JP5274754B2 - Polymer material and polymer light emitting device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer compound having high charge injection property, charge transport property and luminescent efficiency. <P>SOLUTION: The luminescent or charge-transport polymer compound has a (substituted) fluorenediyl group in the main chain as a repeating unit and a functional side chain containing at least one functional group selected from a hole injection and transport group containing one or more hetero-atoms other than nitrogen atom or two or more nitrogen atoms, an electron injection and transport group containing one or more hetero-atoms other than nitrogen atom or two or more nitrogen atoms and a luminescent group containing a condensed polycyclic aromatic hydrocarbon or a heterocyclic group. The functional group is directly bonded to a saturated carbon of the fluorenediyl group or bonded to the fluorenediyl group with the group X through -R<SB>k</SB>-X- bond (R<SB>k</SB>is an alkylene and X is a direct bond or a linking group). <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

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 in various ways because they are soluble in a solvent and can form an organic layer in a light-emitting element by a coating method. For example, as a repeating unit, a cyclopentadiene ring has two benzenes. A polymer compound having the following structure in which a ring is condensed is known (for example, see Non-Patent Document 1 and Patent Document 1).

  In addition, polymer compounds having a functional substituent such as a hole injection / transport group, an electron injection / transport group, or a light emitting group in the side chain of the conjugated main chain are known (for example, Patent Document 2, Patent Document 3, Non-Patent Document (See Patent Document 2 and Non-Patent Document 3).

International Publication No. 99/54385 Pamphlet JP 2004-277568 A WO2001-62822 Advanced Materials, 1999, Vol. 9, No. 10, p. 798 Advanced Material; 2002, 14 (11), 809-811. J. et al. Polymer Science, Part A; 2005, 43 (3), 859-869.

  When a high molecular compound is used as a light emitting material for a light emitting device, in order to emit light with high characteristics, the positive charge (hole) and negative charge (electron) injection and transport properties of the high molecular compound are good. In addition, it is necessary that the luminous efficiency is good. The above known polymer compound has not yet been sufficiently characterized, and a polymer compound having high charge injecting property, transporting property, and luminous efficiency has been desired.

That is, the present invention provides a hole injection containing a fluorenediyl group which may have a substituent in the main chain as a repeating unit, and a hetero atom other than one or more nitrogen atoms or two or more nitrogen atoms At least selected from the group consisting of a transport group, an electron injection transport group containing one or more heteroatoms other than nitrogen atoms or two or more nitrogen atoms, and a light emitting group containing a condensed polycyclic aromatic hydrocarbon or heterocycle A light-emitting or charge-transporting polymer compound having a functional side chain containing one functional group, wherein the functional group is directly bonded to a saturated carbon of the fluorenediyl group, or- Provided is the above polymer compound characterized in that it is bonded to the fluorenediyl group by X via R _k -X- (R _k represents an alkylene group, X represents a direct bond or a linking group). To do.

  The polymer compound of the present invention has the effects of high charge injection and transport properties and high luminous efficiency. When the side chain has a hole injection / transport group, the energy of the highest occupied molecular orbital (HOMO) is increased, the hole injection property and the hole transport property are improved, and the light emission efficiency is increased. When the side chain has an electron injecting and transporting group, the energy of the lowest unoccupied molecular orbital (LUMO) is decreased, the electron injecting property and the electron transporting property are improved, and the light emission efficiency is increased. In the case where the side chain has a light emitting group, it is expected that the light emission efficiency is increased or light is emitted at a wavelength different from the light emission wavelength of the main chain.

When the main chain is an electron transporting polymer compound and the side chain has a hole injecting and transporting group, a new function can be added without hindering the electron transporting property of the main chain. It becomes possible to adjust the transportability. In the case where the main chain is an electron transporting polymer compound and the side chain has a light emitting group, light can be emitted at a wavelength different from the wavelength of the main chain. In addition, when a highly efficient light emitting group is used, the light emission efficiency can be improved. In the case where the main chain is an electron transporting polymer compound and the side chain has an electron injecting and transporting group, the electron transporting property of the main chain can be improved.
By separating the functions of the side chain and the main chain in this way, the function can be imparted without impairing the functionality of the main chain, and higher functionality of the polymer compound is expected.

  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 has a fluorenediyl group which may have a substituent in the main chain.

（式（１）は置換基を有していてもよい。） The full orangeyl group is represented by the following formula (1).

(Formula (1) may have a substituent.)

  When the fluorenediyl group has a substituent, it may have an integer number of substituents selected from 0 to 7 in addition to the functional side chain, and the substituent is an alkyl group, an alkoxy group, an 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 and nitro group are preferred.

  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 , Perfluorohexyl group, perfluorooctyl 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.

An aryl group is an atomic group obtained by removing one hydrogen atom from an aromatic hydrocarbon and having a condensed ring, two or more independent benzene rings or condensed rings bonded directly or via a group such as vinylene. Also included. The aryl group usually has about 6 to 60 carbon atoms, preferably 7 to 48 carbon atoms. Specific examples thereof include phenyl groups, C _{1 to} C ₁₂ alkoxyphenyl groups (C _{1 to} C ₁₂ are carbon numbers). indicates that 1-12. the same applies is less.), C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl, 2-naphthyl, 1-anthracenyl group, 9-anthracenyl group , pentafluorophenyl group and the like, C ₁ -C ₁₂ alkoxyphenyl group, is C ₁ -C ₁₂ alkylphenyl group are preferable. Specific examples C ₁ -C ₁₂ alkoxy, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, Nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified. 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 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, methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, Nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy and the like are exemplified.
C ₁ -C ₁₂ alkylphenoxy such as methyl phenoxy groups as group, ethylphenoxy group, dimethylphenoxy group, propylphenoxy group, 1,3,5-methylphenoxy group, methylethylphenoxy group, isopropylphenoxy group, butylphenoxy 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.

The arylthio group may have a substituent on the aromatic ring, the number of carbon atoms is usually about 3 to 60, specifically, phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 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, the number of carbon atoms is usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkyl group, 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 group exemplified Is done.

Arylalkoxy group may have a substituent, the number of carbon atoms is usually about 7 to 60, specifically, phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxy group, 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 and the like The

The 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 group are exemplified Is done.

Arylalkenyl group has a carbon number of usually about 8 to 60, and examples thereof include 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.

Arylalkynyl group has a carbon number of usually about 8 to 60, and 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 or a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The group or the monovalent heterocyclic group may have a substituent S. The carbon number of the substituted amino group is usually about 1 to 60, preferably 2 to 48, not including the carbon number of the substituent S.
Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino 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, cyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino 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, triazyl amino group phenyl -C 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 groups, 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 groups, 1-naphthyl - C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino groups.

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 or 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-butylsilyldimethylsilyl group, pentyldimethylsilyl group, hexyl Dimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, 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, Examples thereof include a dimethylphenylsilyl group.

  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 has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof 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 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. 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.

  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（１−１）及び（１−２）は置換基を有していてもよい） From the viewpoint of easy synthesis, among the repeating units represented by the above formula (1), the repeating units represented by the following formulas (1-1) and (1-2) are preferable.

(The above formulas (1-1) and (1-2) may have a substituent)

  When the above formulas (1-1) and (1-2) have a substituent, they may have an integer number of substituents selected from 0 to 7 in addition to the functional side chain. This is the same as the illustration in the above formula (1).

  In addition, the polymer compound of the present invention is a hole injection transport group containing one or more heteroatoms other than nitrogen atoms or two or more nitrogen atoms in the side chain, one or more heteroatoms other than nitrogen atoms, or two It has a functional side chain containing at least one functional group selected from the group consisting of the above electron injecting and transporting group containing a nitrogen atom and a light emitting group containing a condensed polycyclic aromatic hydrocarbon or a heterocyclic ring.

  Examples of the hole injecting and transporting group include a monovalent group having a better hole injecting property than the main chain and a monovalent group having a better hole transporting property.

  The hole injection property generally depends on the value of the highest occupied molecular orbital (HOMO) energy of the polymer compound, and the smaller the absolute value of the HOMO energy value, the better the hole injection property.

  Examples of the monovalent group having a better hole injection property than the main chain include a monovalent group having a smaller absolute value of HOMO energy than the main chain.

  HOMO energy can be measured, for example, by measuring the oxidation potential of a polymer compound using cyclic voltammetry (CV) and calculating from the value of the oxidation potential. In the case of the polymer compound of the present invention, the oxidation potential becomes a negative value, and the lower the oxidation potential (the larger the absolute value of the oxidation potential), the smaller the absolute value of the HOMO energy and the better the hole injection property. . When calculating the energy of HOMO from the oxidation potential, the calculation method varies depending on the type of electrode and solvent used in the CV, so refer to the Electrochemical Handbook 5th edition (2000, Maruzen Publishing Co., Ltd.), depending on the type of electrode and solvent. Correct the difference.

  The hole transport property generally depends on the hole mobility of the polymer compound, and the higher the hole mobility, the better the hole injection property.

  Examples of the monovalent group that has better hole transport than the main chain include monovalent groups that have higher hole mobility than the main chain.

  Although the measurement of the hole mobility is not particularly limited, for example, the hole mobility of the polymer compound can be measured using a Time-of-Flight (TOF) method.

  Examples of the electron injecting and transporting group include a monovalent group having a good electron injecting property and a monovalent group having a good electron transporting property compared to the main chain.

  The electron injection property generally depends on the energy value of the lowest unoccupied molecular orbital (LUMO) of the polymer compound. The larger the LUMO absolute energy value, the better the electron injection property.

  Examples of the monovalent group having a better electron injection property than the main chain include a monovalent group having a larger LUMO absolute value than the main chain.

  The LUMO energy can be calculated, for example, by measuring the reduction potential of the polymer compound using cyclic voltammetry (CV) and calculating the reduction potential value. In the case of the polymer compound of the present invention, the reduction potential becomes a negative value. The higher the reduction potential (the smaller the absolute value of the reduction potential), the larger the absolute value of the LUMO energy, and the better the electron injection property. When calculating the LUMO energy from the reduction potential, the calculation method differs depending on the type of electrode and solvent used in the CV, so refer to the Electrochemical Handbook 5th edition (2000, Maruzen Publishing Co., Ltd.), depending on the type of electrode and solvent. Correct the difference.

  The electron transport property generally depends on the electron mobility of the polymer compound, and the higher the electron mobility, the better the electron injection property.

  Examples of the monovalent group that has better electron transport than the main chain include monovalent groups that have higher electron mobility than the main chain.

  Although the measurement of the electron mobility is not particularly limited, for example, the electron mobility of the polymer compound can be measured using a Time-of-Flight (TOF) method.

  A luminescent group is a monovalent group that gives an emission color with a wavelength different from that of the main chain, and generally has a HOMO-LUMO gap (difference between the absolute value of the HOMO energy and the absolute value of the LUMO energy) compared to the main chain. And a monovalent group having a small value.

  The measurement of HOMO and LUMO is the same as described above.

  As the hole injecting and transporting group containing one or more heteroatoms other than nitrogen atoms or two or more nitrogen atoms, monovalent aromatic amine containing two or more nitrogen atoms, monovalent containing two or more nitrogen atoms A monovalent metal complex containing two or more nitrogen atoms, a monovalent group containing one or more nitrogen atoms and one or more heteroatoms other than nitrogen atoms, and a heteroatom other than nitrogen atoms A monovalent group is mentioned.

  Examples of the monovalent aromatic amine containing two or more nitrogen atoms include the following formulas (H-1) to (H-14). Examples of the monovalent carbazole derivative containing two or more nitrogen atoms include the following formula ( H-15) to (H-19) are exemplified, and examples of the monovalent metal complex containing two or more nitrogen atoms include the following formulas (H-20) to (H-22). The monovalent group containing a hetero atom other than an atom and one or more nitrogen atoms includes one R or a residue obtained by removing a hydrogen atom on R from the following formulas (H-23) to (H-25). Illustrative examples of monovalent groups containing heteroatoms other than nitrogen atoms include the following formulas (H-26) to (H-29) from which one R or a hydrogen atom on R is removed. .

  In the above formulas (H-1) to (H-29), R represents a hydrogen atom, 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. 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 , A carboxyl group, a substituted carboxyl group, a cyano group, and a nitro group.

  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 acyl group, acyloxy group, imine residue, amide group, acid imide group, monovalent heterocyclic group, and substituted carboxyl group are the same as those exemplified in the above formula (1).

  In the above formula (H-26), R ′ is selected from a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, an arylalkoxy group, an arylalkylthio group, an arylalkenyl group, an arylalkynyl group, and a monovalent heterocyclic group. It is preferred that

  The alkyl group, aryl group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group and monovalent heterocyclic group are the same as those exemplified in the above formula (1).

The hole injection / transport group may be an oligomer or a polymer.
Specifically, two or more identical or different compounds represented by the above formulas (H-1) to (H-29) are bonded to one R or R from a compound in which R atoms are bonded to each other. Examples include residues excluding hydrogen atoms.

  As an electron injecting and transporting group containing one or more hetero atoms other than nitrogen atoms or two or more nitrogen atoms, monovalent Al and Zn complexes containing one or more hetero atoms other than nitrogen atoms, one or more Monovalent metal complexes other than Al and Zn containing heteroatoms other than nitrogen atoms and elements selected from the second to fourth periods in the periodic table, one or more heteroatoms other than nitrogen atoms, and one or more nitrogen atoms A monovalent group containing only one or more sulfur atoms as a hetero atom, and a monovalent group containing only two or more nitrogen atoms as a hetero atom.

  The following formulas (E-1) to (E-10) are exemplified as monovalent Al and Zn complexes containing one or more heteroatoms other than nitrogen atoms, and the heteroatom and period other than one or more nitrogen atoms are exemplified. The following formulas (E-11) to (E-16) are exemplified as monovalent metal complexes other than Al and Zn containing an element selected from the second to fourth periods in the table, and other than one or more nitrogen atoms Examples of the monovalent group containing a hetero atom of 1 and one or more nitrogen atoms include one R or a residue obtained by removing a hydrogen atom on R from the following formulas (E-17) to (E-27). Examples of monovalent groups containing only one or more sulfur atoms as heteroatoms include the following formulas (E-28) to (E-31) in which one R or a hydrogen atom on R is removed. And monovalent groups containing only two or more nitrogen atoms as heteroatoms are represented by the following formulas (E-32) to ( One R or residues obtained by removing a hydrogen atom on R -40) is exemplified.

  In the above formulas (E-1) to (E-40), R is exemplified by the same ones as shown in (H-1) to (H-29).

The electron injection / transport group may be an oligomer or a polymer.
Specifically, two or more of the same or different compounds represented by the above formulas (E-1) to (E-40) are bonded to each other at a carbon atom to which R is bonded to each other on one R or R. Examples include residues excluding hydrogen atoms.

  The following formulas (E-1) to (E-10) are exemplified as monovalent Al and Zn complexes containing one or more heteroatoms other than nitrogen atoms, and the heteroatom and period other than one or more nitrogen atoms are exemplified. The following formulas (E-11) to (E-16) are exemplified as monovalent metal complexes other than Al and Zn containing an element selected from the second to fourth periods in the table, and other than one or more nitrogen atoms Examples of the monovalent group containing a heteroatom and one or more nitrogen atoms include the following formulas (E-17) to (E-27), and the monovalent group containing only one or more sulfur atoms as a heteroatom. Examples of the group include the following formulas (E-28) to (E-31). Examples of the monovalent group containing only two or more nitrogen atoms as a hetero atom include the following formulas (E-32) to (E-40). ) Is exemplified.

  As the light emitting group containing a condensed polycyclic aromatic hydrocarbon or a heterocyclic ring, a monovalent condensed polycyclic aromatic hydrocarbon group, a monovalent conjugated with two or more condensed polycyclic aromatic hydrocarbon groups Groups, monovalent heterocyclic groups containing only one or more nitrogen atoms and / or oxygen atoms as heteroatoms, and monovalent heterocyclic groups containing one or more sulfur atoms as heteroatoms.

