JP2006348274A - Macromolecular composition for organic electroluminescence - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a macromolecular composition for organic electroluminescence(EL) enabling layer structure to be easily made and thus enabling organic EL devices of high performances such as efficiency to be given. <P>SOLUTION: The macromolecular composition for organic EL comprises a macromolecular material as a charge transport material or luminescent element and a crosslinking agent, wherein the crosslinking agent contains no aromatic ring. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polymer composition for organic electroluminescence.

An organic electroluminescence element (organic EL element) is a general term for an element using an organic compound as a light emitting material or a charge transport material of a light emitting layer. In the production of an organic EL element, a method of wet-coating a solution of a polymer material is superior in productivity as compared with a method of depositing low molecules.
However, when a laminated structure is formed by wet coating, there is a problem that a layer applied earlier is dissolved in a solvent contained in a layer to be applied later, and the laminated structure cannot be created. Therefore, a method of making the solvent insoluble by crosslinking the layer has been proposed.
As one of the methods, there is a method in which a crosslinking group is synthetically attached to a polymer compound itself having light emitting property and charge transporting property (see Patent Documents 1 to 3). However, as in these prior documents, the synthesis process is complicated in order to synthetically add a crosslinking group to the polymer compound itself having light emitting property and charge transporting property.
Further, in Patent Documents 4 and 5, a low molecular compound having a light emitting property and a charge transporting property and a polymer compound having a crosslinking group are mixed, or a polymer compound having a light emitting property and a charge transporting property is In addition, a polymer compound having a crosslinking group or a low molecular compound having a crosslinking group represented by aromatic bisazide is mixed as a crosslinking agent. However, if the crosslinking agent having a crosslinking group has an aromatic ring, the light emitting property and charge transporting property inherent to the light emitting material and charge transporting material may adversely affect.
As another method other than crosslinking, there is a method using solutions of different polarities in adjacent layers. For example, in a polymer organic EL, a method is generally used in which water-soluble PEDOT: PSS is used for the hole injection layer so that it does not dissolve even when an oil-soluble light emitting layer is applied to the upper layer. However, the performance of the obtained device was not sufficient.

US6107452 US2002 / 106529 (Japanese Patent Laid-Open No. 2002-170667) WO96 / 20253 (Special Table 10-511718) WO2002 / 10129 (Special Table 2004-505169) WO2004 / 100282

  An object of the present invention is to provide a polymer composition for organic EL that can easily form a layer structure and can provide an organic EL element excellent in element performance such as efficiency.

That is, the present invention is a polymer composition for organic electroluminescence comprising a polymer material as a charge transport material or a light emitter and a crosslinking agent, wherein the crosslinking agent does not contain an aromatic ring. A polymer composition is provided.
Moreover, this invention relates to the organic electroluminescent element created using the said polymer composition.

  The polymer composition of the present invention can easily form a layer structure, and can provide an organic EL device excellent in device performance. In addition, organic EL elements created using them are preferably used in devices such as curved or flat light sources for liquid crystal display backlights or illumination, segment type display elements, dot matrix flat panel displays, etc. it can.

  The polymer composition of the present invention includes a charge transport material or a polymer material as a light emitter (hereinafter also referred to as a polymer charge transport material or a polymer light emitter, respectively), and further includes a crosslinking agent having no aromatic ring. It is characterized by including.

The crosslinking agent refers to a monomer compound having a substituent that can be polymerized by the action of heat, light, and a thermal polymerization initiator or a photopolymerization initiator. The polymerizable substituent (crosslinking group) represents a substituent that can form a compound by forming a bond between two or more molecules by causing a polymerization reaction. Since the crosslinking agent used in the present invention does not have an aromatic ring, the crosslinking group does not have an aromatic ring.
Examples of such a crosslinking group include a vinyl group, an acetylene group, a butenyl group, an acrylic group, an acrylate group, an acrylamide group, a methacryl group, a methacrylate group, a methacrylamide group, a vinyl ether group, a vinylamino group, a silanol group, and a small member. Examples include a group having a ring (for example, a cyclopropyl group, a cyclobutyl group, an epoxy group, an oxetane group, a diketene group, and an episulfide group), a lactone group, a lactam group, or a group containing a structure of a siloxane derivative.
In addition to the above groups, combinations of groups capable of forming an ester bond or an amide bond can also be used. For example, a combination of an ester group and an amino group, an ester group and a hydroxyl group, or the like.
As the crosslinking agent, among them, a polyfunctional monomer having two or more functions (having two or more crosslinking groups), preferably five or more functions (having five or more crosslinking groups) is excellent in curability and is preferably used. .
As the crosslinking agent, a monomer having a (meth) acrylate group as a crosslinking group (that is, (meth) acrylate. (Meth) acrylate is a general term for acrylate and methacrylate) is preferable. More preferred is (meth) acrylate.
Specific examples of the monofunctional monomer having a (meth) acrylate group include 2-ethylhexyl carbitol acrylate and 2-hydroxyethyl acrylate. Specific examples of the bifunctional monomer having a (meth) acrylate group include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di Examples include (meth) acrylate and 3-methylpentanediol di (meth) acrylate. Specific examples of other polyfunctional monomers having a (meth) acrylate group include trifunctional (meth) acrylates such as trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate; pentaerythritol tetra (meth) Tetrafunctional (meth) acrylate such as acrylate, pentafunctional (meth) acrylate such as dipentaerythritol penta (meth) acrylate, hexafunctional such as dipentaerythritol hexa (meth) acrylate, trispentaerythritol octa (meth) acrylate The above (meth) acrylate etc. are mentioned. Among them, bifunctional or higher, preferably pentafunctional or higher (meth) acrylate, more preferably dipentaerythritol penta or hexaacrylate, or tripentaerythritol octaacrylate, more preferably dipentaerythritol hexaacrylate or tripenta. Erythritol octaacrylate is excellent in curability and is preferably used. In addition, about a crosslinking agent, it describes in the 17th-56th pages of a photopolymer handbook (Industry Investigation Committee, 1989), for example.

The crosslinking agent is usually in the range of usually 1 to 99 parts by weight, preferably 1 to 60 parts by weight, more preferably 5 to 50 parts by weight with respect to 100 parts by weight of the total amount of the polymer charge transport material or polymer light emitter. Contained. When the content of the crosslinking agent is in the range of 1 to 60 parts by mass based on the above criteria, the smoothness of the coating film tends to be favorable, which is preferable.
These crosslinking agents can be used alone or in combination of two or more.

  The polymer composition of the present invention may contain a photopolymerization initiator. Examples of the photopolymerization initiator include an active radical generator that generates an active radical when irradiated with light, and an acid generator that generates an acid. Examples of the active radical generator include acetophenone photopolymerization initiators, benzoin photopolymerization initiators, benzophenone photopolymerization initiators, thioxanthone photopolymerization initiators, and triazine photopolymerization initiators.

  In some cases, the polymer charge transport material or the polymer light emitter itself generates a radical by light and functions as a photopolymerization initiator. In such a case, it is not necessary to add a photopolymerization initiator.

  As the acetophenone photopolymerization initiator, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2 -Hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one, 2-benzyl-2-dimethylamino- Examples include oligomers of 1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, and the like.

  Examples of the benzoin photopolymerization initiator include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether. Examples of the benzophenone photopolymerization initiator include benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′, 4,4′-tetra (tert-butyl). Peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

  Examples of the thioxanthone photopolymerization initiator include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, and the like.

