DE112006002642T5 - Polymer and polymeric luminescent element using this - Google Patents

Abstract

wobei A₁ für -O-, -S- oder -C(O)- steht; Ar⁰¹ für eine direkte Bindung, einen Arylenrest, einen zweiwertigen heterocyclischen Rest oder einen zweiwertigen aromatischen Aminrest steht; R⁰⁵ und R⁰⁷ jeweils unabhängig für eine direkte Bindung, -R₁-, -O-R₁-, -R₁-O-, -R₁-C(O)O-, -R₁-OC(O)-, -R₁-N(R₂₀)-, -O-, -S-, -C(O)O- oder -C(O)- stehen; R₁ für einen...A polymer compound containing at least one type of repeating unit selected from the group consisting of repeating units represented by the following formula (1), characterized by having a substituent selected from the group consisting of the monovalent radicals represented by the following formula (2) or (3), -Ar ₁ - (Z ') p- (1) wherein Ar _{1 represents} an arylene radical, a divalent heterocyclic radical or a divalent aromatic amine radical; Z 'is -CR ₄ = CR ₅ - or -C≡C-; Each of R ₄ and R ₅ independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group; and p is 0 or 1,

wherein A _{1 is} -O-, -S- or -C (O) -; Ar ⁰¹ represents a direct bond, an arylene group, a divalent heterocyclic group or a divalent aromatic amine group; R ⁰⁵ and R ^{07 are} each independently a direct bond, -R ₁ -, -OR ₁ -, -R ₁ -O-, -R ₁ -C (O) O-, -R ₁ -OC (O) -, R _{1 is} -N (R ₂₀ ) -, -O-, -S-, -C (O) O- or -C (O) -; R ₁ for a ...

Description

TECHNICAL AREA

The The present invention relates to a polymer compound and a polymeric one luminescent device (sometimes called a "polymer LED") designated) using the same.

STATE OF THE ART

One is a high molecular weight luminescent material, unlike that with a low molecular weight, in one Solvent soluble. As it is a luminescent Layer of a luminescent device by means of a coating method are different types of luminescent materials has been studied with a high molecular weight. For example for this is a polymer compound, which is two types of itself having repeating units containing an aromatic ring in the main chain and an aryl radical, more specifically a phenyl group (Formula weight: 77), as a terminal group (see Patent Documents 1, 2 and 3).

A another polymer compound having a phenoxazinediyl group and a Phenothiazinediyl group as the repeating unit of the main chain is also known (see patent documents 4 and 5).

However, the above-mentioned polymer compounds are not sufficient as a luminescent material for a polymer LED luminescent layer for practical use in view of properties such as fluorescence intensity and durability. Under the circumstances, it has been desired to find a polymer compound which exhibits more excellent properties than a luminescent material for a polymer LED luminescent layer.
Patent Document 1: WO 99/54385
Patent Document 2: WO 01/49769
Patent Document 3: U.S. Patent No. 5,777,070
Patent Document 4: U.S. Patent No. 2004-72989
Patent Document 5: JP-A-2004-137456

DISCLOSURE OF THE INVENTION

Problem solved by the invention shall be

The The object of the invention is to provide a polymer compound the excellent properties as a luminescent material a luminescent layer of a polymer LED.

Means for releasing of the problem

The Inventors mentioned here have intensive investigations in view to solving the above-mentioned problem carried out. As a result, they have found that a polymer compound which is at least one type of repeating Unit comprising selected from the group consisting from the repeating units, by the following formula (1) and which has a substituent, selected from the group consisting of the monovalent ones Rests represented by the following formula (2) or (3) which shows strong fluorescence intensity and excellent Properties as a luminescent layer of a polymer LED shows. Based on the findings, they came to the present invention.

A Polymer compound according to the present invention has excellent properties as a luminescent material on. A polymeric luminescent device using the polymer compound has high performance and is considered planar Light source that serves as a backlight and a device like a flat screen, used. A polymer compound according to the The present invention may also be referred to as a laser dye, a material for an organic solar battery, an organic semiconductor for use in an organic transistor and a conductive one Thin film material can be used.

BEST TYPE OF PERFORMANCE THE INVENTION

A polymer compound according to the present invention contains at least one type of itself repeating unit represented by the following formula (1).

wobei A₁ für -O-, -S- oder -C(O)- steht; Ar⁰¹ für eine direkte Bindung, einen Arylenrest, einen zweiwertigen heterocyclischen Rest oder einen zweiwertigen aromatischen Aminrest steht; R⁰⁵ und R⁰⁷ jeweils unabhängig für eine direkte Bindung, -R₁-, -O-R₁-, -R₁-O-, -R₁-C(O)O-, -R₁-OC(O)-, -R₁-N(R₂₀)-, -O-, -S-, -C(O)O- oder -C(O)- stehen; R₁ für einen Alkylenrest oder einen Alkenylenrest steht; R₂₀ für ein Wasserstoffatom, einen Alkylrest, einen Arylrest, einen einwertigen heterocyclischen Rest oder eine Cyanogruppe steht, mit der Maßgabe, dass, wenn Ar⁰¹ eine direkte Bindung ist, R⁰⁷ auch eine direkte Bindung ist; R⁰¹ und R⁰² jeweils unabhängig für einen Substituenten stehen; a und b jeweils unabhängig eine ganze Zahl von 0 bis 4 sind; und mehrere Substituenten, die durch R⁰¹ und R⁰² wiedergegeben werden, gleich oder verschieden sein können,

wobei B₁ für -O-, -S- oder -C(O)- steht; Ar⁰² für ein Wasserstoffatom, einen Arylrest, einen einwertigen heterocyclischen Rest oder einen einwertigen aromatischen Aminrest steht; Ar⁰³ für eine direkte Bindung, einen Arylenrest, einen zweiwertigen heterocyclischen Rest oder einen zweiwertigen aromatischen Aminrest steht; R⁰⁶, R⁰⁸ und R⁰⁹ jeweils unabhängig für eine direkte Bindung, -R₁-, -O-R₁-, -R₁-O-, -R₁-C(O)O-, -R₁-OC(O)-, -R₁-N(R₂₀)-, -O-, -S-, -C(O)O- oder -C(O)- stehen; R₁ für einen Alkylenrest oder einen Alkenylenrest steht, R₂₀ für ein Wasserstoffatom, einen Alkylrest, einen Arylrest, einen einwertigen heterocyclischen Rest oder eine Cyanogruppe stehen, mit der Maßgabe, dass, wenn Ar⁰³ eine direkte Bindung ist, R⁰⁹ auch eine direkte Bindung ist; R⁰³ und R⁰⁴ jeweils unabhängig für einen Substituenten stehen; c eine ganze Zahl von 0 bis 4 ist; d eine ganze Zahl von 0 bis 3 ist; und mehrere Substituenten, die durch R⁰³ und R⁰⁴ wiedergegeben werden, gleich oder verschieden sein können.More specifically, the present invention relates to a polymer compound having at least one type of repeating unit selected from the group consisting of repeating units represented by the following formula (1), characterized by containing a substituent selected from the group consisting of the monovalent radicals represented by the following formula (2) or (3), -Ar ₁ - (Z ') _p - (1) wherein Ar _{1 represents} an arylene radical, a divalent heterocyclic radical or a divalent aromatic amine radical; Z 'is -CR ₄ = CR ₅ - or -C≡C-; Each of R ₄ and R ₅ independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group; and p is 0 or 1,

wherein A _{1 is} -O-, -S- or -C (O) -; Ar ^{01 is} a direct bond, an arylene radical, a divalent heterocyclic radical or a divalent aromatic amine radical; R ⁰⁵ and R ^{07 are} each independently a direct bond, -R ₁ -, -OR ₁ -, -R ₁ -O-, -R ₁ -C (O) O-, -R ₁ -OC (O) -, R _{1 is} -N (R ₂₀ ) -, -O-, -S-, -C (O) O- or -C (O) -; R _{1 is} an alkylene radical or an alkenylene radical; R _{20 represents} a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group, with the proviso that when Ar ^{01 is} a direct bond, R ^{07 is} also a direct bond; R ⁰¹ and R ^{02 are} each independently a substituent; a and b are each independently an integer of 0 to 4; and a plurality of substituents represented by R ⁰¹ and R ^{02 may} be the same or different,

wherein B _{1 is} -O-, -S- or -C (O) -; Ar ^{02 represents} a hydrogen atom, an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group; Ar ^{03 represents} a direct bond, an arylene radical, a divalent heterocyclic radical or a divalent aromatic amine radical; R ⁰⁶ , R ⁰⁸ and R ^{09 are} each independently a direct bond, -R ₁ -, -OR ₁ -, -R ₁ -O-, -R ₁ -C (O) O-, -R ₁ -OC (O ) -, -R ₁ -N (R ₂₀ ) -, -O-, -S-, -C (O) O- or -C (O) - stand; R _{1 is} an alkylene radical or an alkenylene radical, R _{20 is} a hydrogen atom, an alkyl radical, an aryl radical, a monovalent heterocyclic radical or a cyano group, with the proviso that when Ar ^{03 is} a direct bond, R ^{09 is} also a direct Bond is; R ⁰³ and R ^{04 are} each independently a substituent; c is an integer of 0 to 4; d is an integer from 0 to 3; and a plurality of substituents represented by R ⁰³ and R ^{04 may} be the same or different.

A Polymer compound of the present invention contains a or several types of repeating units through the above-mentioned formula (1) are reproduced.

In the above-mentioned formula (1), Ar _{1 represents} an arylene group, divalent heterocyclic group or divalent aromatic amine group. Ar ₁ can here except a substituent, by the before is a substituent such as an alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group or cyano group. When Ar _{1 has a} plurality of substituents, the substituents may be the same or different.

In The above-mentioned formula (1) is the arylene group the remaining atomic group, if two hydrogen atoms of one aromatic hydrocarbon are removed. The number of carbon atoms of which is generally about 6 to 60, in which the number of Carbon atoms of a substituent is not included. The aromatic hydrocarbon can be condensed here Ring, independent benzene ring or two or more condensed Rings that are directly or via a residue, such as a vinyl residue, are linked.

Examples for the arylene radical include a phenylene radical (For example, the following formulas 1 to 3), a Naphthalindiylrest (the following formulas 4 to 13), an anthracenylene residue (the following Formulas 14 to 19), a biphenylene group (the following formulas 20 to 25), a triphenylene group (the following formulas 26 to 28), a remainder of a fused ring compound (the following Formulas 29 to 38), a stilbene diyl (the following formulas A to D), a distilbendiyl (the following formulas E and F) and a benzofluorodiyl (the following formulas G, H, I and K).

From that Examples preferably include a phenylene radical (e.g. the above-mentioned formulas 1 to 3), a naphthalenediyl radical (the above-mentioned formulas 4 to 13), an anthracenylene radical (the above-mentioned formulas 14 to 19), a biphenylene radical (the above-mentioned formulas 20 to 25), a triphenylene radical (the above-mentioned formulas 26 to 28), a remainder a condensed ring compound (those mentioned above Formulas 29 to 38), a stilbene diyl group (those mentioned above Formulas A to D), a distilbendiyl radical (those mentioned above Formulas E and F) and a Benzofluorendiylrest (the above mentioned formulas G, H, I and K).

In the above-mentioned formulas 1 to 38, A to I and K is a radical represented by the above-mentioned Formula (2), and a group represented by the above mentioned formula (3) is a hydrogen atom and an alkyl group, an alkoxy group, an alkylthio group, a Alkylsilyl radical, an alkylamino radical, an aryl radical, an aryloxy radical, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, a Arylalkinylrest, an arylamino radical, a monovalent heterocyclic radical or a cyano group. The examples mentioned above have several Rs, which may be the same or different. At least one of Rs is a radical represented by the above Formula (2) or (3) is reproduced, excluding the case where a polymer is a radical represented by formulas (2) or (3) is reproduced at a molecular chain end of the main chain thereof.