  Examples of the monovalent condensed polycyclic aromatic hydrocarbon group include one R or a residue obtained by removing a hydrogen atom on R from the following formulas (L-1) to (L-5), and two or more Examples of the monovalent group to which the condensed polycyclic aromatic hydrocarbon group is bonded include one R or a residue obtained by removing a hydrogen atom on R from the following formulas (L-6) to (L-8). And a monovalent heterocyclic group containing only one or more nitrogen atoms and / or oxygen atoms as heteroatoms is one hydrogen atom on R or R from the following formulas (L-9) to (L-15): Residues excluding atoms are exemplified, and monovalent heterocyclic groups containing one or more sulfur atoms as heteroatoms are represented by one R or R from the following formulas (L-16) to (L-22): Residues from which the hydrogen atom is removed are exemplified.

  In the above formulas (L-1) to (L-22), R is the same as those shown in (H-1) to (H-29).

  In the above formulas (L-9), (L-10), (L-19), (L-20) and (L-21), R ′ is the same as shown in (H-26). Illustrated.

The light emitting group may be an oligomer or a polymer.
Specifically, two or more of the same or different compounds represented by the above formulas (L-1) to (E-22) are bonded to each other from one carbon atom to which R is bonded to one R or R. Examples include residues excluding hydrogen atoms.

  The functional side chain may be present alone or two or more different functional side chains may be present.

  From the viewpoint of improving hole transportability, the functional side chain is preferably a hole injection transport group, a monovalent aromatic amine containing two or more nitrogen atoms, and a monovalent aromatic containing two or more nitrogen atoms. It is more preferably a carbazole derivative, a monovalent metal complex containing two or more nitrogen atoms, or a monovalent group containing one or more nitrogen atoms and one or more heteroatoms other than nitrogen atoms. More preferably, it is a monovalent aromatic amine containing 2 or more, a monovalent carbazole derivative containing 2 or more nitrogen atoms, or a monovalent metal complex containing 2 or more nitrogen atoms, and 2 or more nitrogen atoms. Most preferably, it is a monovalent aromatic amine containing, or a monovalent carbazole derivative containing two or more nitrogen atoms.

（上記式（Ｈ−Ａ）中、Ａｒ_１０１及びＡｒ_１０２はそれぞれ独立にアリーレン基、２価の複素環基又は金属錯体構造を有する２価の基を表し、Ａｒ_１０３、Ａｒ_１０４及びＡｒ_１０５はそれぞれ独立にアリール基及び１価の複素環基を表す。Ａｒ_１０２とＡｒ_１０３、Ａｒ_１０４とＡｒ_１０５は互いに結合し、環を形成していてもよい。） Furthermore, from the viewpoint of improving hole injection / transport properties, the functional side chain is preferably a monovalent group represented by the following formula (HA).

(In the above formula (HA), Ar ₁₀₁ and Ar ₁₀₂ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure, and Ar ₁₀₃ , Ar ₁₀₄ and Ar ₁₀₅ are Each independently represents an aryl group and a monovalent heterocyclic group, Ar ₁₀₂ and Ar ₁₀₃ , Ar ₁₀₄ and Ar ₁₀₅ may be bonded to each other to form a ring)

  The aryl group and monovalent heterocyclic group have the same meaning as described above.

Here, the arylene group is an atomic group obtained by removing two hydrogen atoms from an aromatic hydrocarbon, and those having a condensed ring, two or more independent benzene rings or condensed rings are directly or via a group such as vinylene. Are also included. The arylene group may have a substituent. The type of the substituent is not particularly limited, but from the viewpoint of solubility, fluorescence characteristics, ease of synthesis, characteristics in the case of an element, etc., an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an 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 and nitro group are preferred.
Carbon number of the part except the substituent in an arylene group is about 6-60 normally, Preferably it is 6-20. Moreover, the total carbon number including the substituent of an arylene group is about 6-100 normally.
Examples of the arylene group include a phenylene group (for example, the following formulas 1 to 3), a naphthalenediyl group (the following formulas 4 to 13), an anthracene-diyl group (the following formulas 14 to 19), and a biphenyl-diyl group (the following formulas 20 to 25). ), Fluorene-diyl group (formula 36-38), terphenyl-diyl group (formula 26-28), condensed ring compound group (formula 29-35), indenonaphthalene-diyl (formula GN) And the like.

The divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and the group may have a substituent.
Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and arsenic in the ring. Say things. Of the divalent heterocyclic groups, an aromatic heterocyclic group is preferable. The type of the substituent is not particularly limited, but from the viewpoint of solubility, fluorescence characteristics, ease of synthesis, characteristics in the case of an element, etc., an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an 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 and nitro group are preferred.
Carbon number of the part except the substituent in a bivalent heterocyclic group is about 3-60 normally. Moreover, the total carbon number including the substituent of a bivalent heterocyclic group is about 3-100 normally.

Examples of the divalent heterocyclic group include the following.
Divalent heterocyclic group containing nitrogen as a hetero atom: pyridine-diyl group (formula 39 to 44), diazaphenylene group (formula 45 to 48), quinoline diyl group (formula 49 to 63), quinoxaline diyl group ( The following formulas 64 to 68), acridine diyl group (the following formulas 69 to 72), bipyridyl diyl group (the following formulas 73 to 75), and phenanthroline diyl group (the following formulas 76 to 78).
Groups having a fluorene structure containing oxygen, silicon, nitrogen, selenium and the like as a hetero atom (the following formulas 79 to 93).
A 5-membered ring heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium, boron, phosphorus and the like as a hetero atom (the following formulas 94 to 98, O to Z, AA to AC).
5-membered ring condensed hetero groups containing oxygen, silicon, nitrogen, selenium and the like as a hetero atom (the following formulas 99 to 110).
A 5-membered ring heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium or the like as a hetero atom, and is a dimer or oligomer bonded at the α-position of the hetero atom (the following formulas 111 to 112).
A 5-membered ring heterocyclic group containing oxygen, silicon, nitrogen, sulfur, selenium or the like as a hetero atom, and a group bonded to the phenyl group at the α-position of the hetero atom (the following formulas 113 to 119).
Groups in which a phenyl group, a furyl group, or a thienyl group is substituted on a 5-membered condensed heterocyclic group containing oxygen, nitrogen, sulfur, selenium, etc. as a hetero atom (the following formulas 120 to 125).
A 6-membered heterocyclic group containing oxygen, nitrogen and the like as a hetero atom (the following formulas AD to AG).

The divalent group having a metal complex structure in Ar ₁ is the remaining divalent group obtained by removing two hydrogen atoms from the organic ligand of the metal complex having an organic ligand.
The organic ligand usually has about 4 to 60 carbon atoms. Examples thereof include 8-quinolinol and derivatives thereof, benzoquinolinol and derivatives thereof, 2-phenyl-pyridine and derivatives thereof, and 2-phenyl-benzo. Examples include thiazole and derivatives thereof, 2-phenyl-benzoxazole and derivatives thereof, porphyrin and derivatives thereof.
Examples of the central metal of the complex include aluminum, zinc, beryllium, iridium, platinum, gold, europium, and terbium.
Examples of the metal complex having an organic ligand include a low-molecular fluorescent material, a metal complex known as a phosphorescent material, and a triplet light-emitting complex.

Specific examples of the divalent group having a metal complex structure include the following 126 to 132.

  In the above formulas 1-132, R is exemplified by the same groups as those shown in the above formulas (H-1) to (H-29).

From the viewpoint of synthesis, A ₁₀₂ is preferably an arylene group, and more preferably a group represented by Formulas 1-19.

From the viewpoint of synthesis, A ₁₀₃ , A ₁₀₄ and A ₁₀₅ are preferably each independently an aryl group, and phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group or 9 -Anthracenyl group is more preferable.

Further, from the viewpoint of synthesis, Ar ₁₀₁ is preferably an arylene group.

When Ar ₁₀₂ and Ar ₁₀₃ , Ar ₁₀₄ and Ar ₁₀₅ form a ring, it is preferable to form a ring via —JJ—.
(-JJ- is a direct bond, -O -, - S -, - CH 2 - represents a.)

  From the viewpoint of improving electron transport properties, the functional side chain is preferably an electron injection / transport group, and monovalent Al and Zn complexes containing one or more heteroatoms other than nitrogen atoms, one or more nitrogen atoms A monovalent metal complex other than Al and Zn containing an element selected from the second to fourth periods in the periodic table, a monovalent group containing only one or more sulfur atoms as a hetero atom, or hetero More preferably, it is a monovalent group containing only two or more nitrogen atoms as atoms, monovalent Al and Zn complexes containing hetero atoms other than one or more nitrogen atoms, and one or more sulfur as hetero atoms. More preferably, it is a monovalent group containing only atoms, or a monovalent group containing only two or more nitrogen atoms as heteroatoms.

（上記式（Ｅ−Ａ）〜（Ｅ−Ｃ）中、Ａｒ_１０７及びＡｒ_１１１はそれぞれ独立にアリーレン基、２価の複素環基又は金属錯体構造を有する２価の基を表し、Ａｒ_１０６、Ａｒ_１０８、Ａｒ_１０９及びＡｒ_１１０はそれぞれ独立にアリール基及び１価の複素環基を表し、Ｑ_１は酸素原子、硫黄原子又は−Ｎ（Ｒ_１０１）−を表し、Ｑ_２、Ｑ_３、Ｑ_４、Ｑ_５及びＱ_６は窒素原子又は−Ｃ（Ｒ_１０２）−を表す。
Ｒ_１０１及びＲ_１０２としては、上記Ｒと同様の基を表す。） Furthermore, from the viewpoint of improving electron injection / transport properties, the functional side chain is preferably a monovalent group represented by the following formulas (EA) to (EC).

(In the above formulas (EA) to (EC), Ar ₁₀₇ and Ar ₁₁₁ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure, Ar ₁₀₆ , Ar ₁₀₈ , Ar ₁₀₉ and Ar ₁₁₀ each independently represent an aryl group and a monovalent heterocyclic group, Q ₁ represents an oxygen atom, a sulfur atom or —N (R ₁₀₁ ) —, and Q ₂ , Q ₃ , Q ₄ , Q ₅ and Q _{6 each} represent a nitrogen atom or —C (R ₁₀₂ ) —.
R ₁₀₁ and R ₁₀₂ represent the same groups as R described above. )

  An arylene group, a divalent heterocyclic group, a divalent group having a metal complex structure, an aryl group, and a monovalent heterocyclic group have the same meanings as described above.

In the above formula (EA), Ar ₁₀₆ is preferably a monovalent heterocyclic group from the viewpoint of improving electron injecting and transporting properties.

From the viewpoint of synthesis, in the formula (EB), Ar ₁₀₇ is preferably a divalent heterocyclic group, and is preferably a group represented by formulas 39 to 72 or 111 to 125.

From the viewpoint of synthesis, in the above formula (EB), Ar ₁₀₈ is preferably a monovalent heterocyclic group.

Further, from the viewpoint of synthesis, in the formula (EC), Ar ₁₀₉ and Ar ₁₁₀ are preferably each independently an aryl group, and a phenyl group, a 1-naphthyl group, a 2-naphthyl group, and a 1-anthracenyl group are preferable. 2-anthracenyl group or 9-anthracenyl group is more preferable.

Furthermore, from the viewpoint of synthesis, A ₁₁₁ is preferably an arylene group, and more preferably a group represented by Formulas 1-19.

  In the above formulas (EA) to (EC), from the viewpoint of improving electron injection transportability, the above formula (EA) or (EB) is preferable, and the above formula (EB). More preferably.

  From the viewpoint of improving luminous efficiency, the functional side chain is preferably a luminescent group, and a monovalent condensed polycyclic aromatic hydrocarbon group or two or more condensed polycyclic aromatic hydrocarbon groups are bonded to each other. It is more preferably a monovalent group or a monovalent heterocyclic group containing only one or more nitrogen atoms and / or oxygen atoms as heteroatoms, and two or more condensed polycyclic aromatic hydrocarbon groups are More preferably, it is a bonded monovalent group or a monovalent heterocyclic group containing only one or more nitrogen atoms and / or oxygen atoms as heteroatoms.

（上記式（Ｌ−Ａ）又は（Ｌ−Ｂ）中、Ｑ_７及びＱ_８は酸素原子、硫黄原子、−Ｃ（Ｒ_１０３Ｒ_１０４）−、−Ｓｉ（Ｒ_１０５Ｒ_１０６）−、−Ｎ（Ｒ_１０７）−、−Ｃ（＝Ｏ）−又は−Ｓ（＝Ｏ）−を表し、Ｑ_９、Ｑ_１０、Ｑ_１１及びＱ_１２は窒素原子又は−Ｃ（Ｒ_１０８）−を表す。
Ｒ_１０３〜Ｒ_１０８としては、上記Ｒと同様の基を表す。） From the viewpoint of improving luminous efficiency, the functional side chain is preferably a monovalent group containing a partial structure (LA) or (LB).

(The formula (L-A) or (L-B) in, _{Q 7} and _{Q 8} represents an oxygen atom, a sulfur _{atom, -C (R 103 R 104)} -, - Si (R 105 R 106) -, - N (R ₁₀₇ ) —, —C (═O) — or —S (═O) — is represented, and Q ₉ , Q ₁₀ , Q ₁₁ and Q ₁₂ represent a nitrogen atom or —C (R ₁₀₈ ) —.
R _{103 to} R ₁₀₈ represent the same groups as R described above. )

From the viewpoint of improving luminous efficiency, Q ₇ and Q ₈ are preferably oxygen atoms, —C (R ₁₀₃ R ₁₀₄ ) —, —N (R ₁₀₇ ) — and —C (═O) —, and oxygen atoms , —N (R ₁₀₇ ) — and —C (═O) — are more preferable.

From the viewpoint of improving luminous efficiency, Q ₉ , Q ₁₀ , Q ₁₁ and Q ₁₂ are preferably —C (R ₁₀₈ ) —.

In the polymer compound of the present invention, the functional group in the functional side chain is directly bonded to the saturated carbon of the fluorenediyl group, or -R _k -X- (R _k represents an alkylene group, X Is a direct bond or a linking group), and is characterized by being bonded to the fluorenediyl group by X.

Here, the functional group is directly bonded to the saturated carbon of the fluorenediyl group. The 9-position carbon atom of the fluorenediyl group shown in the following formula is directly bonded to the functional group in the functional side chain. Indicates the case.

R _k in the case where the functional group is attached to the fluorenediyl group X via -R _k -X- represents an alkylene group, the alkylene group may have a substituent, The number of carbon atoms is usually about 1 to 12, and the substituents include alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, arylalkyl groups, arylalkoxy groups, arylalkylthio groups, aryls. Alkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, acyl group, acyloxy group, imino group, amide group, acid imide group, monovalent heterocyclic group, carboxyl group, Examples thereof include a substituted carboxyl group and a cyano group. The carbon number of the alkylene group does not include the carbon number of the substituent.
Preferred examples of the alkylene group include —C ₃ H ₆ —, —C ₄ H ₈ —, —C ₅ H ₁₀ —, —C ₆ H ₁₂ —, —C ₈ H ₁₆ —, —C ₁₀ H ₂₀ — and the like. Is mentioned.

Further X represents a linking group, examples of -O -, - S -, - CO -, - CO 2 -, - SO -, - SO 2 -, - SiR 1 R 2 -, NR 3 -, —BR ⁴ —, —PR ⁵ —, and —P (═O) (R ⁶ ) — are preferred, —O—, —S—, and —NR ³ — are preferred, —O—, and —NR ^3. -Is more preferable.

Here, R ^{1 to} R ⁶ represent a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, or a monovalent heterocyclic group.

  From the viewpoint of synthesis, the functional group is preferably substituted at the 9-position of the fluorenediyl group.

  From the viewpoint of synthesis, it is preferable that the functional group is directly bonded to the 9th position of the fluorenediyl group, and the functional group has two functional substituents at the 9th position of the fluorenediyl group. Is more preferable.

  One of the characteristics desired for a polymer compound for a polymer LED is hole injectability. The hole injection property generally depends on the value of the highest occupied molecular orbital (HOMO) energy of the polymer compound, and the smaller the absolute value of the HOMO energy value, the better the hole injection property. In the polymer compound of the present invention, the absolute value of HOMO energy is preferably 5.6 eV or less, more preferably 5.5 eV or less, and more preferably 5.4 eV or less, from the viewpoint of hole injectability. Most preferably it is.

