JP5251043B2 - Polymer compound and polymer light emitting device - Google Patents

Description

  The present invention relates to a polymer compound and a polymer light-emitting device using the polymer compound.

High-molecular weight light-emitting materials and charge transport materials have been studied variously because they are useful as materials used in organic layers in light-emitting elements and the like. As an example, full orange having two alkyl groups at the 9-position. There has been reported a polymer compound which is a copolymer composed of an yl group and a phenoxazinediyl group having an alkyl group on N (for example, see Non-Patent Document 1).
Macromolecules; 2005, 38, 7983-7991.

However, the above-mentioned polymer compounds reported have not yet been satisfactory in heat resistance and luminous efficiency when used as a light emitting material for a light emitting device.
An object of the present invention is to provide a polymer compound that can provide an element having high heat resistance and high light emission efficiency.

〔上記式（Ｉ）中、Ａｒ₁およびＡｒ₂はそれぞれ独立に、アリール基または１価の複素環基を表し、Ｒ₁およびＲ₂はそれぞれ独立に、アルキル基、アルコキシ基、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、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、シアノ基またはニトロ基を表し、ａおよびｂはそれぞれ独立に、０〜３から選ばれる整数を表す。Ｒ₁およびＲ₂がそれぞれ複数個存在する場合、それらは同一でも異なっていてもよい。〕

〔上記式（ＩＩ）中、Ｒ₅はアルキル基を表し、Ｒ₃およびＲ₄はそれぞれ独立に、アルキル基、アルコキシ基、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、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、シアノ基またはニトロ基を表し、ｃおよびｄはそれぞれ独立に、０〜３から選ばれる整数を表す。Ｒ₃およびＲ₄がそれぞれ複数個存在する場合、それらは同一でも異なっていてもよい。〕 That is, the present invention provides a polymer compound comprising a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II).

[In the above formula (I), Ar ₁ and Ar ₂ each independently represent an aryl group or a monovalent heterocyclic group, and R ₁ and R ₂ each independently represent an alkyl group, an alkoxy group, an alkylthio group, an aryl group Group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy A group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group, a and b are each independently an integer selected from 0 to 3 Represents. When a plurality of R ₁ and R ₂ are present, they may be the same or different. ]

[In the above formula (II), R ₅ represents an alkyl group, and R ₃ and R ₄ each independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an aryl group. Alkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, 1 A valent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group is represented, and c and d each independently represents an integer selected from 0 to 3. When a plurality of R ₃ and R ₄ are present, they may be the same or different. ]

  The polymer compound of the present invention is excellent in heat resistance and luminous efficiency.

  Accordingly, the polymer LED containing the polymer compound of the present invention can be used for a curved or flat light source for a backlight or illumination of a liquid crystal display, a segment type display element, a dot matrix flat panel display, and the like.

  The polymer compound of the present invention contains a repeating unit represented by the formula (I).

Here, the aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, having a condensed ring, two or more independent benzene rings or condensed rings directly or via a group such as vinylene. The combined one is also included. The aryl group generally has about 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms, and the carbon number of the aryl group does not include the carbon number of the substituent. Specific examples thereof include a phenyl group, C ₁ -C ₁₂ alkoxyphenyl group (C ₁ -C ₁₂ is also shown. Hereinafter it is 1 to 12 carbon atoms.), C ₁ -C ₁₂ alkyl Examples include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a pentafluorophenyl group, and the like. C ₁ -C ₁₂ alkoxyphenyl group, C ₁ -C _{A 12} alkylphenyl group is preferred. Specific examples C ₁ -C ₁₂ alkoxyphenyl group, methoxyphenyl group, ethoxyphenyl group, propyloxyphenyl group, isopropyloxyphenyl group, butoxyphenyl group, isobutoxyphenyl group, t-butoxyphenyl, pentyloxyphenyl Group, hexyloxyphenyl group, cyclohexyloxyphenyl group, heptyloxyphenyl group, octyloxyphenyl group, 2-ethylhexyloxyphenyl group, nonyloxyphenyl group, decyloxyphenyl group, 3,7-dimethyloctyloxyphenyl group, lauryl Examples include an oxyphenyl group.
C ₁ -C ₁₂ specifically alkylphenyl group include a methylphenyl group, ethylphenyl group, dimethylphenyl group, propylphenyl group, mesityl group, methylethylphenyl group, isopropylphenyl group, butylphenyl group, isobutylphenyl group, t -Butylphenyl group, pentylphenyl group, isoamylphenyl group, hexylphenyl group, heptylphenyl group, octylphenyl group, nonylphenyl group, decylphenyl group, dodecylphenyl group and the like are exemplified.

The monovalent heterocyclic group refers to a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms, preferably 4 to 20 carbon atoms. Of the monovalent heterocyclic groups, monovalent aromatic heterocyclic groups are preferred. The carbon number of the heterocyclic group does not include the carbon number of the substituent. Here, a heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, and boron in the ring. Say. Specifically, a thienyl group, C ₁ -C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, piperidyl group, quinolyl group, isoquinolyl group and the like, a thienyl group , C ₁ -C ₁₂ alkyl thienyl group, a pyridyl group, a C ₁ -C ₁₂ alkyl pyridyl group are preferable.

In R ₁ and R ₂ of the formula (I), the alkyl group may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group. Octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group Etc. are exemplified.

  The alkoxy group may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyl. Oxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group Perfluorohexyloxy group, perfluorooctyloxy group, methoxymethyloxy group, 2-methoxyethyloxy group and the like.

  The alkylthio group may be linear, branched or cyclic, and may have a substituent. The number of carbon atoms is usually about 1 to 20, specifically, methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group. , Heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group and the like.

The aryloxy group usually has about 6 to 60 carbon atoms, preferably 7 to 48, and specific examples thereof include a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group, and a C _{1 to} C ₁₂ alkylphenoxy group. , 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group and the like, and C ₁ -C ₁₂ alkoxyphenoxy group, C ₁ -C ₁₂ alkylphenoxy group are preferable.
Specific examples C ₁ -C ₁₂ alkoxy phenoxy group, methoxyphenoxy group, ethoxyphenoxy group, propyloxy phenoxy group, isopropyloxy phenoxy group, butoxyphenoxy group, isobutoxyphenoxy phenoxy group, t-butoxyphenoxy group, pentyloxy phenoxy Group, hexyloxyphenoxy group, cyclohexyloxyphenoxy group, heptyloxyphenoxy group, octyloxyphenoxy group, 2-ethylhexyloxyphenoxy group, nonyloxyphenoxy group, decyloxyphenoxy group, 3,7-dimethyloctyloxyphenoxy group, lauryl Examples include an oxyphenoxy group.
Specific examples C ₁ -C ₁₂ alkylphenoxy group, methylphenoxy group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, isopropylphenoxy group, butyl Examples include phenoxy group, isobutylphenoxy group, t-butylphenoxy group, pentylphenoxy group, isoamylphenoxy group, hexylphenoxy group, heptylphenoxy group, octylphenoxy group, nonylphenoxy group, decylphenoxy group, dodecylphenoxy group and the like.

Arylthio group may have a substituent on the aromatic ring, the carbon number of usually about 3 to 60, specifically, phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ ~ C ₁₂ alkylphenylthio group, a 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group, pyridylthio group, pyridazinylthio group, pyrimidylthio group, pyrazylthio group, etc. Toriajiruchio groups.

The arylalkyl group may have a substituent and generally has about 7 to 60 carbon atoms. Specifically, the arylalkyl group may be a phenyl-C ₁ -C ₁₂ alkyl group or a C ₁ -C ₁₂ alkoxyphenyl-C. ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl groups and the like The

The arylalkoxy group may have a substituent, and usually has about 7 to 60 carbon atoms. Specifically, a phenyl-C ₁ -C ₁₂ alkoxy group, a C ₁ -C ₁₂ alkoxyphenyl-
C ₁ -C ₁₂ alkoxy groups, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkoxy groups, 1-naphthyl-C ₁ -C ₁₂ alkoxy groups, 2-naphthyl-C ₁ -C ₁₂ alkoxy groups, etc. Is done.