Of the Alkyl may here be straight, branched or cyclic and carbon atoms of generally about 1 to 20. Specific examples for this include a 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 and lauryl group. To include preferred examples thereof a pentyl group, hexyl group, octyl group, 2-ethylhexyl group, Decyl group and 3,7-dimethyloctyl group.

The alkoxy radical may here be straight, branched or cyclic and carbon atoms of the general NEN about 1 to 20 have. Specific examples thereof include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group and lauryloxy group. Preferred examples thereof include a pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group and 3,7-dimethyloctyloxy group.

Of the Alkylthio may here be straight, branched or cyclic and Have carbon atoms of generally about 1 to 20. specific Examples include a 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 groups, nonylthio group, Decylthio group, 3,7-dimethyloctylthio group and laurylthio group one. Preferred examples thereof include Pentylthio group, hexylthio group, octylthio group, 2-ethylhexylthio groups, Decylthio group and 3,7-dimethyloctylthio group.

Of the Alkylsilyl may here be straight, branched or cyclic and Have carbon atoms of generally about 1 to 60. specific Examples include a methylsilyl group, Ethylsilyl group, propylsilyl group, isopropylsilyl group, butylsilyl group, Isobutylsilyl group, t-butylsilyl group, pentylsilyl group, hexylsilyl group, Cyclohexylsilyl group, heptylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, nonylsilyl group, Decylsilyl group, 3,7-dimethyloctylsilyl group, laurylsilyl group, Trimethylsilyl group, ethyldimethylsilyl group, propyldimethylsilyl group, Isopropyldimethylsilyl group, butyldimethylsilyl group, t-butyldimethylsilyl group, Pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyldimethylsilyl groups, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyldimethylsilyl group and lauryldimethylsilyl group one. Preferred examples thereof include pentylsilyl group, Hexylsilyl group, octylsilyl group, 2-ethylhexylsilyl group, decylsilyl group, 3,7-dimethyloctylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, Octyldimethylsilyl group, 2-ethylhexyldimethylsilyl groups, decyldimethylsilyl group and 3,7-dimethyloctyldimethylsilyl group.

Of the Alkylamino may here be straight, branched or cyclic and may be a monoalkylamino radical or a dialkylamino radical and has generally about 1 to 40 carbon atoms. Specific examples for this include a methylamino group, dimethylamino group, Ethylamino group, diethylamino group, propylamino group, isopropylamino 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 and Laurylamino group. To include preferred examples thereof a pentylamino group, hexylamino group, octylamino group, 2-ethylhexylamino group, Decylamino group and 3,7-dimethyloctylamino group.

The aryl group generally has about 6 to 60 carbon atoms. Specific examples thereof include a phenyl group, C ₁ -C ₁₂ alkoxyphenyl radical (C ₁ -C ₁₂ is 1 to 12 carbon atoms, hereinafter the same definition is used), a C ₁ -C ₁₂ alkylphenyl radical and 1-naphthyl group and 2 Naphthyl group. Preferred examples thereof include a C ₁ -C ₁₂ alkoxyphenyl radical and C ₁ -C ₁₂ alkylphenyl radical.

The aryloxy group has about 6 to 60 carbon atoms. Specific examples thereof include a phenoxy group, C ₁ -C ₁₂ alkoxyphenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyloxy group and 2-naphthyloxy group. Preferred examples thereof include a C ₁ -C ₁₂ alkoxyphenoxy group and C ₁ -C ₁₂ alkylphenoxy group.

The arylalkyl group generally has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl C ₁ -C ₁₂ alkyl radical, C ₁ -C ₁₂ alkoxyphenyl C ₁ -C ₁₂ alkyl radical, C ₁ -C ₁₂ alkylphenyl C ₁ -C ₁₂ alkyl radical, 1-naphthyl C ₁ -C ₁₂ alkyl and 2-naphthyl C ₁ -C ₁₂ alkyl. Preferred examples thereof include a C ₁ -C ₁₂ alkoxyphenyl C ₁ -C ₁₂ alkyl group and C ₁ -C ₁₂ alkylphenyl C ₁ -C ₁₂ alkyl group.

The arylalkoxy radical generally has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkoxyphenyl C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkylphenyl C ₁ -C ₁₂ alkoxy, 1-naphthyl C ₁ -C ₁₂ alkoxy and 2-naphthyl C ₁ -C ₁₂ alkoxy. Preferred examples thereof include a C ₁ -C ₁₂ alkoxyphenyl C ₁ -C ₁₂ alkoxy group and C ₁ -C ₁₂ alkylphenyl C ₁ -C ₁₂ alkoxy group.

The arylalkenyl radical generally has about 8 to 60 carbon atoms. Specific examples for example, phenyl C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ alkoxyphenyl C ₂ -C ₁₂ alkenyl, C ₁ -C ₁₂ alkylphenyl, C ₂ -C ₁₂ alkenyl, 1-naphthyl-C C ₂ -C ₁₂ alkenyl radical and 2-naphthyl C ₂ -C ₁₂ alkenyl radical. Preferred examples thereof include a C ₁ -C ₁₂ alkoxyphenyl C ₂ -C ₁₂ alkenyl group and C ₁ -C ₁₂ alkylphenyl C ₂ -C ₁₂ alkenyl group.

The arylalkynyl group generally has about 8 to 60 carbon atoms. Specific examples thereof include phenyl C ₂ -C ₁₂ alkynyl, C ₁ -C ₁₂ alkoxyphenyl C ₂ -C ₁₂ alkynyl, C ₁ -C ₁₂ alkylphenyl C ₂ -C ₁₂ alkynyl, 1-naphthyl C ₂ -C ₁₂ alkynyl and 2-naphthyl C ₂ -C ₁₂ alkynyl. Preferred examples thereof include a C ₁ -C ₁₂ alkoxyphenyl C ₂ -C ₁₂ alkynyl radical and C ₁ -C ₁₂ alkylphenyl C ₂ -C ₁₂ alkynyl radical.

The arylamino radical generally has about 6 to 60 carbon atoms. Specific examples thereof include a phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenylamino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino group, 1-naphthylamino group and 2-naphthylamino group. Preferred examples thereof include a C ₁ -C ₁₂ alkylphenylamino radical, di (C ₁ -C ₁₂ alkylphenyl) amino radical.

The monovalent heterocyclic radical refers to the remaining atomic group when a single hydrogen atom is removed from a heterocyclic compound, and generally has about 4 to 60 carbon atoms. Specific examples include a thienyl group, C ₁ -C ₁₂ alkylthienyl, pyrrolyl, furyl, pyridyl, and C ₁ -C ₁₂ alkylpyridyl. Preferred examples include a thienyl group, C ₁ -C ₁₂ alkylthienyl group, pyridyl group and C ₁ -C ₁₂ alkylpyridyl group.

If the above-mentioned substituents are an alkyl chain may contain the alkyl chain on a heteroatom or radical, the contains a heteroatom, be interrupted. examples for the heteroatom includes an oxygen atom, sulfur atom and nitrogen atom. Examples of the heteroatom or the residue containing a heteroatom close the following radicals.

Examples for R 'here include a hydrogen atom, a Alkyl radical having 1 to 20 carbon atoms, an aryl radical having 6 to 60 carbon atoms, and a monovalent heterocyclic radical with 4 to 60 carbon atoms, one.

In Formula (1) refers to the divalent heterocyclic group to the remaining atomic group, if two hydrogen atoms of a heterocyclic compound are removed, and has in Generally about 4 to 60 carbon atoms in which the carbon atoms a substituent are not included.

The heterocyclic compound herein refers to an organic compound having a ring structure having not only one carbon atom (s) but also a heteroatom such as oxygen, sulfur, nitrogen, phosphorus or boron. For example, the following groups may be mentioned.
Radicals containing nitrogen as a hetero atom such as a pyridinediyl radical (the following formulas 39-44), a diazaphenylene radical (the following formulas 45-48), a quinolinediyl radical (the following formulas 49-63), a quinoxalinediyl radical (the following formulas 64) -68), an acridinediyl group (the following formulas 69-72), a bipyridyldiyl group (the following formulas 73-75) and a phenanthrolinediyl group (the following formulas 76-78);
Radicals containing a heteroatom such as silicon, nitrogen, oxygen, sulfur or selenium and having a fluorene structure (the following formulas 79 to 93);
Radicals having a 5-membered heterocyclic radical containing a heteroatom such as silicon, nitrogen, oxygen, sulfur or selenium (the following formulas 94 to 98);
Radicals having a 5-membered condensed heterocyclic radical containing a heteroatom such as silicon, nitrogen, oxygen, sulfur or selenium (the following formulas 99 to 108);
Dimers or oligomers of 5-membered heterocyclic groups containing a hetero atom such as sulfur and joined at the α-position to the hetero atom (the following formulas 109 and 110); and
5-membered heterocyclic groups containing a hetero atom such as silicon, nitrogen, oxygen, sulfur or selenium and connected with phenyl groups at the α-position to the hetero atom (the following formulas III to 117).

From these become a dibenzofuranediyl group (those mentioned above Formulas 85-87) and a dibenzothiophenediyl group (described above mentioned formulas 88 to 90) are preferred.

In In the above formulas 39 to 117, R is the same as defined above.

wobei Ar₈ und Ar₉ jeweils unabhängig für einen Arylenrest stehen, der einen Substituenten aufweisen kann; R₇ und R₈ jeweils unabhängig für ein Wasserstoffatom, einen Alkylrest, Arylrest, einwertigen heterocyclischen Rest oder Cyanogruppe stehen; und 1 gleich 0 oder 1 ist,

wobei Ar₁₀ und Ar₁₁ jeweils unabhängig für einen Arylenrest stehen, der einen Substituenten aufweisen kann; Ar₁₂ für einen Arylrest steht, der einen Substituenten aufweisen kann; und weiterhin ein Ring zwischen Ar₁₀ und Ar₁₂, Ar₁₀ und Ar₁₁ oder Ar₁₁ und Ar₁₂ gebildet werden kann,

wobei Ar₁₃ für einen Arylenrest steht, der einen Substituenten aufweisen kann; Ar₁₆ und Ar₁₇ jeweils unabhängig für einen Arylrest stehen, der einen Substituenten aufweisen kann; und weiterhin ein Ring zwischen Ar₁₃ und Ar₁₆, Ar₁₃ und Ar₁₇ oder Ar₁₆ und Ar₁₇ gebildet werden kann,

wobei Ar₁₄ für einen Arylenrest steht, der einen Substituenten aufweisen kann; Ar₁₅ für einen Arylrest steht, der einen Substituenten aufweisen kann; R₁₁ und R₁₂ jeweils unabhängig für ein Wasserstoffatom, einen Alkylrest, Arylrest, einwertigen heterocyclischen Rest oder Cyanogruppe stehen; und r gleich 0 oder 1 ist.In the above-mentioned formula (1), the divalent aromatic amine group refers to the remaining atomic group when two hydrogen atoms are removed from an aromatic amine, and generally has about 4 to 60 carbon atoms in which the number of carbon atoms of a substituent is not included is. Examples of the divalent aromatic amine group include the groups represented by the following general formula (50). -Ar ₆ -N (Ar ₅ ) -Ar ₇ - (50) wherein Ar ₆ and Ar ₇ each independently represent an arylene group which may have a substituent; a group represented by the following general formula (4) or a group represented by the following general formula (5); Ar _{5 represents} an aryl group which may have a substituent, a group represented by the following general formula (6), or a group represented by the following general formula (7); and further, a ring can be formed between Ar ₆ and Ar ₅ , Ar ₅ and Ar ₆ or Ar ₆ and Ar ₇ ,

wherein Ar ₈ and Ar ₉ each independently represent an arylene group which may have a substituent; Each of R ₇ and R ₈ independently represents a hydrogen atom, an alkyl group, aryl group, monovalent heterocyclic group or cyano group; and 1 is 0 or 1,

wherein Ar ₁₀ and Ar ₁₁ each independently represent an arylene group which may have a substituent; Ar _{12 is} an aryl group which may have a substituent; and further, a ring may be formed between Ar ₁₀ and Ar ₁₂ , Ar ₁₀ and Ar ₁₁ or Ar ₁₁ and Ar ₁₂ ,

wherein Ar _{13 is} an arylene group which may have a substituent; Ar ₁₆ and Ar ₁₇ each independently represent an aryl group which may have a substituent; and further, a ring may be formed between Ar ₁₃ and Ar ₁₆ , Ar ₁₃ and Ar ₁₇ or Ar ₁₆ and Ar ₁₇ ,

wherein Ar _{14 is} an arylene radical which may have a substituent; Ar _{15 is} an aryl group which may have a substituent; Each of R ₁₁ and R ₁₂ independently represents a hydrogen atom, an alkyl group, aryl group, monovalent heterocyclic group or cyano group; and r is 0 or 1.