  Examples of the triazine photopolymerization initiator include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- ( 4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4 -Methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2 , 4-Bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (4- Diethylamino-2-methylphenol Nyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, and the like. .

  Examples of active radical generators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biphenyl. Imidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compounds, and the like can also be used. A commercially available thing can also be used as an active radical generator. Examples of commercially available photopolymerization initiators include trade name “Irgacure-907” (acetophenone photopolymerization initiator, manufactured by CIBA-GEIGY).

  Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4-acetoxyphenyl methyl benzyl Onium salts such as sulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, triphenylsulfonium hexafluoroantimonate, diphenyliodonium p-toluenesulfonate, diphenyliodonium hexafluoroantimonate, nitrobenzyl tosylate, benzoin Tosylate can be mentioned.

  Among the compounds described above as active radical generators, there are compounds that generate an acid simultaneously with active radicals. For example, triazine photopolymerization initiators are also used as acid generators.

  These photopolymerization initiators can be used alone or in combination of two or more.

  The polymer composition of the present invention may contain a photopolymerization initiation aid. The photopolymerization initiation assistant is a compound used in combination with a photopolymerization initiator to accelerate the polymerization of the crosslinking agent initiated by the photopolymerization initiator. Examples of the photopolymerization initiation assistant include amine photopolymerization initiation assistants and alkoxyanthracene photopolymerization initiation assistants.

  Examples of the amine photopolymerization initiation assistant include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-benzoic acid 2- Dimethylaminoethyl, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine, 4,4′-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), 4,4′-bis (diethylamino) benzophenone, 4 , 4′-bis (ethylmethylamino) benzophenone.

  Examples of the alkoxyanthracene photopolymerization initiation assistant include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, and 2-ethyl-9,10-diethoxyanthracene. Is mentioned. Commercially available photopolymerization initiation assistants can also be used. Examples of commercially available photopolymerization initiation assistants include trade name “EAB-F” (manufactured by Hodogaya Chemical Co., Ltd.).

  When using such a photopolymerization initiation assistant, the content thereof is usually 10 mol or less, preferably 0.01 mol or more and 5 mol or less, per mol of the photopolymerization initiator. The total amount of the photopolymerization initiator and the photopolymerization initiation assistant is usually 3 parts by mass or more and 30 parts by mass or less, preferably 5 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the total amount of the crosslinking agent.

  The polymer composition of the present invention may further contain a chain transfer agent. Examples of the chain transfer agent include 2,4-diphenyl-4-methyl-1-pentene, n-dodecyl mercaptan, t-dodecyl mercaptan, n-octyl mercaptan, limonene and the like. The content of the chain transfer agent is usually 0.5% or more and 5% or less in terms of weight fraction with respect to the total solid content of the composition of the present invention.

  The polymer composition of the present invention may contain a thermal polymerization initiator. As the thermal polymerization initiator, those generally known as radical polymerization initiators can be used, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis- (2,4-dimethyl). Azo compounds such as valeronitrile) and 2,2′-azobis- (4-methoxy-2,4-dimethylvaleronitrile); benzoyl peroxide, lauroyl peroxide, t-butylperoxypivalate, 1,1′-bis- ( organic peroxides such as t-butylperoxy) cyclohexane; and hydrogen peroxide. When a peroxide is used as the radical polymerization initiator, it may be a redox initiator using the peroxide together with a reducing agent.

Next, the polymer light emitter used in the present invention will be described.
The polymer light emitter used in the present invention has a polystyrene-equivalent number average molecular weight of usually 10 ³ to 10 ⁸ . Among polymer light emitters, conjugated polymer compounds are preferred. Here, the conjugated polymer compound means a polymer compound in which delocalized π electron pairs exist along the main chain skeleton of the polymer compound. As this delocalized electron, an unpaired electron or a lone electron pair may participate in resonance instead of a double bond.

  The polymer light-emitting material used in the present invention may be a homopolymer or a copolymer. For example, polyfluorene [for example, Japanese Journal of Applied Physics (Jpn. J. Appl. Phys.)] Vol. 30, L1941 (1991)], polyparaphenylene (see, for example, Advanced Materials (Adv. Mater.), Vol. 4, page 36 (1992)), polypyrrole, polypyridine, polyaniline, polythiophene, etc. A polyarylene vinylene polymer such as polyparaphenylene vinylene and polythienylene vinylene (see, for example, the published specification of WO 98/27136); a polyphenylene sulfide; a polycarbazole, etc. For example, “Advanced Materials Vol .12 1737-1750 (2000) "and" Organic EL Display Technology Monthly Display December Special Issue P68-73 "].

Of these, polyarylene polymer light emitters are preferred.
Examples of the repeating unit contained in the polyarylene polymer light emitter include an arylene group and a divalent heterocyclic group, and those containing 20 to 100 mol% of these repeating units are preferable, including 50 to 99 mol%. More preferred.
Here, the number of carbon atoms constituting the ring of the arylene group is usually about 6 to 60. Specific examples thereof include a phenylene group, a biphenylene group, a terphenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrene diyl group, and a pentarange. Yl group, indenediyl group, hepterenediyl group, indacenediyl group, triphenylenediyl group, binaphthyldiyl group, phenylnaphthylenediyl group, stilbenediyl group, fluorenediyl group (for example, in the following formula (1), A = -C (R ′) (R ′) —).
The number of carbon atoms constituting the ring of the divalent heterocyclic group is usually about 3 to 60. Specific examples thereof include pyridine-diyl group, diazaphenylene group, quinolinediyl group, quinoxalinediyl group, acridinediyl group, bipyridyl. A diyl group, a phenanthroline diyl group, in the following formula (1), A = —O—, —S—, —Se—, —NR ″ —, —C (R ′) (R ′) —, or —Si ( R ′) (R ′) —.

（式中、Ａは、式中の２個のベンゼン環上の４個の炭素原子と一緒になって５員環又は６員環を完成させるための原子又は原子群を表し、Ｒ^1a、Ｒ^1b、Ｒ^1c、Ｒ^2a、Ｒ^2b及びＲ^2cは、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基、ニトロ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アリールアルキルオキシカルボニル基、ヘテロアリールオキシカルボニル基又はカルボキシル基を表し、Ｒ^1bとＲ^1c、及びＲ^2bとＲ^2cは、それぞれ一緒になって環を形成していてもよい。） More preferably, the polyarylene polymer light emitter contains a repeating unit represented by the following formula (1).

(In the formula, A represents an atom or atomic group for completing a two 5- or 6-membered ring together with four carbon atoms on the benzene ring in the formula, R ^1a, R ^1b , R ^1c , R ^2a , R ^2b and R ^2c are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, aryl Alkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group Substituted silylthio group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group Represents an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group or a carboxyl group, and R ^1b and R ^1c , and R ^2b and R ^2c together form a ring You may do it.)

  A represents an atom or a group of atoms together with four carbon atoms on the two benzene rings in formula (1) to complete a 5-membered ring or a 6-membered ring, and specific examples include: Although shown below, it is not limited to these.