Arylalkylthio group may have a substituent, the number of carbon atoms is usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio groups and the like The

Arylalkenyl group has a carbon number of usually about 8 to 60, and specific examples thereof include a phenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₂ -C ₁₂ alkenyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkenyl group, 1-naphthyl -C ₂ -C ₁₂ alkenyl group, 2-naphthyl -C ₂ -C ₁₂ alkenyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₂ -C ₁₂ alkenyl group, C ₂ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkenyl groups are preferred.

The arylalkynyl group usually has about 8 to 60 carbon atoms, and specific examples thereof include phenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkoxyphenyl-C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group, 1-naphthyl -C ₂ -C ₁₂ alkynyl group, 2-naphthyl -C ₂ -C ₁₂ alkynyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl - C ₂ -C ₁₂ alkynyl group, C ₁ -C ₁₂ alkylphenyl -C ₂ -C ₁₂ alkynyl group are preferable.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The group or monovalent heterocyclic group may have a substituent. Carbon number of a substituted amino group is about 1-60 normally without including the carbon number of this substituent, Preferably it is C2-48.
Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, secondary butyl group, t -Butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ Arukokishifu Niruamino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, a phenyl -C triazyl amino group ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino Group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl-C ₁ -C ₁₂ alkylamino group and the like are exemplified.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The substituted silyl group usually has about 1 to 60 carbon atoms, preferably 3 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, t-butyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyl dimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl - dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, a 3,7-- dimethylsilyl group, lauryldimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl -C ₁ C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group, dimethylphenylsilyl Examples include groups.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  The acyl group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, Examples include a fluoroacetyl group and a pentafluorobenzoyl group.

  The acyloxy group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, Examples include benzoyloxy group, trifluoroacetyloxy group, pentafluorobenzoyloxy group and the like.

The imine residue is an imine compound (refers to an organic compound having —N═C— in the molecule. Examples thereof include aldimine, ketimine, and a hydrogen atom on these N substituted with an alkyl group or the like. And a residue obtained by removing one hydrogen atom from the compound, usually having about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include groups represented by the following structural formulas.

  The amide group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group. And pentafluorobenzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group and the like.

The acid imide group includes a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and has about 4 to 20 carbon atoms. Specific examples include the groups shown below. .

  The substituted carboxyl group means a carboxyl group substituted with an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has about 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms. Specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyl group. Siloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group, 3,7-dimethyloctyloxycarbonyl group, dodecyloxycarbonyl Trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group, phenoxycarbonyl group, naphthoxycarbonyl group, pyridyloxycarbonyl group, etc. It is done. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The carbon number of the substituted carboxyl group does not include the carbon number of the substituent.

〔上記式（ＩＩＩ）中、Ａｒ₃およびＡｒ₄はそれぞれ独立に、アリール基または１価の複素環基を表し、Ｒ₆およびＲ₇はそれぞれ独立に、アルキル基、アルコキシ基、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、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、シアノ基またはニトロ基を表し、ｅおよびｆはそれぞれ独立に、０〜３から選ばれる整数を表す。Ｒ₆およびＲ₇がそれぞれ複数個存在する場合、それらは同一でも異なっていてもよい。〕 From the viewpoint of ease of synthesis of the raw material monomer, among the repeating units represented by the above formula (I), a repeating unit represented by the following formula (III) is preferable.

[In the above formula (III), Ar ₃ and Ar ₄ each independently represents an aryl group or a monovalent heterocyclic group, and R ₆ and R ₇ each independently represent an alkyl group, an alkoxy group, an alkylthio group, an aryl group Group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy Represents a group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group, and e and f are each independently an integer selected from 0 to 3 Represents. When a plurality of R ₆ and R ₇ are present, they may be the same or different. ]

Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, The definitions and specific examples of acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group and substituted carboxyl group are the definitions of R ₁ and R ₂ in the formula (I). This is the same as the specific example.

From the viewpoint of improving the solubility of the polymer compound of the present invention in an organic solvent, in the above formula (III), R ₆ and R ₇ are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, An arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group is preferable, and an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group An arylthio group, an arylalkyl group, an arylalkoxy group or an arylalkylthio group is more preferable, an alkyl group, an alkoxy group, an aryl group or an aryloxy group is more preferable, and an alkyl group or an aryl group is preferable. Most preferred.

From the viewpoint of ease of synthesis of the raw material monomer, in the above formula (III), Ar ₃ and Ar ₄ are preferably each independently an aryl group, a phenyl group, a 1-naphthyl group, a 2-naphthyl group, 1 -Anthracenyl group, 2-anthracenyl group or 9-anthracenyl group is more preferable, and phenyl group, 1-naphthyl group or 2-naphthyl group is further preferable.

〔上記式（ＩＶ）中、Ｒ₈はアルキル基、アルコキシ基、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、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、シアノ基またはニトロ基を表し、ｇは０〜５から選ばれる整数を表す。Ｒ₈が複数個存在する場合、それらは同一でも異なっていてもよい。〕 Furthermore, from the viewpoint of ease of synthesis of the raw material monomer, in the above formula (III), Ar ₃ and Ar ₄ are preferably each independently a group represented by the following formula (IV).

[In the above formula (IV), R ₈ is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group Or represents a nitro group, g represents an integer selected from 0 to 5. When a plurality of R ₈ are present, they may be the same or different. ]

Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, The definitions and specific examples of acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group and substituted carboxyl group are the definitions of R ₁ and R ₂ in the formula (I). This is the same as the specific example.

From the viewpoint of improving the solubility of the polymer compound of the present invention in an organic solvent, in the above formula (IV), R ₈ is an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, An arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group is preferable, and an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group More preferably an arylalkoxy group or an arylalkylthio group, and still more preferably an alkyl group, an alkoxy group, an aryl group or an aryloxy group.

  From the viewpoint of ease of synthesis of the raw material monomer, in the formula (IV), g is preferably an integer selected from 0 to 3, and more preferably an integer selected from 1 to 3.

  From the viewpoint of ease of synthesis of the raw material monomer, in the above formula (III), e and f are preferably 0 or 1, and most preferably e and f are 0.

  Specific examples of the repeating unit represented by the above formula (I) include repeating units represented by the following formulas (I-1) to (I-7).

〔上記式（ＩＩ）中、Ｒ₅はアルキル基を表し、Ｒ₃およびＲ₄はそれぞれ独立に、アルキル基、アルコキシ基、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、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、シアノ基またはニトロ基を表し、ｃおよびｄはそれぞれ独立に、０〜３から選ばれる整数を表す。Ｒ₃およびＲ₄がそれぞれ複数個存在する場合、それらは同一でも異なっていてもよい。 The polymer compound of the present invention has a repeating unit represented by the following formula (II) in addition to the repeating unit represented by the above formula (I).

[In the above formula (II), R ₅ represents an alkyl group, and R ₃ and R ₄ each independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an aryl group. Alkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, 1 A valent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group is represented, and c and d each independently represents an integer selected from 0 to 3. When a plurality of R ₃ and R ₄ are present, they may be the same or different.

Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, The definitions and specific examples of acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group and substituted carboxyl group are the definitions of R ₁ and R ₂ in formula (I) and This is the same as a specific example.