Ar ₈ and Ar _{9 of} the above-mentioned formula (4), Ar ₁₀ and Ar _{11 of} the formula (5), Ar _{13 of} the formula (6) and Ar _{14 of} the formula (7) may have a substituent such as an alkyl group, alkoxy group, alkylthio group, alkylsilyl group, alkylamino group, aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, arylamino group, monovalent heterocyclic group or cyano group.

Further, Ar _{5 of} the above-mentioned formula (50), Ar _{12 of} the formula (5), Ar ₁₆ and Ar _{17 of} the formula (6) and Ar _{15 of} the formula (7) may have a substituent such as an alkyl group, alkoxy group, alkylthio group, Alkylsilyl, alkylamino, aryl, aryloxy, arylalkyl, arylalkoxy, arylalkenyl, arylalkynyl, arylamino, monovalent heterocyclic, or cyano.

specific Examples of the divalent aromatic amino group include the following radicals.

In In the above formulas 118 to 122, R is as the same as defined above.

wobei R_p1, R_q1, R_p2, R_q2, R_p3, R_q3, R_p4 und R_q4 jeweils unabhängig für einen Rest, der durch die vorstehend erwähnte Formel (2) wiedergegeben wird, einen Rest, der durch die vorstehend erwähnte Formel (3) wiedergegeben wird, einen Alkylrest, Alkoxyrest, Alkylthiorest, Alkylsilylrest, Alkylaminorest, Arylrest, Aryloxyrest, Arylalkylrest, Arylalkoxyrest, Arylalkenylrest, Arylalkinylrest, Arylaminorest, einwertigen heterocyclischen Rest oder Cyanogruppe stehen; a für eine ganze Zahl von 0 bis 3 steht; b für eine ganze Zahl von 0 bis 5 steht; wenn mehrere Reste, die durch R_p1, R_q1, R_p2, R_q2, R_p3, R_q3, R_p4 und R_q4 wiedergegeben werden, vorhanden sind, sie gleich oder verschieden sein können; R_w1, R_x1, R_w2, R_x2, R_w3, R_x3, R_w4 und R_x4 jeweils unabhängig für ein Wasserstoffatom, einen Alkylrest, Alkoxyrest, Alkylthiorest, Alkylsilylrest, Alkylaminorest, Arylrest, Aryloxyrest, Arylalkylrest, Arylalkoxyrest, Arylalkenylrest, Arylalkinylrest, Arylaminorest, einwertigen heterocyclischen Rest oder Cyanogruppe stehen; und jedes der Paare R_w1 und R_x1, R_w2 und R_x2, R_w3, und R_x3 und R_w4 und R_x4 sich gegenseitig verbinden kann, wodurch ein Ring gebildet wird.In a polymer compound according to the present invention, in view of fluorescence intensity and heat resistance of the polymer compound, the arylene group is preferably represented by the following formula (1-1) or (1-2), and particularly preferably represented by the following formula (1-3) or (1 -4),

wherein R _p1 , R _q1 , R _p2 , R _q2 , R _p3 , R _q3 , R _p4 and R _q4 each independently represents a group represented by the above-mentioned formula (2), a group represented by the above-mentioned Formula (3), an alkyl group, alkoxy, alkylthio, alkylsilyl, alkylamino, aryl, aryloxy, arylalkyl, arylalkoxy, arylalkenyl, arylalkynyl, arylamino, monovalent heterocyclic or cyano group; a is an integer from 0 to 3; b is an integer from 0 to 5; when a plurality of radicals represented by R _p1 , R _q1 , R _p2 , R _q2 , R _p3 , R _q3 , R _p4 and R _q4 are present, they may be the same or different; R _w1 , R _x1 , R _w2 , R _x2 , R _w3 , R _x3 , R _w4 and R _{x4 are} each independently hydrogen, alkyl, alkoxy, alkylthio, alkylsilyl, alkylamino, aryl, aryloxy, arylalkyl, arylalkoxy, arylalkenyl, Arylalkynyl, arylamino, monovalent heterocyclic or cyano; and each of the pairs R _w1 and R _x1 , R _w2 and R _x2 , R _w3 , and R _x3 and R _w4 and R _x4 can mutually connect, thereby forming a ring.

In the above-mentioned formulas (1-1), (1-2), (1-3) and (1-4), with respect to solubility in an organic solvent, characteristics of the device is ease of synthesis for a polymer compound and fluorescence intensity each of R _p1 , R _q1 , R _p2 , R _q2 , R _p3 , R _q3 , R _p4 and R _q4 preferably represents a group represented by the above-mentioned formula (2) and a group represented by the above-mentioned Formula (3) is an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group or an arylalkoxy group; and more preferably an alkyl group, an alkoxy group or an aryl group.

In the above-mentioned formulas (1-1), (1-2), (1-3) and (1-4), with respect to solubility in an organic solvent, characteristics of the device is ease of synthesis for a polymer compound and fluorescence intensity each of R _w1 , R _x1 , R _w2 , R _x2 , R _w3 , R _x3 , R _w4 and R _x4 preferably represents an alkyl group, alkoxy group, aryl group, aryloxy group, arylalkyl group or an arylalkoxy group; and more preferably an alkyl group or an aryl group.

Examples of the alkyl group, alkoxy group and aryl group include straight, branched or cyclic alkyl groups generally having about 1 to 20 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, isoamyl group, hexyl group Cyclohexyl, heptyl, cyclohexylmethyl, octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, lauryl, trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, and perfluorooctyl; Alkoxy groups generally having about 1 to 20 carbon atoms, such as methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, cyclohexylmethyloxy 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 and 2-methoxyethyloxy group; and aryl groups generally having about 6 to 60 carbon atoms, such as a phenyl group, C ₁ -C ₁₂ alkoxyphenyl, C ₁ -C ₁₂ alkylphenyl, 1-naphthyl, 2-naphthyl, 1-anthracenyl, 2-anthracenyl, 9 Anthracenyl group and pentafluorophenyl group.

Specific examples of the C ₁ -C ₁₂ alkoxy include methoxy, ethoxy, propyloxy, isopropyloxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7- Dimethyloctyloxy and lauryloxy. Specific examples of the C ₁ -C ₁₂ alkylphenyl group include 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 and dodecylphenyl group one.

Examples of the groups represented by the above-mentioned formulas (1-1), (1-2), (1-3) and (1-4) in which each of the pairs R _w1 and R _x1 , R _w2 and R _x2 , R _w3 and R _x3 and R _w4 and R _x4 counter to form a ring, include radicals represented by the following radicals of formulas (1-1-2), (1-2-2), (1-3-2) and (1-4- 2) are reproduced. These may further have a substituent.

Reste der Formeln (1-1-2)

Remains of the formulas (1-1-2)

Reste der Formeln (1-2-2)

Remainders of the formulas (1-2-2)

Reste der Formeln (1-3-2)

Remainders of the formulas (1-3-2)

Reste der Formeln (1-4-2)

Remainders of the formulas (1-4-2)

In the above-mentioned formulas (1-1) and (1-2) is used in With regard to polymerization and improvement of heat resistance a = b = 0 is preferred.

From The polymer compounds of the present invention are described in terms of on ease of synthesis for a monomer polymer compounds, the radicals represented by the formulas (1-1), (1-3) and (1-4) are, preferably and more preferably polymer compounds, the contain a group represented by the formula (1-1) becomes.

In view of improving the solubility of a synthesized polymer compound in an organic solvent in equilibrium with heat resistance, R _w1 and R _{x1 are} each preferably an alkyl group, more preferably an alkyl group having 3 or more carbon atoms, more preferably having 7 or more carbon atoms, and which further preferably has 8 or more; and most preferably an n-octyl group having a structure represented by the following formula (80).

wobei Ring C und Ring D jeweils unabhängig für einen aromatischen Ring stehen; Ring C und Ring D einen Substituenten aufweisen können, ausgewählt aus der Gruppe, bestehend aus einem Rest, welcher durch die vorstehend erwähnte Formel (2) wiedergegeben wird, einem Rest, welcher durch die vorstehend erwähnte Formel (3) wiedergegeben wird, einem Alkylrest, einem Alkoxyrest, einem Alkylthiorest, einem Alkylsilylrest, einem Alkylaminorest, einem Arylrest, einem Aryloxyrest, einem Arylalkylrest, einem Arylalkoxyrest, einem Arylalkenylrest, einem Arylalkinylrest, einem Arylaminorest, einem einwertigen heterocyclischen Rest und einer Cyanogruppe; wenn mehrere Substituenten vorhanden sind, sie gleich oder verschieden sein können; und E gleich O oder S ist.Further, in view of ease of synthesis for a polymer compound and fluorescence intensity, a divalent heterocyclic group is particularly preferably represented by the following formula (70):

wherein ring C and ring D each independently represent an aromatic ring; Ring C and Ring D may have a substituent selected from the group consisting of a group represented by the above-mentioned formula (2), a group represented by the above-mentioned formula (3), an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group and a cyano group; when more substituents are present, they may be the same or different; and E is O or S.

wobei X für O oder S steht; R^a für einen Substituenten steht; m unabhängig für eine ganze Zahl von 0 bis 5 steht; n unabhängig für eine ganze Zahl von 0 bis 3 steht. Wenn mehrere Substituenten, welche durch R^a wiedergegeben werden, vorhanden sind, können sie gleich oder verschieden sein.As an example of the group represented by the above-mentioned formula (70), there may be mentioned any of the groups represented by the following formulas (2a) to (2d):

where X is O or S; R ^{a is} a substituent; m is independently an integer from 0 to 5; n is independently an integer from 0 to 3. When plural substituents represented by R ^a are present, they may be the same or different.

