- (3 ″- Methylphenyl) amino] -1,1′-biphenyl, 4,4′-bis [N-phenyl-N- (3 ″ -methoxyphenyl) amino] -1,1′-biphenyl, 4,4′-bis [ N-phenyl-N- (1 ″ -naphthyl) amino] -1,1′-biphenyl, 3,3′-dimethyl-4,4′-bis [N-phenyl-N- (3 ″ -methylphenyl) amino ] -1,1'-biphenyl, 1, -Bis [4 '-[N, N-di (4 "-methylphenyl) amino] phenyl] cyclohexane, 9,10-bis [N- (4'-methylphenyl) -N- (4" -n-butyl) Phenyl) amino] phenanthrene, 3,8-bis (N, N-diphenylamino) -6-phenylphenanthridine, 4-methyl-N, N-bis [4 ", 4" '-bis [N', N '-Di (4-methylphenyl) amino] biphenyl-4-yl] aniline, N, N'-bis [4- (diphenylamino) phenyl] -N, N'-diphenyl-1,3-diaminobenzene, N , N′-bis [4- (diphenylamino) phenyl] -N, N′-diphenyl-1,4-diaminobenzene, 5,5 ″ -bis [4- (bis [4-methylphenyl] amino] phenyl- 2, 2 ': 5', 2 -Terthiophene, 1,3,5-tris (diphenylamino) benzene, 4,4 ', 4 "-tris (N-carbazolyl) triphenylamine, 4,4', 4" -tris [N, N-bis (4 "'-tert-butylbiphenyl-4" "-yl) amino] triphenylamine, 1,3,5-tris [N- (4'-diphenylamino] benzene, polythiophene and its derivatives, poly-N -Vinylcarbazole and its derivatives are more preferred.

  When a polymer compound composed of the repeating unit represented by the general formula (1) and another compound having a hole injection / transport function are used in combination, the repetition represented by the general formula (1) in the hole injection / transport layer The content of the polymer compound composed of units is preferably 0.1% by weight or more, more preferably 0.5 to 99.9% by weight, still more preferably 3 to 97% by weight.

In the hole injecting and transporting layer, a compound having a hole injecting and transporting function and an electron accepting compound may be used in combination. Examples of the electron-accepting compound include TBPAH (tris (4-bromophenyl) aminium hexachloroantimonate) described in JP-A No. 11-283750, FeCl ₃ , and tris (described in JP-A No. 2003-31365). Lewis acids such as boron compounds such as pentafluorophenyl) borane. When the electron accepting compound is used in combination, the content of the electron accepting compound is preferably in the range of 0.1 to 50% by weight with respect to the hole injecting and transporting layer.

  The light emitting layer 4 is a layer containing a compound having a function of injecting holes and electrons, a function of transporting them, and a function of generating excitons by recombination of holes and electrons.

  The light emitting layer can be formed using at least one polymer compound composed of the repeating unit represented by the general formula (1) and / or another compound having a light emitting function.