  HOMO energy can be measured, for example, by measuring the oxidation potential of a polymer compound using cyclic voltammetry (CV) and calculating from the value of the oxidation potential. In the case of the polymer compound of the present invention, the oxidation potential becomes a negative value, and the lower the oxidation potential (the larger the absolute value of the oxidation potential), the smaller the absolute value of the HOMO energy and the better the hole injection property. .

  One of the characteristics desired for a polymer compound for a polymer LED is electron injectability. The electron injection property generally depends on the energy value of the lowest unoccupied molecular orbital (LUMO) of the polymer compound, and the larger the absolute value of the LUMO energy value, the better the electron injection property. In the polymer compound of the present invention, the absolute value of LUMO energy is preferably 2.2 eV or more, more preferably 2.4 eV or more, and more preferably 2.5 eV or more from the viewpoint of electron injectability. Most preferred.

  Similar to the measurement of the HOMO energy, the LUMO energy can be calculated from the reduction potential value by measuring the reduction potential of the polymer compound using, for example, cyclic voltammetry (CV). In the case of the polymer compound of the present invention, the reduction potential becomes a negative value. The higher the reduction potential (the smaller the absolute value of the reduction potential), the larger the absolute value of the LUMO energy, and the better the electron injection property.

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 preferable example of the high molecular compound in this invention is described here.

  From the viewpoint of luminous efficiency, device durability, and ease of synthesis, the repeating unit of the main chain is represented by the following formulas (1-1-1) to (1-1-6) or (1-2-1) to ( 1-2-6) is preferred. The following formulas (1-1-1) to (1-1-6) and (1-2-1) to (1-2-6) may have a substituent. Examples of the substituent include the same as the substituent.

（式中、Ｊは−Ｒ_k−Ｘ−を表し、Ｒ_k、及びＸは前記と同じ意味を表し、Ｒ_kがＦｕｎに結合し、Ｆｕｎは１個以上の窒素原子以外のヘテロ原子若しくは２個以上の窒素原子を含む正孔注入輸送基及び／又は１個以上の窒素原子以外のヘテロ原子若しくは２個以上の窒素原子を含む電子注入輸送基及び／又は縮合多環芳香族炭化水素若しくは複素環を含む発光基を含む機能性側鎖を表し、Ｒ_W1〜Ｒ_W4及びＲ_X1〜Ｒ_X4はそれぞれ独立に、水素原子、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、シアノ基又はニトロ基を表し、ＲｗとＲｘはそれぞれ互いに結合して環を形成していてもよい。）

(In the formula, J represents -R _k -X-, R _k and X have the same meaning as described above, R _k is bonded to Fun, and Fun is a hetero atom other than one or more nitrogen atoms or 2 Hole injection / transport group containing one or more nitrogen atoms and / or one or more hetero atoms other than nitrogen atom or electron injection / transport group containing two or more nitrogen atoms and / or condensed polycyclic aromatic hydrocarbon or hetero Represents a functional side chain containing a light-emitting group containing a ring, and R _{W1 to} R _W4 and R _{X1 to} R _X4 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group. Group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, silyl group, substituted silyl group, halogen atom, Represents an alkyl group, an acyloxy 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 Rw and Rx are bonded to each other to form a ring. (It may be formed.)

R _k and X are the same as those exemplified above.

From the viewpoints of luminous efficiency, element durability, and ease of synthesis, the above formulas (1-1-1) to (1-1-6) and (1-2-1) to (1-2-6) In the case where the alkylene group represented by R _k in J has a substituent, the substituent 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. Group, arylalkylthio group, arylalkenyl group, arylalkynyl group, monovalent heterocyclic group, alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, aryl More preferably, it is an alkoxy group or a monovalent heterocyclic group, and more preferably an alkyl group, an alkoxy group, an aryl group or a monovalent heterocyclic group. Preferred, an alkyl group, an alkoxy group, and most preferably an aryl group.

From the viewpoint of luminous efficiency, device durability, and ease of synthesis, when X is a linking group, X is —O—, —S—, —CO—, —, —SiR ¹ R ² —, —NR. ^3- or -BR ^4- is preferred, -O-, -S-, -SiR ¹ R ^2- , or -NR ^3- is more preferred, -O-, -S-, or -NR ³ - and more preferably, -O-, or -NR ³ - and most preferably.

  A hole injection / transport group containing one or more heteroatoms other than nitrogen atoms or two or more nitrogen atoms and / or an electron injection / transport group containing one or more heteroatoms other than nitrogen atoms or two or more nitrogen atoms And / or the light emitting group containing a condensed polycyclic aromatic hydrocarbon or a heterocyclic ring is the same as those exemplified above.

  From the viewpoints of luminous efficiency, element durability, and ease of synthesis, the above formulas (1-1-1) to (1-1-6) and (1-2-1) to (1-2-6) In the case where Fun is a hole injecting and transporting group, it is preferably a residue obtained by removing one R or a hydrogen atom on R from the above formulas (H-1) to (H-29). It is a residue obtained by removing one hydrogen atom on R or R from formulas (H-1) to (H-3), (H-5), and (H-15) to (H-17). Is more preferably a residue obtained by removing one R or a hydrogen atom on R from the above formulas (H-1), (H-2), (H-15), and (H-16). Further preferred.

  From the viewpoints of luminous efficiency, element durability, and ease of synthesis, the above formulas (1-1-1) to (1-1-6) and (1-2-1) to (1-2-6) Among these, when Fun is an electron injecting and transporting group, it is preferably a residue obtained by removing one R or a hydrogen atom on R from the above formulas (E-1) to (E-40). It is more preferably a residue obtained by removing one R or a hydrogen atom on R from (E-1) to (E-10) and (E-28) to (E-31). E-1), (E-2), (E-4) to (E-6), (E-28), and (E-31) from which one R or a hydrogen atom on R is removed More preferably, it is a group obtained by removing one R or a hydrogen atom on R from (E-1), (E-2), (E-28), and (E-31). Most preferred.

  From the viewpoints of luminous efficiency, element durability, and ease of synthesis, the above formulas (1-1-1) to (1-1-6) and (1-2-1) to (1-2-6) Among them, when Fun is a luminescent group, it is preferably a residue obtained by removing one R or a hydrogen atom on R from the above formulas (L-1) to (L-22). It is more preferably a residue obtained by removing one R or a hydrogen atom on R from (-6) to (L-8) and (L-9) to (L-16). 6), (L-7), and (L-9) to (L-14), more preferably a residue obtained by removing one R or a hydrogen atom on R, and the above formula (L-6 ), (L-7), and (L-9) to (L-14), most preferably a residue obtained by removing one R or a hydrogen atom on R.

  From the viewpoints of luminous efficiency, device durability, and ease of synthesis, the above formulas (H-1) to (H-29), (E-1) to (E-40), and (L-1) to (L) L-22), R is a hydrogen atom, 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, preferably a hydrogen atom, 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 a monovalent heterocyclic ring. More preferably a hydrogen atom, an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group. Ku, a hydrogen atom, an alkyl group, and most preferably an alkoxy group, or an aryl group.

  From the viewpoints of luminous efficiency, device durability, and ease of synthesis, the repeating units in the main chain are represented by the formulas (1-1-1) to (1-1-6) and (1-2-1) to ( In 1-2-6), the above formulas (1-1-1) to (1-1-4) or (1-2-1) to (1-2-4) are preferable. It is more preferable that it is (1-1-2), (1-1-4), (1-2-2), or (1-2-4).

  From the viewpoints of luminous efficiency, device durability, and ease of synthesis, the above formulas (1-1-1) to (1-1-6) and (1-2-1) to (1-2) When the group represented by 6) has a substituent, the substituent is an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, aryl. An alkenyl 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 a monovalent group And more preferably an alkyl group, an alkoxy group, an aryl group, or a monovalent heterocyclic group. , Alkyl group, and most preferably an alkoxy group, or an aryl group.

The specific example of the high molecular compound in this invention is described here.
When the side chain has a hole injecting and transporting group, (5-1-1) to (5-4-2) are exemplified.
When the side chain has an electron injecting and transporting group, (6-1) to (6-4-2) are exemplified.
When the side chain has a luminescent group, (7-1) to (7-4-2) are exemplified.

The polymer compound of the present invention is a copolymer containing one or more other repeating units in addition to the above repeating units from the viewpoint of changing the emission wavelength, increasing the luminous efficiency, improving the heat resistance, and the like. Preferably there is. As the repeating unit other than the repeating unit, a repeating unit represented by the following formula (8) is preferable.
-Ar _1- (8)
(In the formula, each Ar ₁ independently represents an arylene group, a divalent heterocyclic group, or a divalent group having a metal complex structure.)

Examples of the divalent group having an arylene group, divalent heterocyclic group or metal complex structure include the same groups as described above.

（式中、Ｒ_a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、シアノ基又はニトロ基を示す。ａは０〜４の整数を示す。Ｒ_aが複数存在する場合、それらは同一でも異なっていてもよい。）

（式中、Ｒ_b及びＲ_c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、シアノ基又はニトロ基を示す。ｂ及びｃはそれぞれ独立に０〜３の整数を示す。Ｒ_b及びＲ_cがそれぞれ複数存在する場合、それらは同一でも異なっていてもよい。
）

（式中、Ｒ_d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、シアノ基又はニトロ基を示す。ｄは０〜２の整数を示す。Ａｒ₂及びＡｒ₃はそれぞれ独立に、アリーレン基、２価の複素環基又は金属錯体構造を有する２価の基を示す。ｍ及びｎはそれぞれ独立に０又は１を示す。Ｘ₁は、Ｏ、Ｓ、ＳＯ、ＳＯ₂、Ｓｅ、又はＴｅを示す。Ｒ_dが複数存在する場合、それらは同一でも異なっていてもよい。）

（式中、Ｒ_e及びＲ_f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、シアノ基又はニトロ基を示す。ｅ及びｆはそれぞれ独立に０〜４の整数を示す。Ｘ₂は、Ｏ、Ｓ、ＳＯ₂、Ｓｅ、Ｔｅ、Ｎ−Ｒ⁷、又はＳｉＲ⁸Ｒ⁹を示す。Ｘ₃及びＸ₄は、それぞれ独立にＮ又はＣ−Ｒ¹⁰を示す。Ｒ⁷、Ｒ⁸ _、Ｒ⁹及びＲ¹⁰はそれぞれ独立に、水素原子、アルキル基、アリール基、アリールアルキル基又は１価の複素環基を示す。Ｒ_e、Ｒ_f及びＲ¹⁰が複数存在する場合、それらは同一でも異なっていてもよい。）
式（１２）で示される繰り返し単位の中央の５員環の例としては、チアジアゾール、オキサジアゾール、トリアゾール、チオフェン、フラン、シロールなどが挙げられる。 Among the repeating units represented by the above formula (8), the repeating units represented by the following formula (9), formula (10), formula (11) or formula (12) are preferable.

(Wherein, R _a represents 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, an 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 nitro group A represents an integer of 0 to 4. When _a plurality of R _a are present, they may be the same or different.

(Wherein R _b and R _c 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, 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 A group, a cyano group or a nitro group, b and c each independently represent an integer of 0 to 3. When a plurality of R _b and R _c are present, they may be the same or different.
)

Wherein R _d 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, an 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 nitro group D represents an integer of 0 to _2. Ar ₂ and Ar ₃ each independently represent an arylene group, a divalent heterocyclic group or a divalent group having a metal complex structure, and m and n are each Independently represents 0 or 1. X ₁ represents O, S, SO, SO ₂ , Se, or Te, and when a plurality of R _d are present, they are the same But it may be different.)

(Wherein R _e and R _f are each independently 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 A group, a cyano group, or a nitro group, e and f each independently represent an integer of 0 to 4. X ₂ is O, S, SO ₂ , Se, Te, N—R ⁷ , or SiR ⁸ R ^9. .X ₃ and X ₄ illustrates a are each independently show N or ^{C-R 10 .R 7, R} 8, R 9 and R ¹⁰ are independently a hydrogen atom, an alkyl group, .R _e indicating the aryl group, arylalkyl group or monovalent heterocyclic group, if R _f and R ¹⁰ is plurally present, they may be the same or different.)
Examples of the central 5-membered ring of the repeating unit represented by the formula (12) include thiadiazole, oxadiazole, triazole, thiophene, furan, silole and the like.

（式中、Ａｒ₄、Ａｒ₅、Ａｒ₆及びＡｒ₇はそれぞれ独立にアリーレン基又は２価の複素環基を示す。Ａｒ₈、Ａｒ₉及びＡｒ₁₀はそれぞれ独立にアリール基、又は１価の複素環基を示す。Ａｒ₄、Ａｒ₅、Ａｒ₆、Ａｒ₇、及びＡｒ₈は置換基を有していてもよい。ｏ及びｐはそれぞれ独立に０又は１を示し、０≦ｏ＋ｐ≦１である。） Moreover, it is preferable that the repeating unit shown by following formula (13) is included also from a viewpoint of changing a light emission wavelength, a viewpoint of improving luminous efficiency, and a viewpoint of improving heat resistance.

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

Specific examples of the repeating unit represented by the above formula (13) include those represented by the following formulas 133 to 140.

In the above formula, R is the same as that in formulas 1-132. In order to increase the solubility in a solvent, it is preferable to have at least one other than a hydrogen atom, and it is preferable that the symmetry of the shape of the repeating unit including a substituent is small.
In the above-mentioned formula, in the substituent in which R contains alkyl, it is preferable that one or more alkyls having a cyclic or branched structure are contained in order to enhance the solubility of the polymer compound in the solvent.
Furthermore, in the above formula, when R contains an aryl group or a heterocyclic group as a part thereof, they may further have one or more substituents.

In the repeating unit represented by the above formula (13), Ar ₄ , Ar ₅ , Ar ₆ and Ar ₇ are each independently an arylene group, and Ar ₈ , Ar ₉ and Ar ₁₀ are each independently an aryl group. preferable. Among them, it is preferable that Ar ₈ , Ar ₉ and Ar ₁₀ are each independently an aryl group having 3 or more substituents, and Ar ₈ , Ar ₉ and Ar ₁₀ are phenyl groups having 3 or more substituents, More preferred is a naphthyl group having three or more substituents or an anthranyl group having three or more substituents, and Ar ₈ , Ar ₉ and Ar ₁₀ are phenyl groups having three or more substituents. Further preferred.

（式中、Ｒ¹¹、Ｒ¹²及びＲ¹³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、シリルオキシ基、置換シリルオキシ基、１価の複素環基又はハロゲン原子を表す。） Among them, it is preferable that Ar ₈ , Ar ₉ and Ar ₁₀ are each independently the following formula (13-1) and o + p = 1.

Wherein R ¹¹ , R ¹² and R ¹³ are each independently an alkyl group, alkoxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkoxy group, arylalkylthio group, aryl An alkenyl group, an arylalkynyl group, an amino group, a substituted amino group, a silyl group, a substituted silyl group, a silyloxy group, a substituted silyloxy group, a monovalent heterocyclic group or a halogen atom.

More preferably, in the above formula (13-1), R ₁₁ and R ₁₃ are each independently an alkyl group having 3 or less carbon atoms, an alkoxy group having 3 or less carbon atoms, or an alkylthio group having 3 or less carbon atoms, and R Examples include those in which ₁₂ is an alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, or an alkylthio group having 3 to 20 carbon atoms.

Moreover, it is preferable that the repeating unit shown by the said Formula (8) from a viewpoint of luminous efficiency is a condensed ring, and shows by said Formula 30-38, GN, 49-93, O-Z, and AA-AC. More preferably, it is a divalent group.
Among these, from the viewpoint of synthesis, a divalent group represented by the above formulas 30 to 32, 36, G, J, K, M, 49 to 68, 79 to 93 is preferable. 36, G, K, M, 54, 65, 67, 79, 82, 83, 87, 93, more preferably a divalent group represented by the above formulas 36, G, K, 79, 82, 83. , 87 and 93 are more preferable.

  The polymer compound of the present invention may be a random, block or graft copolymer, or may be a polymer having an intermediate structure thereof, such as a random copolymer having a block property. Good. 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 or a block or graft copolymer is 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 includes a heteroatom other than one or more nitrogen atoms or a hole injection transport group including two or more nitrogen atoms, a heteroatom other than one or more nitrogen atoms, or two or more nitrogen atoms. Having a functional side chain containing at least one functional group selected from the group consisting of an electron injecting and transporting group and a light emitting group containing a condensed polycyclic aromatic hydrocarbon or a heterocyclic ring, Directly bonded to the saturated carbon of the yl group, or bonded to the fluorenediyl group with X via —R _k —X— (R _k represents an alkylene group, X represents a direct bond or a linking group). Represents an optionally substituted fluorenediyl group.
Y ₁ and Y ₂ each independently represent a substituent capable of condensation polymerization.