Examples of the substituent represented by R ^a are the same as those exemplified as the aforementioned substituents represented by R. In view of the solubility of a polymer compound, m is preferably an integer of 1 to 3, and n is preferably an integer of 1 or 2.

wobei Y für O oder S steht; R^j und R^k jeweils unabhängig für einen Rest, welcher durch die vorstehend erwähnte Formel (2) wiedergegeben wird, einen Rest, welcher durch die vorstehend erwähnte Formel (3) wiedergegeben wird, ein Wasserstoffatom, einen Alkylrest, einen Alkoxyrest oder einen Arylrest stehen.The group represented by the above-mentioned formula (2a) is preferably a group represented by the following formula (2E) in view of ease of synthesis for a polymer compound and fluorescence intensity.

where Y is O or S; R ^j and R ^k each independently represent a group represented by the above-mentioned formula (2), a group represented by the above-mentioned formula (3), a hydrogen atom, an alkyl group, an alkoxy group or an aryl group ,

In the above-mentioned formula (2E), R ^j and R ^{k are} preferably the same in view of ease of synthesis for a polymer compound (more specifically, both of them are hydrogen atoms, alkyl groups, alkoxy groups or aryl groups), and more preferably alkoxy groups. Examples of the alkyl groups and aryl groups represented by R ^j and R ^k are the same as those exemplified as a substituent represented by R. Examples of the alkoxy groups represented by R ^j and R ^k preferably include a butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy, in view of solubility and fluorescence intensity of a polymer compound group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group, decyloxy group, 3,7-dimethyloctyloxy group and lauryloxy group; and further preferably includes a pentyloxy group, hexyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group and 3,7-dimethyloctyloxy group.

wobei R jeweils unabhängig für ein Wasserstoffatom, einen Rest, welcher durch die vorstehend erwähnte Formel (2) wiedergegeben wird, einen Rest, welcher durch die vorstehend erwähnte Formel (3) wiedergegeben wird, einen Alkylrest, einen Alkoxyrest, einen Alkylthiorest, einen Alkylsilylrest, einen Alkylaminorest, einen Arylrest, einen Aryloxyrest, einen Arylalkylrest, einen Arylalkoxyrest, einen Arylalkenylrest, einen Arylalkinylrest, einen Arylaminorest, einen einwertigen heterocyclischen Rest oder eine Cyanogruppe stehen; und im Hinblick auf Hitzebeständigkeit einer Polymerverbindung oder Polymerisation davon vorzugsweise einen Rest, welcher wiedergegeben wird durch

wobei R als dasselbe wie vorstehend definiert ist.Examples of a repeating unit represented by the above-mentioned formula (70) include a group which is represented by

wherein each R independently represents a hydrogen atom, a group represented by the above-mentioned formula (2), a group represented by the above-mentioned formula (3), an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino, aryl, aryloxy, arylalkyl, arylalkoxy, arylalkenyl, arylalkynyl, arylamino, monovalent heterocyclic or cyano group; and in view of heat resistance of a polymer compound or polymerization thereof, preferably a group represented by

where R is the same as defined above.

In The above formula has a single structural formula more Rs on. They can be the same or different. Examples for a group represented by R in the formula are, are the same as those as substituents which represented by R can be illustrated.

In the above-mentioned formula (1), Z 'is -C (R ₄ ) = C (R ₅ ) - or -C≡C-, wherein R ₄ and R ₅ each independently represent a hydrogen atom, an alkyl group, aryl group, monovalent ones heterocyclic radical or cyano group. In terms of stability, -C (R ₄ ) = C (R ₅ ) - is preferred.

wobei R als dasselbe wie vorstehend definiert ist.Preferred examples of the repeating units wherein Z 'is -C (R ₄ ) = C (R ₅ ) - include those represented by the following formulas 128 to 135:

where R is the same as defined above.

The Reference symbol p is 0 or 1. With regard to photooxidation stability p is preferably 0.

In the above-mentioned formula (2), A _{1 represents} -O-, -S- or -C (O) -.

In the above-mentioned formula (2), Ar ^{01 represents} a direct bond, an arylene group, a divalent heterocyclic group or a divalent aromatic amine group.

Of the Arylene radical, divalent heterocyclic radical or divalent aromatic Amine residue is the same as defined above.

In the above-mentioned formula (2), R ^{05 is} a direct bond, -R ₁ -, * -OR ₁ -, * -R ₁ -O-, * -R ₁ -C (O) O-, * -R ₁ -OC (O) -, * -R ₁ -N (R ₂₀ ) -, -O-, -S-, * -C (O) O- or -C (O) - (wherein * represents a position for Binding to Ar ⁰¹ ); R ^{07 is} a direct bond, -R ₁ -, -OR ₁ - *, R ₁ -O- *, -R ₁ -C (O) O- *, -R ₁ -OC (O) - *, - R ₁ -N (R ₂₀ ) - *, -O-, -S-, -C (O) O- * or -C (O) - (wherein * represents a site for binding to Ar ⁰¹ ). R ₁ is an alkylene radical or an alkenylene radical. R ₂₀ represents a hydrogen atom, an alkyl radical, aryl radical, monovalent radical or cyano group. In view of ease of synthesis and stability, R ^{05 is} preferably a direct bond, -R ₁ - or * -OR ₁ - and R ^{07 is} preferably a direct bond, -R ₁ - or -R ₁ -O- *.

In the above-mentioned formula (2), R ⁰¹ and R ^{02 are} each independently a substituent. Examples the substituent includes alkyl, alkoxy, alkylthio, alkylsilyl, alkylamino, aryl, aryloxy, arylalkyl, arylalkoxy, arylalkenyl, arylalkynyl, arylamino, monovalent heterocyclic, and cyano.

The reference symbols a and b are each independently an integer of 0 to 4, and a plurality of substituents represented by R ⁰¹ and R ⁰² may be the same or different.

wobei R als dasselbe wie in R⁰¹ definiert ist. R₁ ist als dasselbe wie vorstehend definiert.Specific examples of the group represented by the above-mentioned formula (2) include those listed below,

where R is defined as the same as in R ⁰¹ . R ₁ is the same as defined above.

In the above-mentioned formula (3), B _{1 is} -O-, -S- or -C (O) -.

In the above-mentioned formula (3), Ar ^{02 represents} a hydrogen atom, an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group.

The aryl radical here generally has about 6 to 60 carbon atoms. Specific examples thereof include a phenyl group, C ₁ -C ₁₂ alkoxyphenyl radical (C ₁ -C ₁₂ is 1 to 12 carbon atoms and hereinafter the same definition is used), C ₁ -C ₁₂ alkylphenyl radical, 1-naphthyl group and 2-naphthyl group , Of these, C ₁ -C ₁₂ alkoxyphenyl and C ₁ -C ₁₂ alkyl phenyl are preferred.

Of the monovalent heterocyclic radical refers to the remaining Atomic group, when a single hydrogen atom of a heterocyclic Remainder is removed and generally about 2 to 60 carbon atoms having.

Examples of the monovalent heterocyclic group include those mentioned below:
monovalent heterocyclic groups containing nitrogen as a hetero atom, such as pyridinyl group, diazaphenyl group, quinolinyl group, quinoxalinyl group, acridinyl group, bipyridinyl group and phenanthrolinyl group;
Radicals containing a heteroatom such as silicon, nitrogen, sulfur, selenium or oxygen and having a fluorene structure (radicals having rings and represented by the above-mentioned formulas 79 to 93);
5-membered heterocyclic groups containing a heteroatom such as silicon, nitrogen, sulfur, selenium or oxygen (groups having a ring represented by the above-mentioned formulas 94 to 98 such as be given);
5-membered condensed heterocyclic groups containing a hetero atom such as silicon, nitrogen, sulfur, selenium or oxygen (groups having rings represented by the above-mentioned formulas 99 to 108);
Dimers or oligomers of 5-membered heterocyclic groups containing a heteroatom such as sulfur and joined at the α-position to the heteroatom (groups having rings represented by the above-mentioned formulas 109 and 110); and
A 5-membered heterocyclic radical containing a heteroatom such as silicon, nitrogen, sulfur, selenium or oxygen, and connected to phenyl radicals at the α-position to the heteroatom (radicals having rings represented by the above-mentioned formulas III to 117).

wobei R als dasselbe wie in R⁰¹ definiert ist.The monovalent aromatic amine radical refers to the remaining atomic group when a single hydrogen atom is removed from an aromatic amine and generally has from about 4 to 60 carbon atoms in which the number of carbon atoms of a substituent is not included. Examples of the monovalent aromatic amine group include groups represented by the following formulas 123 to 127,

where R is defined as the same as in R ⁰¹ .

In the above-mentioned formula (3), R ^{06 is} a direct bond, -R ₁ -, -OR ₁ - *, -R ₁ -O- *, -R ₁ -C (O) O- *, -R ₁ -OC (O) - *, -R ₁ -N (R ₂₀ ) - *, -O-, -S-, -C (O) O- * or -C (O) - (where * for a position for binding to A ⁰² ); R _{1 is} an alkylene radical or an alkenylene radical; and R _{20 is} hydrogen, alkyl, aryl, monovalent or cyano. In view of ease of synthesis and stability, R ^{06 is} preferably a direct bond, -R ₁ - or -R ₁ -O- *.

R ⁰⁸ is a direct bond, -R ₁ -, * -OR ₁ -, * -R ₁ -O-, * -R ₁ -C (O) O-, * -R ₁ -OC (O) -, * -R ₁ -N (R ₂₀ ) -, -O-, -S-, * -C (O) O- or -C (O) - (wherein * represents a site for binding to Ar ⁰³ ); and R ^{09 is} a direct bond, -R ₁ -, -OR ₁ - *, -R ₁ -O- *, -R ₁ -C (O) O- *, -R ₁ -OC (O) - * , -R ₁ -N (R ₂₀ ) - *, -O-, -S-, -C (O) O- * or -C (O) - (wherein * represents a site for binding to Ar ⁰³ ). R ¹ is an alkylene radical or an alkenylene radical. R ₂₀ represents a hydrogen atom, an alkyl radical, aryl radical, monovalent radical or cyano group. In view of ease of synthesis and stability, R ^{08 is} preferably a direct bond, -R ₁ - or * -R ₁ -O-, and R ^{09 is} preferably a direct bond or -R ₁ - or R ⁰³ and R ⁰⁴ are each independently a substituent. examples for the substituents include alkyl, alkoxy, alkylthio, alkylsilyl, alkylamino, aryl, aryloxy, arylalkyl, arylalkoxy, arylalkenyl, arylalkynyl, arylamino, monovalent heterocyclic, and cyano.

The reference symbol c is an integer of 0 to 4 and d is an integer of 0 to 3. Several substituents represented by R ⁰³ and R ⁰⁴ may be the same or different.

wobei R als dasselbe wie in R⁰³ definiert ist. R₁ ist als dasselbe wie vorstehend definiert.Specific examples of the group represented by the above-mentioned formula (3) include those listed below,

where R is defined as the same as in R ⁰³ . R ₁ is the same as defined above.

Of the polymer compounds of the present invention, those having a repeating unit represented by the following formula (30) are preferred in view of solubility and fluorescence intensity. -Ar ₄ - (Z) _t - (30) Ar _{4 of} the above-mentioned formula (30) represents an arylene group, divalent heterocyclic group or divalent aromatic amine group. Examples of Ar ₄ are the same as those illustrated in Ar ₁ . However, the examples of Ar ₄ include none of those represented by the above-mentioned formulas (2) and (3).

In the formula (30), Z represents -CR ₇ = CR ₈ - or -C≡C-. Each of R ₇ and R ₈ independently represents a hydrogen atom, an alkyl group, aryl group, monovalent heterocyclic group or cyano group, and t represents 0 or 1. In view of stability, -CR ₇ = CR ₈ - is preferred. With regard to photooxidation stability, t is stronger ker preferred 0.

wobei R als dasselbe wie vorstehend definiert ist. Jedoch sind die Reste, welche durch die vorstehend erwähnten Formeln (2) und (3) wiedergegeben werden, nicht eingeschlossen.Specific examples of the repeating unit represented by the formula (30) preferably include the structures represented by the above-mentioned formulas 1 to 117, A to F, 118 to 122 and the following formulas 128 to 133 , Of these, preferable examples include a phenylene group (for example, the above-mentioned formulas 1 to 3), a naphthalenediyl group (the above-mentioned formulas 4 to 13), an anthracenylene group (the above-mentioned formulas 14 to 19), a biphenylene group (the above-mentioned formulas 20 to 25), a triphenylene group (the above-mentioned formulas 26 to 28), a condensed ring compound group (the above-mentioned formulas 29 to 38), a dibenzofuranediyl group (the above-mentioned formulas 85 to 87), a dibenzothiophenediyl group (the above-mentioned formulas 88 to 90), a stilbenediyl group, a distilbendiyl group, a bivalent aromatic amine group (the above-mentioned formulas 118, 119 and 122), an arylenevinylene group (the above-mentioned formulas 128 to 133) and a benzofluorodiyl (the above-mentioned formulas G, H, I and no. Of these, particularly preferable examples thereof include a phenylene group, a biphenylene group, a fluorenediyl group (the above-mentioned formulas 36 to 38), a dibenzofuranediyl group (the above-mentioned formulas 85 to 87), a dibenzothiophenediyl group (the above-mentioned formulas 88 to 90), a stilbenediyl group , a distilbendiyl group, a benzofluorodiyl group (the aforementioned formulas G, H, I and K) and a divalent aromatic amine group,

where R is the same as defined above. However, the groups represented by the above-mentioned formulas (2) and (3) are not included.