  Examples of the compound having a light emitting function other than the polymer compound composed of the repeating unit represented by the general formula (1) include an acridone derivative, a quinacridone derivative, a diketopyrrolopyrrole derivative, a polycyclic aromatic compound [for example, rubrene, Anthracene, tetracene, pyrene, perylene, chrysene, decacyclene, coronene, tetraphenylcyclopentadiene, pentaphenylcyclopentadiene, 9,10-diphenylanthracene, 9,10-bis (phenylethynyl) anthracene, 1,4-bis (9 ′ -Ethynylanthcenyl) benzene, 4,4'-bis (9 "-ethynylanthracenyl) biphenyl, dibenzo [f, f] diindeno [1,2,3-cd: 1 ', 2', 3'- lm] perylene derivatives], triarylamine derivatives (for example, compounds having a hole injecting and transporting function) And the above-mentioned compounds), organometallic complexes [for example, zinc of tris (8-quinolinolato) aluminum, bis (10-benzo [h] quinolinolato) beryllium, 2- (2′-hydroxyphenyl) benzothiazole Salt, zinc salt of 4-hydroxyacridine, zinc salt of 3-hydroxyflavone, beryllium salt of 5-hydroxyflavone, aluminum salt of 5-hydroxyflavone], stilbene derivative [eg 1,1,4,4-tetraphenyl -1,3-butadiene, 4,4′-bis (2,2-diphenylvinyl) biphenyl, 4,4′-bis [(1,1,2-triphenyl) ethenyl] biphenyl], coumarin derivatives (for example, Coumarin 1, Coumarin 6, Coumarin 7, Coumarin 30, Coumarin 106, Coumarin 13 , Coumarin 151, Coumarin 152, Coumarin 153, Coumarin 307, Coumarin 311, Coumarin 314, Coumarin 334, Coumarin 338, Coumarin 343, Coumarin 500), pyran derivatives (eg DCM1, DCM2), oxazone derivatives (eg Nile Red) , Benzothiazole derivatives, benzoxazole derivatives, benzimidazole derivatives, pyrazine derivatives, cinnamate derivatives, poly-N-vinylcarbazole and derivatives thereof, polythiophene and derivatives thereof, polyphenylene and derivatives thereof, polyfluorene and derivatives thereof, polyphenylene vinylene And its derivatives, polybiphenylene vinylene and its derivatives, polyterphenylene vinylene and its derivatives, polynaphthylene vinylene and its derivatives Derivatives, polythienylenevinylene and its derivatives. Examples of the compound having a light emitting function other than the polymer compound composed of the repeating unit represented by the general formula (1) include an acridone derivative, a quinacridone derivative, a polycyclic aromatic compound, a triarylamine derivative, an organometallic complex, and a stilbene derivative. Preferably, a polycyclic aromatic compound and an organometallic complex are more preferable.

  The organic electroluminescent element of the present invention preferably contains a polymer compound composed of a repeating unit represented by the general formula (1) in the light emitting layer.

  When the polymer compound composed of the repeating unit represented by the general formula (1) and the compound having a light emitting function other than the polymer compound composed of the repeating unit represented by the general formula (1) are used in combination, the compound occupies in the light emitting layer. The ratio of the polymer compound composed of the repeating unit represented by the general formula (1) is preferably adjusted to 0.001 to 99.999% by weight.

The light-emitting layer can also be formed from a host compound and a guest compound (dopant) as described in J. Appl. Phys., 65 , 3610 (1989) and Japanese Patent Application Laid-Open No. 5-214332.

  The high molecular compound which consists of a repeating unit represented by General formula (1) can also be used as a host compound of a light emitting layer, and can also be used as a guest compound. In the case of forming a light emitting layer using a polymer compound composed of the repeating unit represented by the general formula (1) as a host compound, examples of the guest compound include compounds having other light emitting functions. Polycyclic aromatic compounds are preferred.

When the light emitting layer is formed using the polymer compound composed of the repeating unit represented by the general formula (1) as a host compound, the guest compound is compared to the polymer compound composed of the repeating unit represented by the general formula (1). The light emitting layer is preferably represented by the general formula (1): 0.001 to 40% by weight, more preferably 0.01 to 30% by weight, and still more preferably 0.1 to 20% by weight. It can be formed using a polymer compound composed of units as a host material and a compound having a light emitting function other than the polymer compound composed of repeating units represented by the general formula (1) as at least one guest material.

  The organic electroluminescent element of the present invention preferably contains a polymer compound composed of a repeating unit represented by the general formula (1) as a host material in the light emitting layer.

  When the polymer compound composed of the repeating unit represented by the general formula (1) is used as a host material in combination with another compound having a light emitting function, the repeating unit represented by the general formula (1) in the light emitting layer is used. The resulting polymer compound is preferably 40.0% to 99.9%, more preferably 60.0 to 99.9% by weight.

  The amount of the guest material used is 0.001 to 40% by weight, preferably 0.05 to 30% by weight, more preferably 0 to the polymer compound composed of the repeating unit represented by the general formula (1). .1 to 20% by weight. Moreover, a guest material may be used independently and may be used together.