式中、Ｒ、Ｒ’、Ｒ’’はそれぞれ独立に、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシルオキシ基、置換アミノ基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基又は１価の複素環基を表す。Ｒ’はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基、ニトロ基又は１価の複素環基を表す。Ｒ’’はそれぞれ独立に、水素原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基又は１価の複素環基を表す。

In the formula, R, R ′ and R ″ each independently represent a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group. Represents a group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyloxy group, substituted amino group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group or monovalent heterocyclic group. Each R ′ is independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl; Group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, Represents a nitro group or a monovalent heterocyclic group. R '' each independently represents a hydrogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an alkenyl group, an alkynyl group, An arylalkenyl group, an arylalkynyl group, an acyl group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, or a monovalent heterocyclic group is represented.

R, R ′, R ″ halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group , Arylalkenyl group, arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyl group, acyloxy group, and monovalent heterocyclic group, specific examples Is the same as described above for R ^1a , R ^1b , R ^1c , R ^2a , R ^2b and R ^2c .
In A, —O—, —S—, —Se—, —NR ″ —, —CR′R′— or —SiR′R′— are preferable, —O—, —S—, —CR ′. R'- is more preferred.
Halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group in R ^1a , R ^1b , R ^1c , R ^2a , R ^2b and R ^2c , Arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group Substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, and heteroaryloxycarbonyl group Is the same as above The

Examples of the repeating unit represented by the above formula (1) include the following structures.

式中、ベンゼン環上の水素原子は、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基、ニトロ基又は１価の複素環基に置換されていてもよい。ベンゼン環の隣接位に２つの置換基が存在する場合、それらが互いに結合して環を形成してもよい。

In the formula, a hydrogen atom on the benzene ring is a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an alkenyl group, Alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group , A nitro group or a monovalent heterocyclic group may be substituted. When two substituents are present at adjacent positions of the benzene ring, they may be bonded to each other to form a ring.

The polymer light-emitting material used in the present invention may contain, for example, a repeating unit derived from an aromatic amine in addition to an arylene group and a divalent heterocyclic group. In this case, hole injection property and transport property can be imparted to the polymer light emitter.
In this case, the molar ratio of the repeating unit derived from an arylene group and a repeating unit composed of a divalent heterocyclic group and an aromatic amine is usually in the range of 99: 1 to 20:80.

  As the repeating unit derived from an aromatic amine, a repeating unit represented by the following formula (2) is preferable.

In the formula, Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ each independently represent an arylene group or a divalent heterocyclic group. Ar ⁸ , Ar ⁹ and Ar ¹⁰ each independently represent an aryl group or a monovalent heterocyclic group. o and p each independently represent 0 or 1, and 0 ≦ o + p ≦ 2.

Here, the definition and specific examples of the arylene group and divalent heterocyclic group are the same as those described above. The definition and specific examples of the aryl group and monovalent heterocyclic group are the same as those described in R ^1a , R ^1b , R ^1c , R ^2a , R ^2b and R ^2c .

Specific examples of the repeating unit represented by the above formula (2) include the following structures.

  In the formula, the hydrogen atom on the aromatic ring is a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl Group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, A substituent selected from a nitro group, a monovalent heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group, and a carboxyl group Place It may be.

  Among the repeating units represented by the above formula (2), the repeating unit represented by the following formula (3) is particularly preferable.

In the formula, R ⁷ , R ⁸ and R ⁹ are each independently a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, aryl Alkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, Substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group or carboxyl Represents group . x and y each independently represents an integer of 0 to 4. z shows the integer of 0-2. w shows the integer of 0-5.

  The polymer light emitter used in the present invention may be a random, block or graft copolymer, or a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. Also good. From the viewpoint of obtaining a polymer light emitter having a high quantum yield of light emission, a random copolymer having a block property and a block or graft copolymer are preferable to a complete random copolymer. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

  The terminal group of the polymer light-emitting material used in the present invention is protected with a stable group, because if the polymerization active group remains as it is, there is a possibility that the light emission characteristics and life when the device is made will be reduced. Also good. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferred, and examples thereof include a structure bonded to an aryl group or heterocyclic group via a carbon-carbon bond. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

The polymer light-emitting material used in the present invention preferably has a number average molecular weight of about 10 ³ to 10 ^{8 in} terms of polystyrene, and in particular, when the number average molecular weight is about 10 ⁴ to 10 ^{6 in} terms of polystyrene, preferable.

  In addition, since light emission from a thin film is used, a polymer light-emitting body having light emission in a solid state is preferably used.

Examples of the method for synthesizing the polymer light emitter used in the present invention include a method of polymerizing a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) catalyst, FeCl _{3 and the} like. Examples thereof include a method of polymerizing with an oxidizing agent, a method of electrochemically oxidatively polymerizing, a method of decomposing an intermediate polymer having an appropriate leaving group, and the like. Among these, the method of polymerizing by Suzuki coupling reaction, the method of polymerizing by Grignard reaction, and the method of polymerizing by Ni (0) catalyst are preferable because the reaction control is easy.
When a polymer light emitter is used as a light emitting material of an organic EL device, the purity affects the light emission characteristics. Therefore, the monomer before polymerization may be polymerized after being purified by a method such as distillation, sublimation purification, or recrystallization. Preferably, after the synthesis, purification treatment such as reprecipitation purification and fractionation by chromatography is preferable.

  Examples of the solvent include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene and the like. Although depending on the structure and molecular weight of the polymer light emitter, the polymer light emitter can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

  The amount of the solvent is usually about 1000 to 100000 parts by weight with respect to 100 parts by weight of the polymer light emitter.

  The polymer composition of the present invention may contain a low molecular weight or oligomer, a dendrimer luminescent dye, a charge transport material, and the like, if necessary, in addition to the polymer light emitter.

Examples of the polymer charge transport material used in the present invention include a polymer hole transport material and a polymer electron transport material.
Among these, polymer hole transport materials include polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyl. Examples include diamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thienylene vinylene) or derivatives thereof.

  Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of the polysilane or derivatives thereof include compounds described in Chem. Rev. 89, 1359 (1989), GB 2300196 published specification, and the like. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

  Since polysiloxane or a derivative thereof has almost no hole transporting property in the siloxane skeleton structure, those having the structure of the low molecular hole transporting material in the side chain or main chain are preferably used. Particularly, those having a hole transporting aromatic amine in the side chain or main chain are exemplified.

  Of the polymer hole transport materials, polymer compounds composed of repeating units derived from aromatic amines are particularly preferred. The repeating unit derived from an aromatic amine is preferably represented by the above formula (2), and more preferably represented by the above formula (3).

  Among the polymer charge transport materials, known polymer electron transport materials can be used, and examples thereof include polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof, and the like.

  When the polymer material used in the present invention is used in an organic EL device, the purity affects the device performance such as light emission characteristics. Therefore, a method such as distillation, sublimation purification, recrystallization, column chromatography, etc. is used for the monomer before polymerization. It is preferable to carry out the polymerization after purification with 1. In addition, after the polymerization, purification is performed by conventional separation operations such as acid washing, alkali washing, neutralization, water washing, organic solvent washing, reprecipitation, centrifugation, extraction, column chromatography, dialysis, purification operation, drying and other operations. It is preferable to

The polymer composition of the present invention contains a polymer charge transport material or polymer light emitter and a crosslinking agent. The composition of the present invention may further contain a solvent. In addition, additives such as a charge transport material, a light emitting material, a surfactant, and a stabilizer may be included. The ratio of the polymer charge transport material or polymer light emitter in the composition is 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%, based on the total weight of the composition excluding the solvent.
Moreover, the ratio of the solvent in this composition is 1 wt%-99.9 wt% normally with respect to the total weight of a composition, Preferably it is 60 wt%-99.5 wt%, More preferably, 80 wt%-99.0 wt% %.