A polymer compound according to the present invention may contain at least one of the groups represented by the above-mentioned formulas (2) and / or (3) as a substituent of Ar _{1 of} the above-mentioned formula (1) which is the main chain of the above-mentioned Polymer, ie, substituent (s) of an arylene group, divalent heterocyclic groups or divalent aromatic amine groups (the number of types of substituents may be one or two or more), or at least one of the terminal groups present at the ends of the polymer chain molecule (the number of types of terminal residues may be one or two or more).

With respect to polymerization of a polymer compound, Ar _{1 of} the above-mentioned formula (1) preferably has at least one of the groups represented by the aforementioned formulas (2) and / or (3).

you Note that a polymer compound according to the present invention a repeating unit other than the repeating units represented by the above mentioned Formulas (1) and (30) can be reproduced, provided that fluorescent properties and charge transport properties not be affected. More specifically, one will Polymer compound consisting essentially of the repeating Units represented by the formula (1) are formed is, and a polymer compound consisting essentially of the repeating units represented by formulas (1) and (30) are formed, is preferred. The repeating units may be by vinylene or unconjugated unit be linked or can vinylen and not contain conjugated unit. Examples of the linking Structure containing the non-conjugated unit, include the radicals listed below are combinations of the radicals listed below are, and a Vinylenrest and combination of two or more of the radicals listed below. R 'is here a radical selected from the same substituents, as mentioned above, and Ar stands for one Hydrocarbon radical having 6 to 60 carbon atoms.

A polymer compound according to the present invention has a polystyrene reduced number average molecular weight of 10 ³ to 10 ^8, and preferably 3 × 10 ³ to 5 × 10 ⁶ in terms of film-forming ability, more preferably 5 × 10 ³ to 2 × 10 ⁶ and further preferably 1 × 10 ⁴ to 1 × 10 ⁶ .

A polymer compound according to the present invention is preferably fluorescent in a state of solid. More preferably, a polymer compound is fluorescent in a state of solid, and has a polystyrene-reduced number average molecular weight of 10 ³ to 10 ⁸ .

Farther may be a polymer compound according to the present Invention be phosphorescent.

Examples for a good solvent for one Polymer compound according to the present invention include Chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, Mesitylene, decalin and n-butylbenzene. The amount of a polymer compound varies depending on the structure and the molecular weight from that; however, in general, the polymer compound may be in each these solvents in an amount of 0.1 wt .-% or be more included.

A Polymer compound according to the present invention may be a random, block or graft copolymer, a polymer, which has an intermediate structure of these For example, a random copolymer, which partially a Block copolymer structure, be. To a polymer compound, which has a high fluorescence quantum yield a random copolymer partially having a block copolymer structure has a block copolymer or a graft copolymer rather than a complete random copolymer preferred. As well are a dendrimer, which has a branched main chain, and a dendrimer, which has three or more terminal sections including.

One A process for producing a polymer compound according to The present invention will now be described.

<< The case where repeating unit Ar _{1 represented} by the above-mentioned formula (1) has a group represented by the above-mentioned formula (2) or (3) (side-chain substitution) as a substituent >>

wobei R ein Rest, welcher durch die vorstehend erwähnte Formel (2) wiedergegeben wird, ein Rest, welcher durch die vorstehend erwähnte Formel (3) wiedergegeben wird, ein Wasserstoffatom, ein Alkylrest, ein Alkoxyrest, ein Alkylthiorest, ein Alkylsilylrest, ein Alkylaminorest, ein Arylrest, ein Aryloxyrest, ein Arylalkylrest, ein Arylalkoxyrest, ein Arylalkenylrest, ein Arylalkinylrest, ein Arylaminorest, ein einwertiger heterocyclischer Rest oder eine Cyanogruppe ist. In dem vorstehend erwähnten Fall sind mehrere Rs vorhanden. Sie können gleich oder verschieden sein. Jedoch ist mindestens einer der Rs ein Rest, welcher durch die vorstehend erwähnte Formel (2) oder (3) wiedergegeben wird. D₁ und D₂ stehen jeweils unabhängig für ein Halogenatom, einen Alkylsulfonatrest, Arylsulfonatrest, Arylalkylsulfonatrest, einen Borsäureesterrest, Sulfoniummethylrest, Phosphoniummethylrest, Phosphonatmethylrest, monohalogenierte Methylgruppe, Borsäuregruppe, Formylgruppe, Cyanomethylgruppe oder Vinylgruppe.A polymer compound according to the present invention can be produced by condensation polymerization using a compound represented by the following formula as one of the materials.

wherein R represents a group represented by the above-mentioned formula (2), a group represented by the above-mentioned formula (3), a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylsilyl group, an alkylamino group, is an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, an arylalkenyl group, an arylalkynyl group, an arylamino group, a monovalent heterocyclic group or a cyano group. In the case mentioned above, there are several Rs. They can be the same or different. However, at least one of Rs is a group represented by the above-mentioned formula (2) or (3). Each of D ₁ and D ₂ independently represents a halogen atom, an alkylsulfonate residue, arylsulfonate residue, arylalkylsulfonate residue, a boric acid ester residue, sulfoniummethyl residue, phosphoniummethyl residue, phosphonate methyl residue, monohalogenated methyl group, boric acid group, formyl group, cyanomethyl group or vinyl group.

Examples for the alkylsulfonate residue include a methanesulfonate group, Ethanesulfonate group and trifluoromethanesulfonate group. Examples for the arylsulfonate radical include a benzenesulfonate group and p-toluenesulfonate group. Examples of the Arylalkylsulfonatrest include a benzylsulfonate group. examples for the boric acid ester residue include the groups which are represented by the following formulas.

Examples of the sulfonium methyl group include the groups represented by the following formulas: -CH ₂ S ⁺ Me ₂ X ^- -CH ₂ S ⁺ Ph ₂ X ^- (X represents a halogen atom).

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

Examples of the phosphonate methyl group include the groups represented by the following formula: -CH ₂ P (O) (OR ''') ₂ (R '''represents an alkyl radical, aryl radical or arylalkyl radical).

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

• [1] Polymerisation einer Verbindung, welche eine Aldehydgruppe aufweist, und einer Verbindung, welche eine Phosphoniumbase aufweist, durch die Wittig-Reaktion;
• [2] Polymerisation einer Verbindung, welche eine Aldehydgruppe aufweist, und einer Phosphoniumbase durch die Wittig-Reaktion;
• [3] Polymerisation einer Verbindung, welche eine Vinylgruppe aufweist, und einer Verbindung, welche ein Halogenatom aufweist, durch die Heck-Reaktion;
• [4] Polymerisation einer Verbindung, welche eine Vinylgruppe aufweist, und eines Halogenatoms durch die Heck-Reaktion;
• [5] Polymerisation einer Verbindung, welche eine Aldehydgruppe aufweist, und einer Verbindung, welche einen Alkylsulfonatrest aufweist, durch das Horner-Wadsworth-Emmons-Verfahren;
• [6] Polymerisation einer Verbindung, welche eine Aldehydgruppe aufweist, und eines Alkylsulfonatrests durch das Homer-Wadsworth-Emmons-Verfahren;
• [7] Kondensationspolymerisation einer Verbindung, welche zwei oder mehrere halogenierte Methylgruppen aufweist, durch das Dehydrohalogenierungsverfahren;
• [8] Kondensationspolymerisation einer Verbindung, welche zwei oder mehrere Sulfoniumbasen aufweist, durch das Sulfoniumsalz-Zersetzungsverfahren;
• [9] Polymerisation einer Verbindung, welche eine Aldehydgruppe aufweist, und eines Rests, welcher eine Acetonitrilgruppe aufweist, durch die Knoevenagel-Reaktion;
• [10] Polymerisation einer Verbindung, welche eine Aldehydgruppe aufweist, und einer Acetonitrilgruppe durch die Knoevenagel-Reaktion; und
• [11] Polymerisation einer Verbindung, welche zwei oder mehrere Aldehydgruppen aufweist, durch die McMurry-Reaktion.

Examples of a condensation polymerization method include those mentioned below, provided that when one main chain has a vinylene group, other monomers can be used as required.

• [1] polymerization of a compound having an aldehyde group and a compound having a phosphonium base by the Wittig reaction;
• [2] polymerization of a compound having an aldehyde group and a phosphonium base by the Wittig reaction;
• [3] polymerization of a compound having a vinyl group and a compound having a halogen atom by the Heck reaction;
• [4] polymerization of a compound having a vinyl group and a halogen atom by the Heck reaction;
• [5] polymerization of a compound having an aldehyde group and a compound having an alkylsulfonate residue by the Horner-Wadsworth-Emmons method;
• [6] polymerizing a compound having an aldehyde group and an alkylsulfonate residue by the Homer-Wadsworth-Emmons method;
• [7] condensation polymerization of a compound having two or more halogenated methyl groups by the dehydrohalogenation method;
• [8] condensation polymerization of a compound having two or more sulfonium bases by the sulfonium salt decomposition method;
• [9] polymerization of a compound having an aldehyde group and a residue having an acetonitrile group by the Knoevenagel reaction;
• [10] polymerization of a compound having an aldehyde group and an acetonitrile group by the Knoevenagel reaction; and
• [11] Polymerization of a compound having two or more aldehyde groups by the McMurry reaction.

• [12] ein Polymerisationsverfahren durch die Suzuki-Kupplungsreaktion;
• [13] ein Polymerisationsverfahren durch die Grignard-Reaktion;
• [14] ein Polymerisationsverfahren durch einen Ni(0)-Katalysator;
• [15] ein Polymerisationsverfahren durch ein Oxidationsmittel, wie FeCl₃, eine elektrochemische Oxidationspolymerisation; und
• [16] ein Zersetzungsverfahren eines intermediären Polymers, welches eine passende Abgangsgruppe aufweist.

Examples of a method for producing a polymer compound according to the present invention include

• [12] a polymerization process by the Suzuki coupling reaction;
• [13] a polymerization process by the Grignard reaction;
• [14] a polymerization process by a Ni (0) catalyst;
• [15] a polymerization method by an oxidizing agent such as FeCl ₃ , an electrochemical oxidation polymerization; and
• [16] a decomposition method of an intermediate polymer having a proper leaving group.

As the reaction using a Ni (0) catalyst, a polymerization method in the presence of a zero-valent nickel complex {Ni (COD) ₂ } may be mentioned.

Examples for the zerovalent nickel (0) complex Bis (1,5-cyclooctadiene) nickel (0), (ethylene) bis (triphenylphosphine) nickel and tetrakis (triphenylphosphine) nickel. Of these, bis (1,5-cyclooctadiene) nickel (0) preferred because it is commonly used and inexpensive is.

Farther Preferably, a neutral ligand is added to the yield to improve.