  When the light emitting layer is formed using the polymer compound composed of the repeating unit represented by the general formula (1) as a guest material, the host material includes a polycyclic aromatic compound, a triarylamine derivative, an organometallic complex, and Stilbene derivatives are preferred, and polycyclic aromatic compounds and organometallic complexes are more preferred.

  When using the high molecular compound which consists of a repeating unit represented by General formula (1) as a guest material, Preferably, the high molecular compound which consists of a repeating unit represented by General formula (1) is 0.001-40. % By weight, more preferably 0.01 to 30% by weight, still more preferably 0.1 to 20% by weight.

  The electron injection / transport layer 5 is a layer containing a compound having a function of facilitating injection of electrons from the cathode and / or a function of transporting injected electrons.

  Examples of the compound having an electron injecting function used in the electron injecting and transporting layer include organometallic complexes, oxadiazole derivatives, triazole derivatives, triazine derivatives, perylene derivatives, quinoline derivatives, quinoxaline derivatives, diphenylquinone derivatives, nitro-substituted fluorenones. Derivatives, thiopyrandioxide derivatives and the like. Examples of organometallic complexes include organoaluminum complexes such as tris (8-quinolinolato) aluminum, organic beryllium complexes such as bis (10-benzo [h] quinolinolato) beryllium, beryllium salts of 5-hydroxyflavone, 5- Examples thereof include an aluminum salt of hydroxyflavone. Preferred is an organoaluminum complex, and more preferred is an organoaluminum complex having an unsubstituted or substituted 8-quinolinolate ligand. Examples of the organoaluminum complex having an unsubstituted or substituted 8-quinolylate ligand include compounds represented by general formula (a) to general formula (c).

(Q) ₃ -Al (a)
(Wherein Q represents an unsubstituted or substituted 8-quinolinolato ligand)
(Q) ₂ -Al-OL '(b)
(In the formula, Q represents an unsubstituted or substituted 8-quinolinolate ligand, OL ′ represents a phenolate ligand, and L ′ represents a hydrocarbon group having 6 to 24 carbon atoms having a phenyl group. To express)
(Q) _2- Al-O-Al- (Q) ₂ (c)
(Wherein Q represents an unsubstituted or substituted 8-quinolinolato ligand)

Specific examples of organoaluminum complexes having an unsubstituted or substituted 8-quinolinolato ligand include, for example, tris (8-quinolinolato) aluminum, tris (4-methyl-8-quinolinolato) aluminum, tris (5-methyl). -8-quinolinolato) aluminum, tris (3,4-dimethyl-8-quinolinolato) aluminum, tris (4,5-dimethyl-8-quinolinolato) aluminum, tris (4,6-dimethyl-8-quinolinolato) aluminum,
Bis (2-methyl-8-quinolinolato) (phenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-methylphenolato) aluminum, bis (2-methyl-8-quinolinolato) (3-methylphenolate) ) Aluminum, bis (2-methyl-8-quinolinolato) (4-methylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2-phenylphenolato) aluminum, bis (2-methyl-8-quinolinolato) ) (3-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,3-dimethylphenolate) aluminum, Bis (2-methyl-8-quinolinolate) ( , 6-Dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,4-dimethylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum Bis (2-methyl-8-quinolinolato) (3,5-di-tert-butylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,6-diphenylphenolato) aluminum, bis (2 -Methyl-8-quinolinolato) (2,4,6-triphenylphenolate) aluminum, bis (2-methyl-8-quinolinolato) (2,4,6-trimethylphenolato) aluminum, bis (2-methyl- 8-quinolinolate) (2,4,5,6-tetramethylphenolate) aluminum, bi (2-methyl-8-quinolinolato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinolato) (2-naphtholato) aluminum, bis (2,4-dimethyl-8-quinolinolato) (2-phenyl) Phenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3-phenylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (4-phenylphenolate) aluminum, bis (2 , 4-dimethyl-8-quinolinolato) (3,5-dimethylphenolate) aluminum, bis (2,4-dimethyl-8-quinolinolato) (3,5-di-tert-butylphenolate) aluminum,
Bis (2-methyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-8-quinolinolato) aluminum, bis (2,4-dimethyl-8-quinolinolato) aluminum-μ-oxo-bis (2, 4-dimethyl-8-quinolinolato) aluminum, bis (2-methyl-4-ethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-ethyl-8-quinolinolato) aluminum, bis (2- Methyl-4-methoxy-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-4-methoxy-8-quinolinolato) aluminum, bis (2-methyl-5-cyano-8-quinolinolato) aluminum-μ- Oxo-bis (2-methyl-5-cyano-8-quinolinolato) aluminum, bi (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum-μ-oxo-bis (2-methyl-5-trifluoromethyl-8-quinolinolato) aluminum.