〔上記式（Ｖ）中、Ｒ₁₁はアルキル基を表し、Ｒ₉およびＲ₁₀はそれぞれ独立に、アルキル基、アルコキシ基、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、アリールアルコキシ基、アリールアルキルチオ基、アリールアルケニル基、アリールアルキニル基、アミノ基、置換アミノ基、シリル基、置換シリル基、ハロゲン原子、アシル基、アシルオキシ基、イミン残基、アミド基、酸イミド基、１価の複素環基、カルボキシル基、置換カルボキシル基、シアノ基またはニトロ基を表し、ｈおよびｉはそれぞれ独立に、０〜３から選ばれる整数を表す。Ｒ₉およびＲ₁₀がそれぞれ複数個存在する場合、それらは同一でも異なっていてもよい。〕 From the viewpoint of ease of synthesis of the raw material monomer, among the repeating units represented by the above formula (II), a repeating unit represented by the following formula (V) is preferable.

[In the above formula (V), R ₁₁ represents an alkyl group, and R ₉ and R ₁₀ are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an aryl group. Alkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, 1 A valent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group is represented, and h and i each independently represent an integer selected from 0 to 3. When a plurality of R ₉ and R ₁₀ are present, they may be the same or different. ]

Alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, substituted amino group, substituted silyl group, halogen atom, The definitions and specific examples of acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group and substituted carboxyl group are the definitions of R ₁ and R ₂ in formula (I) and This is the same as a specific example.

From the viewpoint of improving the solubility of the polymer compound of the present invention in an organic solvent, in the above formula (V), R ₉ and R ₁₀ are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, An arylthio group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group or a monovalent heterocyclic group is preferable, and an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group An arylthio group, an arylalkyl group, an arylalkoxy group or an arylalkylthio group is more preferable, an alkyl group, an alkoxy group, an aryl group or an aryloxy group is more preferable, and an alkyl group or an aryl group is preferable. Most preferred.

  From the viewpoint of ease of synthesis of the raw material monomer, h and i are preferably 0 or 1 in the above formula (V), and h and i are more preferably 0.

  Specific examples of the repeating unit represented by the formula (II) include repeating units represented by the following formulas (II-1) to (II-8).

  The polymer compound of the present invention may contain two or more repeating units represented by the above formula (I) and the above repeating unit (II).

The polymer compound of the present invention comprises (I) and (II), and preferably comprises only (I) and (II).
As for content of (I) and (II) in the polymer compound of the present invention, (I) / (II) is usually in the range of 0.05 to 100.

〔上記式（Ｘ）中、Ａｒ₁、Ａｒ₂、Ｒ₁、Ｒ₂、Ｒ₃、Ｒ₄、Ｒ₅、ａ、ｂ、ｃおよびｄの定義および好ましい例については前記と同様である。ｕは５〜９９の範囲の値、ｖは１〜９５の範囲の値、ｕ＋ｖ＝１００であり、ｕ／ｖは０．０５〜９９の範囲の値である。
上記式（Ｘ）で示される高分子化合物は、ランダム共重合体、ブロック共重合体、交互共重合体のいずれであってもよい。〕 Specific examples of the polymer compound of the present invention include a polymer compound represented by the following formula (X).

[In the above formula (X), the definitions and preferred examples of Ar ₁ , Ar ₂ , R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , a, b, c and d are the same as described above. u is a value in the range of 5 to 99, v is a value in the range of 1 to 95, u + v = 100, and u / v is a value in the range of 0.05 to 99.
The polymer compound represented by the formula (X) may be any of a random copolymer, a block copolymer, and an alternating copolymer. ]

The polymer compound of the present invention, from the viewpoint of the life characteristics of the device, it is preferable that the number average molecular weight in terms of polystyrene is 10 ³ to 10 ^8, more preferably 10 ³ to 10 ^7, 10 ⁴ ~ More preferably, it is 10 ⁷ .

  Here, for the number average molecular weight and the weight average molecular weight, the number average molecular weight and the weight average molecular weight in terms of polystyrene were determined by size exclusion chromatography (SEC) (manufactured by Shimadzu Corporation: LC-10Avp). The polymer to be measured was dissolved in tetrahydrofuran so as to have a concentration of about 0.5 wt%, and 50 μL was injected into GPC. Tetrahydrofuran was used as the mobile phase of GPC, and flowed at a flow rate of 0.6 mL / min. As for the column, two TSKgel SuperHM-H (manufactured by Tosoh) and one TSKgel SuperH2000 (manufactured by Tosoh) were connected in series. A differential refractive index detector (manufactured by Shimadzu Corporation: RID-10A) was used as the detector.

  The polymer compound of the present invention may be an alternating, random, block or graft copolymer, or a polymer having an intermediate structure thereof, such as a random copolymer having a block property. May be. From the viewpoint of obtaining a polymer light emitter having a high quantum yield of fluorescence or phosphorescence, 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.

  In addition, since the terminal group of the polymer compound of the present invention may be protected with a stable group, if the polymerization active group is left as it is, there is a possibility that the light emission characteristics and life when the device is formed may be reduced. 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.

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

Next, the manufacturing method of the high molecular compound of this invention is demonstrated.
For example, the polymer compound of the present invention can be produced by using a compound represented by Y ₁ -A-Y ₂ as one of the raw materials and subjecting it to condensation polymerization.
In the formula, -A- represents a repeating unit represented by the above formula (I) or (II).
Y ₁ and Y ₂ each independently represent a substituent capable of condensation polymerization.

Substituents involved in condensation polymerization (Y ₁ and Y ₂ ) include halogen atoms, alkyl sulfonate groups, aryl sulfonate groups, aryl alkyl sulfonate groups, borate ester groups, sulfonium methyl groups, phosphonium methyl groups, phosphonate methyl groups, Examples thereof include a monohalogenated methyl group, —B (OH) ₂ , formyl group, cyano group, and vinyl group.

  Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Examples of the alkyl sulfonate group include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. Examples of the aryl sulfonate group include benzyl. Examples include sulfonate groups.

（式中、Ｍｅはメチル基を、Ｅｔはエチル基を示す。） Examples of the borate group include groups represented by the following formula.

(In the formula, Me represents a methyl group, and Et represents an ethyl group.)

Examples of the sulfonium methyl group include groups represented by the following formula.
_{^{-CH 2 S + Me 2 X -}} , -CH 2 S + Ph 2 X -
(X represents a halogen atom, and Ph represents a phenyl group.)

Examples of the phosphonium methyl group include groups represented by the following formula.
-CH ₂ P ⁺ Ph ₃ X ^-
(X represents a halogen atom.)

Examples of the phosphonate methyl group include groups represented by the following formula.
-CH ₂ PO (OR ') ₂
(X represents a halogen atom, and R ′ represents an alkyl group, an aryl group, or an arylalkyl group.)

  Examples of the monohalogenated methyl group include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group.

The preferred substituents involved in the condensation polymerization vary depending on the type of polymerization reaction. For example, when using a zerovalent nickel complex such as a Yamamoto coupling reaction, a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate. Groups. In the case of using a nickel catalyst or a palladium catalyst such as a Suzuki coupling reaction, an alkyl sulfonate group, a halogen atom, a borate group, -B (OH) _{2 and the} like can be mentioned.

In the production of the polymer compound of the present invention, specifically, a compound having a plurality of substituents involved in condensation polymerization, which is a monomer, is dissolved in an organic solvent, if necessary, for example, using an alkali or a suitable catalyst. The organic solvent can be used at a temperature not lower than the melting point and not higher than the boiling point.
For example, “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, “Organic Synthesis”, Collective Volume 6. (Collective Volume VI), 407-411, John Wiley & Sons, Inc., 1988, Chemical Review (Chem. Rev.), 95, 2457 (1995), Journal of Organometallic. Chemistry (J. Organomet. Chem.), 576, 147 (1999), Macromolecular Chemistry Macromolecular Known methods described in the symposium (Macromol. Chem., Macromol. Symp.), Vol. 12, 229 (1987) can be used.

  The polymer compound of the present invention can be produced using a known condensation reaction depending on the substituent involved in the condensation polymerization.

For example, 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) complex, a method of polymerizing by an oxidizing agent such as FeCl ₃ , an electrochemical oxidative polymerization Examples thereof include a method and a method by decomposition of an intermediate polymer having an appropriate leaving group.