  In addition, when the polymer compound of the present invention has a repeating unit other than -A-, a compound having two substituents involved in condensation polymerization, which becomes a repeating unit other than -A-, coexists. What is necessary is just to carry out condensation polymerization.

Examples of the compound having two condensation-polymerizable substituents that are repeating units other than the repeating unit represented by -A- include compounds represented by Y ₃ -Ar ₁ -Y ₄ (wherein Ar ₁ Is the same as above, and Y ₃ and Y ₄ each independently represent a substituent involved in condensation polymerization.
In addition to the compound represented by Y ₁ -A-Y ₂ , the polymer compound of the present invention can be produced by condensation polymerization of a compound represented by Y ₃ -Ar ₁ -Y ₄ .

（式中、Ａｒ₄、Ａｒ₅、Ａｒ₆、Ａｒ₇、Ａｒ₈、Ａｒ₉、Ａｒ₁₀、ｏ及びｐの定義及び好ましい例については前記と同じ。Ｙ₅及びＹ₆はそれぞれ独立に縮合重合に関与する置換基を示す。） Moreover, as a compound which has a substituent which participates in two polymerization condensation corresponding to the said Formula (13) used as repeating units other than the repeating unit shown by the said Formula (1), it shows by following formula (14). Compounds.

(In the formula, the definitions and preferred examples of Ar ₄ , Ar ₅ , Ar ₆ , Ar ₇ , Ar ₈ , Ar ₉ , Ar ₁₀ , o and p are the same as described above. Y ₅ and Y ₆ are each independently condensation polymerization. The substituent which participates in is shown.)

In the production method of the present invention, the substituent involved in the condensation polymerization includes a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, a sulfonium methyl group, a phosphonium methyl group, a phosphonate methyl group, Examples thereof include a monohalogenated methyl group, —B (OH) ₂ , formyl group, cyano group, vinyl group and the like.

  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.

A preferable substituent as a substituent involved in the condensation polymerization varies depending on the type of polymerization reaction. For example, when a zerovalent nickel complex such as a Yamamoto coupling reaction is used, 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 present invention, specifically, a compound having a plurality of substituents involved in condensation polymerization, which is a monomer, is dissolved in an organic solvent as necessary. For example, using an alkali or a suitable catalyst, It can be carried out at a temperature between the melting point and 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 Macro Rekyura Symposium (Makromol., Macromol.Symp.), Vol. 12, page 229 (1987) may be a known method described, for example.

  In the method for producing a polymer compound of the present invention, a known condensation reaction can be used 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 or 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 , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ ) involved in the condensation polymerization are each independently a halogen atom, an alkyl sulfonate group, or an aryl sulfonate group. Alternatively, a production method selected from arylalkyl sulfonate groups and performing condensation polymerization in the presence of a nickel zero-valent complex is preferable.
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 , Y ₂ , Y ₃ , Y ₄ , Y ₅ and Y ₆ ) involved in the condensation polymerization are each independently a halogen atom, an alkyl sulfonate group, an aryl Total number of moles of halogen atom, alkyl sulfonate group, aryl sulfonate group and arylalkyl sulfonate group (J) selected from sulfonate group, arylalkyl sulfonate group, boric acid group or boric acid ester group, and possessed by all raw material compounds And the ratio of the total number of moles of boric acid groups (—B (OH) ₂ ) and boric acid ester groups (K) is substantially 1 (usually K / J is in the range of 0.7 to 1.2). And a production method of condensation polymerization using a nickel catalyst or a palladium catalyst 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.

Next, the use of the polymer compound of the present invention will be described.
The polymer compound of the present invention usually emits fluorescence or phosphorescence in a solid state and can be used as a polymer light emitter (high molecular weight light emitting material).
Further, the polymer compound has an excellent charge transport ability, and can be suitably used as a polymer LED material or a charge transport material. The polymer LED using the polymer light emitter is a high-performance polymer LED that can be driven with low voltage and high efficiency. Therefore, the polymer LED can be preferably used for a backlight of a liquid crystal display or a device such as a curved or flat light source for illumination, a segment type display element, a dot matrix flat panel display.
The polymer compound of the present invention can also be used as a material for conductive thin films such as laser dyes, organic solar cell materials, organic semiconductors for organic transistors, conductive thin films, and organic semiconductor thin films.
Furthermore, it can also be used as a light-emitting thin film material that emits fluorescence or phosphorescence.

Next, the polymer LED of the present invention will be described.
The polymer LED of the present invention has an organic layer between electrodes composed of an anode and a cathode, and the organic layer contains the polymer compound of the present invention.
The organic layer may be any of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, an interlayer layer, and the like, but the organic layer is preferably a light emitting layer.

  Here, the light emitting layer refers to a layer having a function of emitting light, the hole transporting layer refers to a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. Say. Further, the interlayer layer is present adjacent to the light emitting layer between the light emitting layer and the anode, and serves to isolate the light emitting layer and the anode or the light emitting layer from the hole injection layer or the hole transport layer. It is a layer that has. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer. The electron injection layer and the hole injection layer are collectively referred to as a charge injection layer. Two or more light emitting layers, hole transport layers, hole injection layers, electron transport layers, and electron injection layers may be used independently.

  When the organic layer is a light emitting layer, the light emitting layer which is an organic layer may further contain a hole transporting material, an electron transporting material or a light emitting material. Here, the light-emitting material refers to a material that exhibits fluorescence and / or phosphorescence.

  When the polymer compound of the present invention and the hole transporting material are mixed, the mixing ratio of the hole transporting material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. %. When the polymer material of the present invention and the electron transporting material are mixed, the mixing ratio of the electron transporting material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. Further, when the polymer compound of the present invention and the luminescent material are mixed, the mixing ratio of the luminescent material is 1 wt% to 80 wt%, preferably 5 wt% to 60 wt% with respect to the entire mixture. When the polymer compound of the present invention is mixed with a luminescent material, a hole transporting material and / or an electron transporting material, the mixing ratio of the luminescent material is 1 wt% to 50 wt% with respect to the entire mixture, It is preferably 5 wt% to 40 wt%, and the total of the hole transporting material and the electron transporting material is 1 wt% to 50 wt%, preferably 5 wt% to 40 wt%. Therefore, the content of the polymer compound of the present invention is 98 wt% to 1 wt%, preferably 90 wt% to 20 wt%.

As the hole transporting material, the electron transporting material, and the light emitting material to be mixed, known low molecular compounds, triplet light emitting complexes, or high molecular compounds can be used, but high molecular compounds are preferably used.
As the hole transporting material, electron transporting material, and light emitting material of the polymer compound, WO99 / 13692, WO99 / 48160, GB2340304A, WO00 / 53656, WO01 / 19834, WO00 / 55927, GB23448316, WO00 / 46321, WO00 / 06665, WO99 / 54943, WO99 / 54385, US5777070, WO98 / 06773, WO97 / 05184, WO00 / 35987, WO00 / 53655, WO01 / 34722, WO99 / 24526, WO00 / 22027, WO00 / 22026, WO98 / 27136, US573636 , WO98 / 21262, US5741921, WO97 / 09394, WO96 / 29356, WO96 / 10617, EP07070. 0, WO 95/07955, JP 2001-181618, JP 2001-123156, JP 2001-3045, JP 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000-80167, JP 10-324870, JP 10-114891, JP 9-111233, JP 9-45478, and the like, and derivatives thereof And copolymers, polyarylenes, derivatives and copolymers thereof, polyarylene vinylenes, derivatives and copolymers thereof, and (co) polymers of aromatic amines and derivatives thereof.
Examples of low molecular weight fluorescent materials include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, dyes such as polymethine, xanthene, coumarin, and cyanine, and 8-hydroxyquinoline or derivatives thereof. A complex, an aromatic amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.
Specifically, for example, known ones such as those described in JP-A-57-51781 and 59-194393 can be used.

Examples of triplet light-emitting complexes include Ir (ppy) ₃ , Btp ₂ Ir (acac) having iridium as a central metal, PtOEP having platinum as a central metal, Eu (TTA) ₃ phen having a central metal as europium, and the like. Can be mentioned.

三重項発光錯体は具体的には、例えばNature, (1998), 395, 151、Appl. Phys. Lett. (1999), 75(1), 4、Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105(Organic Light-Emitting Materials and DevicesＩＶ), 119、J. Am. Chem. Soc., (2001), 123, 4304、Appl. Phys. Lett., (1997), 71(18), 2596、Syn. Met., (1998), 94(1), 103、Syn. Met., (1999), 99(2), 1361、Adv. Mater., (1999), 11(10), 852 、Jpn.J.Appl.Phys.,34, 1883 (1995)などに記載されている。

Specific examples of triplet light-emitting complexes include Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met., (1998), 94 (1), 103, Syn. Met., (1999), 99 (2), 1361, Adv. Mater., (1999), 11 (10), 852, Jpn. J. Appl. Phys., 34, 1883 (1995).

The composition of the present invention contains at least one material selected from a hole transport material, an electron transport material, and a light emitting material and the polymer compound of the present invention, and can be used as a light emitting material or a charge transport material. .
The content ratio of the polymer compound of the present invention and at least one material selected from the hole transport material, the electron transport material, and the light emitting material may be determined according to the use, but in the case of the use of the light emitting material, The same content ratio as in the above light emitting layer is preferable.

  Two or more kinds of the polymer compounds of the present invention can be mixed and used as a composition. In order to enhance the properties of the polymer LED, a polymer compound containing a hole injection / transport group in the side chain, a polymer compound containing an electron injection / transport group in the side chain, and a polymer compound containing a light emitting group in the side chain are selected. A composition containing two or more of the polymer compounds is preferred.

  As the film thickness of the light emitting layer of the polymer LED of the present invention, the optimum value varies depending on the material to be used, and it may be selected so that the driving voltage and the light emission efficiency are appropriate values, for example, 1 nm to 1 μm, Preferably it is 2 nm-500 nm, More preferably, it is 5 nm-200 nm.

  Examples of the method for forming the light emitting layer include a method by film formation from a solution. 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 spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used. Printing methods such as a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method are preferable in that pattern formation and multicolor coating are easy.

The ink composition used in the printing method or the like only needs to contain at least one polymer compound of the present invention. Besides the polymer compound of the present invention, a hole transport material, an electron transport material, a light emitting material, Additives such as solvents and stabilizers may be included.
The ratio of the polymer compound of the present invention in the ink composition is usually 20 wt% to 100 wt%, preferably 40 wt% to 100 wt%, based on the total weight of the composition excluding the solvent.
Further, when the solvent is contained in the ink composition, the ratio of the solvent is 1 wt% to 99.9 wt%, preferably 60 wt% to 99.5 wt%, more preferably the total weight of the composition. It is 80 wt%-99.0 wt%.
The viscosity of the ink composition varies depending on the printing method. However, when the ink composition passes through a discharge device such as an ink jet printing method, the viscosity is 1 at 25 ° C. in order to prevent clogging at the time of discharge and flight bending. It is preferably in the range of ˜20 mPa · s.

The solution of the present invention may contain an additive for adjusting viscosity and / or surface tension in addition to the polymer compound of the present invention. As the additive, a high molecular weight polymer compound (thickener) for increasing the viscosity, a poor solvent, a low molecular weight compound for decreasing the viscosity, a surfactant for decreasing the surface tension, and the like are appropriately combined. Use it.
The high molecular weight polymer compound may be any compound that is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission or charge transport. For example, high molecular weight polystyrene, polymethyl methacrylate, or a polymer compound of the present invention having a large molecular weight can be used. The weight average molecular weight is preferably 500,000 or more, more preferably 1,000,000 or more.
A poor solvent can also be used as a thickener. That is, the viscosity can be increased by adding a small amount of a poor solvent for the solid content in the solution. When a poor solvent is added for this purpose, the type and addition amount of the solvent may be selected as long as the solid content in the solution does not precipitate. Considering the stability during storage, the amount of the poor solvent is preferably 50 wt% or less, more preferably 30 wt% or less with respect to the entire solution.

  The solution of the present invention may contain an antioxidant in addition to the polymer compound of the present invention in order to improve storage stability. The antioxidant is not particularly limited as long as it is soluble in the same solvent as the polymer compound of the present invention and does not inhibit light emission or charge transport, and examples thereof include phenol-based antioxidants and phosphorus-based antioxidants.

When the solution of the present invention is used as an ink composition, the solvent to be used is not particularly limited, but a solvent that can dissolve or uniformly disperse materials other than the solvent constituting the ink composition is preferable. Examples of the solvent include chloro solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran, dioxane and anisole, toluene, xylene and the like. Aromatic hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone , Ketone solvents such as benzophenone and acetophenone, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, methyl benzoate and phenyl acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol Polyethyl alcohol and derivatives thereof such as noethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol, methanol, ethanol, propanol, isopropanol And alcohol solvents such as cyclohexanol, sulfoxide solvents such as dimethyl sulfoxide, and amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.
Of these, aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, ester solvents, ketone solvents are preferred from the viewpoint of solubility of polymer compounds, uniformity during film formation, viscosity characteristics, and the like. Toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, s-butylbenzene, anisole, ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene, biphenyl Cyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, 2-propylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 2 Decanone, dicyclohexyl ketone, acetophenone, benzophenone more preferable.
The number of solvents in the solution is preferably two or more, more preferably two to three, and even more preferably two from the viewpoints of film formability and device characteristics.

When two kinds of solvents are contained in the solution, one of the solvents may be in a solid state at 25 ° C. From the viewpoint of film formability, one type of solvent is preferably a solvent having a boiling point of 180 ° C. or higher, and more preferably 200 ° C. or higher. From the viewpoint of viscosity, it is preferable that 1 wt% or more of the aromatic polymer dissolves at 60 ° C. in one of the two solvents, and one solvent out of the two solvents contains 1 wt% at 25 ° C. The above aromatic polymer is preferably dissolved.
When two or more kinds of solvents are contained in the solution, the solvent having the highest boiling point is preferably 40 to 90 wt% of the weight of the total solvent in the solution from the viewpoint of viscosity and film formability, and 50 to 90 wt%. % Is more preferable, and 65 to 85 wt% is more preferable.

  The polymer compound of the present invention contained in the solution may be one type or two or more types, and may contain a polymer compound other than the polymer compound of the present invention as long as device characteristics and the like are not impaired.

  The solution of the present invention may contain water, metal and a salt thereof in the range of 1 to 1000 ppm. Specific examples of the metal include lithium, sodium, calcium, potassium, iron, copper, nickel, aluminum, zinc, chromium, manganese, cobalt, platinum, iridium and the like. Moreover, silicon, phosphorus, fluorine, chlorine, bromine may be included in a range of 1 to 1000 ppm.

  Using the solution of the present invention, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic method A thin film can be produced by a printing method, an offset printing method, an inkjet printing method, or the like. Among these, the solution of the present invention is preferably used for a film forming method by a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method, and more preferably used for a film forming by an ink jet method.

Examples of thin films that can be produced using the solution of the present invention include luminescent thin films, conductive thin films, and organic semiconductor thin films.
The conductive thin film of the present invention 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 / □.
In the organic semiconductor thin film of the present invention, the higher one of the electron mobility and the hole mobility is preferably 10 ⁻⁵ cm ² / V / second or more. More preferably, it is 10 ^<-3 > cm < ² > / V / second or more, More preferably, it is 10 ^<-1 > cm < ² > / V / second or more.
An organic transistor can be formed by forming the 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.

  In addition, as the polymer LED of the present invention, a polymer LED having an electron transport layer provided between the cathode and the light emitting layer, a polymer LED having a hole transport layer provided between the anode and the light emitting layer, Examples include a polymer LED 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.