  A compound having an electron injection function may be used alone or in combination.

  As the cathode 6, it is preferable to use a metal, an alloy or a conductive compound having a relatively small work function as an electrode material. Examples of the electrode material used for the cathode include lithium, lithium-indium alloy, sodium, sodium-potassium alloy, calcium, magnesium, magnesium-silver alloy, magnesium-indium alloy, indium, ruthenium, titanium, manganese, yttrium, and aluminum. , Aluminum-lithium alloy, aluminum-calcium alloy, aluminum-magnesium alloy, lithium fluoride, and graphite thin film. These electrode materials may be used alone or in combination.

  For the cathode, these electrode materials can be formed on the electron injecting and transporting layer by, for example, vapor deposition, sputtering, ion vapor deposition, ion plating, or cluster ion beam.

  The cathode may have a single layer structure or a multilayer structure. The sheet electrical resistance of the cathode is preferably several hundred Ω or less. The thickness of the cathode is usually 5 to 1000 nm, preferably 10 to 500 nm, although it depends on the electrode material used. In order to take out light emitted from the organic electroluminescence device of the present invention with high efficiency, at least one of the anode and the cathode is preferably transparent or translucent, and generally has a transmittance of emitted light of 70% or more. Thus, it is preferable to set the material and thickness of the anode or cathode.

  The organic electroluminescent device of the present invention may contain a singlet oxygen quencher in at least one of the hole injection transport layer, the light emitting layer, and the electron injection transport layer. Although it does not specifically limit as a singlet oxygen quencher, For example, rubrene, a nickel complex, diphenylisobenzofuran is mentioned, Preferably it is rubrene.

The layer containing the singlet oxygen quencher is not particularly limited, but is preferably a light emitting layer or a hole injection transport layer, and more preferably a hole injection transport layer. When a singlet oxygen quencher is contained in the hole injecting and transporting layer, it may be uniformly contained in the hole injecting and transporting layer, and a layer adjacent to the hole injecting and transporting layer (for example, a light emitting layer, a light emitting function). May be contained in the vicinity of the electron injecting and transporting layer).
The content of the singlet oxygen quencher is 0.01 to 50% by weight, preferably 0.05 to 30% by weight, based on the total amount constituting the layer to be contained (for example, hole injection transport layer). Preferably, it is 0.1 to 20% by weight.

The formation method of the hole injection transport layer, the light emitting layer, and the electron injection transport layer is not particularly limited. For example, a vacuum deposition method, an ionization deposition method, a solution coating method (for example, a spin coating method, a casting method, Micro gravure coating method, gravure coating method, bar coating method, wire bar coating method, dip coating method, roll coating method, spray coating method, Langmuir-Blodget method, screen printing method, flexographic printing method, offset printing method, inkjet printing Method). When forming each layer such as a hole injecting and transporting layer, a light emitting layer, and an electron injecting and transporting layer by a vacuum deposition method, the conditions for vacuum deposition are not particularly limited, but a vacuum of about 10 ⁻³ Pa or less is usually used. Below, it is preferable to carry out at a boating temperature (deposition source temperature) of about 50 to 500 ° C., a substrate temperature of about −50 to 300 ° C., and a deposition rate of about 0.005 to 50 nm / sec. In this case, each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer is preferably formed continuously under vacuum. It becomes possible to manufacture an organic electroluminescent element excellent in various characteristics by forming continuously. When each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer is formed using a plurality of compounds by vacuum deposition, the temperature of each boat containing the compounds is individually controlled and co-evaporated. It is preferable to do.