  Among these, a method of polymerizing by Suzuki coupling reaction, a method of polymerizing by Grignard reaction, and a method of polymerizing by nickel zero-valent complex are preferable because the structure can be easily controlled.

In the production method of the present invention, the substituents (Y ₁ and Y ₂ ) involved in the condensation polymerization are each independently selected from a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, or an aryl alkyl sulfonate group, and have a nickel zero valence. A production method in which condensation polymerization is performed in the presence of a complex is preferred.
As raw material compounds, dihalogenated compounds, bis (alkyl sulfonate) compounds, bis (aryl sulfonate) compounds, bis (aryl alkyl sulfonate) compounds, halogen-alkyl sulfonate compounds, halogen-aryl sulfonate compounds, halogen-aryl alkyl sulfonate compounds, Examples include alkyl sulfonate-aryl sulfonate compounds, alkyl sulfonate-aryl alkyl sulfonate compounds, and aryl sulfonate-aryl alkyl sulfonate compounds.

  In this case, for example, a halogen-alkyl sulfonate compound, a halogen-aryl sulfonate compound, a halogen-aryl alkyl sulfonate compound, an alkyl sulfonate-aryl sulfonate compound, an alkyl sulfonate-aryl alkyl sulfonate compound, or an aryl sulfonate-aryl alkyl sulfonate compound as a raw material compound. By using it, a method for producing a polymer compound with a controlled sequence can be mentioned.

In the production method of the present invention, the substituents (Y ₁ and Y ₂ ) involved in the condensation polymerization are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a boric acid group, Or the total number of moles of halogen atoms, alkyl sulfonate groups, aryl sulfonate groups and aryl alkyl sulfonate groups (J) selected from boric acid ester groups and contained in all raw material compounds, and boric acid groups (-B (OH) ₂ ) And the total number of moles of boric acid ester groups (K) is substantially 1 (usually K / J is in the range of 0.7 to 1.2), and a condensation polymerization using a nickel catalyst or a palladium catalyst. The manufacturing method is preferred.
Specific examples of the combination of raw material compounds include a combination of a dihalogenated compound, a bis (alkyl sulfonate) compound, a bis (aryl sulfonate) compound or a bis (aryl alkyl sulfonate) compound and a diboric acid compound or a diboric acid ester compound. .
Also, halogen-boric acid compounds, halogen-boric acid ester compounds, alkyl sulfonate-boric acid compounds, alkyl sulfonate-boric acid ester compounds, aryl sulfonate-boric acid compounds, aryl sulfonate-boric acid ester compounds, arylalkyl sulfonate-borates Examples include acid compounds, arylalkyl sulfonate-boric acid compounds, and arylalkyl sulfonate-boric acid ester compounds.

  In this case, for example, as a raw material compound, a halogen-boric acid compound, a halogen-boric acid ester compound, an alkyl sulfonate-boric acid compound, an alkyl sulfonate-boric acid ester compound, an aryl sulfonate-boric acid compound, an aryl sulfonate-boric acid ester compound, The method of manufacturing the polymeric compound which controlled the sequence by using an arylalkyl sulfonate-boric acid compound, an arylalkyl sulfonate-boric acid compound, and an arylalkyl sulfonate-boric acid ester compound is mentioned.

  Although the organic solvent varies depending on the compound and reaction used, it is generally preferable that the solvent used is sufficiently deoxygenated to allow the reaction to proceed in an inert atmosphere in order to suppress side reactions. Similarly, it is preferable to perform a dehydration treatment. However, this is not the case in the case of a two-phase reaction with water, such as the Suzuki coupling reaction.

  Solvents include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloropentane and bromopentane. Halogenated saturated hydrocarbons such as chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol Alcohols such as formic acid, acetic acid, propionic acid, dimethyl ether, diethyl ether, methyl-t-butyl ether, tetra Ethers such as drofuran, tetrahydropyran, dioxane, trimethylamine, triethylamine, N, N, N ′, N′-tetramethylethylenediamine, amines such as pyridine, N, N-dimethylformamide, N, N-dimethylacetamide, N Amides such as N, diethylacetamide and N-methylmorpholine oxide. These solvents may be used alone or in combination. Of these, ethers are preferable, and tetrahydrofuran and diethyl ether are more preferable.

  In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding.

  When the polymer compound of the present invention is used for a polymer LED or the like, its purity affects the performance of the device such as light emission characteristics. Therefore, after the monomer before polymerization is purified by a method such as distillation, sublimation purification, recrystallization, It is preferable to polymerize. Further, after the polymerization, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography.

The composition of the present invention is a composition comprising the polymer compound of the present invention,
A composition comprising at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light-emitting material, and at least one polymer compound of the present invention, Examples thereof include a composition containing at least two kinds of molecular compounds.

  When the composition of the present invention contains a hole transport material, the ratio of the hole transport material in the composition is usually 1% by weight to 80% by weight, preferably 5% by weight to 60% by weight. %. When the composition of the present invention contains an electron transport material, the proportion of the electron transport material in the composition is usually 1% by weight to 80% by weight, preferably 5% by weight to 60% by weight. is there. When the composition contains a light emitting material, the proportion of the light emitting material in the composition is usually 1% by weight to 80% by weight, preferably 5% by weight to 60% by weight.

When the composition of the present invention contains at least two polymer compounds of the present invention,
Examples thereof include those containing a polymer compound having a different ratio of the repeating unit represented by the formula (I) constituting the polymer compound and the repeating unit represented by the formula (II).

When the composition of the present invention contains at least two kinds of the polymer compound of the present invention, the two kinds of polymer compounds are different from each other in content of the repeating unit represented by the formula (II) by 10% or more. Is preferable because the hole transport property of the composition can be easily adjusted.
Moreover, it is preferable from a viewpoint that at least 1 type of the high molecular compound which comprises this composition has 20% or more of repeating units shown by Formula (II) has high hole transportability.

  The liquid composition of the present invention is useful for production of light-emitting elements such as polymer light-emitting elements and organic transistors. The liquid composition comprises the polymer compound and a solvent. In the present specification, the “liquid composition” means a liquid that is liquid at the time of device fabrication, and typically means a liquid at normal pressure (ie, 1 atm) and 25 ° C. The liquid composition is generally called an ink, an ink composition, a solution or the like.

  The liquid composition of the present invention contains, in addition to the polymer compound, a light emitting material, a hole transport material, an electron transport material, a stabilizer, an additive for adjusting viscosity and / or surface tension, an antioxidant, and the like. You may go out. Each of these optional components may be used alone or in combination of two or more.

  Examples of the luminescent material that may be contained in the liquid composition of the present invention include naphthalene derivatives, anthracene, anthracene derivatives, perylene, perylene derivatives, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, 8- Metal complexes having a hydroxyquinoline metal complex as a ligand, metal complexes having an 8-hydroxyquinoline derivative as a ligand, other fluorescent metal complexes, aromatic amines, tetraphenylcyclopentadiene, tetraphenylcyclopentadiene derivatives, Tetraphenylcyclobutadiene, tetraphenylcyclobutadiene derivative, stilbene, silicon-containing aromatic, oxazole, furoxan, thiazole, tetraarylmethane, thiadiazole, pyrazole, metacyclophane, acetyl Luminescent material emission system and the like. Specific examples include those described in JP-A-57-51781, JP-A-59-194393, and the like.

  Examples of the hole transport material that the liquid composition of the present invention may contain include, for example, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, Arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof Derivatives and the like.

  Examples of the electron transport material that may be contained in the liquid composition of the present invention include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyano Anthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, etc. Can be mentioned.

  Examples of the stabilizer that may be contained in the liquid composition of the present invention include phenolic antioxidants and phosphorus antioxidants.