  As the film formation method of the polymer composition of the present invention, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method Application methods such as screen printing, flexographic printing, offset printing, and inkjet printing can be used. Printing methods such as a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method are preferable in that pattern formation and multicolor coating are easy.

  The viscosity of the polymer composition of the present invention varies depending on the printing method, but in order to prevent clogging and flight bending at the time of ejection when the ink composition is passed through the ejection device as in the ink jet printing method. It is preferable that it is the range of 1-20 mPa * s in 25 degreeC.

  Although there is no restriction | limiting in particular as a solvent used for the polymer composition of this invention, What can melt | dissolve or disperse | distribute uniformly materials other than the solvent in this composition is preferable. When the material constituting the composition is soluble in a nonpolar solvent, the solvent is a chlorinated solvent such as chloroform, methylene chloride or dichloroethane, an ether solvent such as tetrahydrofuran, toluene, xylene, tetralin or anisole. Aromatic hydrocarbon solvents such as n-hexylbenzene, cyclohexylbenzene, monochlorobenzene, o-dichlorobenzene, aliphatic hydrocarbon solvents such as decalin, bicyclohexyl, etc., and ketones such as acetone, methyl ethyl ketone, 2-heptanone Examples of the solvent include ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, and propylene glycol monomethyl ether acetate.

  The layer formed using the polymer composition of the present invention can suppress dissolution when the upper layer is wet-coated, for example, by being cured by the action of heat or light. When an upper layer is wet-coated on the upper layer to be wet-coated, it is preferable to cure the polymer composition of the present invention using the upper layer. In the case where wet coating is not performed on the upper layer to be wet coated, there is no risk of dissolution, so a composition containing no crosslinking agent may be used in the upper layer.

  In the organic EL device produced using the polymer composition of the present invention, the thickness of the charge transport layer or the light emitting layer varies depending on the material used, and is selected so that the driving voltage and the luminous efficiency are appropriate. For example, it is 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

Further, the organic EL device produced using the polymer composition of the present invention has a charge transport layer or a light emitting layer between electrodes composed of an anode and a cathode, and the charge transport layer or the light emitting layer is a composition of the present invention. It is formed using an object.
Examples of the charge transport layer include an electron transport layer (usually between the cathode and the light emitting layer) and a hole transport layer (usually between the anode and the light emitting layer).
When the charge transport layer is a hole transport layer, if there is only one charge transport layer between the anode and the light-emitting layer, the layer is a hole injection layer, a hole transport layer, or a hole injection / transport layer. Any name may be used.

Among the hole transport layers, the layer in contact with the anode is referred to as a hole injection layer. The polymer composition of the present invention is characterized by excellent performance when used as a hole injection layer.
In the device in which the hole transport layer is formed from the polymer composition of the present invention, the hole transport layer has a structure in contact with the anode (when the hole transport layer is a hole injection layer). The element is preferable in that it exhibits excellent performance.

  The substrate on which the organic EL element of the present invention is formed may be any substrate that does not change when an electrode is formed and an organic layer is formed, and examples thereof include glass, plastic, polymer film, and silicon substrate. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

  In the organic EL device produced using the polymer composition of the present invention, it is usually preferable that at least one of an electrode composed of an anode and a cathode is transparent or translucent, and the anode side is transparent or translucent. As the material for the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the manufacturing method include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Further, as the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used.

  The film thickness of the anode can be appropriately selected in consideration of light transmittance and electrical conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.

  In order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

  As a material for the cathode used in the organic EL device produced using the polymer composition of the present invention, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, or the like Two or more of these alloys, or one or more of them and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, or graphite or graphite intercalation compound Etc. are used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers.

  The film thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. In addition, a layer made of a conductive polymer or a layer having an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided between the cathode and the organic material layer. A protective layer for protecting the organic EL element may be attached. In order to use the organic EL element stably for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the element from the outside.

  As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a heat effect resin or a photo-curing resin is preferable. Used for. If the space is maintained by using the spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It is easy to suppress damage to the element. Among these, it is preferable to take any one or more measures.

  The organic EL element produced using the polymer composition of the present invention can be used as a planar light source, a segment display device, a dot matrix display device, a backlight of a liquid crystal display device, and the like.

  In order to obtain planar light emission using the organic EL device produced using the polymer composition of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light and a method of forming either one or both of an anode and a cathode in a pattern. A segment type display element capable of displaying numbers, letters, simple symbols, etc. can be obtained by forming a pattern by any of these methods and arranging several electrodes so that they can be turned ON / OFF independently. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymer light emitters having different emission colors or a method using a color filter or a light emission conversion filter. The dot matrix element can be driven passively or may be driven actively in combination with TFTs. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
The number average molecular weight in terms of polystyrene was determined by SEC.
Column: TOSOH TSKgel SuperHM-H (2) + TSKgel SuperH2000 (4.6mm Id x 15cm), detector: RI (SHIMADZU RID-10A) is used. Tetrahydrofuran (THF) was used as the mobile phase.

Synthesis example 1
<Synthesis of Polymer Compound 1>
N, N′-bis (4-bromophenyl) -N, N′-bis (4-n-butylphenyl) -1,4-phenylenediamine (3.3 g, 4.8 mmol) and 2,2′-bipyridyl (1.9 g, 12 mmol) was dissolved in 132 mL of dehydrated tetrahydrofuran, and the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (3.3 g, 12 mmol) was added to this solution, and the temperature was raised to 60 ° C. The reaction was allowed for 5 hours. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 30 mL / methanol 480 mL / ion exchanged water 160 mL and stirred for 1 hour, and then the deposited precipitate was filtered. It was dried under reduced pressure for 2 hours and dissolved in 150 mL of toluene. Thereafter, 120 g of 1N hydrochloric acid was added and stirred for 3 hours, the aqueous layer was removed, 140 mL of 25% aqueous ammonia was added to the organic layer, and the aqueous layer was removed after stirring for 3 hours. The organic layer was washed twice with 600 ml of water. The organic layer was divided into two parts, each was added dropwise to 600 mL of methanol, stirred for 1 hour, the deposited precipitate was filtered and dried under reduced pressure for 2 hours. The yield of the obtained polymer (hereinafter referred to as polymer compound 1) was 3.26 g. The average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 1.6 × 10 ⁴ and Mw = 1.2 × 10 ⁵ , respectively.