  When each layer is formed by a solution coating method, a component for forming each layer or its component and a binder resin are dissolved or dispersed in a solvent to obtain a coating solution. Examples of the solvent include organic solvents (hexane solvents such as hexane, octane, decane, toluene, xylene, ethylbenzene, 1-methylnaphthalene, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dichloromethane, chloroform, etc. , Halogenated hydrocarbon solvents such as tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, ethyl lactate, methanol, propanol, butanol , Pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, alcohol solvents such as ethylene glycol, dibutyl ether, teto Ether solvents such as hydrofuran, dioxane, dimethoxyethane, anisole, N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, dimethyl sulfoxide And polar solvents) and water. A solvent may be used independently and may be used together. When the components of the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer are dispersed in a solvent, for example, a ball mill, a sand mill, a paint shaker, an attritor, or a homogenizer is used as a dispersion method. Can be used.

  Examples of the binder resin that can be used in each layer such as a hole injection transport layer, a light emitting layer, and an electron injection transport layer include poly-N-vinyl carbazole, polyarylate, polystyrene, polyester, polysiloxane, polymethyl methacrylate, poly Methyl acrylate, polyether, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, polyphenylene oxide, polyethersulfone, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyphenylene vinylene and derivatives thereof, polyfluorene and derivatives thereof, Examples thereof include polymer compounds such as polythienylene vinylene and its derivatives. Binder resins may be used alone or in combination. The concentration of the coating solution is not particularly limited, but can be set to a concentration range suitable for producing a desired thickness by the coating method to be carried out, usually 0.1 to 50% by weight, preferably , 0.5 to 30% by weight. When the binder resin is used, the amount used is not particularly limited, but it is usually based on the total amount of the binder resin and the components forming each layer such as the hole injection transport layer, the light emitting layer, and the electron injection transport layer. It is used such that the content of the binder resin is 5 to 99.9% by weight, preferably 10 to 99% by weight (relative to the total amount of each component in the case of forming a single-layer element).

  The thickness of each layer such as the hole injecting and transporting layer, the light emitting layer, and the electron injecting and transporting layer is not particularly limited, but is usually 5 nm to 5 μm.

  In addition, the organic electroluminescent device of the present invention produced under the above conditions is provided with a protective layer (sealing layer) for the purpose of preventing contact with oxygen, moisture, etc. For example, it can be protected by enclosing it in paraffin, liquid paraffin, silicon oil, fluorocarbon oil, zeolite-containing fluorocarbon oil). Examples of the material used for the protective layer include organic polymer materials (for example, fluorine resin, epoxy resin, silicone resin, epoxy silicone resin, polystyrene, polyester, polycarbonate, polyamide, polyimide, polyamideimide, polyparaxylene, polyethylene, Polyphenylene oxide), inorganic materials (for example, diamond thin film, amorphous silica, electrically insulating glass, metal oxide, metal nitride, metal carbide, metal sulfide), and photocurable resin. The material used for the protective layer may be used alone or in combination. The protective layer may have a single layer structure or a multilayer structure.

  Moreover, the organic electroluminescent element of this invention can also provide a metal oxide film (for example, aluminum oxide film) and a metal fluoride film as a protective film in an electrode.

  The organic electroluminescent element of the present invention can also be provided with an interface layer (intermediate layer) on the surface of the anode. Examples of the material for the interface layer include organic phosphorus compounds, polysilanes, aromatic amine derivatives, and phthalocyanine derivatives.

  Furthermore, the surface of an electrode, for example, an anode, can be used by treating the surface with acid, ammonia / hydrogen peroxide, or plasma.