  As an additive for adjusting the viscosity and / or surface tension which the liquid composition of the present invention may contain, for example, a high molecular weight compound (thickener) for increasing the viscosity, a poor solvent, a viscosity A low molecular weight compound for lowering, a surfactant for lowering surface tension, and the like may be used in appropriate combination.

  The high molecular weight compound is not particularly limited as long as it does not inhibit light emission or charge transport, and is usually soluble in the solvent of the liquid composition. As the high molecular weight compound, for example, high molecular weight polystyrene, high molecular weight polymethyl methacrylate, or the like can be used. The high molecular weight compound preferably has a polystyrene equivalent weight average molecular weight of 500,000 or more, more preferably 1,000,000 or more. A poor solvent can also be used as a thickener.

  The antioxidant that may be contained in the liquid composition of the present invention is not limited as long as it does not inhibit light emission or charge transport. When the composition contains a solvent, it is usually soluble in the solvent. is there. Examples of the antioxidant include phenolic antioxidants and phosphorus antioxidants. By using an antioxidant, the storage stability of the polymer compound and the solvent can be improved.

  When the liquid composition of the present invention contains a hole transport material, the ratio of the hole transport material in the liquid composition is usually 1 wt% to 80 wt%, preferably 5 wt% to 60% by weight. When the liquid composition of the present invention contains an electron transport material, the ratio of the electron transport material in the liquid composition is usually 1% by weight to 80% by weight, preferably 5% by weight to 60% by weight. %.

When forming a film using this liquid composition in the preparation of a polymer light emitting device, it is only necessary to remove the solvent by drying after applying the liquid composition, and also to mix the charge transport material and the light emitting material. In this case, the same technique can be applied, which is very advantageous in manufacturing. In addition, in the case of drying, you may dry in the state heated at about 50-150 degreeC, and may be dried under reduced pressure to about 10 ^<-3 > Pa.

  The film formation method using the liquid composition includes spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, and cap. Coating methods such as a coating method, a capillary coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an inkjet printing method, and a nozzle coating method can be used.

  The ratio of the solvent in the liquid composition is usually 1% by weight to 99.9% by weight, preferably 60% by weight to 99.9% by weight, and more preferably 90% by weight with respect to the total weight of the liquid composition. % By weight to 99.8% by weight. The viscosity of the liquid composition varies depending on the printing method, but it is preferably in the range of 0.5 to 500 mPa · s at 25 ° C. In the case of the liquid composition passing through the discharge device, such as an ink jet printing method, In order to prevent flight bending, the viscosity is preferably in the range of 0.5 to 20 mPa · s at 25 ° C.

  As the solvent contained in the liquid composition, those capable of dissolving or dispersing components other than the solvent in the liquid composition are preferable. Examples of the solvent include chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorinated solvents such as chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, toluene, xylene, and trimethyl. Aromatic hydrocarbon solvents such as benzene and mesitylene, aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether Polyethylene alcohol and its derivatives such as ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerol, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol, cyclohexanol, etc. Examples thereof include alcohol-based solvents, sulfoxide-based solvents such as dimethyl sulfoxide, and amide-based solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in combination. Among the solvents, it is preferable to include one or more organic solvents having a structure containing at least one benzene ring and having a melting point of 0 ° C. or lower and a boiling point of 100 ° C. or higher in view of viscosity, film formability, and the like. To preferred.

  Solvents include aromatic hydrocarbon solvents and aliphatic hydrocarbon solvents from the viewpoints of solubility in organic solvents other than the solvent in the liquid composition, uniformity during film formation, viscosity characteristics, etc. Ester solvents and ketone solvents are preferred, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, mesitylene, n-propylbenzene, i-propylbenzene, n-butylbenzene, i-butylbenzene, s-butylbenzene, anisole , Ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene, bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, methylbenzoate, 2-propylcyclohexanone, 2-heptanone, - heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2-decanone, dicyclohexyl ketone are preferred, xylene, anisole, mesitylene, cyclohexylbenzene, and it is more preferable to contain at least one of bicyclohexyl methyl benzoate.

  The type of solvent contained in the liquid composition is preferably two or more, more preferably two to three, and more preferably two from the viewpoints of film forming properties and device characteristics. Further preferred.

  When two kinds of solvents are contained in the liquid composition, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, it is preferable that one type of solvent has a boiling point of 180 ° C. or higher, and the other one type of solvent preferably has a boiling point of less than 180 ° C. One type of solvent has a boiling point of 200 ° C. More preferably, the solvent has a boiling point of less than 180 ° C. Further, from the viewpoint of viscosity, at 60 ° C., it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved in the solvent, and one of the two solvents has 25 ° C. In this case, it is preferable that 0.2% by weight or more of the component excluding the solvent from the liquid composition is dissolved.

  When the liquid composition contains three kinds of solvents, one or two kinds of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, at least one of the three solvents is preferably a solvent having a boiling point of 180 ° C. or higher, and at least one solvent is preferably a solvent having a boiling point of 180 ° C. or lower. At least one of the types of solvents is a solvent having a boiling point of 200 ° C. or more and 300 ° C. or less, and at least one of the solvents is more preferably a solvent having a boiling point of 180 ° C. or less. Further, from the viewpoint of viscosity, it is preferable that two of the three types of solvents have 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition dissolved at 60 ° C. in the solvent. Of these solvents, it is preferable that 0.2% by weight or more of the component obtained by removing the solvent from the liquid composition is dissolved in the solvent at 25 ° C.

  When two or more kinds of solvents are contained in the liquid composition, the solvent having the highest boiling point is 40 to 90% by weight of the total solvent contained in the liquid composition from the viewpoint of viscosity and film formability. Preferably, it is 50 to 90% by weight, more preferably 65 to 85% by weight.

<Application>
The polymer compound of the present invention can be used not only as a light emitting material but also as a conductive material by thin film, organic semiconductor material, organic transistor, optical material, solar cell or doping.

  The thin film of the present invention will be described. This thin film is formed using the polymer compound. Examples of the thin film include a light-emitting thin film, a conductive thin film, and an organic semiconductor thin film.

  The light-emitting thin film preferably has a quantum yield of light emission of 50% or more, more preferably 60% or more, and further preferably 70% or more from the viewpoint of the brightness of the device, the light emission voltage, and the like. .

  The conductive thin film preferably has a surface resistance of 1 KΩ / □ or less. The electrical conductivity can be increased by doping the thin film with a Lewis acid, an ionic compound or the like. The surface resistance is more preferably 100Ω / □ or less, and further preferably 10Ω / □ or less.

The organic semiconductor thin film has a higher electron mobility or hole mobility, preferably 10 ⁻⁵ cm ² / V / second or more, more preferably 10 ⁻³ cm ² / V / second or more, More preferably, it is 10 ^-1 cm ² / V / second or more. In addition, an organic transistor can be manufactured using an organic semiconductor thin film. Specifically, an organic transistor can be formed by forming an organic semiconductor thin film on a Si substrate on which an insulating film such as SiO ₂ and a gate electrode are formed, and forming a source electrode and a drain electrode with Au or the like. .

  Next, a polymer field effect transistor which is an embodiment of the organic transistor will be described.

  The polymer compound of the present invention can be suitably used as a material for a polymer field effect transistor, especially as an active layer. As a structure of a polymer field effect transistor, a source electrode and a drain electrode are usually provided in contact with an active layer made of a polymer, and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween. Just do it.

  The polymer field effect transistor is usually formed on a supporting substrate. The material of the support substrate is not particularly limited as long as the characteristics as a field effect transistor are not hindered, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The polymer field effect transistor can be produced by a known method, for example, a method described in JP-A-5-110069.

  In forming the active layer, it is very advantageous and preferable to use an organic solvent-soluble polymer compound. As a film-forming method from a solution obtained by dissolving an organic solvent-soluble polymer compound in a solvent, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating Application methods such as a method, a dip coating method, a slit coating method, a cap coating method, a capillary coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an ink jet printing method, and a nozzle coating method can be used. .