不活性雰囲気下、３００ｍｌ三つ口フラスコに１‐ナフタレンボロン酸５．００ｇ（２９ｍｍｏｌ）、２−ブロモベンズアルデヒド６．４６ｇ（３５ｍｍｏｌ）、炭酸カリウム１０.０ｇ（７３ｍｍｏｌ）、トルエン３６ｍｌ、イオン交換水３６ｍｌを入れ、室温で撹拌しつつ２０分間アルゴンバブリングした。続いてテトラキス（トリフェニルホスフィン）パラジウム１６．８ｍｇ（０.１５ｍｍｏｌ）を入れ、さらに室温で撹拌しつつ１０分間アルゴンバブリングした。１００℃に昇温し、２５時間反応させた。室温まで冷却後、トルエンで有機層を抽出、硫酸ナトリウムで乾燥後、溶媒を留去した。トルエン：シクロヘキサン＝１：２混合溶媒を展開溶媒としたシリカゲルカラムで生成することにより、化合物Ａ５.１８ｇ（収率８６％）を白色結晶として得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ７．３９〜７．６２（ｍ、５Ｈ）、７．７０（ｍ、２Ｈ）、７．９４（ｄ、２Ｈ）、８．１２（ｄｄ、２Ｈ）、９．６３（ｓ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ２３３ Synthesis example 2
(Synthesis of Compound A)

Under an inert atmosphere, in a 300 ml three-necked flask, 5.00 g (29 mmol) of 1-naphthaleneboronic acid, 6.46 g (35 mmol) of 2-bromobenzaldehyde, 10.0 g (73 mmol) of potassium carbonate, 36 ml of toluene, 36 ml of ion-exchanged water And argon bubbling was performed for 20 minutes while stirring at room temperature. Subsequently, 16.8 mg (0.15 mmol) of tetrakis (triphenylphosphine) palladium was added, and argon was bubbled for 10 minutes while stirring at room temperature. The temperature was raised to 100 ° C. and reacted for 25 hours. After cooling to room temperature, the organic layer was extracted with toluene, dried over sodium sulfate, and the solvent was distilled off. By producing on a silica gel column using a mixed solvent of toluene: cyclohexane = 1: 2 as a developing solvent, 5.18 g of Compound A (yield 86%) was obtained as white crystals.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.39-7.62 (m, 5H), 7.70 (m, 2H), 7.94 (d, 2H), 8.12 (dd, 2H), 9.63 (s, 1H)
MS (APCI (+)): (M + H) ^<+> 233

不活性雰囲気下で３００ｍｌの三つ口フラスコに化合物Ａ８．００ｇ（３４.４ｍｍｏｌ）と脱水したテトラヒドロフラン（ＴＨＦ）４６ｍｌを入れ、−７８℃まで冷却した。
続いてｎ−オクチルマグネシウムブロミド（１.０ｍｏｌ／ｌＴＨＦ溶液）５２ｍｌを３０分かけて滴下した。滴下終了後０℃まで昇温し、１時間撹拌後、室温まで昇温して４５分間撹拌した。氷浴して１Ｎ塩酸２０ｍｌを加えて反応を終了させ、酢酸エチルで有機層を抽出、硫酸ナトリウムで乾燥した。溶媒を留去した後トルエン：ヘキサン＝１０：１混合溶媒を展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｂ７．６４ｇ（収率６４％）を淡黄色のオイルとして得た。ＨＰＬＣ測定では２本のピークが見られたが、ＬＣ−ＭＳ測定では同一の質量数であることから、異性体の混合物であると判断した。 Synthesis example 3
(Synthesis of Compound B)

Under an inert atmosphere, 8.00 g (34.4 mmol) of Compound A and 46 ml of dehydrated tetrahydrofuran (THF) were placed in a 300 ml three-necked flask and cooled to -78 ° C.
Subsequently, 52 ml of n-octylmagnesium bromide (1.0 mol / l THF solution) was added dropwise over 30 minutes. After completion of dropping, the temperature was raised to 0 ° C., stirred for 1 hour, then warmed to room temperature and stirred for 45 minutes. The reaction was terminated by adding 20 ml of 1N hydrochloric acid in an ice bath, and the organic layer was extracted with ethyl acetate and dried over sodium sulfate. After distilling off the solvent, the residue was purified by a silica gel column using a mixed solvent of toluene: hexane = 10: 1 as a developing solvent to obtain 7.64 g (yield: 64%) of Compound B as a pale yellow oil. Although two peaks were observed in the HPLC measurement, they were judged to be a mixture of isomers because they were the same mass number in the LC-MS measurement.

不活性雰囲気下、５００ｍｌ三つ口フラスコに化合物Ｂ（異性体の混合物）５.００ｇ（１４.４ｍｍｏｌ）と脱水ジクロロメタン７４ｍｌを入れ、室温で撹拌、溶解させた。
続いて、三フッ化ホウ素のエーテラート錯体を室温で１時間かけて滴下し、滴下終了後室温で４時間撹拌した。撹拌しながらエタノール１２５ｍｌをゆっくりと加え、発熱がおさまったらクロロホルムで有機層を抽出、２回水洗し、硫酸マグネシウムで乾燥した。溶媒を留去後、ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｃの３．２２ｇ（収率６８％）を無色のオイルとして得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、３Ｈ）、１．０３〜１．２６（ｍ、１４Ｈ）、２．１３（ｍ、２Ｈ）、４．０５（ｔ、１Ｈ）、７．３５（ｄｄ、１Ｈ）、７．４６〜７．５０（ｍ、２Ｈ）、７．５９〜７．６５（ｍ、３Ｈ）、７．８２（ｄ、１Ｈ）、７．９４（ｄ、１Ｈ）、８．３５（ｄ、１Ｈ）、８．７５（ｄ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ３２９ Synthesis example 4
(Synthesis of Compound C)

Under an inert atmosphere, 5.00 g (14.4 mmol) of Compound B (mixture of isomers) and 74 ml of dehydrated dichloromethane were placed in a 500 ml three-necked flask, and dissolved by stirring at room temperature.
Subsequently, an etherate complex of boron trifluoride was dropped at room temperature over 1 hour, and the mixture was stirred at room temperature for 4 hours after completion of the dropping. While stirring, 125 ml of ethanol was slowly added. When the exotherm subsided, the organic layer was extracted with chloroform, washed twice with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was purified by a silica gel column using hexane as a developing solvent to obtain 3.22 g (yield 68%) of Compound C as a colorless oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 3H), 1.03-1.26 (m, 14H), 2.13 (m, 2H), 4.05 (t, 1H), 7.35 (dd, 1H), 7 .46-7.50 (m, 2H), 7.59-7.65 (m, 3H), 7.82 (d, 1H), 7.94 (d, 1H), 8.35 (d, 1H) ), 8.75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 329

不活性雰囲気下２００ｍｌ三つ口フラスコにイオン交換水２０ｍｌをいれ、撹拌しながら水酸化ナトリウム１８．９ｇ（０.４７ｍｏｌ）を少量ずつ加え、溶解させた。水溶液が室温まで冷却した後、トルエン２０ｍｌ、化合物Ｃ５.１７ｇ（１５.７ｍｍｏｌ）、臭化トリブチルアンモニウム１．５２ｇ（４.７２ｍｍｏｌ）を加え、５０℃に昇温した。
臭化ｎ−オクチルを滴下し、滴下終了後５０℃で９時間反応させた。反応終了後トルエンで有機層を抽出し、２回水洗し、硫酸ナトリウムで乾燥した。ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｄの５．１３ｇ（収率７４％）を黄色のオイルとして得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．５２（ｍ、２Ｈ）、０．７９（ｔ、６Ｈ）、１．００〜１．２０（ｍ、２２Ｈ）、２．０５（ｔ、４Ｈ）、７．３４（ｄ、１Ｈ）、７．４０〜７．５３（ｍ、２Ｈ）、７．６３（ｍ、３Ｈ）、７．８３（ｄ、１Ｈ）、７．９４（ｄ、１Ｈ）、８．３１（ｄ、１Ｈ）、８．７５（ｄ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ４４１ Synthesis example 5
(Synthesis of Compound D)