For example, the following structures a) to d) are specifically 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.)
Further, for each of these structures, a structure in which an interlayer layer is provided adjacent to the light emitting layer between the light emitting layer and the anode is also exemplified. That is,
a ′) Anode / interlayer layer / light emitting layer / cathode b ′) Anode / hole transport layer / interlayer layer / light emitting layer / cathode c ′) Anode / interlayer layer / light emitting layer / electron transport layer / cathode d ′ ) Anode / hole transport layer / interlayer layer / light emitting layer / electron transport layer / cathode

  When the polymer LED of the present invention has a hole transport layer, the hole transport material used is polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, polysiloxane having an aromatic amine in a side chain or a main chain. Derivatives, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5- Thienylene vinylene) or a derivative thereof.

  Specifically, as the hole transporting material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, and JP-A-2-209988 are disclosed. Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as a hole transporting material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, a polyaniline or a derivative thereof , Polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or a polymer hole transporting material such as poly (2,5-thienylene vinylene) or a derivative thereof, and more preferably polyvinyl carbazole or a derivative thereof It is a derivative, polysilane or a derivative thereof, or a polysiloxane derivative having an aromatic amine in the side chain or main chain.

  Examples of the hole transport material of the low molecular weight compound include pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives. In the case of a low molecular weight hole transporting material, it is preferably used by being dispersed in a polymer binder.

  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. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

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

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

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

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

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing a hole transporting material is preferable. Chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as toluene and xylene. Hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane Polyhydric alcohols such as propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl sulfoxide, etc. And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.

  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, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  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 LED of the present invention has an electron transporting layer, known materials can be used as the electron transporting material, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or Derivatives thereof, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline Or a derivative thereof, polyfluorene or a derivative thereof, and the like are exemplified.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.

  Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  There are no particular restrictions on the method for forming the electron transport layer, but for low molecular weight electron transport materials, vacuum deposition from powder or film deposition from a solution or melted state is preferred for polymer electron transport materials. Or the method by the film-forming from a molten state is illustrated, respectively. When forming a film from a solution or a molten state, the above polymer binder may be used in combination.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing an electron transport material and / or a polymer binder is preferable. Chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as toluene and xylene. Hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane Polyhydric alcohols such as propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl sulfoxide, etc. And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.

  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, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  The film thickness of the electron 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 the thickness is too thick, the driving 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 an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, 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 laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

In the present invention, a polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to the cathode, and a charge injection layer adjacent to the anode. The provided polymer LED is mentioned.
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 / electron 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 / electron 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 For each of these structures, the light emitting layer is adjacent to the light emitting layer between the light emitting layer and the anode. A structure in which an interlayer is provided is also exemplified. In this case, the interlayer layer may also serve as a hole injection layer and / or a hole transport layer.

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

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 or less, and the leakage current between the light emitting pixels is reduced. In order to achieve this, 10 ⁻⁵ S / cm to 10 ² is more preferable, and 10 ⁻⁵ S / cm to 10 ¹ is more preferable.

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. 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 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 anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, 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 phthalocyanines (such as copper phthalocyanine), and carbon .

  An insulating layer having a thickness of 2 nm or less has a function of facilitating charge injection. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials. As the polymer LED provided with the insulating layer having a thickness of 2 nm or less, the polymer LED provided with the insulating layer having a thickness of 2 nm or less adjacent to the cathode, or the insulating layer having a thickness of 2 nm or less provided adjacent to the anode. Polymer LED is mentioned.

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode u) Anode / hole transporting layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode w) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode x) anode / Light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode y) anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode z) anode / film Insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode aa) anode / hole transport layer / light emitting layer / electron transport Layer / insulating layer with a thickness of 2 nm or less / cathode ab) anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode For example, a structure in which an interlayer is provided adjacent to the light emitting layer between the light emitting layer and the anode is also exemplified. In this case, the interlayer layer may also serve as a hole injection layer and / or a hole transport layer.

When an interlayer layer is applied to the above structures a) to ab), the interlayer layer is provided between the anode and the light emitting layer, and constitutes the light emitting layer with the anode or the hole injection layer or the hole transport layer. It is preferably made of a material having an ionization potential intermediate to that of the polymer compound.
Examples of materials used for the interlayer layer include polymers containing aromatic amines such as polyvinyl carbazole or derivatives thereof, polyarylene derivatives having aromatic amines in the side chain or main chain, arylamine derivatives, and triphenyldiamine derivatives. .
Although there is no restriction | limiting in the film-forming method of an interlayer layer, For example, when using a polymeric material, the method by the film-forming from a solution is illustrated.
As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing a hole transporting material is preferable. Chlorinated solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and aromatic solvents such as toluene and xylene. Hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane Polyhydric alcohols such as propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl sulfoxide, etc. And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents can be used alone or in combination.
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, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.
The film thickness of the interlayer layer may be selected so that the optimum value varies depending on the material used, and the driving voltage and the light emission efficiency are appropriate values. For example, it is 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.
When the interlayer layer is provided adjacent to the light emitting layer, particularly when both layers are formed by a coating method, the materials of the two layers are mixed to adversely affect the characteristics of the device. There is. When the light emitting layer is formed by the coating method after the interlayer layer is formed by the coating method, as a method for reducing the mixing of the materials of the two layers, the interlayer layer is formed by the coating method, and then the interlayer layer is formed. A method of forming a light emitting layer after heating to insolubilize in an organic solvent used for forming a light emitting layer can be mentioned. The heating temperature is usually about 150 ° C. to 300 ° C., and the time is usually about 1 minute to 1 hour. In this case, in order to remove components that have not been insolubilized by heating, the interlayer layer can be removed by rinsing with a solvent used for forming the light emitting layer after heating and before forming the light emitting layer. When solvent insolubilization by heating is sufficiently performed, rinsing with a solvent can be omitted. In order to sufficiently insolubilize the solvent by heating, it is preferable to use a polymer compound containing at least one polymerizable group in the molecule as the polymer compound used in the interlayer layer. Furthermore, the number of polymerizable groups is preferably 5% or more with respect to the number of repeating units in the molecule.

The substrate on which the polymer LED of the present invention is formed may be any substrate that does not change when the electrode is formed and the organic layer is formed, and examples thereof include glass, plastic, polymer film, and silicon substrate. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.
Usually, at least one of the anode and the cathode of the polymer LED of the present invention is transparent or translucent. The anode side is preferably transparent or translucent.
As the material of the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, as the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used.
The film thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.
In order to facilitate charge injection on the anode, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, or the like. A layer may be provided.

As a material of the cathode used in the polymer LED of the present invention, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, or the like Two or more of these alloys, or one or more of them and an alloy of one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, or graphite or graphite intercalation compound Etc. are used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, and the like. The cathode may have a laminated structure of two or more layers.
The thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

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

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

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

  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. 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.

The number average molecular weight in terms of polystyrene was determined by SEC.
Column: TOSOH TSKgel SuperHM-H (2) + TSKgel SuperH2000 (4.6 mm Id × 15 cm), detector: RI (SHIMADZU RID-10A) is used. Tetrahydrofuran (THF) was used as the mobile phase.

アルゴン雰囲気下、３００ｍＬ四つ口フラスコ中でＮ−フェニル−１，４−フェニレンジアミン（５．５３ｇ，３０ｍｍｏｌ）、４−ブロモ−ｎ−ブチルベンゼン（２５．５７ｇ，１２０ｍｍｏｌ）、Ｐｄ₂（ｄｂａ）₃（８２０ｍｇ，０．９ｍｍｏｌ）、ｔ−ＢｕＯＮａ（８．６５ｇ，９０ｍｍｏｌ）、及びトルエン（１２０ｍｌ）を混合した。反応溶液に（ｔ−Ｂｕ）₃Ｐ（３６０ｍｇ，１．８ｍｍｏｌ）を加え、３時間１００℃に加温した。冷却後、トルエン２００ｍｌを加え、ＮａＣｌ水溶液（１００ｍｌ×３）、次いで水（２００ｍｌ）で洗った。有機層を硫酸ナトリウムで乾燥させた後、濃縮した。得られた液体をシリカゲルカラムクロマトグラフィー（トルエン：ヘキサン＝１：３）で精製を行った後、更にシリカゲルカラムクロマトグラフィー（ヘキサン→トルエン：ヘキサン＝１：３）で精製を行うことにより化合物Ｍ−１を１０．２ｇ得た。
¹Ｈ−ＮＭＲ；δ０．９７（９Ｈ，ｔ），１．３７（６Ｈ，ｍ），１．５８（６Ｈ，ｍ），２．５５（６Ｈ，ｔ），６．８５−７．０７（１８Ｈ，ｍ），７．１７（２Ｈ，ｔ）． (Synthesis Example 1)
Synthesis of Compound M-1

N-phenyl-1,4-phenylenediamine (5.53 g, 30 mmol), 4-bromo-n-butylbenzene (25.57 g, 120 mmol), Pd ₂ (dba) in a 300 mL four-necked flask under an argon atmosphere ₃ (820 mg, 0.9 mmol), t-BuONa (8.65 g, 90 mmol), and toluene (120 ml) were mixed. (T-Bu) ₃ P (360 mg, 1.8 mmol) was added to the reaction solution, and the mixture was heated to 100 ° C. for 3 hours. After cooling, 200 ml of toluene was added and washed with an aqueous NaCl solution (100 ml × 3) and then with water (200 ml). The organic layer was dried over sodium sulfate and concentrated. The obtained liquid was purified by silica gel column chromatography (toluene: hexane = 1: 3), and further purified by silica gel column chromatography (hexane → toluene: hexane = 1: 3) to give compound M- 10.2 g of 1 was obtained.
¹ H-NMR; δ 0.97 (9H, t), 1.37 (6H, m), 1.58 (6H, m), 2.55 (6H, t), 6.85-7.07 (18H , M), 7.17 (2H, t).

アルゴン雰囲気下、１００ｍＬ四つ口フラスコ中で化合物Ｍ−１（１．４５ｇ，２．５ｍｍｏｌ）、ＮＢＳ（０．４９ｇ，０．２７ｍｍｏｌ）、及びＤＭＦ（２０ｍｌ）を混合し、０℃で４時間撹拌した。反応終了後ヘキサン１００ｍｌを加え、ＫＣｌ水溶液（１００ｍｌ×２）、次いで水（１００ｍｌ×２）で洗った。有機層を硫酸ナトリウムで乾燥させた後、濃縮した。得られた液体をシリカゲルカラムクロマトグラフィー（トルエン：ヘキサン＝１：６）で２回、精製を行うことにより化合物Ｍ−２を９６０ｍｇ得た。
ＬＣ−ＭＳ（ＡＰＣＩ法）；ｍ／ｚ ６６０．２（〔Ｍ＋Ｈ〕⁺）． (Synthesis Example 2)
Synthesis of compound M-2

Compound M-1 (1.45 g, 2.5 mmol), NBS (0.49 g, 0.27 mmol), and DMF (20 ml) were mixed in a 100 mL four-necked flask under an argon atmosphere, and the mixture was stirred at 0 ° C. for 4 hours. Stir. After completion of the reaction, 100 ml of hexane was added and washed with an aqueous KCl solution (100 ml × 2) and then with water (100 ml × 2). The organic layer was dried over sodium sulfate and concentrated. The obtained liquid was purified twice by silica gel column chromatography (toluene: hexane = 1: 6) to obtain 960 mg of compound M-2.
LC-MS (APCI method); m / z 660.2 ([M + H] ⁺ ).

アルゴン雰囲気下、３００ｍＬ−三つ口フラスコ中で、８−ブロモオクテン（１．９１ｇ，１０ｍｍｏｌ）、及びＴＨＦ（１０ｍｌ）を混合した。ここへ９−ＢＢＮ／０．５Ｍ−ＴＨＦ溶液（２０ｍｌ，１０ｍｍｏｌ）を２０分かけて室温で滴下し、１２時間室温で撹拌を行った。
反応溶液中に化合物Ｍ−２（２．６４ｇ，４．０ｍｍｏｌ）、ＰｄＣｌ₂（ｄｐｐｆ）（１６０ｍｇ，０．２０ｍｍｏｌ）、ＴＨＦ（１０ｍｌ）、及び３Ｍ−ＮａＯＨ水溶液（７ｍｌ）を混合し、４．５時間還流させた。反応終了後、冷却し、ヘキサン（２０ｍｌ）を加えた。水で冷却しながら過酸化水素水（２ｍｌ）を１０分かけて滴下し、室温で３時間撹拌した。得られた有機層を水（２００ｍｌ×３）で洗浄し、硫酸ナトリウムで乾燥後、濃縮した。シリカゲルカラムクロマトグラフィー（トルエン：ヘキサン＝１：１０→トルエン：ヘキサン＝１：３）で２回精製することにより化合物Ｍ−３を１．８１ｇ得た。
ＬＣ−ＭＳ（ＡＰＣＩ法）；ｍ／ｚ ７７２．３（〔Ｍ＋Ｈ〕⁺）． (Synthesis Example 3)
Synthesis of compound M-3

Under an argon atmosphere, 8-bromooctene (1.91 g, 10 mmol) and THF (10 ml) were mixed in a 300 mL three-necked flask. A 9-BBN / 0.5M-THF solution (20 ml, 10 mmol) was added dropwise thereto at room temperature over 20 minutes, and the mixture was stirred at room temperature for 12 hours.
Compound M-2 (2.64 g, 4.0 mmol), PdCl ₂ (dppf) (160 mg, 0.20 mmol), THF (10 ml), and 3M-NaOH aqueous solution (7 ml) were mixed in the reaction solution. Refluxed for 5 hours. After completion of the reaction, the reaction mixture was cooled and hexane (20 ml) was added. Hydrogen peroxide (2 ml) was added dropwise over 10 minutes while cooling with water, and the mixture was stirred at room temperature for 3 hours. The obtained organic layer was washed with water (200 ml × 3), dried over sodium sulfate, and concentrated. By purification twice by silica gel column chromatography (toluene: hexane = 1: 10 → toluene: hexane = 1: 3), 1.81 g of compound M-3 was obtained.
LC-MS (APCI method); m / z 772.3 ([M + H] ⁺ ).

アルゴン雰囲気下、１００ｍＬナス型フラスコ中で２，７−ジブロモフルオレノン（０．３７９ｇ，１．１ｍｍｏｌ）、化合物Ｍ−１（１．３７ｇ，２．３ｍｍｏｌ）、メタンスルホン酸（１滴，触媒量）、及びトルエン（６ｍｌ）を混合し、１５時間、還流させた。冷却後、トルエン３０ｍｌを加え、ＮａＨＣＯ₃水溶液（１００ｍｌ×３）、次いで水（５０ｍｌ×２）で洗った。有機層を硫酸ナトリウムで乾燥させた後、濃縮した。得られた液体をシリカゲルカラムクロマトグラフィー（トルエン：ヘキサン＝３：１）で精製を行った後、更にシリカゲルカラムクロマトグラフィー（トルエン：ヘキサン＝６：１）で精製を行うことにより化合物Ｍ−４を８２０ｍｇ得た。
ＬＣ−ＭＳ（ＡＰＣＩ法）；ｍ／ｚ １４８２．５（〔Ｍ＋Ｈ〕⁺）． (Synthesis Example 4)
Synthesis of compound M-4

2,7-dibromofluorenone (0.379 g, 1.1 mmol), compound M-1 (1.37 g, 2.3 mmol), methanesulfonic acid (1 drop, catalytic amount) in a 100 mL eggplant-shaped flask under argon atmosphere And toluene (6 ml) were mixed and refluxed for 15 hours. After cooling, 30 ml of toluene was added, and the mixture was washed with an aqueous NaHCO ₃ solution (100 ml × 3) and then with water (50 ml × 2). The organic layer was dried over sodium sulfate and concentrated. The obtained liquid was purified by silica gel column chromatography (toluene: hexane = 3: 1), and further purified by silica gel column chromatography (toluene: hexane = 6: 1) to give compound M-4. 820 mg was obtained.
LC-MS (APCI method); m / z 1482.5 ([M + H] ⁺ ).