  A sealed polymer field effect transistor obtained by sealing after producing a polymer field effect transistor is preferred. Thereby, the polymer field effect transistor is shielded from the atmosphere, and deterioration of the characteristics of the polymer field effect transistor can be suppressed.

  Examples of the sealing method include a method of covering with an ultraviolet (UV) curable resin, a thermosetting resin, an inorganic SiONx film, or the like, and a method of bonding a glass plate or film with a UV curable resin, a thermosetting resin, or the like. In order to effectively cut off from the atmosphere, it is preferable to carry out the steps from the preparation of the polymer field effect transistor to the sealing without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

  Next, an organic solar cell will be described. A solid photoelectric conversion element utilizing the photovoltaic effect as an organic photoelectric conversion element which is one embodiment of an organic solar battery will be described.

  The polymer compound of the present invention is used as a material of an organic photoelectric conversion element, particularly as an organic semiconductor layer of a Schottky barrier type element utilizing an interface between an organic semiconductor and a metal, and between an organic semiconductor and an inorganic semiconductor or between organic semiconductors. It can be suitably used as an organic semiconductor layer of a pn heterojunction element utilizing an interface.

  Furthermore, as an electron-donating polymer and an electron-accepting polymer in a bulk heterojunction device with an increased donor-acceptor contact area, an organic photoelectric conversion device using a polymer / low-molecular composite system, for example, electron accepting It can be suitably used as an electron donating conjugated polymer (dispersion support) of a bulk heterojunction organic photoelectric conversion element in which a fullerene derivative is dispersed as a body.

  As the structure of the organic photoelectric conversion element, for example, in a pn heterojunction type element, a p-type semiconductor layer is formed on an ohmic electrode, for example, ITO, and an n-type semiconductor layer is further stacked thereon. It is sufficient that an ohmic electrode is provided.

  The organic photoelectric conversion element is usually formed on a support substrate. The material of the support substrate is not particularly limited as long as the characteristics as the organic photoelectric conversion element are not impaired, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The organic photoelectric conversion element can be produced by a known method, for example, the method described in Synth. Met., 102, 982 (1999) or the method described in Science, 270, 1789 (1995).

  Next, the polymer light emitting device of the present invention will be described.

  The polymer light emitting device of the present invention has an electrode composed of an anode and a cathode, and a light emitting layer provided between the electrodes and containing the polymer compound.

  Further, as the polymer light-emitting device of the present invention, (1) a polymer light-emitting device in which an electron transport layer is provided between the cathode and the light-emitting layer, and (2) a hole transport layer is provided between the anode and the light-emitting layer. Examples thereof include a polymer light emitting device provided, and (3) a polymer light emitting device in which an electron transport layer is provided between the cathode and the light emitting layer and a hole transport layer is provided between the anode and the light emitting layer.

More specifically, the following structures a) to d) are exemplified.
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

Here, the light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. It is. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently.
In addition, the hole transport layer adjacent to the light emitting layer may be referred to as an interlayer layer.

  Although there is no restriction | limiting in the film-forming method of a light emitting layer, The method by film-forming from a solution is illustrated.

  As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a slit coating method, a cap coating method, Coating methods such as capillary coating, spray coating, screen printing, flexographic printing, offset printing, ink jet printing, and nozzle coating can be used.

  When forming a film from a solution by using the polymer compound of the present invention at the time of preparing a polymer light emitting device, it is only necessary to remove the solvent by drying after coating this solution, and charge transport materials and light emitting materials can be used. Even in the case of mixing, the same technique can be applied, which is very advantageous in production.

  The film thickness of the light emitting layer varies depending on the material used and may be selected so that the drive voltage and the light emission efficiency are appropriate. For example, the film thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 5 nm to 200 nm.

  In the polymer light emitting device of the present invention, a light emitting material other than the polymer compound may be mixed and used in the light emitting layer. In the polymer light emitting device of the present invention, a light emitting layer containing a light emitting material other than the polymer compound may be laminated with a light emitting layer containing the polymer compound.

  As the light emitting material other than the polymer compound, known materials can be used. Examples of the low molecular weight compound include naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine-type, xanthene-type, coumarin-type and cyanine-type pigments, 8-hydroxyquinoline and metal complexes of its derivatives, aromatic amines, and the like. , Tetraphenylcyclopentadiene and derivatives thereof, tetraphenylbutadiene and derivatives thereof, and the like can be used. Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

  When the polymer light-emitting device of the present invention has a hole transport layer, the hole transport material used includes polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, and polysiloxane having an aromatic amine in the side chain or main chain. Derivatives, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thieni Lembinylene) and its derivatives are exemplified. Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209988, Examples described in JP-A-3-7992 and JP-A-3-152184 are exemplified.

  Among these, as the hole transport material used for the hole transport layer, polyvinyl carbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having an aromatic amine compound group in the side chain or main chain, polyaniline and derivatives thereof A polymer hole transport material such as polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, more preferably polyvinyl carbazole and derivatives thereof, Polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  Polyvinylcarbazole and derivatives thereof are obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of the polysilane and derivatives thereof include compounds described in Chemical Review, Vol. 89, page 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 the polysiloxane derivative 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.

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, In the low molecular hole transport material, the method by the film-forming from a mixed solution with a polymer binder is illustrated. In the case of a polymer hole transport material, a method of film formation from a solution is exemplified.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, cap Coating methods such as a coating method, a capillary coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an inkjet printing method, and a nozzle coating method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The film thickness of the hole transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the polymer light-emitting device of the present invention has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and Derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinodimethane and derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and Examples thereof include polyfluorene and derivatives thereof. Specifically, JP-A 63-70257, 63-175860, JP 2-135359, 2-135361, 2-209988, 3-37992, Examples described in JP-A-3-152184 are exemplified.

  Of these, oxadiazole derivatives, benzoquinone and derivatives thereof, anthraquinone and derivatives thereof, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, polyfluorene and derivatives thereof are preferred. More preferred are-(4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline.

  There are no particular restrictions on the method for forming the electron transport layer, but for low molecular weight electron transport materials, the vacuum evaporation method from powder, or the method by film formation from a solution or molten state, the polymer electron transport material is a solution or melt. Each method is exemplified by film formation from the state. When forming a film from a solution or a molten state, a polymer binder may be used in combination.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve an electron transport material and / or a polymer binder. Examples of the solvent include chlorine solvents such as chloroform, methylene chloride, and dichloroethane; ether solvents such as tetrahydrofuran; aromatic hydrocarbon solvents such as toluene and xylene; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from a solution or a molten state include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, slit coating, and cap. Coating methods such as a coating method, a capillary coating method, a spray coating method, a screen printing method, a flexographic printing method, an offset printing method, an inkjet printing method, and a nozzle coating method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those not strongly absorbing visible light are suitably used. Examples of the polymer binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, Examples include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  The film thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are moderate values, but at least a thickness that does not cause pinholes is required. If the thickness is too thick, the drive voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , An electron injection layer).

  Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or the insulating layer may be provided adjacent to the electrode, and the adhesion at the interface is improved or mixing is prevented. For this purpose, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

  The order and number of layers to be stacked, and the thickness of each layer may be appropriately selected in consideration of light emission efficiency and element lifetime.

  In the present invention, a polymer light emitting device provided with a charge injection layer (electron injection layer, hole injection layer) is a polymer light emitting device provided with a charge injection layer adjacent to the cathode, or a charge injection adjacent to the anode. Examples thereof include a polymer light emitting device provided with a layer.