Under an inert atmosphere, 20 ml of ion-exchanged water was placed in a 200 ml three-necked flask, and 18.9 g (0.47 mol) of sodium hydroxide was added little by little with stirring to dissolve. After the aqueous solution was cooled to room temperature, 20 ml of toluene, 5.17 g (15.7 mmol) of Compound C and 1.52 g (4.72 mmol) of tributylammonium bromide were added, and the temperature was raised to 50 ° C.
N-Octyl bromide was added dropwise, and after completion of the addition, the mixture was reacted at 50 ° C. for 9 hours. After completion of the reaction, the organic layer was extracted with toluene, washed twice with water, and dried over sodium sulfate. By purifying with a silica gel column using hexane as a developing solvent, 5.13 g (yield 74%) of Compound D was obtained as a yellow oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.52 (m, 2H), 0.79 (t, 6H), 1.00-1.20 (m, 22H), 2.05 (t, 4H), 7.34 (d, 1H), 7 40 to 7.53 (m, 2H), 7.63 (m, 3H), 7.83 (d, 1H), 7.94 (d, 1H), 8.31 (d, 1H), 8. 75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 441

空気雰囲気下、５０ｍｌの三つ口フラスコに化合物Ｄ４．００ｇ（９．０８ｍｍｏｌ）と酢酸：ジクロロメタン＝１：１混合溶媒５７ｍｌを入れ、室温で撹拌、溶解させた。続いて三臭化ベンジルトリメチルアンモニウム７．７９ｇ（２０．０ｍｍｏｌ）を加えて撹拌しつつ、塩化亜鉛を三臭化ベンジルトリメチルアンモニウムが完溶するまで加えた。室温で２０時間撹拌後、５％亜硫酸水素ナトリウム水溶液１０ｍｌを加えて反応を停止し、クロロホルムで有機層を抽出、炭酸カリウム水溶液で２回洗浄し、硫酸ナトリウムで乾燥した。ヘキサンを展開溶媒とするフラッシュカラムで２回精製した後、エタノール：ヘキサン＝１：１、続いて１０：１混合溶媒で再結晶することにより、化合物Ｅの４．１３ｇ（収率７６％）を白色結晶として得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．６０（ｍ、２Ｈ）、０．９１（ｔ、６Ｈ）、１．０１〜１．３８（ｍ、２２Ｈ）、２．０９（ｔ、４Ｈ）、７．６２〜７．７５（ｍ、３Ｈ）、７．８９（ｓ、１Ｈ）、８．２０（ｄ、１Ｈ）、８．４７（ｄ、１Ｈ）、８．７２（ｄ、１Ｈ）
ＭＳ（ＡＰＰＩ（＋））：（Ｍ＋Ｈ）⁺ ５９８ Synthesis Example 6
(Synthesis of Compound E)

Under an air atmosphere, 4.00 g (9.08 mmol) of Compound D and 57 ml of a mixed solvent of acetic acid: dichloromethane = 1: 1 were placed in a 50 ml three-necked flask, and the mixture was stirred and dissolved at room temperature. Subsequently, 7.79 g (20.0 mmol) of benzyltrimethylammonium tribromide was added and stirred, and zinc chloride was added until benzyltribromide tribromide was completely dissolved. After stirring at room temperature for 20 hours, the reaction was stopped by adding 10 ml of 5% aqueous sodium bisulfite solution, and the organic layer was extracted with chloroform, washed twice with aqueous potassium carbonate solution, and dried over sodium sulfate. After purification twice with a flash column using hexane as a developing solvent, 4.13 g (76% yield) of Compound E was obtained by recrystallization with ethanol: hexane = 1: 1, followed by a 10: 1 mixed solvent. Obtained as white crystals.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.60 (m, 2H), 0.91 (t, 6H), 1.01-1.38 (m, 22H), 2.09 (t, 4H), 7.62-7.75 (m, 3H), 7.89 (s, 1H), 8.20 (d, 1H), 8.47 (d, 1H), 8.72 (d, 1H)
MS (APPI (+)): (M + H) ^<+> 598

Synthesis example 7
<Synthesis of Polymer Compound 2>
After charging 22.5 g of compound E and 17.6 g of 2,2′-bipyridyl in a reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this, 1500 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 31 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes and then reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this reaction solution was cooled, and then a mixed solution of 25% aqueous ammonia 200 ml / methanol 900 ml / ion exchanged water 900 ml was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was washed with a 1N aqueous hydrochloric acid solution, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with about 3% aqueous ammonia, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with ion-exchanged water, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was poured into methanol and re-precipitated.
Next, the produced precipitate was recovered, washed with methanol, and then dried under reduced pressure to obtain 6.0 g of a polymer. This polymer is referred to as polymer compound 2. The obtained polymer compound 2 had a polystyrene-reduced weight average molecular weight of 8.2 × 10 ⁵ and a number average molecular weight of 1.0 × 10 ⁵ .

Synthesis example 8
<Synthesis of Polymer Compound 3>
9,9-Dioctylfluorene-2,7-bis (ethylene boronate) (0.64 g, 1.2 mmol), N, N′-bis (4-bromophenyl) -N, N′— under nitrogen atmosphere Bis (4-n-butylphenyl) 1,4-phenylenediamine (0.75 g, 1.1 mmol) was dissolved in toluene (8.5 g), and tetrakis (triphenylphosphine) palladium (4 mg, 0.0036 mmol) was added. Stir for 10 minutes at room temperature. Then, 4 mL of 20% tetraethylammonium hydride aqueous solution was added, heated to 110 ° C., and reacted for 18 hours while stirring. Thereafter, bromobenzene (0.28 g, 1.78 mmol) was dissolved in 1 mL of toluene and added to the reaction solution, followed by stirring at 110 ° C. for 2 hours. Thereafter, phenylboronic acid (0.22 g, 1.49 mmol) was added to the reaction solution, and the mixture was stirred at 110 ° C. for 2 hours. After cooling to 50 ° C., the organic layer was added dropwise to 200 mL of a methanol / water (1/1) mixture and stirred for 1 hour. The precipitate was filtered, washed with methanol and ion exchange water, and dried under reduced pressure. Then, it melt | dissolved in 50 mL of toluene, and refine | purified through the silica column (silica amount 15mL). The purified solution was added dropwise to 150 mL of methanol and stirred for 1 hour, and the precipitate was filtered and dried under reduced pressure to obtain polymer compound 3. The yield of the obtained polymer compound 3 was 0.70 g. The average molecular weight in terms of polystyrene of the polymer compound 3 was Mn = 3.0 × 10 ⁴ and Mw = 6.1 × 10 ⁴ .

Synthesis Example 9
<Synthesis of Polymer Compound 4>
(Synthesis of Compounds F, G, and J, and I)
Under an inert atmosphere, N, N′-bis (4-bromophenyl) -N, N′-bis (4-n-butylphenyl) 1,4-phenylenediamine (1.911 g), N, N′-bis (4-Bromophenyl) phenylamine (0.484 g) and 2,2′-bipyridyl (1.687 g) were dissolved in 109 mL of dehydrated tetrahydrofuran previously bubbled with argon. After raising the temperature of this solution to 60 ° C., bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (2.971 g) was added, stirred and allowed to react for 5 hours. The reaction solution was cooled to room temperature, dropped into a mixed solution of 25% ammonia water 14 mL / methanol 109 mL / ion-exchanged water 109 mL, stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure, and dissolved in 120 mL of toluene. I let you. After dissolution, 0.48 g of radiolite was added and stirred for 30 minutes, and the insoluble material was filtered. The obtained filtrate was purified through an alumina column. Next, 236 mL of 4% aqueous ammonia was added, and after stirring for 2 hours, the aqueous layer was removed. Further, about 236 mL of ion-exchanged water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was poured into 376 ml of methanol and stirred for 0.5 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 4) was 1.54 g.
The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 7.4 × 10 ³ and Mw = 7.6 × 10 ⁴ , respectively.