アルゴン雰囲気下、１００ｍＬナス型フラスコ中で２，７−ジヒドロ−９，９−ジヒドロフルオレン（０．２６ｇ，０．８ｍｍｏｌ）、化合物Ｍ−３（１．８５ｇ，２．４ｍｍｏｌ）、テトラブチルアンモニウムブロミド（５０ｍｇ，０．８ｍｍｏｌ）、５０％水酸化ナトリウム水溶液（５ｍｌ）、及びトルエン（２０ｍｌ）を混合し、１３時間、還流させた。冷却後、トルエン３０ｍｌを加え、水（５０ｍｌ×２）で洗った。有機層を硫酸ナトリウムで乾燥させた後、濃縮した。得られた液体をシリカゲルカラムクロマトグラフィー（トルエン：ヘキサン＝１：５）で精製を行った後、更にシリカゲルカラムクロマトグラフィー（トルエン：ヘキサン＝１：４０）で精製を行うことにより化合物Ｍ−５を８２０ｍｇ得た。
ＬＣ−ＭＳ（ＡＰＣＩ法）；ｍ／ｚ １７０５（〔Ｍ＋Ｈ〕⁺）． (Synthesis Example 5)
Synthesis of compound M-5

2,7-dihydro-9,9-dihydrofluorene (0.26 g, 0.8 mmol), compound M-3 (1.85 g, 2.4 mmol), tetrabutylammonium bromide in a 100 mL eggplant type flask under argon atmosphere (50 mg, 0.8 mmol), 50% aqueous sodium hydroxide solution (5 ml), and toluene (20 ml) were mixed and refluxed for 13 hours. After cooling, 30 ml of toluene was added and washed with water (50 ml × 2). The organic layer was dried over sodium sulfate and concentrated. The obtained liquid was purified by silica gel column chromatography (toluene: hexane = 1: 5), and further purified by silica gel column chromatography (toluene: hexane = 1: 40) to give compound M-5. 820 mg was obtained.
LC-MS (APCI method); m / z 1705 ([M + H] ⁺ ).

アルゴン雰囲気下、３００ｍＬ−三つ口フラスコ中で、８−ブロモオクテン（１２．６１ｇ，６６ｍｍｏｌ）、及びＴＨＦ（４０ｍｌ）を混合した。ここへ９−ＢＢＮ／０．５Ｍ−ＴＨＦ溶液（１３２ｍｌ，６６ｍｍｏｌ）を５０分かけて室温で滴下し、１６時間室温で撹拌を行った。
反応溶液中に化合物９−ブロモアントラセン（７．７１ｇ，３０ｍｍｏｌ）、ＰｄＣｌ₂（ｄｐｐｆ）（１．２２ｇ，１．５ｍｍｏｌ）、ＴＨＦ（６０ｍｌ）、及び３Ｍ−ＮａＯＨ水溶液（４０ｍｌ）を混合し、６．５時間還流させた。反応終了後、冷却し、ヘキサン（７０ｍｌ）を加えた。水で冷却しながら過酸化水素水（１０ｍｌ）を３０分かけて滴下し、室温で４時間撹拌した。得られた有機層を水（２００ｍｌ×３）で洗浄し、硫酸ナトリウムで乾燥後、濃縮した。シリカゲルカラムクロマトグラフィー（ヘキサン→トルエン：ヘキサン＝１：２）で精製することにより、化合物Ｍ−６を３．４ｇ得た。
ＬＣ−ＭＳ（ＡＰＣＩ法）；ｍ／ｚ ３７０．１（〔Ｍ＋Ｈ〕⁺）．
¹Ｈ−ＮＭＲ；δ１．４２（８Ｈ，ｔ），１．８６（４Ｈ，ｍ），３．４１（２Ｈ，ｔ），３．６０（２Ｈ，ｔ），７．４６（４Ｈ，ｍ），７．９９（２Ｈ，ｄ），８．２６（２Ｈ，ｄ），８．３３（１Ｈ，ｓ）． (Synthesis Example 6)
Synthesis of compound M-6

Under an argon atmosphere, 8-bromooctene (12.61 g, 66 mmol) and THF (40 ml) were mixed in a 300 mL three-necked flask. A 9-BBN / 0.5M-THF solution (132 ml, 66 mmol) was added dropwise thereto at room temperature over 50 minutes, and the mixture was stirred at room temperature for 16 hours.
The compound 9-bromoanthracene (7.71 g, 30 mmol), PdCl ₂ (dppf) (1.22 g, 1.5 mmol), THF (60 ml), and 3M-NaOH aqueous solution (40 ml) were mixed in the reaction solution. Reflux for 5 hours. After completion of the reaction, the reaction mixture was cooled and hexane (70 ml) was added. Hydrogen peroxide (10 ml) was added dropwise over 30 minutes while cooling with water, and the mixture was stirred at room temperature for 4 hours. The obtained organic layer was washed with water (200 ml × 3), dried over sodium sulfate, and concentrated. By purification by silica gel column chromatography (hexane → toluene: hexane = 1: 2), 3.4 g of compound M-6 was obtained.
LC-MS (APCI method); m / z 370.1 ([M + H] ⁺ ).
¹ H-NMR; δ 1.42 (8H, t), 1.86 (4H, m), 3.41 (2H, t), 3.60 (2H, t), 7.46 (4H, m), 7.9 (2H, d), 8.26 (2H, d), 8.33 (1H, s).

アルゴン雰囲気下、１００ｍＬナス型フラスコ中で２，７−ジヒドロ−９，９−ジヒドロフルオレン（０．６２ｇ，１．９ｍｍｏｌ）、化合物Ｍ−６（１．５４ｇ，４．１ｍｍｏｌ）、テトラブチルアンモニウムブロミド（１４０ｍｇ，１．９ｍｍｏｌ）、５０％水酸化ナトリウム水溶液（１０ｍｌ）、及びトルエン（２０ｍｌ）を混合し、５時間、還流させた。冷却後、トルエン４０ｍｌを加え、水（５０ｍｌ×２）で洗った。有機層を硫酸ナトリウムで乾燥させた後、濃縮した。得られた液体をシリカゲルカラムクロマトグラフィー（トルエン：ヘキサン＝１：１）で精製を行った後、更にシリカゲルカラムクロマトグラフィー（ヘキサン）で精製を行うことにより化合物Ｍ−７を８３０ｍｇ得た。
ＬＣ−ＭＳ（ＡＰＣＩ法）；ｍ／ｚ ９０１．１（〔Ｍ＋Ｈ〕⁺）．
¹Ｈ−ＮＭＲ；δ０．７２（２Ｈ，ｍ），１．１８−１．３５（６Ｈ，ｍ），１．５７（２Ｈ，ｍ），１．８３（２Ｈ，ｍ），２，００（２Ｈ，ｔ），３．６６（２Ｈ，ｔ），７．５５（１０Ｈ，ｍ），８．１０（２Ｈ，ｄ），８．３４（２Ｈ，ｄ），８．４１（１Ｈ，ｓ）． (Synthesis Example 7)
Synthesis of compound M-7

2,7-dihydro-9,9-dihydrofluorene (0.62 g, 1.9 mmol), compound M-6 (1.54 g, 4.1 mmol), tetrabutylammonium bromide in a 100 mL eggplant type flask under argon atmosphere (140 mg, 1.9 mmol), 50% aqueous sodium hydroxide solution (10 ml), and toluene (20 ml) were mixed and refluxed for 5 hours. After cooling, 40 ml of toluene was added and washed with water (50 ml × 2). The organic layer was dried over sodium sulfate and concentrated. The obtained liquid was purified by silica gel column chromatography (toluene: hexane = 1: 1), and further purified by silica gel column chromatography (hexane) to obtain 830 mg of compound M-7.
LC-MS (APCI method); m / z 901.1 ([M + H] ⁺ ).
¹ H-NMR; δ 0.72 (2H, m), 1.18-1.35 (6H, m), 1.57 (2H, m), 1.83 (2H, m), 2,000 (2H) , T), 3.66 (2H, t), 7.55 (10H, m), 8.10 (2H, d), 8.34 (2H, d), 8.41 (1H, s).

アルゴン雰囲気下、２００ｍＬナス型フラスコ中で２，７−ジヒドロ−９，９−ジヒドロフルオレン（２．９４ｇ，８．７ｍｍｏｌ）、フェニル−ジ−ｐ−トルイルアミン（４．９９ｇ，１８．３ｍｍｏｌ）、メタンスルホン酸（０．８４ｇ，触媒量）、及びトルエン（４４ｍｌ）を混合し、１５時間、還流させた。冷却後、トルエン１５０ｍｌを加え、２Ｍ ＮａＨＣＯ₃水溶液（１００ｍｌ×３）、次いで水（１００ｍｌ×２）で洗った。有機層を硫酸ナトリウムで乾燥させた後、濃縮した。得られたオイルをシリカゲルカラムクロマトグラフィー（トルエン：ヘキサン＝３：１）で精製を行うことにより化合物Ｍ−８を１．３３ｇ得た。
ＬＣ−ＭＳ（ＡＰＣＩ法）；ｍ／ｚ ８６５（〔Ｍ＋Ｈ〕⁺）． (Synthesis Example 8)
Synthesis of Compound M-8

2,7-dihydro-9,9-dihydrofluorene (2.94 g, 8.7 mmol), phenyl-di-p-toluylamine (4.99 g, 18.3 mmol) in a 200 mL eggplant-shaped flask under argon atmosphere Methanesulfonic acid (0.84 g, catalytic amount) and toluene (44 ml) were mixed and refluxed for 15 hours. After cooling, 150 ml of toluene was added and washed with 2M aqueous NaHCO ₃ solution (100 ml × 3) and then with water (100 ml × 2). The organic layer was dried over sodium sulfate and concentrated. The obtained oil was purified by silica gel column chromatography (toluene: hexane = 3: 1) to obtain 1.33 g of Compound M-8.
LC-MS (APCI method); m / z 865 ([M + H] ⁺ ).

不活性雰囲気下、化合物Ｍ−４（０．５００ｇ）、及び２，２’−ビピリジル（０．１２６ｇ）をあらかじめアルゴンでバブリングした、脱水テトラヒドロフラン２４ｍＬに溶解した。次に、ビス（１、５−シクロオクタジエン）ニッケル（０）｛Ｎｉ（ＣＯＤ）₂｝（０．２２３ｇ）を加えて攪拌し、この溶液を６０℃まで昇温後、３時間反応させた。
反応液を室温まで冷却し、２５％アンモニア水１ｍＬ／メタノール２４ｍＬ／イオン交換水２４ｍＬ混合溶液中に滴下して１時間攪拌した後、析出した沈殿をろ過して減圧乾燥した。続いてトルエン１０ｍｌに溶解させ、ラヂオライト０．０４ｇを加えて３０分攪拌し、不溶解物を濾過した後、濾液をアルミナカラムを通して精製を行った。次に４％アンモニア水２０ｍＬを加え、２時間攪拌した後に水層を除去した。さらに有機層にイオン交換水約２０ｍＬを加え１時間攪拌した後、水層を除去した。その後、有機層をメタノール６０ｍｌに注加して０．５時間攪拌した。そして析出した沈殿をろ過して減圧乾燥することにより、高分子化合物Ｐ−１を０．２８ｇ得た。
また、ポリスチレン換算の数平均分子量及び重量平均分子量は、それぞれＭｎ＝９．８ｘ１０⁴、Ｍｗ＝２．３ｘ１０⁵であった。 Example 1
Synthesis of polymer compound P-1

Under an inert atmosphere, Compound M-4 (0.500 g) and 2,2′-bipyridyl (0.126 g) were dissolved in 24 mL of dehydrated tetrahydrofuran previously bubbled with argon. Next, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.223 g) was added and stirred, and this solution was heated to 60 ° C. and reacted for 3 hours. .
The reaction solution was cooled to room temperature, dropped into a mixed solution of 25% ammonia water 1 mL / methanol 24 mL / ion exchanged water 24 mL and stirred for 1 hour, and then the deposited precipitate was filtered and dried under reduced pressure. Subsequently, the mixture was dissolved in 10 ml of toluene, 0.04 g of radiolite was added and stirred for 30 minutes, insoluble matters were filtered, and the filtrate was purified through an alumina column. Next, 20 mL of 4% aqueous ammonia was added and stirred for 2 hours, and then the aqueous layer was removed. Further, about 20 mL of ion-exchanged water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was poured into 60 ml of methanol and stirred for 0.5 hour. And 0.28g of high molecular compound P-1 was obtained by filtering the depositing deposit and drying under reduced pressure.
The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 9.8 × 10 ⁴ and Mw = 2.3 × 10 ⁵ , respectively.

不活性雰囲気下、化合物Ｍ−５（０．３００ｇ）、及び２，２’−ビピリジル（０．０６６ｇ）をあらかじめアルゴンでバブリングした、脱水テトラヒドロフラン１３ｍＬに溶解した。次に、ビス（１、５−シクロオクタジエン）ニッケル（０）｛Ｎｉ（ＣＯＤ）₂｝（０．１１６ｇ）を加えて攪拌し、この溶液を６０℃まで昇温後、３時間反応させた。
反応液を室温まで冷却し、２５％アンモニア水１ｍＬ／メタノール１３ｍＬ／イオン交換水１３ｍＬ混合溶液中に滴下して１時間攪拌した後、析出した沈殿をろ過して減圧乾燥した。続いてトルエン５ｍｌに溶解させ、ラヂオライト０．０２ｇを加えて３０分攪拌し、不溶解物を濾過した後、濾液をアルミナカラムを通して精製を行った。次に４％アンモニア水１０ｍＬを加え、２時間攪拌した後に水層を除去した。さらに有機層にイオン交換水約１０ｍＬを加え１時間攪拌した後、水層を除去した。その後、有機層を４ｇまで減圧濃縮し、メタノール１５ｍｌに注加して０．５時間攪拌した。そして析出した沈殿をろ過して減圧乾燥することにより高分子化合物Ｐ−２を０．１２ｇ得た。
また、ポリスチレン換算の数平均分子量及び重量平均分子量は、それぞれＭｎ＝７．４ｘ１０⁴、Ｍｗ＝１．５ｘ１０⁵であった。 (Example 2)
Synthesis of polymer compound P-2

Under an inert atmosphere, Compound M-5 (0.300 g) and 2,2′-bipyridyl (0.066 g) were dissolved in 13 mL of dehydrated tetrahydrofuran previously bubbled with argon. Next, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.116 g) was added and stirred, and this solution was heated to 60 ° C. and reacted for 3 hours. .
The reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 1 mL / methanol 13 mL / ion-exchanged water 13 mL and stirred for 1 hour, and then the deposited precipitate was filtered and dried under reduced pressure. Subsequently, the mixture was dissolved in 5 ml of toluene, 0.02 g of radiolite was added and stirred for 30 minutes, insoluble matters were filtered, and the filtrate was purified through an alumina column. Next, 10 mL of 4% aqueous ammonia was added and stirred for 2 hours, and then the aqueous layer was removed. Further, about 10 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was concentrated under reduced pressure to 4 g, poured into 15 ml of methanol and stirred for 0.5 hour. And 0.12g of polymer compound P-2 was obtained by filtering the depositing deposit and drying under reduced pressure.
The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 7.4 × 10 ⁴ and Mw = 1.5 × 10 ⁵ , respectively.