For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode
f) Anode / light emitting layer / charge injection layer / cathode
g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode
h) Anode / charge injection layer / hole transport layer / light emitting layer / cathode
i) Anode / hole transport layer / light emitting layer / charge injection layer / cathode
j) Anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode
k) Anode / charge injection layer / light emitting layer / charge transport layer / cathode
l) Anode / light-emitting layer / electron transport layer / charge injection layer / cathode
m) Anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode
n) Anode / charge injection layer / hole transport layer / light emitting layer / charge transport layer / cathode o) Anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) Anode / charge injection layer / Hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode

  Specific examples of the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer provided between the anode material and the hole transport material included in the hole transport layer. A layer containing a material having a value ionization potential, a layer provided between a cathode and an electron transport layer, and a layer containing a material having an intermediate value of electron affinity between the cathode material and the electron transport material contained in the electron transport layer, etc. Is exemplified.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, and leakage between light emitting pixels in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm. Usually, in order to make the electric conductivity of the conductive polymer 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of the anion include polystyrene sulfonate ion, alkylbenzene sulfonate ion, camphor sulfonate ion, and the like, and examples of the cation include lithium ion, sodium ion, potassium ion, tetrabutylammonium ion, and the like.

  The thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

  The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer. Polyaniline and derivatives thereof, polythiophene and derivatives thereof, polypyrrole and derivatives thereof, polyphenylene vinylene and derivatives thereof, polythienylene vinylene And derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanine (copper phthalocyanine, etc.), carbon, etc. .

  The insulating layer has a function of facilitating charge injection. The average thickness of this insulating layer is usually 0.1 to 20 nm, preferably 0.5 to 10 nm, more preferably 1 to 5 nm. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. Examples of the polymer light emitting device provided with the insulating layer include a polymer light emitting device provided with an insulating layer adjacent to the cathode and a polymer light emitting device provided with an insulating layer adjacent to the anode.

Specific examples include the following structures q) to ab).
q) anode / insulating layer / light emitting layer / cathode r) anode / light emitting layer / insulating layer / cathode s) anode / insulating layer / light emitting layer / insulating layer / cathode t) anode / insulating layer / hole transport layer / light emitting layer / Cathode u) anode / hole transport layer / light emitting layer / insulating layer / cathode v) anode / insulating layer / hole transport layer / light emitting layer / insulating layer / cathode w) anode / insulating layer / light emitting layer / electron transport layer / Cathode x) anode / light emitting layer / electron transport layer / insulating layer / cathode y) anode / insulating layer / light emitting layer / electron transport layer / insulating layer / cathode z) anode / insulating layer / hole transport layer / light emitting layer / Electron transport layer / cathode
aa) Anode / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode
ab) Anode / insulating layer / hole transporting layer / light emitting layer / electron transporting layer / insulating layer / cathode

  The substrate on which the polymer light-emitting device 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. Examples thereof include substrates such as glass, plastic, polymer film, and silicon. Is done. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

  In the present invention, it is usually preferred that at least one of the anode and cathode electrodes 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 their composite films 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 production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as this anode.

  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, and more preferably 50 nm to 500 nm. It is.

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

  As a material for the cathode, 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, and the like Two or more alloys, or one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is 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 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. The protective layer which protects may be mounted | worn. In order to stably use the polymer light emitting device for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the device from the outside.

  As the protective layer, resins, metal oxides, metal fluorides, metal borides 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 thermosetting resin or a photocurable resin is preferable. Used for. If a space is maintained using a 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 becomes easy to suppress giving an image to an element. Among these, it is preferable to take any one or more measures.

  The polymer light-emitting device of the present invention can be used in a display device such as a planar light source, a segment display device, a dot matrix display device, a liquid crystal display device (for example, a backlight).

  In order to obtain planar light emission using the polymer light emitting device 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, a method of forming either one of the anode or the cathode, or both electrodes in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. 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 compounds having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively, or may be actively driven in combination with a TFT or the like. 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.

  Furthermore, the planar light emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. For example, the light source for illumination includes light emission colors such as white light emission, red light emission, green light emission, and blue light emission. If a flexible substrate is used, it can be used as a curved light source or display device.

  Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

Synthesis Example 1 Synthesis of N-octylphenoxazine In an inert atmosphere, phenoxazine (10.0 g), sodium hydroxide (21.9 g), tetraethylammonium bromide (0.37 g), and dimethyl sulfoxide (34 mL) were mixed. Then, the temperature was raised to 80 ° C., 18 mL of water was added, and 1-bromooctane (12.9 g) was added dropwise over 50 minutes. Then, the temperature was raised to 90 ° C. and stirred for 1 hour, and then cooled to room temperature. Next, the precipitated solid was dissolved in 160 mL of toluene, washed twice with water (100 mL), once with 1N hydrochloric acid (100 mL), washed three times with water (100 mL), and passed through a silica gel column. Concentration under reduced pressure and vacuum drying were performed to obtain 16.0 g (purity 99.4%) of the target N-octylphenoxazine.

¹ H-NMR (299.4 MHz, CDCl ₃ ): 0.89 (t, 3H), 1.15 to 1.47 (m, 10H), 1.65 (br, 2H), 3.45 (br, 2H), 6.31-6.88 (br, 8H).
LC-MS (APPI-MS (posi)): 296 [M + H] ⁺

Synthesis Example 2 Synthesis of 3,7-dibromo-N-octylphenoxazine To a solution prepared by adding dichloromethane (55 mL) to N-octylphenoxazine (15.0 g) in an inert atmosphere, 1,3-dibromo was added. A solution consisting of -5,5-dimethylhydantoin (15.1 g) and 15.8 mL of N, N-dimethylformamide was added dropwise at room temperature over 30 minutes and stirred for 1 hour, followed by stirring at room temperature for 6 hours. The obtained precipitate was filtered, washed with methanol, and then dried under reduced pressure to obtain 16.6 g of the intended 3,7-dibromo-N-octylphenoxazine (purity 99.7%).

¹ H-NMR (299.4 MHz, CDCl ₃ ): 0.89 (t, 3H), 1.18-1.46 (m, 10H), 1.59 (br, 2H), 3.38 (br, 2H), 6.29 (d, 2H), 6.73 (s, 2H), 6.88 (d, 2H).
LC-MS (APPI-MS (posi)): 452 [M + H] ⁺

Synthesis Example 3 Synthesis of Polymer Compound <P-1> 2,7-bis (1,3,2-dioxaborolan-2-yl) -9,9-dioctylfluorene (1.37 g) under an inert atmosphere 2,7-dibromo-9,9-dioctylfluorene (1.22 g), 3,7-dibromo-N-octylphenoxazine (0.18 g), palladium acetate (0.5 mg), tri (2-methylphenyl) ) Phosphine (4.7 mg), Aliquat 336 (0.24 g, manufactured by Aldrich) and toluene (22 ml) were mixed and heated to 105 ° C. To this reaction solution, a 2M Na ₂ CO ₃ aqueous solution (3.6 ml) was added dropwise and refluxed for 2.5 hours. After the reaction, phenylboric acid (26.0 mg) was added, and the mixture was further refluxed for 2 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the mixture was washed 3 times with water (25 ml), 3 times with 3% aqueous acetic acid (25 ml) and 3 times with water (25 ml), and purified by passing through an alumina column and a silica gel column. The obtained toluene solution was added dropwise to methanol (800 ml) and stirred for 1 hour, and then the obtained solid was collected by filtration and dried. The yield of the obtained polymer compound <P-1> was 1.86 g.
The polymer compound <P-1> had a polystyrene equivalent number average molecular weight of 9.1 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 2.1 × 10 ⁵ .