  Compounds F, G, and J were synthesized according to WO2000 / 046321. Compound I was synthesized according to US2004127666.

Synthesis Example 10
(Synthesis of Compound H)
The reaction was carried out in a glove box. To a 5 L three-necked flask, 345.53 g of potassium carbonate, 24.9 g of potassium iodide, 39.65 g of 18-Crown-6, 2.5 L of DMF, 162.86 g of 2-Chloroethylethyl ether were added and stirred. Subsequently, 254.1 g of 9,9-di (4-hydroxyphenyl) -2,7-dibromofluorene (US5447960) was added little by little. The mixture was stirred at 116 ° C. overnight, cooled, poured into 2 L of ice water, stirred, and allowed to stand overnight. The solid was filtered and washed with water. After air drying, 365.05 g of crude product was obtained. Recrystallization from 1-propanol / n-octane gave 316.02 g of compound H.

Synthesis Example 11
<Synthesis of Polymer Compound 5>
Aliquat 336 1.72g, Compound F 6.2171g, Compound G 0.5085g, Compound H 6.2225g, Compound I 0.5487g was taken into a 500 ml 4 neck flask, and nitrogen-substituted. Toluene (100 ml) was added, dichlorobis (triphenylphosphine) palladium (II) (7.6 mg) and sodium carbonate aqueous solution (24 ml) were added, and the mixture was stirred under reflux for 3 hours. Then, phenylboric acid (0.40 g) was added and stirred overnight. Sodium N, N-diethyldithiocarbamate aqueous solution was added, and the mixture was further stirred under reflux for 3 hours. The reaction solution was separated, and the organic phase was washed with an acetic acid aqueous solution and water, and then dropped into methanol to precipitate a polymer. After filtration and drying under reduced pressure, the product was dissolved in toluene, passed through a silica gel-alumina column, and washed with toluene. The obtained toluene solution was dropped into methanol to precipitate the polymer. After filtration and drying under reduced pressure, the polymer obtained was dissolved in toluene and added dropwise to methanol to precipitate the polymer. Filtration and drying under reduced pressure yielded 7.72 g of polymer compound 5. Mn = 1.2 × 10 ⁵ and Mw = 2.9 × 10 ⁵ .

Synthesis Example 12
<Synthesis of Polymer Compound 6>
In a 200 ml separable flask, 0.91 g of Aliquat 336, 5.23 g of compound F, and 4.55 g of compound J were taken and purged with nitrogen. 70 ml of toluene was added, and 2.0 mg of palladium acetate and 15.1 mg of tris (o-tolyl) phosphine were added and refluxed. After 19 ml of an aqueous sodium carbonate solution was added dropwise and stirred overnight under reflux, 0.12 g of phenylboric acid was added and stirred for 7 hours. 300 ml of toluene was added, the reaction solution was separated, and the organic phase was washed with an acetic acid aqueous solution and water, and then a sodium N, N-diethyldithiocarbamate aqueous solution was added and stirred for 4 hours. After separation, the solution was passed through a silica gel-alumina column and washed with toluene. The solution was dropped into methanol to precipitate the polymer. After filtration and drying under reduced pressure, the obtained polymer was dissolved in toluene, and the obtained toluene solution was added dropwise to methanol to precipitate the polymer. Filtration and drying under reduced pressure gave 6.33 g of polymer compound 6. Mn = 8.8 × 10 ⁴ and Mw = 3.2 × 10 ⁵ .

Example 1-9 and Comparative Example 1-4
As shown in Table 1, the polymer compound was mixed in toluene at 1 wt%, and the additives were mixed and dissolved in the types and addition amounts shown in Table 1. Thereafter, the solution was filtered through a 0.2 micron diameter Teflon (registered trademark) filter to prepare a coating solution.
The obtained solution was formed on a glass substrate by spin coating. Those containing no photoinitiator were baked under a nitrogen atmosphere at 300 ° C./20 min. For materials containing photoinitiators, UV exposure using a high-pressure mercury lamp with an illuminance of 50 W / cm ² measured with i-line (365 nm) is performed in a nitrogen atmosphere for 1 minute, and then baked at 150 ° C./20 min in a nitrogen atmosphere. I baked. Thereafter, these substrates were rinsed with toluene, and the film thickness before and after the toluene rinse was measured with a stylus type film thickness meter (Alphastep manufactured by KLA Tencor). Toluene rinsing was performed by a method in which toluene was placed on a substrate in a state of rising by surface tension using a spin coater, and then rotated at 4000 rpm to shake off the toluene on the substrate. The results are shown in Table 1.

ＤＰＨＡ：ジペンタエリスリトールヘキサアクリレート（日本化薬製KAYARAD DPHA）
ＴＰＥ−Ａ：トリスペンタエリスリトールオクタアクリレート（広栄化学製）
ブタンジオールジアクリレート：１，４−ブタンジオールジアクリレート（Ａｌｆａ Ａｅｓａｒ社製）
ＨＭＭ：下記式で表されるヘキサメトキシメチルメラミン 架橋剤

Ｉ３６９：イルガキュア３６９；チバ・スペシャルティー・ケミカルズ社製光開始剤
Ｉ９０７：イルガキュア９０７；チバ・スペシャルティー・ケミカルズ社製光開始剤
ＴＡＺＰＰ：トリアジンＰＰ；日本シイベルヘグナー社製光開始剤

DPHA: Dipentaerythritol hexaacrylate (KAYARAD DPHA manufactured by Nippon Kayaku)
TPE-A: Trispentaerythritol octaacrylate (manufactured by Guangei Chemical)
Butanediol diacrylate: 1,4-butanediol diacrylate (Alfa Aesar)
HMM: Hexamethoxymethylmelamine represented by the following formula: Crosslinker

I369: Irgacure 369; Photoinitiator manufactured by Ciba Specialty Chemicals I907: Irgacure 907; Photoinitiator manufactured by Ciba Specialty Chemicals TAZPP: Triazine PP; Photoinitiator manufactured by Nippon Sibel Hegner

Examples 10-19 and Comparative Example 5-7
<Creation of hole injection layer>
The solutions of Examples 1 to 9 and Comparative Example 4 were formed by spin coating on a glass substrate with an ITO film having a thickness of 150 nm formed by sputtering, and as shown in Table 1, those containing no photoinitiator were nitrogen. Baking under an atmosphere of 300 ° C./20 min under an atmosphere, including a photoinitiator, UV exposure with a high-pressure mercury lamp having an illuminance of 50 W / cm ² measured with i-line (365 nm) in a nitrogen atmosphere for 1 minute After that, it was baked under baking conditions of 150 ° C./20 min in a nitrogen atmosphere (Examples 10-19 and Comparative Example 7).
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is formed by spin coating using a solution of PEDOT: poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Stark Vitec, Baytron), hot The plate was dried at 200 ° C. for 10 minutes to form a PEDOT layer as a hole injection layer with a thickness of 50 nm (Comparative Examples 5 and 6).
Slight haze was observed in the film of the hole injection layer formed from the solution containing a large amount of the crosslinking agent of Example 1. In other hole injection layers, smooth films without haze were obtained.