２，７−ジブロモ−９，９−ジ−ｎ−オクチルフルオレン２６．３ｇ（４８．０ｍｍｏｌ）、２，７−ジブロモ−９，９−ビス（３−メチルブチル）フルオレン５．６ｇ（１２．０ｍｍｏｌ）及び２，２’−ビピリジル２２ｇ（１４．１ｍｍｏｌ）を脱水したテトラヒドロフラン１６００ｍＬに溶解した後、窒素でバブリングして系内を窒素置換した。窒素雰囲気下において、この溶液に、ビス（１、５−シクロオクタジエン）ニッケル（０）｛Ｎｉ（ＣＯＤ）₂｝（４０．６６ｇ（１４７．８ｍｍｏｌ））加え、６０℃まで昇温し、攪拌しながら８時間反応させた。反応後、この反応液を室温（約２５℃）まで冷却し、２５％アンモニア水１２００ｍＬ／メタノール１２００ｍＬ／イオン交換水１２００ｍＬ混合溶液中に滴下して０．５時間攪拌した後、析出した沈殿をろ過して２時間減圧乾燥し、その後、トルエン１１１０ｍＬに溶解させてからろ過を行い、ろ液にトルエンを加え、約２８００ｍＬの溶液とした後に、１規定塩酸水２０００ｍｌで１時間、４％アンモニア水２２００ｍＬで１時間、イオン交換水１０００ｍＬで１０分間、さらにイオン交換水１０００ｍＬで１０分間、有機層を洗浄した。有機層を５０℃にて、５９２ｇになるまで減圧濃縮した後に、メタノール３３３０ｍＬに滴下して０．５時間攪拌し、析出した沈殿をろ過し、メタノール５００ｍＬで２回洗浄した後に、５０℃にて５時間減圧乾燥した。得られた高分子化合物Ｐ−３の収量は１２．６ｇであった。
高分子化合物Ｐ−３のポリスチレン換算の数平均分子量及び重量平均分子量は、それぞれＭｎ＝８．７ｘ１０⁴、Ｍｗ＝１．８ｘ１０⁵であった (Synthesis Example 9)
Synthesis of polymer compound P-3

2,7-dibromo-9,9-di-n-octylfluorene 26.3 g (48.0 mmol), 2,7-dibromo-9,9-bis (3-methylbutyl) fluorene 5.6 g (12.0 mmol) In addition, 22 g (14.1 mmol) of 2,2′-bipyridyl was dissolved in 1600 mL of dehydrated tetrahydrofuran, and the inside of the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (40.66 g (147.8 mmol)) was added to this solution, and the temperature was raised to 60 ° C. and stirred. The reaction was allowed to proceed for 8 hours. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 1200 mL / methanol 1200 mL / ion-exchanged water 1200 mL, and stirred for 0.5 hour, and then the deposited precipitate was filtered. And then dried under reduced pressure for 2 hours, then dissolved in 1110 mL of toluene and filtered. Toluene was added to the filtrate to make a solution of about 2800 mL, and then 1N hydrochloric acid solution 2000 mL for 1 hour, 4% aqueous ammonia 2200 mL The organic layer was washed with 1000 mL of ion exchanged water for 10 minutes, and further with 1000 mL of ion exchanged water for 10 minutes. The organic layer was concentrated under reduced pressure to 592 g at 50 ° C., then dropped into 3330 mL of methanol and stirred for 0.5 hour, the deposited precipitate was filtered, washed twice with 500 mL of methanol, and then at 50 ° C. It was dried under reduced pressure for 5 hours. The yield of the obtained polymer compound P-3 was 12.6 g.
The number average molecular weight and weight average molecular weight in terms of polystyrene of the polymer compound P-3 were Mn = 8.7 × 10 ⁴ and Mw = 1.8 × 10 ⁵ , respectively.

２，７−ジブロモ−９，９−ジオクチルフルオレン（０．５０ｇ、０．９０ｍｍｏｌ）、Ｎ，Ｎ’−ビス（４−ｎ−ブチルフェニル）−Ｎ，Ｎ’−ビス（４−ブロモフェニル）−１，４−フェニレンジアミン（０．２７ｇ、０．３７ｍｍｏｌ）及び２，２’−ビピリジル（０．４７ｇ、３．１ｍｍｏｌ）を脱水したテトラヒドロフラン３０ｍＬに溶解した後、窒素でバブリングして系内を窒素置換した。窒素雰囲気下において、この溶液に、ビス（１、５−シクロオクタジエン）ニッケル（０）｛Ｎｉ（ＣＯＤ）₂｝（０．９０ｇ、３．３ｍｏｌ）加え、６０℃まで昇温し、３時間反応させた。反応後、この溶液を冷却した後、２５％アンモニア水１０ｍｌ／メタノール１２０ｍｌ／イオン交換水５０ｍｌ混合溶液中にそそぎ込み、約１時間攪拌した。次に、生成した沈殿を、ろ過することにより回収した。この沈殿をエタノールで洗浄した後、２時間減圧乾燥した。次に、この沈殿をトルエン３０ｍＬに溶解し、１Ｎ塩酸３０ｍＬを加えて１時間攪拌し、水層を除去して有機層に４％アンモニア水３０ｍＬを加え、１時間攪拌した後に水層を除去した。有機層はメタノール２００ｍＬに滴下して１時間攪拌し、析出した沈殿をろ過して２時間減圧乾燥し、トルエン３０ｍＬに溶解させた。その後、アルミナカラム（アルミナ量２０ｇ）を通して精製を行い、回収したトルエン溶液をメタノール２５０ｍＬに滴下して１時間攪拌し、析出した沈殿をろ過して２時間減圧乾燥させた。得られた高分子化合物Ｐ−４の収量は０．３２ｇであった。
高分子化合物Ｐ−４のポリスチレン換算数平均分子量は、２．３ｘ１０⁴であり、ポリスチレン換算重量平均分子量は８．５ｘ１０⁴であった。 (Synthesis Example 10)
Synthesis of polymer compound P-4

2,7-dibromo-9,9-dioctylfluorene (0.50 g, 0.90 mmol), N, N′-bis (4-n-butylphenyl) -N, N′-bis (4-bromophenyl)- 1,4-phenylenediamine (0.27 g, 0.37 mmol) and 2,2′-bipyridyl (0.47 g, 3.1 mmol) were dissolved in 30 mL of dehydrated tetrahydrofuran, and then bubbled with nitrogen to nitrogen the system. Replaced. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (0.90 g, 3.3 mol) was added to this solution, and the temperature was raised to 60 ° C. for 3 hours. Reacted. After the reaction, this solution was cooled and then poured into a mixed solution of 25% aqueous ammonia 10 ml / methanol 120 ml / ion-exchanged water 50 ml and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. The precipitate was washed with ethanol and dried under reduced pressure for 2 hours. Next, this precipitate was dissolved in 30 mL of toluene, 30 mL of 1N hydrochloric acid was added and stirred for 1 hour, the aqueous layer was removed, 30 mL of 4% aqueous ammonia was added to the organic layer, and the aqueous layer was removed after stirring for 1 hour. . The organic layer was dropped into 200 mL of methanol and stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure for 2 hours, and dissolved in 30 mL of toluene. Then, it refine | purified through an alumina column (alumina amount 20g), and the collect | recovered toluene solution was dripped at methanol 250mL, it stirred for 1 hour, the depositing precipitate was filtered, and it dried under reduced pressure for 2 hours. The yield of the obtained polymer compound P-4 was 0.32 g.
The polymer compound P-4 had a polystyrene equivalent number average molecular weight of 2.3 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 8.5 × 10 ⁴ .

不活性雰囲気下、化合物Ｍ−４（０．５１６ｇ）、２，７−ジブロモ−９，９−ジオクチルフルオレン（０．２５４ｇ）、２，７−ビス（１，３，２−ジオキサボロラン−２−イル）−９，９−ジオクチルフルオレン（０．４２４ｇ）、酢酸パラジウム（０．５ｍｇ）、トリ（２−メチルフェニル）ホスフィン（２．０ｍｇ）、Ａｌｉｑｕａｔ３３６（０．２ｇ，アルドリッチ製）、トルエン（１０ｍｌ）と２Ｍ Ｎａ_２ＣＯ_３水溶液（２ｍｌ）を混合し、３時間還流させた。反応後、フェニルホウ酸（２０ｍｇ）とＴＨＦ（２ｍｌ）の混合溶液を加え、さらに４時間還流させた。次いでジエチルジチアカルバミン酸ナトリウム水溶液を加え８５℃で４時間撹拌した。冷却後、水（３０ｍｌ）で３回、３％酢酸水溶液（３０ｍｌ）で４回、水（３０ｍｌ）で３回洗浄し、アルミナカラム、シリカゲルカラムを通すことにより精製した。得られたトルエン溶液をメタノール（２５０ｍｌ）に滴下し、１時間撹拌した後、得られた固体をろ取し乾燥させた。得られた高分子化合物Ｐ−５の収量は７１９ｍｇであった。
高分子化合物Ｐ−５のポリスチレン換算数平均分子量は、４．５ｘ１０^４であり、ポリスチレン換算重量平均分子量は１．１ｘ１０^５であった。 (Example 3)
Synthesis of polymer compound P-5

Under an inert atmosphere, Compound M-4 (0.516 g), 2,7-dibromo-9,9-dioctylfluorene (0.254 g), 2,7-bis (1,3,2-dioxaborolan-2-yl ) -9,9-dioctylfluorene (0.424 g), palladium acetate (0.5 mg), tri (2-methylphenyl) phosphine (2.0 mg), Aliquat 336 (0.2 g, manufactured by Aldrich), toluene (10 ml) And 2M Na ₂ CO ₃ aqueous solution (2 ml) were mixed and refluxed for 3 hours. After the reaction, a mixed solution of phenylboric acid (20 mg) and THF (2 ml) was added, and the mixture was further refluxed for 4 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 85 ° C. for 4 hours. After cooling, the mixture was washed 3 times with water (30 ml), 4 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 (250 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-5 was 719 mg.
The polymer compound P-5 had a polystyrene-equivalent number average molecular weight of 4.5 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.1 × 10 ⁵ .

不活性雰囲気下、化合物Ｍ−５（０．４７５ｇ）、２，７−ジブロモ−９，９−ジオクチルフルオレン（０．２０４ｇ）、２，７−ビス（１，３，２−ジオキサボロラン−２−イル）−９，９−ジオクチルフルオレン（０．３３９ｇ）、酢酸パラジウム（０．４ｍｇ）、トリス（２−メチルフェニル）ホスフィン（１．８ｍｇ）、Ａｌｉｑｕａｔ３３６（０．２ｇ，アルドリッチ製）、トルエン（９ｍｌ）と２Ｍ Ｎａ_２ＣＯ_３水溶液（２ｍｌ）を混合し、３時間還流させた。反応後、フェニルホウ酸（２０ｍｇ）とＴＨＦ（２ｍｌ）の混合溶液を加え、さらに４時間還流させた。次いでジエチルジチアカルバミン酸ナトリウム水溶液を加え８５℃で４時間撹拌した。冷却後、水（３０ｍｌ）で３回、３％酢酸水溶液（３０ｍｌ）で４回、水（３０ｍｌ）で３回洗浄し、アルミナカラム、シリカゲルカラムを通すことにより精製した。得られたトルエン溶液をメタノール（２５０ｍｌ）に滴下し、１時間撹拌した後、得られた固体をろ取し乾燥させた。得られた高分子化合物Ｐ−６の収量は４５１ｍｇであった。
高分子化合物Ｐ−６のポリスチレン換算数平均分子量は、６．６ｘ１０^４であり、ポリスチレン換算重量平均分子量は１．７ｘ１０^５であった。 Example 4
Synthesis of polymer compound P-6

Under an inert atmosphere, Compound M-5 (0.475 g), 2,7-dibromo-9,9-dioctylfluorene (0.204 g), 2,7-bis (1,3,2-dioxaborolan-2-yl ) -9,9-dioctylfluorene (0.339 g), palladium acetate (0.4 mg), tris (2-methylphenyl) phosphine (1.8 mg), Aliquat 336 (0.2 g, manufactured by Aldrich), toluene (9 ml) And 2M Na ₂ CO ₃ aqueous solution (2 ml) were mixed and refluxed for 3 hours. After the reaction, a mixed solution of phenylboric acid (20 mg) and THF (2 ml) was added, and the mixture was further refluxed for 4 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 85 ° C. for 4 hours. After cooling, the mixture was washed 3 times with water (30 ml), 4 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 (250 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-6 was 451 mg.
The polymer compound P-6 had a polystyrene equivalent number average molecular weight of 6.6 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 1.7 × 10 ⁵ .

不活性雰囲気下、化合物Ｍ−４（０．５３４ｇ）、２，７−ジブロモ−３，６−オクチルオキシジベンゾフラン（０．４９０ｇ）、２，７−ビス（１，３，２−ジオキサボロラン−２−イル）−９，９−ジオクチルフルオレン（０．６４０ｇ）、ビス（トリフェニルホスフィン）パラジウムジクロリド（０．９ｍｇ）、Ａｌｉｑｕａｔ３３６（０．２ｇ，アルドリッチ製）、トルエン（９ｍｌ）と２Ｍ Ｎａ_２ＣＯ_３水溶液（３ｍｌ）を混合し、３時間還流させた。反応後、フェニルホウ酸（２０ｍｇ）とＴＨＦ（２ｍｌ）の混合溶液を加え、さらに４時間還流させた。次いでジエチルジチアカルバミン酸ナトリウム水溶液を加え８５℃で４時間撹拌した。冷却後、水（３０ｍｌ）で３回、３％酢酸水溶液（３０ｍｌ）で４回、水（３０ｍｌ）で３回洗浄し、アルミナカラム、シリカゲルカラムを通すことにより精製した。得られたトルエン溶液をメタノール（２５０ｍｌ）に滴下し、１時間撹拌した後、得られた固体をろ取し乾燥させた。得られた高分子化合物Ｐ−７の収量は７７２ｍｇであった。
高分子化合物Ｐ−７のポリスチレン換算数平均分子量は、８．０ｘ１０^４であり、ポリスチレン換算重量平均分子量は３．１ｘ１０^５であった。
２，７−ジブロモ−３，６−ジオクチルオキシジベンゾフランは特開２００４−０５９８９９に記載の方法で合成した。 (Example 5)
Synthesis of polymer compound P-7

Under an inert atmosphere, Compound M-4 (0.534 g), 2,7-dibromo-3,6-octyloxydibenzofuran (0.490 g), 2,7-bis (1,3,2-dioxaborolane-2- Yl) -9,9-dioctylfluorene (0.640 g), bis (triphenylphosphine) palladium dichloride (0.9 mg), Aliquat 336 (0.2 g, manufactured by Aldrich), toluene (9 ml) and 2M Na ₂ CO ₃ aqueous solution (3 ml) was mixed and refluxed for 3 hours. After the reaction, a mixed solution of phenylboric acid (20 mg) and THF (2 ml) was added, and the mixture was further refluxed for 4 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 85 ° C. for 4 hours. After cooling, the mixture was washed 3 times with water (30 ml), 4 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 (250 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-7 was 772 mg.
The polymer compound P-7 had a polystyrene equivalent number average molecular weight of 8.0 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 3.1 × 10 ⁵ .
2,7-dibromo-3,6-dioctyloxydibenzofuran was synthesized by the method described in JP-A-2004-059899.

不活性雰囲気下、化合物Ｍ−５（０．３５６ｇ）、２，７−ジブロモ−３，６−オクチルオキシジベンゾチオフェン（０．５７５ｇ）、２，７−ビス（１，３，２−ジオキサボロラン−２−イル）−９，９−ジオクチルフルオレン（０．６４０ｇ）、ビス（トリフェニルホスフィン）パラジウムジクロリド（０．９ｍｇ）、Ａｌｉｑｕａｔ３３６（０．２ｇ，アルドリッチ製）、トルエン（９ｍｌ）と２Ｍ Ｎａ_２ＣＯ_３水溶液（３ｍｌ）を混合し、３時間還流させた。反応後、フェニルホウ酸（２０ｍｇ）とＴＨＦ（２ｍｌ）の混合溶液を加え、さらに４時間還流させた。次いでジエチルジチアカルバミン酸ナトリウム水溶液を加え８５℃で４時間撹拌した。冷却後、水（３０ｍｌ）で３回、３％酢酸水溶液（３０ｍｌ）で４回、水（３０ｍｌ）で３回洗浄し、アルミナカラム、シリカゲルカラムを通すことにより精製した。得られたトルエン溶液をメタノール（２５０ｍｌ）に滴下し、１時間撹拌した後、得られた固体をろ取し乾燥させた。得られた高分子化合物Ｐ−８の収量は９８ｍｇであった。
高分子化合物Ｐ−８のポリスチレン換算数平均分子量は、２．７ｘ１０^４であり、ポリスチレン換算重量平均分子量は８．０ｘ１０^４であった。
２，７−ジブロモ−３，６−ジオクチルオキシジベンゾチオフェンは特開２００４−００２７０３に記載の方法で合成した。 (Example 6)
Synthesis of polymer compound P-8

Under an inert atmosphere, Compound M-5 (0.356 g), 2,7-dibromo-3,6-octyloxydibenzothiophene (0.575 g), 2,7-bis (1,3,2-dioxaborolane-2 -Yl) -9,9-dioctylfluorene (0.640 g), bis (triphenylphosphine) palladium dichloride (0.9 mg), Aliquat 336 (0.2 g, manufactured by Aldrich), toluene (9 ml) and 2M Na ₂ CO ₃ Aqueous solution (3 ml) was mixed and refluxed for 3 hours. After the reaction, a mixed solution of phenylboric acid (20 mg) and THF (2 ml) was added, and the mixture was further refluxed for 4 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 85 ° C. for 4 hours. After cooling, the mixture was washed 3 times with water (30 ml), 4 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 (250 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-8 was 98 mg.
The polymer compound P-8 had a polystyrene equivalent number average molecular weight of 2.7 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 8.0 × 10 ⁴ .
2,7-dibromo-3,6-dioctyloxydibenzothiophene was synthesized by the method described in JP-A-2004-002703.