Example 1
[Synthesis of Polymer Compound <P-2>]
Under an inert atmosphere, 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-bis (4-hexyloxy-phenyl) fluorene ( 1.54 g), 2,7-dibromo-9,9-bis (4-hexyloxy-phenyl) fluorene (1.15 g), 3,7-dibromo-N-octylphenoxazine (0.14 g), palladium acetate (0.7 mg), tri (2-methylphenyl) phosphine (8.7 mg), Aliquat 336 (0.28 g, manufactured by Aldrich) and toluene (23 ml) were mixed and heated to 105 ° C. To this reaction solution, 2M Na ₂ CO ₃ aqueous solution (3.9 ml) was added dropwise and refluxed for 4 hours. After the reaction, phenylboric acid (34.3 mg) was added, and the mixture was further refluxed for 1.5 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 80 ° C. for 2.5 hours. After cooling, the mixture was washed 3 times with water (30 ml), 3 times with 3% aqueous acetic acid (30 ml) and 3 times with water (30 ml), and purified by passing through an alumina column and a silica gel column. The obtained toluene solution was added dropwise to methanol (800 ml) and stirred for 3 hours, and then the obtained solid was collected by filtration and dried. The yield of the obtained polymer compound <P-2> was 1.83 g.
The polymer compound <P-2> had a polystyrene equivalent number average molecular weight of 7.8 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 2.0 × 10 ⁵ .
2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9-bis (4-hexyloxy-phenyl) fluorene and 2,7- Dibromo-9,9-bis (4-hexyloxy-phenyl) fluorene was synthesized by the method described in WO2003 / 095586.

[Measurement of Glass Transition Temperature of Polymer Compound <P-2>]
The glass transition temperature was measured by DSC (DSC2920, manufactured by TA Instruments). The sample was held at 200 ° C. for 5 minutes, then rapidly cooled to −50 ° C. and held for 30 minutes. After raising the temperature to 30 ° C., the measurement was carried out to 300 ° C. at a rate of 5 ° C. per minute.
The obtained polymer compound <P-2> had a glass transition temperature of 191 ° C., a high glass transition temperature, and excellent heat resistance.

[Production and Evaluation of Electroluminescence (EL) Element]

Preparation of Polymer Compound <P-3> Solution Polymer compound <P-3> synthesized by the method described in WO2002 / 045185 was dissolved in xylene to prepare a xylene solution having a polymer concentration of 0.5% by weight.

Preparation of Polymer Compound <P-2> Solution The polymer compound <P-2> obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.2% by weight.

Production of EL element A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) is 0.2 μm on a glass substrate on which an ITO film is formed with a thickness of 150 nm by sputtering. A thin film having a thickness of 70 nm was formed by spin coating using the liquid filtered through a membrane filter, and dried on a hot plate at 200 ° C. for 10 minutes. Next, using the xylene solution of the polymer compound <P-3> obtained above, a film was formed by spin coating at a rotational speed of 3000 rpm, and dried on a hot plate at 200 ° C. for 15 minutes. The film thickness after film formation was about 10 nm. Further, using the xylene solution of the polymer compound <P-2> obtained above, a film was formed at a rotational speed of 1200 rpm by spin coating. The film thickness after film formation was about 80 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, barium was deposited as a cathode by about 5 nm, and then aluminum was deposited by about 100 nm to produce an EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 480 nm was obtained from this device. The maximum luminous efficiency was 11.9 cd / A, which was high efficiency.

(Comparative Example 1)
[Measurement of Glass Transition Temperature of Polymer Compound <P-1>]
The glass transition temperature was measured by the same method as for the polymer compound <P-2>.
The obtained polymer compound <P-1> had a glass transition temperature of 76 ° C.

[Production and Evaluation of Electroluminescence (EL) Element]
Preparation of Polymer Compound <P-1> Solution The polymer compound <P-1> obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.2% by weight.
Production of EL element A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, BaytronP AI4083) is 0.2 μm on a glass substrate on which an ITO film is formed with a thickness of 150 nm by sputtering. A thin film having a thickness of 70 nm was formed by spin coating using the liquid filtered through a membrane filter, and dried on a hot plate at 200 ° C. for 10 minutes. Next, using the xylene solution of the polymer compound <P-3> obtained above, a film was formed by spin coating at a rotational speed of 3000 rpm, and dried on a hot plate at 200 ° C. for 15 minutes. The film thickness after film formation was about 10 nm. Further, using the xylene solution of the polymer compound <P-1> obtained above, a film was formed at a rotational speed of 1200 rpm by spin coating. The film thickness after film formation was about 107 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, barium was deposited as a cathode by about 5 nm, and then aluminum was deposited by about 100 nm to produce an EL device. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 470 nm was obtained from this device. The maximum luminous efficiency was 5.19 cd / A.

Claims (17)

A polymer compound comprising a repeating unit represented by the following formula (I) and a repeating unit represented by the following formula (II).

[In the above formula (I), Ar ₁ and Ar ₂ each independently represent an aryl group or a monovalent heterocyclic group, and R ₁ and R ₂ each independently represent an alkyl group, an alkoxy group, an alkylthio group, an aryl group Group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy A group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group, a and b are each independently an integer selected from 0 to 3 Represents. When a plurality of R ₁ and R ₂ are present, they may be the same or different. ]

[In the above formula (II), R ₅ represents an alkyl group, and R ₃ and R ₄ each independently represents an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an aryl group. Alkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, 1 A valent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group is represented, and c and d each independently represents an integer selected from 0 to 3. When a plurality of R ₃ and R ₄ are present, they may be the same or different. ] The polymer compound according to claim 1, wherein the repeating unit represented by the formula (I) is a repeating unit represented by the following formula (III).

[In the above formula (III), Ar ₃ and Ar ₄ each independently represents an aryl group or a monovalent heterocyclic group, and R ₆ and R ₇ each independently represent an alkyl group, an alkoxy group, an alkylthio group, an aryl group Group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy Represents a group, an imine residue, an amide group, an acid imide group, a monovalent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group, and e and f are each independently an integer selected from 0 to 3 Represents. When a plurality of R ₆ and R ₇ are present, they may be the same or different. ] The polymer compound according to claim 2, wherein in the formula (III), Ar ₃ and Ar ₄ are each independently a group represented by the following formula (IV).

[In the above formula (IV), R ₈ is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, Amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, substituted carboxyl group, cyano group Or represents a nitro group, g represents an integer selected from 0 to 5. When a plurality of R ₈ are present, they may be the same or different. ]   4. The polymer compound according to claim 2, wherein e and f are 0 in the formula (III). The polymer compound according to any one of claims 1 to 4, wherein the repeating unit represented by the formula (II) is a repeating unit represented by the following formula (V).

[In the above formula (V), R ₁₁ represents an alkyl group, and R ₉ and R ₁₀ are each independently an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an aryl group. Alkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imine residue, amide group, acid imide group, 1 A valent heterocyclic group, a carboxyl group, a substituted carboxyl group, a cyano group or a nitro group is represented, and h and i each independently represent an integer selected from 0 to 3. When a plurality of R ₉ and R ₁₀ are present, they may be the same or different. ] 6. The polymer compound according to claim 5, wherein h and i are 0 in the formula (V). The polymer compound according to any one of claims 1 to 6, which has a polystyrene-reduced number average molecular weight of 10 ³ to 10 ⁸ .   A composition comprising at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material, and at least one polymer compound according to any one of claims 1 to 7. .   A composition comprising at least two polymer compounds according to any one of claims 1 to 7.   The polymer which has an electrode which consists of an anode and a cathode, and the light emitting layer which is provided between this electrode and contains the polymer compound as described in any one of Claims 1-7, or the composition as described in Claim 8 or 9. Light emitting element.   11. A planar light source comprising the polymer light emitting device according to claim 10.   11. A display device comprising the polymer light emitting device according to claim 10.   A liquid composition comprising the polymer compound according to any one of claims 1 to 7 and a solvent.   A liquid composition comprising the composition according to claim 8 or 9 and a solvent.   A thin film comprising the polymer compound according to any one of claims 1 to 7 or the composition according to claim 8 or 9.   An organic transistor comprising the polymer compound according to any one of claims 1 to 7 or the composition according to claim 8 or 9.   A solar cell comprising the polymer compound according to any one of claims 1 to 7 or the composition according to claim 8 or 9.