  The organic electroluminescent element of the present invention can be usually used as a DC drive type element, but can also be used as an AC drive type element. The organic electroluminescence device of the present invention may be a segment type, a passive drive type such as a simple matrix drive type, or an active drive type such as a TFT (thin film transistor) type or an MIM (metal-insulator-metal) type. It may be. The driving voltage is usually 2 to 30V. The organic electroluminescent element of the present invention includes a panel-type light source (for example, a backlight for a clock, a liquid crystal panel, etc.), various light emitting elements (for example, an alternative to a light emitting element such as an LED), and various display elements (for example, information display Element (PC monitor, mobile phone / mobile terminal display element)], various signs, various sensors, and the like.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated further in detail, this invention is not limited to a following example. In addition, the molecular weight in each Example shows the number average molecular weight of polystyrene conversion. The glass transition temperature was measured with a differential scanning calorimeter.

Production of polymer compound consisting of repeating unit of formula (51) (without polymer terminal treatment) N, N′-diphenyl-1,4-phenylenediamine 5.31 g, 2,5-bis (4′-bromophenyl) -A mixture of 11.15 g of 3,4-diphenylthiophene, 4.86 g of sodium tert-butoxide and 300 mL of o-xylene was charged with 92 mg of tris (dibenzylideneacetone) dipalladium and 162 mg of tritert-butylphosphine under nitrogen flow. Xylene (2 mL) solution was added. The mixture was stirred at 130 ° C. for 20 hours under a nitrogen atmosphere, and insoluble materials were removed by filtration while hot. The filtrate was returned to room temperature and discharged into 600 mL of acetone, and the precipitate was collected by filtration. The obtained solid was washed with acetone and water and dissolved in toluene. This solution was discharged into acetone, and the precipitate was collected by filtration and dried under reduced pressure to obtain 11.56 g of the objective compound as a yellow solid.
Molecular weight: 12700
Glass transition temperature: 250 ° C
UV (λmax): 382 (CHCl ₃ )

Production of polymer compound consisting of repeating unit of formula (52) (polymer end untreated) 3.43 g of N, N′-diphenylbenzidine, 2,5-bis (4′-bromophenyl) -3,4-diphenyl To a mixture of 5.57 g of thiophene, 2.43 g of sodium tert-butoxide and 200 mL of o-xylene, a solution of 46 mg of tris (dibenzylideneacetone) dipalladium and 81 mg of tritert-butylphosphine in o-xylene (1 mL) was added under a nitrogen stream. Added. The mixture was stirred at 120 ° C. for 3 hours under a nitrogen atmosphere. The reaction solution was returned to room temperature and discharged into 500 mL of acetone, and the precipitate was collected by filtration. The obtained solid was washed with acetone and water and dissolved in chloroform by heating. The insoluble material was removed by filtration, and the filtrate was discharged into methanol. The precipitate was collected by filtration and dried under reduced pressure to obtain 2.85 g of the target compound as a yellow solid.
Molecular weight: 12900
Glass transition temperature: 282 ° C
UV (λmax): 382 (CHCl ₃ )

Manufacture of high molecular compound (polymer terminal unprocessed) consisting of repeating unit of formula (53) 3.75 g of N, N′-di (2-naphthyl) -1,4-phenylenediamine, 2,5-bis (4 '-Bromophenyl) -3,4-diphenylthiophene 5.57 g, sodium tert-butoxide 2.43 g and o-xylene 300 mL in a nitrogen stream under a nitrogen stream, 46 mg of tris (dibenzylideneacetone) dipalladium and tritert-butyl A solution of 81 mg of phosphine in o-xylene (1 mL) was added. After stirring with heating at 120 ° C. for 3 hours under a nitrogen atmosphere, the reaction solution was returned to room temperature and discharged into 1000 mL of acetone, and the precipitate was collected by filtration. The obtained solid was washed with acetone and water, and dried under reduced pressure to obtain 7.52 g of the objective compound as a yellowish green solid.
Molecular weight: 10100
Glass transition temperature: 256 ° C
UV (λmax): 387 (tetrachloroethane)