不活性雰囲気下、化合物Ｍ−７（０．３２５ｇ）、２，７−ジブロモ−９，９−ジオクチルフルオレン（０．４６１ｇ）、２，７−ビス（１，３，２−ジオキサボロラン−２−イル）−９，９−ジオクチルフルオレン（０．６４０ｇ）、ビス（トリフェニルホスフィン）パラジウムジクロリド（０．９ｍｇ）、Ａｌｉｑｕａｔ３３６（０．２ｇ，アルドリッチ製）、トルエン（９ｍｌ）と２Ｍ Ｎａ_２ＣＯ_３水溶液（３ｍｌ）を混合し、３時間還流させた。反応後、フェニルホウ酸（２０ｍｇ）とＴＨＦ（２ｍｌ）の混合溶液を加え、さらに４時間還流させた。次いでジエチルジチアカルバミン酸ナトリウム水溶液を加え８５℃で４時間撹拌した。冷却後、水（３０ｍｌ）で３回、３％酢酸水溶液（３０ｍｌ）で４回、水（３０ｍｌ）で３回洗浄し、アルミナカラム、シリカゲルカラムを通すことにより精製した。得られたトルエン溶液をメタノール（２５０ｍｌ）に滴下し、１時間撹拌した後、得られた固体をろ取し乾燥させた。得られた高分子化合物Ｐ−９の収量は５１０ｍｇであった。
高分子化合物Ｐ−９のポリスチレン換算数平均分子量は、８．３ｘ１０^４であり、ポリスチレン換算重量平均分子量は１．６ｘ１０^５であった。 (Example 7)
Synthesis of polymer compound P-9

Under an inert atmosphere, Compound M-7 (0.325 g), 2,7-dibromo-9,9-dioctylfluorene (0.461 g), 2,7-bis (1,3,2-dioxaborolan-2-yl ) -9,9-dioctylfluorene (0.640 g), bis (triphenylphosphine) palladium dichloride (0.9 mg), Aliquat 336 (0.2 g, manufactured by Aldrich), toluene (9 ml) and 2M Na ₂ CO ₃ aqueous solution ( 3 ml) and refluxed for 3 hours. After the reaction, a mixed solution of phenylboric acid (20 mg) and THF (2 ml) was added, and the mixture was further refluxed for 4 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 85 ° C. for 4 hours. After cooling, the mixture was washed 3 times with water (30 ml), 4 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 (250 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-9 was 510 mg.
The polymer compound P-9 had a polystyrene equivalent number average molecular weight of 8.3 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 1.6 × 10 ⁵ .

不活性雰囲気下、化合物Ｍ−８（０．３１２ｇ）、２，７−ジブロモ−９，９−ジオクチルフルオレン（０．４６１ｇ）、２，７−ビス（１，３，２−ジオキサボロラン−２−イル）−９，９−ジオクチルフルオレン（０．６４０ｇ）、ビス（トリフェニルホスフィン）パラジウムジクロリド（０．９ｍｇ）、Ａｌｉｑｕａｔ３３６（０．２ｇ，アルドリッチ製）、トルエン（９ｍｌ）と２Ｍ Ｎａ_２ＣＯ_３水溶液（３ｍｌ）を混合し、３時間還流させた。反応後、フェニルホウ酸（２０ｍｇ）とＴＨＦ（２ｍｌ）の混合溶液を加え、さらに４時間還流させた。次いでジエチルジチアカルバミン酸ナトリウム水溶液を加え８５℃で４時間撹拌した。冷却後、水（３０ｍｌ）で３回、３％酢酸水溶液（３０ｍｌ）で４回、水（３０ｍｌ）で３回洗浄し、アルミナカラム、シリカゲルカラムを通すことにより精製した。得られたトルエン溶液をメタノール（２５０ｍｌ）に滴下し、１時間撹拌した後、得られた固体をろ取し乾燥させた。得られた高分子化合物Ｐ−１０の収量は５１０ｍｇであった。
高分子化合物Ｐ−１０のポリスチレン換算数平均分子量は、９．４ｘ１０^４であり、ポリスチレン換算重量平均分子量は２．５ｘ１０^５であった。 (Synthesis Example 11)
Synthesis of polymer compound P-10

Under inert atmosphere, compound M-8 (0.312 g), 2,7-dibromo-9,9-dioctylfluorene (0.461 g), 2,7-bis (1,3,2-dioxaborolan-2-yl ) -9,9-dioctylfluorene (0.640 g), bis (triphenylphosphine) palladium dichloride (0.9 mg), Aliquat 336 (0.2 g, manufactured by Aldrich), toluene (9 ml) and 2M Na ₂ CO ₃ aqueous solution ( 3 ml) and refluxed for 3 hours. After the reaction, a mixed solution of phenylboric acid (20 mg) and THF (2 ml) was added, and the mixture was further refluxed for 4 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added, and the mixture was stirred at 85 ° C. for 4 hours. After cooling, the mixture was washed 3 times with water (30 ml), 4 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 (250 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-10 was 510 mg.
The polymer compound P-10 had a polystyrene equivalent number average molecular weight of 9.4 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 2.5 × 10 ⁵ .

  Cyclic voltammetry (manufactured by BAS: ALS600) was used to measure the energy of HOMO and LUMO, and measurement was performed in an acetonitrile solvent containing 0.1 wt% tetrabutylammonium tetrafluoroborate. After the polymer compound was dissolved in chloroform so as to be about 0.2 wt%, 1 mL of a chloroform solution of the polymer compound was applied on the working electrode, and chloroform was vaporized to form a polymer compound thin film. The measurement was performed in a glove box substituted with nitrogen using a silver / silver ion electrode as a reference electrode, a glassy carbon electrode as a working electrode, and a platinum electrode as a counter electrode. The potential sweep rate was both measured at 50 mV / s.

(Example 8)
<Measurement of oxidation potential>
The polymer compound P-1 was dissolved in chloroform to prepare a 0.2 wt% solution. 0.05 mL of the solution was applied onto a platinum electrode, and chloroform was removed to prepare a polymer compound P-1 thin film. The measurement was performed by the method described above. The energy of HOMO was calculated from the obtained oxidation potential.

Example 9
<Measurement of oxidation potential>
The oxidation potential of the polymer compound P-2 was measured by the method described above. The energy of HOMO was calculated from the obtained oxidation potential.

(Comparative Example 1)
<Measurement of oxidation potential>
The oxidation potential of the polymer compound P-3 was measured by the method described above. The energy of HOMO was calculated from the obtained oxidation potential.

(Example 10)
<Measurement of oxidation potential>
The oxidation potential of the polymer compound P-5 was measured by the method described above. The energy of HOMO was calculated from the obtained oxidation potential.

(Example 11)
<Measurement of oxidation potential>
The oxidation potential of the polymer compound P-6 was measured by the method described above. The energy of HOMO was calculated from the obtained oxidation potential.

<Measurement of oxidation potential>
The oxidation potential of the polymer compound P-10 was measured by the method described above. The energy of HOMO was calculated from the obtained oxidation potential.

(Example 12)
Preparation of Solution The polymer compound P-1 obtained above was dissolved in toluene to prepare a toluene 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, a film was formed at a rotational speed of 1000 rpm by spin coating using the toluene solution obtained above. The film thickness after film formation was about 71 nm. Further, this was dried at 80 ° C. under reduced pressure for 1 hour, and then lithium fluoride was deposited by about 4 nm, calcium was deposited by about 5 nm as a cathode, and then aluminum was deposited by about 72 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 voltage to the obtained device, EL light emission having a peak at 500 nm was obtained from this device. The intensity of EL emission was almost proportional to the current density. The maximum luminous efficiency of the device was 0.58 cd / A.
The voltage when the luminance was 1.0 cd / m ² was 3.44V.

(Example 13)
Preparation of Solution The polymer compound P-5 obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.5% by weight.
Production of EL device An EL device was produced in the same manner as in Example 12 except that the xylene solution obtained above was used. At this time, the spin coat rotation speed was 1500 rpm, and the film thickness of the obtained polymer was 74 nm.
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 intensity of EL emission was almost proportional to the current density. The maximum luminous efficiency of the device was 0.59 cd / A.
The voltage when the luminance was 1.0 cd / m ² was 3.48V.

(Comparative Example 3)
Preparation of Solution The polymer compound P-10 obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.5% by weight.
Production of EL device An EL device was produced in the same manner as in Example 12 except that the xylene solution obtained above was used. At this time, the spin coat rotation speed was 1500 rpm, and the film thickness of the obtained polymer was 74 nm.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 425 nm was obtained from this device. The intensity of EL emission was almost proportional to the current density. The maximum luminous efficiency of the device was 0.11 cd / A.
The voltage when the luminance was 1.0 cd / m ² was 3.84V.

(Comparative Example 4)
Preparation of Solution The polymer compound P-4 obtained above was dissolved in toluene to prepare a toluene solution having a polymer concentration of 1.8% by weight.
Production of EL device An EL device was produced in the same manner as in Example 12 except that the toluene solution obtained above was used. At this time, the spin coat rotation speed was 2400 rpm, and the film thickness of the obtained polymer was 76 nm.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 460 nm was obtained from this device. The intensity of EL emission was almost proportional to the current density. The maximum light emission efficiency of the device was 0.35 cd / A.
The voltage when the luminance was 1.0 cd / m ² was 3.96V.

(Example 14)
Preparation of Solution The polymer compound P-9 obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.5% by weight.
Production of EL device An EL device was produced in the same manner as in Example 12 except that the xylene solution obtained above was used. At this time, the spin coat rotational speed was 2000 rpm, and the film thickness of the obtained polymer was 71 nm.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 435 nm was obtained from this device. The intensity of EL emission was almost proportional to the current density. The maximum luminous efficiency of the device was 1.08 cd / A.
The voltage when the luminance was 1.0 cd / m ² was 3.53V.

(Example 15)
Preparation of Solution The polymer compound P-7 obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.5% by weight.
Production of EL device An EL device was produced in the same manner as in Example 12 except that the xylene solution obtained above was used. At this time, the spin coat rotation speed was 1200 rpm, and the film thickness of the obtained polymer was 77 nm.
EL device performance By applying a voltage to the obtained device, EL light emission having a peak at 450 nm was obtained from this device. The intensity of EL emission was almost proportional to the current density. The maximum light emission efficiency of the device was 0.12 cd / A.

(Example 16)
Preparation of Solution The polymer compound P-8 obtained above was dissolved in xylene to prepare a xylene solution having a polymer concentration of 1.5% by weight.
Production of EL device An EL device was produced in the same manner as in Example 12 except that the xylene solution obtained above was used. At this time, the spin coat rotation speed was 1200 rpm, and the film thickness of the obtained polymer was 89 nm.
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 intensity of EL emission was almost proportional to the current density. The maximum luminous efficiency of the device was 1.72 cd / A.

  The polymer compound of the present invention has the effects of high charge injection and transport properties and high luminous efficiency. When the side chain has a hole injection / transport group, the energy of the highest occupied molecular orbital (HOMO) is increased, the hole injection property and the hole transport property are improved, and the light emission efficiency is increased. When the side chain has an electron injecting and transporting group, the energy of the lowest unoccupied molecular orbital (LUMO) is decreased, the electron injecting property and the electron transporting property are improved, and the light emission efficiency is increased. In the case where the side chain has a light emitting group, it is expected that the light emission efficiency is increased or light is emitted at a wavelength different from the light emission wavelength of the main chain.

When the main chain is an electron transporting polymer compound and the side chain has a hole injecting and transporting group, a new function can be added without hindering the electron transporting property of the main chain. It becomes possible to adjust the transportability. In the case where the main chain is an electron transporting polymer compound and the side chain has a light emitting group, light can be emitted at a wavelength different from the wavelength of the main chain. In addition, when a highly efficient light emitting group is used, the light emission efficiency can be improved. In the case where the main chain is an electron transporting polymer compound and the side chain has an electron injecting and transporting group, the electron transporting property of the main chain can be improved.
By separating the functions of the side chain and the main chain in this way, the function can be imparted without impairing the functionality of the main chain, and higher functionality of the polymer compound is expected.

  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.

Claims (27)

Has in the main chain as a repeating unit may fluorenediyl group optionally having a substituent, a hole injection transport group is a monovalent aromatic Amin containing two or more nitrogen atoms, and the partial structure (L A light-emitting or charge-transporting polymer compound having a functional side chain containing at least one functional group selected from the group consisting of a light-emitting group that is a monovalent group containing -B), The group is directly bonded to the saturated carbon of the fluorenediyl group or the group at X via —R _k —X— (R _k represents an alkylene group, X represents a direct bond or a linking group). The above polymer compound, which is bonded to a fluorenediyl group.
(In the formula _{(L-B), Q 9} , Q 10, Q 11 and _{Q 12} is - _{C (R 108)} - represents a.

R ₁₀₈ is a hydrogen atom, 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 nitro group Represent. )   The polymer compound according to claim 1, wherein the functional group is a monovalent group including a partial structure (LB). The polymer compound according to any one of claims 1-2 absolute value of HOMO is less than 5.6eV polymer compounds. The polymer compound according to any one of claims 1 to 3 , wherein the polymer compound has an LUMO absolute value of 2.2 eV or more. The polymer compound according to any one of claims 1 to 4 , which has a polystyrene-reduced number average molecular weight of 10 ³ to 10 ⁸ . The functional side chain is directly bonded to the 9-position of an optionally substituted fluorenediyl group, or —R _k —X— (R _k represents an alkylene group, X is a direct bond) or polymeric compound according to any one of claim 1 to 5 through a representative) a linking group X attached to the fluorenediyl group. It contains 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 6. Characteristic composition. A composition comprising at least two polymer compounds according to any one of claims 1 to 6 . A solution comprising the polymer compound according to any one of claims 1 to 6 . A solution comprising the composition according to any one of claims 7 to 8 . Two or more types of organic solvents are contained, The solution as described in any one of Claims 9-10 characterized by the above-mentioned. The solution according to any one of claims 9 to 11 , which has a viscosity of 1 to 20 mPa · s at 25 ° C. A light-emitting thin film comprising the polymer compound according to any one of claims 1 to 6 . The luminescent thin film according to claim 13 , wherein the quantum yield of light emission is 50% or more. A conductive thin film comprising the polymer compound according to any one of claims 1 to 6 . An organic semiconductor thin film comprising the polymer compound according to any one of claims 1 to 6 . An organic transistor comprising the organic semiconductor thin film according to claim 16 . The method for forming a thin film according to any one of claims 13 to 16, wherein an inkjet method is used. Between electrodes consisting of an anode and a cathode, characterized by comprising an organic layer containing the composition according to any one of claims 1 to polymer compounds, or claims 7 to according to any one of 6 8 A polymer light emitting device. The polymer light-emitting device according to claim 19 , wherein the organic layer is a light-emitting layer. 21. The polymer light emitting device according to claim 20, wherein the light emitting layer further contains a hole transport material, an electron transport material or a light emitting material. Between electrodes consisting of an anode and a cathode, and a light-emitting layer and a charge transport layer, any of the charge transport layer according to claim 1 polymer compound according to any one of 6 or claim 7 and 8 The polymer light emitting device according to claim 19 , comprising the composition according to claim 1. A light-emitting layer and a charge transport layer are provided between electrodes composed of an anode and a cathode, a charge injection layer is provided between the charge transport layer and the electrode, and the charge injection layer is any one of claims 1 to 6 . The polymer light emitting device according to claim 19 , comprising the polymer compound according to claim 1 or the composition according to any one of claims 7 to 8 . A planar light source comprising the polymer light-emitting device according to any one of claims 19 to 23 . A segment display device comprising the polymer light-emitting device according to any one of claims 19 to 23 . 24. A dot matrix display device comprising the polymer light emitting device according to any one of claims 19 to 23 . The liquid crystal display device which is characterized in that a backlight polymer light-emitting device according to any one of claims 19-23.