Of the neutral ligand used herein is a ligand which has neither an anion nor a cation. Examples of this include nitrogen-containing ligands, such as 2,2'-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline and N, N'-tetramethylethylenediamine; and tertiary phosphine ligands, such as triphenylphosphine, tritolylphosphine, Tributylphosphine and triphenoxyphosphine, a. A nitrogen-containing Ligand is preferred because it is generally used and inexpensive is, and 2,2'-bipyridyl is used for high reactivity and high yield particularly preferred. To the yield of a polymer it is preferred to use a system containing bis (1,5-cyclooctadiene) nickel (0). and the 2,2'-bipyridyl as a neutral ligand was given to it.

The polymerization solvent is not particularly limited unless it is the polymerization inhibits. Examples thereof include an amide-based solvent, an aromatic hydrocarbon-based solvent, an ether-based solvent, and an ester-based solvent.

Examples for the amide-based solvent N, N-dimethylformamide and N, N-dimethylacetamide.

Examples for the solvent based on aromatic Hydrocarbon, which is a solvent that is an aromatic hydrocarbon compound preferably benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, Butylbenzene, naphthalene and tetralin. Of these, toluene, xylene, Tetralin and tetramethylbenzene, etc. are preferred.

Farther include examples of the solvent ether-based, which is a solvent that is a compound in which hydrocarbon radicals are attached to an oxygen atom Diisopropyl ether, tetrahydrofuran, 1,4-dioxane, Diphenyl ether, ethylene glycol dimethyl ether and tert-butyl methyl ether one. Of these, tetrahydrofuran and 1,4-dioxane are preferred because they good solvents for a polymer compound are.

Around Can improve polymerization and solubility these solvents are used in the mixture.

A Polymerization reaction is generally carried out in an inert gas atmosphere, such as argon or nitrogen.

The Polymerization time is generally about 0.5 to 100 hours. In terms of manufacturing cost is 30 hours or less preferred.

The Polymerization temperature is generally about 0 up to 200 ° C. To increase the yield and heating costs is lower, 0 to 100 ° C is preferred.

you note that the polymerization reaction is generally under one Inert gas atmosphere, such as argon or nitrogen, in one Reaction system is performed in which a zerovalent Nickel catalyst is not deactivated.

Examples for the reaction, which in the presence of a Pd catalyst is performed, conclude the Suzuki coupling reaction one.

Examples for the palladium catalyst used in the Suzuki coupling reaction to be used include palladium acetate, a Palladium [tetrakis (triphenylphosphine)] complex and a bis (tricyclohexylphosphine) palladium complex one.

Examples for the phosphorus ligand include triphenylphosphine, Tri (o-tolyl) phosphine and 1,3-bis (diphenylphosphino) propane.

For example the reaction becomes complex in a system which palladium [tetrakis (triphenylphosphine)] used with the addition of an inorganic base such as potassium carbonate, Sodium carbonate or barium hydroxide, an organic base, such as Triethylamine, or an inorganic salt, such as cesium fluoride, in an amount of one equivalent or more, preferably 1 to 10 equivalents relative to the monomer. The reaction can be carried out in a two-phase system using a aqueous inorganic salt solution become. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane and tetrahydrofuran one. The reaction temperature varies depending on the solvent to be used; however is preferably a temperature of about 50 to 160 ° C. used. The reaction temperature can be near the Boiling point of the solvent, which are used should be raised, and reflux can be performed become. The reaction time is about 0.2 hours to 200 hours. Note that the polymerization reaction is generally carried out under an inert gas atmosphere, such as argon or nitrogen, in a reaction system is carried out in which a zero-valent Pd (0) catalyst is not deactivated.

Of these, polymerization in accordance with the Wittig reaction, polymerization by the Heck reaction, polymerization by the Homer-Wadsworth-Emmons method, polymerization by Knoevenagel reaction, polymerization by the Suzuki coupling reaction, polymerization by the Gri gnard reaction and polymerization by a Ni (0) catalyst, since structural control can easily be made. Furthermore, polymerization by the Ni (0) catalyst is more preferred because of the availability of starting materials and simple polymerization process.

<< The case where one Polymer chain, which is a repeating unit, which by the formula (1) is shown, and a radical which represented by the above-mentioned formula (2) and / or (3) is at least one of the ends of the molecular chain >>

A Polymer compound according to the present invention can be prepared, for example, by adding a monomer which corresponds to one or more types of repeating units, is polymerized to a polymer which has a leaving group one end of it, and the polymer with a A monomer corresponding to those represented by the formula (2) and / or (3); or can be prepared by adding a monomer containing one or more Types of repeating units corresponds, in the presence a monomer corresponding to those which are replaced by the Formula (2) and / or (3) are polymerized.

A polymer compound according to the present invention can be prepared by reacting one or more types of monomers represented by the general formula (101) and / or (102) with monomers represented by the general formula (104) and / or ( 105). Y ₁ -Ar ₁ -Y ₂ (101) Y ₃ -Ar ₂ -Y ₄ (102) Y ₇ -E ₁ (104) Y ₈ -E ₂ (105) wherein Ar ₁ and Ar ₂ each independently represent an arylene group, divalent heterocyclic group or divalent aromatic amine group; Each of E ₁ and E ₂ independently represents a group represented by the above-mentioned formula (2) and / or (3); Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₇ and Y ₈ each independently represent a leaving group; however, E ₁ and E ₂ are different from each other.

Examples of the leaving group include a halogen atom, alkylsulfonyloxy, arylsulfonyloxy, and a group represented by -B (OR ₁₁ ) ₂ (wherein R _{11 is} a hydrogen atom or an alkyl group).

Examples for the halogen atom include a chlorine atom, bromine atom and iodine atom. Of these, a chlorine atom and a bromine atom are preferred and a bromine atom is the most preferred. The alkylsulfonyloxy radical may be substituted with a Floratom. For example, the Trifluoromethanesulfonyloxy group. The arylsulfonyloxy radical may be substituted with an alkyl radical. For example, you can mentions a phenylsulfonyloxy group and a trisulfonyloxy group become.

In the group represented by -B (OR ₁₁ ) ₂ , R _{11 is} a hydrogen atom or an alkyl group. Examples of the alkyl group, which generally has about 1 to 20 carbon atoms, include a methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group and dodecyl group. The alkyl radicals may be linked together to form a ring.

Specific examples of the group represented by -B (OR ₁₁ ) ₂ include groups which are represented by

Preferred examples thereof are groups which are represented by

The total supply of monomers, which by the general Formulas (104) and (105) is in the Generally 0.1 to 20 mol%, and preferably 0.2 to 10 mol%, relative to total feed of monomers, which by the general Formulas (101) and (102) are reproduced.

Examples of the method for producing a polymer compound according to the present invention include a method of polymerizing the above-mentioned corresponding monomers in accordance with the Suzuki reaction (Chem. Rev.) Vol. 95, p. 2457, (1995) ; a method of polymerizing the monomers in accordance with the Grignard reaction ( High-Performance Material Series, Vol. 2, Synthesis and Reaction of a Polymer (II), p. 432-433, published by Kyoritsu Shuppan Co., Ltd. ); a method of polymerizing the monomers in accordance with the Yamamoto polymerization method (Prog. Polym. Sci.), Vol. 17, pp. 1153-1205, (1992) a method of polymerizing the monomers by an oxidizing agent such as FeCl ₃ ; and a method of polymerizing the monomers in accordance with electrochemical oxidation polymerization ( Experimental Chemical Course, 4th Edition, Vol. 28, p. 339-340, published by Maruzen Co., Ltd. ) one.

The case where the Suzuki reaction is used will be explained. In this case, a polymer is prepared by monomers wherein Y ₁ and Y ₂ each independently represent a group represented by the formula -B (OR ₁₁ ) ₂ (wherein R _{11 is} a hydrogen atom or an alkyl group); Y ₃ and Y _{4 are} each independently a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group; Y _{7 is} the group represented by the formula B (OR ₁₁ ) ₂ (wherein R _{11 is} a hydrogen atom or an alkyl group); and Y ₈ represents a halogen atom, an alkylsulfonyloxy group or an arylsulfonyloxy group, in the presence of a Pd (0) catalyst are reacted.

Note that it is sometimes necessary in this case that at least one type of monomer (two or more types) having two leaving groups with which the reaction is to be carried out has two radicals represented by the formula -B (OR ₁₁ ) ₂ (wherein R _{11 is} a hydrogen atom or an alkyl group), and at least one of them has two halogen atoms, two Alkylsulfonyloxyreste or two Arylsulfonyloxyreste. In such a reaction case, monomers represented by the formulas (101) and (102) are reacted for about 0.2 to 100 hours, and then a monomer (105) is added to the reaction system for about 0.5 to 50 hours for a long time, and then a monomer (104) is added to the reaction system and allowed to react for about 0.5 to 50 hours.

The reaction is carried out by reacting a Pd (0) catalyst such as palladium [tetrakis (triphenylphosphine)] (0), palladium acetate (e.g., a catalyst obtained by reducing palladium acetate with a triphenylphosphine derivative) or a dichlorobis ( triphenylphosphine) palladium (II), and an inorganic base such as potassium carbonate, sodium carbonate or barium carbonate, an organic base such as triethylamine, or an inorganic salt such as cesium fluoride in an amount of one equivalent or more, preferably 1 to 10 equivalents relative to the monomer is added. The reaction can be carried out in a two-phase system using an aqueous inorganic salt solution. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane and tetrahydrofuran. The reaction temperature varies depending on the solvent used shall be; however, a temperature of about 50 to 160 ° C is preferably used. The reaction temperature may be raised to near the boiling point of the solvent to be used, and reflux may be performed. The reaction time is about 0.2 hours to 200 hours. Note that the polymerization reaction is generally conducted under an inert gas atmosphere such as argon or nitrogen in a reaction system in which a zero valent Pd (0) catalyst is not deactivated.

The case where the Yamamoto polymerization method is used will be explained. In the case, a reaction using monomers in which Y ₁ , Y ₂ , Y ₃ , Y ₄ , Y ₇ and Y _{8 are} each independently a halogen atom, alkylsulfonyloxy or arylsulfonyloxy in the presence of a Ni (0) complex is used performed to obtain a desired polymer. The reaction is generally carried out by mixing all of the monomers (102), (103), (104) and (105).

The Polymerization was carried out in the presence of a Ni (0) complex. As the nickel complex, zero-valent nickel may be used as it is become. Alternatively, a nickel salt in the presence of a reducing agent reacted, resulting in a zero-valent nickel in a reaction system prepared and used in the reaction. examples for the zerovalent nickel complex include bis (1,5-cyclooctadiene) nickel (0), (Ethylene) bis (triphenylphosphine) nickel (0) and tetrakis (triphenylphosphine) nickel one. Of these, bis (1,5-cyclooctadiene) nickel (0) is preferred since it is generally used and inexpensive. Farther Preferably, a neutral ligand is added to the yield to improve. The neutral ligand used here refers to a ligand which does not contain anions and cations having. Examples include nitrogen containing ligands such as 2,2'-bipyridyl, 1,10-phenanthroline, methylenebisoxazoline and N, N'-tetramethylethylenediamine; and tertiary phosphine ligands, such as triphenylphosphine, tritolylphosphine, tributylphosphine and triphenoxyphosphine, one. In terms of general versatility and low cost, a nitrogen-containing ligand is preferred and 2,2'-bipyridyl is used for high reactivity and high yield particularly preferred. In particular, the yield of a polymer, it is preferred to use a reaction system, which contains bis (1,5-cyclooctadiene) nickel (0) upon addition of 2,2'-bipyridyl as a neutral ligand. at a method of reacting zero-valent nickel in the reaction system For example, nickel chloride or nickel acetate may be used as a Nickel salt can be mentioned. Examples of the reducing agent include zinc, sodium hydride, hydrazine and a derivative thereof and lithium aluminum hydride. If necessary, can Additives such as ammonium iodide, lithium iodide or potassium iodide, be used. A polymerization solvent is not particularly limited, unless it inhibits the polymerization; however, the solvent preferably contains one or more aromatic hydrocarbon type solvents and / or an ethereal solvent. Examples of that close aromatic hydrocarbon solvents Benzene, toluene, xylene, trimethylbenzene, tetramethylbenzene, butylbenzene, Naphthalene and tetralin. Of these, toluene, xylene, tetralin and tetramethylbenzene preferred. Examples of the ether solvent include diisopropyl ether, tetrahydrofuran, 1,4-dioxane, diphenyl ether, Ethylene glycol dimethyl ether and tert-butyl methyl ether. From that becomes a good solvent for a polymer compound, such as tetrahydrofuran or 1,4-dioxane, preferred. Of the solvents Tetrahydrofuran is the most preferred. To polymerize and to improve solubility, may be a solvent mixture from an aromatic hydrocarbon based solvent and / or an ether solvent and any other (m / n) Solvent (s) (except the solvent based on aromatic hydrocarbon and / or the ether solvent) used, unless the mixture inhibits the polymerization.