<Preparation of solution composition for light emitting layer>
As shown in Table 2, the polymer compound was dissolved in toluene at 0.5 wt%, and the additives were mixed and dissolved in the types and addition amounts shown in Table 2. Thereafter, the solution was filtered through a 0.2 micron diameter Teflon (registered trademark) filter to prepare a coating solution.

<Creation and evaluation of element>
On the prepared hole injection layer, a film having a thickness of about 70 nm was formed by spin coating using the prepared polymer light emitting coating solution. Furthermore, after drying this at 90 degreeC under pressure reduction for 1 hour, as a cathode buffer layer, 4 nm of lithium fluoride was vapor-deposited as a cathode, 5 nm of calcium, and then 100 nm of aluminum were vapor-deposited, and the organic EL element was produced. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻⁵ Torr. By applying voltage stepwise to the obtained element having a light emitting part of 2 mm × 2 mm (area 4 mm ² ), the luminance of EL light emission from the polymer light emitter was measured, and the current efficiency value was obtained therefrom. . Table 2 shows the maximum value of current efficiency of the obtained element and the center wavelength of EL emission.

  As shown in Table 1, the film coated with the polymer solution composition of the example is cured by the action of heat or light, the dissolution of the film after toluene rinsing is suppressed, and a layer structure is formed by wet coating. it can. Further, as shown in Table 2, the hole injection layer made from the polymer solution composition of the example was used as compared with the polymer light emitting device using the hole injection layer of the PEDOT layer of the comparative example. The polymer light emitting device showed a marked improvement in efficiency. As shown in Table 1, the layer using the cross-linking agent having an aromatic ring in the molecule of Comparative Example 4 was less efficient as shown in Table 2, although dissolution of the film after toluene rinsing was suppressed.

Example 20 and Comparative Example 8-9
As shown in Table 3, the polymer compound was mixed in toluene at 1 wt%, and the additives were mixed and dissolved in the types and addition amounts shown in Table 3. Thereafter, the solution was filtered through a 0.2 micron diameter Teflon (registered trademark) filter to prepare a coating solution.
The obtained solution was formed on a glass substrate by spin coating. This was baked under a nitrogen atmosphere at 300 ° C./20 min. Thereafter, these substrates were rinsed with toluene, and the film thickness before and after the toluene rinse was measured with a stylus-type film thickness meter (DEKTAK manufactured by Beco). Toluene rinsing was performed by a method in which toluene was placed on a substrate in a state of rising by surface tension using a spin coater, and then rotated at 4000 rpm to shake off the toluene on the substrate. The results are shown in Table 3.

ＯＸＴ１２１：下記式で表される東亞合成製架橋剤

ｎ＝１：８０〜８５％、ｎ＝２：１０〜１５％、ｎ＞３：＜５％

OXT121: Toagosei's cross-linking agent represented by the following formula

n = 1: 80-85%, n = 2: 10-15%, n> 3: <5%

Example 23 and Comparative Examples 11-12
<Creation of hole injection layer>
The solutions of Example 20, Comparative Examples 8 and 9 were formed by spin coating on a glass substrate with an ITO film having a thickness of 150 nm formed by sputtering, and baked under a baking condition of 300 ° C./20 min in a nitrogen atmosphere. .

<Preparation of solution composition for light emitting layer>
The polymer compound 5 was dissolved in 1 wt% in toluene. Thereafter, the solution was filtered through a 0.2 micron diameter Teflon (registered trademark) filter to prepare a coating solution.

<Creation and evaluation of element>
On the prepared hole injection layer, a film having a thickness of about 70 nm was formed by spin coating using the prepared polymer light emitting coating solution. Furthermore, after drying this at 90 degreeC under pressure reduction for 1 hour, as a cathode buffer layer, 4 nm of lithium fluoride was vapor-deposited as a cathode, 5 nm of calcium, and then 100 nm of aluminum were vapor-deposited, and the organic EL element was produced. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻⁵ Torr. By applying voltage stepwise to the obtained element having a light emitting part of 2 mm × 2 mm (area 4 mm ² ), the luminance of EL light emission from the polymer light emitter was measured, and the current efficiency value was obtained therefrom. . Table 4 shows the maximum value of current efficiency of the obtained element and the center wavelength of EL emission.

  As shown in Table 3, the film coated with the polymer solution composition of the example is cured by the action of heat or light, dissolution of the film after toluene rinsing is suppressed, and a layer structure can be formed by wet coating. . Further, as shown in Table 4, compared to the polymer light emitting device using the hole injection layer of the comparative example, the polymer light emission using the hole injection layer made from the polymer solution composition of the example. The device showed a significant efficiency improvement. The layer of Comparative Example 9 using a crosslinking agent having an aromatic ring in the molecule was less efficient as shown in Table 4, although the dissolution of the film after toluene rinsing was suppressed as shown in Table 3.

Claims (20)

  A polymer composition for organic electroluminescence comprising a polymer material as a charge transport material or a light emitter and a crosslinking agent, wherein the crosslinking agent does not contain an aromatic ring.   The crosslinking group of the crosslinking agent is a vinyl group, acetylene group, butenyl group, acrylic group, acrylate group, acrylamide group, methacryl group, methacrylate group, methacrylamide group, vinyl ether group, vinylamino group, silanol group, cyclopropyl group, 2. The polymer composition according to claim 1, which is at least one selected from the group consisting of a cyclobutyl group, an epoxy group, an oxetane group, a diketene group, an episulfide group, a lactone group, and a lactam group.   The polymer composition according to claim 1 or 2, wherein the cross-linking agent is pentafunctional or higher.   The polymer composition according to any one of claims 1 to 3, wherein the crosslinking agent is (meth) acrylate.   The polymer composition according to claim 1, wherein the crosslinking agent is a (meth) acrylate of an aliphatic alcohol.   The polymer composition according to claim 1, wherein the crosslinking agent is a bifunctional or higher functional (meth) acrylate.   The polymer composition according to claim 1, wherein the crosslinking agent is a pentafunctional or higher functional (meth) acrylate.   The polymer composition according to claim 1, wherein the crosslinking agent is dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, or tripentaerythritol octa (meth) acrylate.   The polymer composition according to claim 1, wherein the crosslinking agent is dipentaerythritol penta or hexaacrylate.   The polymer composition according to claim 1, wherein the crosslinking agent is dipentaerythritol hexaacrylate or tripentaerythritol octaacrylate.   The polymer composition according to any one of claims 1 to 10, wherein the polymer material is a conjugated polymer compound.   The polymer composition according to any one of claims 1 to 11, wherein the polymer material has a repeating unit derived from an aromatic amine.   The polymer composition according to any one of claims 1 to 12, further comprising a solvent and in a solution state.   The organic electroluminescent element in which a charge transport layer or a light emitting layer is formed from the polymer composition as described in any one of Claims 1-13.   The organic electroluminescent element in which a positive hole transport layer is formed from the polymer composition as described in any one of Claims 1-13.   The organic electroluminescence device according to claim 15, wherein the hole transport layer has a structure in contact with an anode.   A planar light source using the organic electroluminescence element according to any one of claims 14 to 16.   A segment display device using the organic electroluminescence element according to any one of claims 14 to 16.   A dot matrix display device comprising the organic electroluminescence element according to any one of claims 14 to 16 as a backlight.   A liquid crystal display device comprising the organic electroluminescence element according to any one of claims 12 to 16 as a backlight.