Production of polymer compound consisting of repeating unit of formula (54) (polymer end untreated) [1] Synthesis of N, N′-bis (4-hexylphenyl) benzidine 4,4′-diiodobiphenyl 16.57 g , 4-hexylaniline 18.09 g, 1,1′-bis (diphenylphosphino) ferrocene palladium dichloride: 1.80 g of dichloromethane complex, 3.33 g of 1,1′-bis (diphenylphosphino) ferrocene, sodium tert-butoxide A mixture of 10.12 g and 600 mL of tetrahydrofuran was heated and stirred at 65 ° C. for 3 hours. The insoluble material was removed by filtration, the filtrate was concentrated to dryness, washed with methanol and water, and dried under reduced pressure to give 15.42 g of the desired product as a pale yellow solid.
[2] Synthesis of polymer compound consisting of repeating unit of formula (54) (without polymer terminal treatment) N, N′-bis (4-hexylphenyl) benzidine 10.14 g, 2,5-bis (4′- To a mixture of 11.10 g of bromophenyl) -3,4-diphenylthiophene, 4.86 g of sodium tert-butoxide and 200 mL of o-xylene under a nitrogen stream, 92 mg of tris (dibenzylideneacetone) dipalladium and 162 mg of tritert-butylphosphine Of o-xylene (2 mL) was added. The mixture was stirred at 140 ° C. for 10 hours under a nitrogen atmosphere, and insoluble materials were removed by filtration while hot. The filtrate was returned to room temperature and discharged into 600 mL of acetone, and the precipitate was collected by filtration. The precipitate was dissolved in chloroform, washed with water, and separated to obtain a chloroform layer. The solution was dried over anhydrous magnesium sulfate and the solvent was distilled off. The concentrated residue was washed with acetone and dried under reduced pressure to obtain 15.05 g of the objective compound as a yellow solid.
Molecular weight: 35900
Glass transition temperature: 191 ° C
UV (λmax): 391 (CHCl ₃ )
Bromine content: 190ppm

Production of polymer compound consisting of repeating unit of formula (54) (compound obtained by converting halogen terminal of polymer with diphenylamine) 24 mg of diphenylamine, 5.00 g of the compound obtained in Example 4, 15.5 mg of sodium tert-butoxide and To a mixture of 70 mL of o-xylene, a solution of 0.6 mg of tris (dibenzylideneacetone) dipalladium and 1.1 mg of tritert-butylphosphine was added in a nitrogen stream. The mixture was stirred at 145 ° C. for 6 hours under a nitrogen atmosphere, and the reaction solution was returned to room temperature. 70 mL of o-xylene and 150 mL of water were added, and the organic layer obtained by liquid separation was discharged into an acetone-water mixture. The precipitated solid was dissolved in chloroform, and this solution was discharged into acetone. The obtained precipitate was collected by filtration and dried under reduced pressure to obtain 4.03 g of the objective compound as a yellow solid.
Molecular weight: 38900
Glass transition temperature: 191 ° C
UV (λmax): 389 nm (CHCl ₃ )
Bromine content: 10ppm or less

  The repeating unit of the polymer compound produced in Examples 1 to 5 is shown below.

Production of Organic Electroluminescent Device A glass substrate having an ITO transparent electrode (anode) having a thickness of 200 nm was subjected to ultrasonic cleaning using a neutral detergent, Semico Clean (manufactured by Furuuchi Chemical), ultrapure water, acetone, and ethanol. The substrate was dried with nitrogen gas and further UV / ozone cleaned. First, a chloroform solution of the polymer compound obtained in Example 4 (a solution obtained by dissolving 20 mg of a polymer compound in 4 mL of chloroform was added to a chloroform solution of 5 g / L tris (pentafluorophenyl) borane) on an ITO transparent electrode. (4 mL added solution) was formed by spin coating with a thickness of 27 nm, and dried under reduced pressure (100 ° C., 30 minutes) on a hot plate to form a layer. Next, this glass substrate was fixed to a substrate holder of a vapor deposition apparatus, and the vapor deposition tank was depressurized to 3 × 10 ⁻⁴ Pa. N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine was deposited at a deposition rate of 0.2 nm / sec to a thickness of 40 nm, and then tris (8-quinolinolato) aluminum was deposited at a deposition rate of 0. Vapor deposition was performed at a thickness of 50 nm at 2 nm / sec. Further, lithium fluoride was deposited at a thickness of 0.5 nm at 0.2 nm / sec. Aluminum was vapor-deposited thereon as a cathode to produce an organic electroluminescent device. In addition, vapor deposition was implemented, maintaining the pressure reduction state of a vapor deposition tank. A DC voltage was applied to the produced organic electroluminescence device, and the organic electroluminescence device was continuously driven at a constant current density of 10 mA / cm ^{2 in} a dry atmosphere at 50 ° C. Initially, green light emission of 3.7 V and luminance of 217 cd / m ² was confirmed. The 30% luminance decay time was 350 hours.