The reaction process can be carried out in accordance with the method described in JP-A-2000-44544 is described. In the Yamamoto polymerization, a polymerization reaction may be generally conducted under an inert gas atmosphere such as argon or nitrogen in a tetrahydrofuran solvent at a temperature of 60 ° C in the presence of a zerovalent nickel complex and a neutral ligand. The polymerization time is generally about 0.5 to 100 hours. In terms of manufacturing cost, 10 hours or less is preferable. The polymerization temperature is generally about 0 to 200 ° C. In order to increase the yield and reduce heating costs, 20 to 100 ° C is preferred.

If a neutral ligand is used is the amount of use preferably about 0.5 to 10 mol, relative to zero valency Nickel complex (1 mole), in terms of reaction yield and cost, stronger preferably 0.8 to 1.5 moles and more preferably 0.9 to 1.1 moles.

The use amount of a zerovalent nickel complex is not particularly limited so long as it does not inhibit a polymerization reaction. However, if the usage amount is low, is usually the molecular weight is low. If the usage amount is excessively large, aftertreatment is usually complicated. For this reason, the use amount is preferably 0.1 to 10 mol, relative to a monomer (1 mol), more preferably 1 to 5 mol, and more preferably 1.7 to 3.5 mol. Note that the polymerization reaction is generally carried out under an inert gas atmosphere, such as argon or nitrogen, in a reaction system in which a zerovalent nickel complex catalyst is not deactivated.

To Conclusion of producing a polymer compound according to the present invention, the polymer compound, if necessary, conventional Be subjected to a process such as a separation process, cleaning process and drainage process, which wash with acid, Wash with alkali, neutralize, wash with water, wash with an organic solvent, reprecipitation, centrifugal separation, extraction and column chromatography lock in.

If a polymer compound according to the present invention Invention is used as an electronic material, has the Purity thereof an effect on various properties thereof. Therefore, in the production process of the present invention the above-mentioned separation process and purification process preferably done well to an unreacted Monomer, a byproduct, a catalyst residue and so on in sufficient way to remove.

drainage can be performed under the conditions under which a remaining solvent sufficiently can be removed. To the denaturation of a polymer compound To avoid, the drainage is preferably in one inert atmosphere and under opaque conditions carried out. It is further preferred that the drainage is carried out at a temperature at which a Polymer compound can not be thermally denatured.

A Polymer compound of the present invention may be used as a luminescent Material and further as a cargo transport material, organic Semiconductor material, optical material or conductive Material can be used by doping.

<Polymer Composition>

A polymer composition of the present invention contains a polymer compound (which is different from a polymer compound according to the present invention) which is fluorescent in a state of solid and has a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁸ , and contains a polymer compound according to the present invention. The polymer compound (which is different from a polymer compound according to the present invention) is not particularly limited as long as it improves the characteristics of the resulting device such as solubility in a solvent, fluorescence intensity, life and brightness. Examples of such a polymer compound include those described in U.S. Pat JP-A-2001-247861 . JP-A-2001-507511 . JP-A-2001-504533 . JP-A-2001-278958 . JP-A-2001-261796 . JP-A-2001-226469 and in Japanese Patent No. 3161058 are described, but are not limited to. Examples of the polymer compound (which is different from a polymer compound according to the present invention) include, but are not, a polyfluorene compound, polyfluorene polymer compound, polyarylene compound, polyarylene polymer compound, polyarylene vinylene compound, polyarylene vinylene polymer compound, polystilbene compound, polystilbene polymer compound, polystilbene vinylene compound, polystilbene vinylene polymer compound, polypyridine diyl compound, polypyridine diyl polymer compound, alkoxy polythiophene compound and alkoxy polythiophene polymer compound limited to it. Of these, a polyfluorene polymer compound, polyarylene polymer compound, polyarylene vinylene polymer compound, polystilbene polymer compound and polystilbene vinylene polymer compound are preferred.

One Mixing ratio of a polymer compound according to the The present invention may not be limited as long as it Features of the resulting device, such as solubility in a solvent, fluorescence intensity, Life and brightness, improved. The mixing ratio this generally falls in the range of 5 to 95%, relative to the entire polymer composition.

As a polymer composition according to the present invention, there can be mentioned a composition containing two or more types of polymer compounds according to the present invention having a substituent. Examples of the polymer compound according to the present invention having a substituent include a polyfluorene polymer, polyarylene polymer, polyarylene vinylene polymer, polystilbene polymer, polystilbene vinylene polymer, polypyridine polymer and alko xypolythiophene polymer. A polymer compound according to the present invention is obtained by using the above-mentioned polymer compounds in a suitable combination of two or more types. The mixing ratio thereof is not particularly limited; however, the ratio of the polymer compound contained in a composition in the largest amount preferably falls in the range of 5 to 90% by weight relative to the entire polymer composition.

<composition (liquid composition)>

A composition according to the present invention contains a polymer compound according to the present invention and a polymer compound (which is different from the polymer compound of the present invention) having a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁸ . Examples of the polymer compound (other than the polymer compound of the present invention) having a polystyrene-reduced number average molecular weight of 10 ³ to 10 ⁸ include poly (phenylene) and a derivative thereof, poly (benzofluorene) and a derivative thereof, a poly (dibenzofuran) and a derivative thereof, a poly (dibenzothiophene) and a derivative thereof, a poly (carbazole) and a derivative thereof, a poly (thiophene) and a derivative thereof, a poly (phenylenevinylene) and a derivative thereof, a poly (fluorenvinylene) and a derivative thereof, a poly (dibenzofluorenvinylene) and a derivative thereof, and a poly (benzofuranvinylene) and a derivative thereof. Note that the derivatives are other than the repeating units represented by the above-mentioned formula (1).

A liquid composition according to the present invention The invention is for producing a luminescent device, such as polymeric luminescent device, and an organic transistor usable. The liquid composition consists of the Polymer compounds mentioned above, and a solvent. The term "liquid Composition "used herein refers to a Composition in the liquid state at the time of in which the manufacture of a device is started, and relates more specifically, a composition in the liquid Condition at normal pressure (i.e., 1 atm.) And 25 ° C. Farther For example, the liquid composition will generally be, for example as an ink, an ink composition, or in some cases called a solution.

A liquid composition according to the present invention Invention may except those mentioned above Polymer compounds a luminescent material with low Molecular weight, a hole transport material, an electron transport material, a stabilizer, an additive for regulating the viscosity and / or surface tension, an antioxidant and so on contain. These optional components can be individually or used in combination with two or more types.

Examples of the low molecular weight fluorescent material which may be contained in a liquid composition according to the present invention include low molecular weight compounds such as a naphthalene derivative, anthracene, an anthracene derivative, perylene, a perylene derivative, a polymethine pigment, a xanthene pigment a coumarin pigment, a cyanine pigment, a metal complex having a metal complex of 8-hydroxyquinoline as a ligand, a metal complex having an 8-hydroxyquinoline derivative as a ligand, other fluorescent metal complexes, an aromatic amine, tetraphenylcyclopentadiene, a tetraphenylcyclopentadiene derivative, tetraphenylcyclobutadiene, a tetraphenylcyclobutadiene derivative, a stilbene compound, a silicon-containing aromatic compound, an oxazole compound, a furoxan compound, a thiazole compound, a tetraarylmethane compound, a thiadiazole compound, a pyrazole compound, a metacyclophane compound and an acetylene compound. More specifically, known compounds which are known in JP-A-57-51781 and JP-A-59-194393 be mentioned.

Examples for the hole transport material, which is in a liquid Composition according to the present invention may include a polyvinylcarbazole and a derivative thereof, a polysilane and a derivative thereof, a polysiloxane derivative, which is an aromatic amine in a side chain or the main chain a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, polyaniline and a derivative thereof Polythiophene and a derivative thereof, a polypyrrole and a derivative a polyp-phenylenevinylene) and a derivative thereof and a Poly (2,5-thienylenevinylene) and a derivative thereof.

Examples of the electron transport material which may be contained in a liquid composition according to the present invention include an oxadiazole derivative, anthraquinodimethane and a derivative thereof, benzoquinone and a derivative thereof, naphthoquinone and a derivative thereof, anthraquinone and A derivative thereof, tetracyanoanthraquinodimethane and a derivative thereof, a fluorenone derivative, diphenyldicyanoethylene and a derivative thereof, a diphenoquinone derivative, metal complexes of 8-hydroxyquinoline and a derivative thereof, a polyquinoline and a derivative thereof, a polyquinoxaline and a derivative thereof, and a polyfluorene and a derivative one of them.

Examples for the stabilizer, which is in a liquid composition be included according to the present invention can include, a phenolic antioxidant and a phosphorus antioxidant one.

Examples for the additive for regulating the viscosity and / or surface tension, that in a liquid Composition according to the present invention may be included, close a connection with high Molecular weight (thickener) for increasing the viscosity, a bad solvent, a low compound Molecular weight for reducing the viscosity and a Surfactants for reducing the surface tension. These can be used in a suitable combination.

When the high molecular weight compound can use any compound provided it does not inhibit light emission and charge transport. In general, a compound is used that is in the solvent a liquid composition is soluble. When an example of the high molecular weight compound a polystyrene having a high molecular weight, or a polymethyl methacrylate having a high molecular weight has to be used. The polystyrene-reduced weight average the molecular weight of the high molecular weight compound is preferably 500,000 or more and stronger preferably 1,000,000. Furthermore, a bad solvent be used as a thickener.

When the antioxidant that is in a liquid composition be included according to the present invention Any antioxidant can be used unless it has light emission and inhibits charge transport. When a composition is a solvent generally contains an antioxidant that is in the solvent is soluble, used. Examples of the antioxidant include a phenolic antioxidant and a phosphorus antioxidant one. The use of the antioxidant can increase storage stability improve the polymer compounds and the solvent.

If a liquid composition according to the present invention contains a hole transport material, is the content of the hole transport material in the liquid composition generally 1 wt .-% to 80 Wt .-% and preferably 5 wt .-% to 60 wt .-%. If a liquid Composition according to the present invention contains an electron transport material is the content of the electron transport material in the liquid Composition generally 1 wt .-% to 80 wt .-% and preferably From 5% to 60% by weight.

In producing a polymeric luminescent device, a film is produced using the liquid composition. In this case, all that should be done is just applying the liquid composition and removing a solvent by dehydration. A liquid composition containing a charge transfer material and a luminescent material may be applied in the same manner. Therefore, a liquid composition is useful in terms of manufacturing. Drainage may be carried out in a heated state of about 50 ° C to 150 ° C or in a state of reduced pressure of about 10 ^{- 3} Pa.

Examples for the film-producing method using a liquid composition include a spin coating process, Casting process, micro gravure coating process, gravure coating process, Doctor blade coating method, roll coating method, wire bar coating method, Dip coating method, spray coating method, Screen printing, flexographic printing, offset printing and ink jet printing method.