  The device was allowed to stand at 100 ° C. for 1 hour, and it was confirmed that there was no significant change in light emission characteristics.

Evaluation of film forming property Using a chloroform solution of the polymer compound obtained in Example 4 (a solution in which 20 mg of the polymer compound was dissolved in 4 mL of chloroform) was formed on a glass substrate with a thickness of 50 nm by a spin coating method. When a film obtained by drying under reduced pressure (100 ° C., 30 minutes) on a hot plate was observed, a uniform film was formed. From this, it was found that this compound is excellent in amorphous stability.

[Comparative Example 1]
Evaluation of film formability In Example 7, instead of the compound obtained in Example 4, a film was formed using a polymer compound consisting of a repeating unit represented by the formula (61) (commercial compound of American Dye Source). A part of the crystallized portion was observed.

It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element. It is a cross-sectional schematic diagram of an example of an organic electroluminescent element.

Explanation of symbols

1: Substrate 2: Anode 3: Hole injection / transport layer 3a: Hole injection / transport component 4: Light emitting layer 4a: Light emitting component 5: Electron injection / transport layer 5 ": Electron injection / transport layer 5a: Electron injection / transport component 6: Cathode 7: Power supply

Claims (10)

General formula (1):

^(Wherein, Z 1 to Z ⁴ represents a substituent, p1 and p2 represents an integer of 0 to 5, p3 and p4 is an integer of 0 to 4, Ar ¹ and Ar ² are monovalent aromatic And Y represents a divalent aromatic group.)
The high molecular compound which consists of a repeating unit represented by these. In the general formula (1), Z ¹ and Z ² , Z ³ and Z ⁴ , p 1 and p 2, p 3 and p ⁴ are simultaneously the same, and Ar ¹ and Ar ² are the same monovalent aromatic hydrocarbon The polymer compound according to claim 1, wherein Y is a divalent aromatic hydrocarbon group.   An organic electroluminescence device comprising at least one layer containing at least one polymer compound comprising a repeating unit represented by the general formula (1) according to claim 1 or 2 between a pair of electrodes.   The organic electroluminescence device according to claim 3, wherein the layer containing the polymer compound composed of the repeating unit represented by the general formula (1) according to claim 1 or 2 is a charge injection transport layer.   The organic electroluminescent device according to claim 4, wherein the charge injection transport layer is a hole injection layer.   6. The organic electroluminescent device according to claim 5, wherein the charge injection transport layer is a hole transport layer.   The organic electroluminescent element according to claim 3, wherein the layer containing the polymer compound composed of the repeating unit represented by the general formula (1) according to claim 1 or 2 is a light emitting layer.   The organic electroluminescent element according to claim 3, further comprising a light emitting layer between the pair of electrodes.   The organic electroluminescent element according to claim 3, further comprising an electron injecting and transporting layer between the pair of electrodes. General formula (2):

^(Wherein, Z ¹ to Z 4, it is p1 to p4, ^Z 1 ^{to Z} 4 in the general formula (1) has the same meaning as p1 to p4, X is a halogen atom.)
A compound represented by formula (3):

H-N (Ar < ¹ >)-Y-N (Ar < ² >)-H (3)

^(Wherein, Ar 1 to Ar ² and Y are as defined ^Ar 1 to Ar ² and Y in the general formula (1).)
A method for producing a polymer compound comprising a repeating unit represented by the general formula (1) according to claim 1, wherein the compound represented by formula (1) is polymerized in the presence of a base.

Images