Of the Content of the solvent in a liquid Composition is generally 1 wt .-% to 99.9 Wt .-%, preferably 60 wt .-% to 99.9 wt .-% and more preferably 90 wt .-% to 99.8 wt .-%, relative to the total weight of the liquid Composition. The viscosity of a liquid Composition varies depending on the printing method; however, it preferably falls in the range of 0.5 to 500 mPa · s at 25 C. If a liquid composition passed through an ejection device, as is the case of inkjet printing, the viscosity drops at 25 ° C preferably in the range of 0.5 to 20 mPa · s, to prevent the clogging of the ejection nozzles and to prevent liquid spray droplets flying away from a right direction.

When the solvent that is in a liquid composition is to be contained, a solvent is preferred, which is capable of components (except the solvent), which are contained in the liquid composition, too dissolve and disperse. Examples of the solvent close to chlorine-based solvents, such as Chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, Chlorobenzene and o-dichlorobenzene; on solvent Ether base, such as tetrahydrofuran and dioxane; on solvent based on aromatic hydrocarbon, such as toluene, xylene, Trimethylbenzene and mesitylene; on aliphatic hydrocarbon based solvents cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane; solvent ketone-based, such as acetone, methyl ethyl ketone and cyclohexanone; solvent ester-based, such as ethyl acetate, butyl acetate, methyl benzoate and ethylcellosolve; polyhydric alcohols and derivatives thereof, such as ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, Ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, Triethylene glycol monoethyl ether, glycerol and 1,2-hexanediol; solvent alcohol-based, such as methanol, ethanol, propanol, isopropanol and cyclohexanol; Sulfoxide-based solvents such as dimethylsulfoxide; Amide-based solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These solvents can used singly or in combination of two or more types become. At least one type of solvent consisting of selected from the solvents mentioned above and at least one benzene ring, a melting point of 0 ° C. or less and has a boiling point of 100 ° C or more, is preferable in view of viscosity and film-forming ability contain.

When the type of solvent becomes a solvent based on aromatic hydrocarbon, aliphatic hydrocarbon solvent, Ester-based solvents and solvents ketone-based in terms of properties, such as solubility of components (except a solvent) of a liquid Composition in an organic solvent, uniformity the film produced and viscosity preferred. preferred Examples include toluene, xylene, ethylbenzene, Diethylbenzene, trimethylbenzene, mesitylene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, s-butylbenzene, anisole, ethoxybenzene, 1-methylnaphthalene, cyclohexane, cyclohexanone, cyclohexylbenzene, Bicyclohexyl, cyclohexenylcyclohexanone, n-heptylcyclohexane, n-hexylcyclohexane, Methyl benzoate, 2-propylcyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonane, 2-decanone and dicyclohexyl ketone. Stronger preferably, at least one type of solvent is selected xylene, anisole, mesitylene, cyclohexylbenzene and bicyclohexylmethylbenzoate, contain.

The Number of types of solvents in a liquid Composition are included with regard to Film producibility and characteristics of the resulting device preferably 2 or more, more preferably 2 to 3 and more preferably 2.

If 2 types of solvents in a liquid Composition may include one at 25 ° C in a solid state. With regard to movie production preferably has one of the 2 types of solvents a boiling point of 180 ° C or more on and the other has a boiling point of less than 180 ° C. Stronger Preferably, one of the two types of solvents has one Boiling point of 200 ° C or more and the other points a boiling point of less than 180 ° C. Furthermore is in terms of viscosity, 0.2% by weight or more of the components (except the solvent) of a liquid Composition preferably in the solvent at 60 ° C. solved. 0.2% by weight or more of the components (except the solvent) of a liquid composition is preferably in one of the 2 types of solvents dissolved at 25 ° C.

If 3 types of solvents in a liquid Composition can contain 1 to 2 types of Solvents thereof at 25 ° C in a solid Condition exist. In terms of movie production has at least a type of solvent of the 3 types of solvents preferably a boiling point of 180 ° C or more and At least one type of solvent has a boiling point of 180 ° C or less. More preferably, at least a type of solvent of the 3 types of solvents a boiling point of 200 ° C to 300 ° C (both inclusive) and has at least one type of solvent Boiling point of 180 ° C or less. Continue to solve in terms of viscosity, two types of solvents of the 3 types of solvents preferably 0.2% by weight or more of the components (except the solvent) a liquid composition at 60 ° C. One Type of solvent of the 3 types of solvents preferably dissolves 0.2% by weight or more of the components (except the solvent) of a liquid composition at 25 ° C.

When two types or more of solvents are contained in a liquid composition, in terms of viscosity and film-forming ability, the solvent having the highest boiling point is preferably in an amount of 40 to 90% by weight, more preferably 50 to 90% by weight. -% and further preferably 65 to 85 wt .-%, based on the weight of all solvents contained in the liquid composition.

- thinner Movie -

One thin film according to the present invention is described. The thin film is made of a polymer compound, as mentioned above. As the types of thin For example, a movie can be a shining thinner Film, conductive thin film and thinner organic semiconductor film may be mentioned.

Of the Luminous thin film preferably has a Lumineszenzquantenausbeute of 50% or more, more preferably 60% or more and more preferably 70% or more in terms of brightness of the resulting Device and voltage for light emission.

Of the conductive thin film preferably has one Surface resistance of 1 KΩ / ⎕ or less up. The thin film containing a Lewis acid or an ionic compound can be doped in electrical Conductivity improves. The surface resistance is more preferably 100 KΩ / □ or less and more preferably 10 KΩ / ⎕ or less.

The thin organic semiconductor film preferably has greater electron mobility or greater hole mobility. The mobility of either one of them is preferably 10 ^-5 cm ² / V / s or more, more preferably 10 ^-3 cm ² / V / s or more, and further preferably 10 ^-1 cm ² / V / s or more. The thin organic semiconductor film may be used to produce an organic transistor. To describe more specifically, a thin organic semiconductor film is formed on an Si substrate having an insulating film such as SiO ₂ and a gate electrode formed thereon, and a thin film. The source electrode and the drain electrode are made of Au, for example. In this way, an organic transistor can be obtained.

- Organic transistor (polymeric electric field effect transistor) -

When Next will be a polymeric electric field effect transistor, which belongs to a group of organic transistors, described.

A Polymer compound according to the present invention may suitably be used as a material for a polymeric electric field effect transistor can be used, more precisely as an active layer. In the structure of the polymeric electric Field effect transistor are a source electrode and a drain electrode generally in contact with an active layer, which consists of a polymer is arranged. Furthermore, a gate electrode be created so that they have an insulating layer, which in contact is generated with the active layer, sliding in between.

One polymeric electric field effect transistor is generally generated on a carrier substrate. The material for the carrier substrate is not particularly limited, as far as there are characteristics of the polymeric electric field effect transistor does not inhibit. A glass substrate, a flexible film substrate, and a plastic substrate can be used.

A polymeric electric field effect transistor can be produced by a known method, for example, a method disclosed in U.S. Pat JP-A-5-110069 is described.

At the Generating the active layer is a polymer compound which is disclosed in U.S. Pat an organic solvent is soluble, very useful and becomes from a manufacturing point of view prefers. Examples of a method for generating a film is used from a solution in which a polymer compound dissolved in an organic solvent is soluble in the organic solvent solved, include a spin coating process, Casting process, micro gravure coating process, gravure coating process, Doctor blade coating method, roll coating method, wire bar coating method, Dip coating method, spray coating method, Screen printing, flexographic printing, offset printing and ink jet printing method.

After this a polymeric electric field effect transistor has been generated is preferably sealed, whereby a sealed polymeric electrical Field effect transistor is obtained. Due to the sealing is the polymer electric field effect transistor isolated from air, whereby suppressing a reduction in the characteristics of the transistor becomes.

When A sealing process can be a method of covering a transistor with a UV-curing resin, a thermosetting Resin or an inorganic film of, for example, a SiONx film and a method of bonding a glass plate or a film with a UV-curing resin or a thermosetting one Resin to be mentioned. To a polymeric electric field effect transistor effectively isolate from air after the transistor is made is a method which includes a sealing step, preferably carried out without exposure to air (For example, in a dry nitrogen atmosphere or in a vacuum).

- Organic Solar Battery -

When Next, an organic solar battery will be explained. More specifically, an organic photoelectric device for conversion, resulting in a group of organic solar batteries heard, for example, a fixed photoelectric device for conversion, which uses the photovoltaic effect explained.

A Polymer compound according to the present invention may suitably be used as a material for an organic Photoelectric device for conversion can be used. More accurate That is, the polymer compound may be suitably referred to as the organic compound Semiconductor layer of a device of the Schottky barrier type, which is the interface between an organic semiconductor and a metal used. Furthermore, the Polymer compound suitably as the organic semiconductor layer a device of the type pn heterojunction, which the interface between an organic semiconductor and an inorganic semiconductor or between organic semiconductors used to be used.

Farther may be a polymer compound according to the present Invention suitably as an electron donor polymer or a Electron acceptor polymer of a bulk heterojunction device, which increases in a donor-acceptor contact area is used and as a conjugated electron donor polymer (Dispersion carrier material) of an organic photoelectric Device for conversion, which is a polymer / low molecular weight Compound composite system used as an organic photoelectric Bulk heterojunction type bulk conversion device, in which a fullerene derivative which acts as an electron acceptor is used, dispersed.

The organic photoelectric conversion device, for example a device of the pn heterojunction type can be constructed be by placing a layer of a p-type semiconductor on a ohmic electrode, for example ITO, is generated and further laminated a layer of n-type semiconductor and an ohmic Electrode provided on the layer of an n-type semiconductor becomes.

A Organic photoelectric conversion device generally becomes generated on a carrier substrate. The material for the carrier substrate is not particularly limited, as far as it is not the characteristics of the resulting organic photoelectric Inhibits device for conversion; however, one can also Glass substrate, flexible film substrate and plastic substrate used become.

An organic photoelectric conversion apparatus can be prepared by a known method, for example, the methods described in U.S. Patent No. 5,376,854 Synth. Met., 102, 982 (1999) and Science, 270, 1789 (1995) to be discribed.

- Polymer luminescent device (Polymer-LED) -

If a polymer compound according to the present invention Invention as a luminescent material for a polymer LED is used because luminescence and phosphorescence from a thin film used, the polymer compound of present invention in a solid state, preferably fluorescent or phosphorescent.

A Polymer LED according to the present invention has a luminescent layer between the electrodes, which consists of an anode and a cathode, on and is characterized in that the luminescent layer is a polymer compound or a polymer composition according to the present invention.

Examples of the polymer LED according to the present invention include a polymeric luminescent device having a layer comprising a conductive polymer between at least one of Electrodes and the luminescent layer adjacent to the electrode, and a polymeric luminescent device having an insulating layer with an average thickness of 2 nm or less between at least one of the electrodes and the luminescent layer and adjacent to the electrode.

Examples for the polymer LED according to the present invention The invention includes a polymer LED comprising an electron transport layer between a cathode and a luminescent layer, a Polymer LED, which has a hole transport layer between an anode and a luminescent layer, a polymer LED, which an electron transport layer between a cathode and a luminescent layer and a hole transport layer between an anode and the luminescent layer.

• a) Anode/lumineszierende Schicht/Kathode
• b) Anode/Lochtransportschicht/lumineszierende Schicht/Kathode
• c) Anode/lumineszierende Schicht/Elektronentransportschicht/Kathode
• d) Anode/Lochtransportschicht/lumineszierende Schicht/Elektronentransportschicht/Kathode

(Das Symbol "/" bedeutet, dass einzelne Schichten angrenzend aneinander laminiert sind. Dieselbe Definition wird nachstehend eingesetzt.)Examples of the structure of a polymer LED according to the present invention include structures represented by the following items a) to d).

• a) anode / luminescent layer / cathode
• b) anode / hole transport layer / luminescent layer / cathode
• c) anode / luminescent layer / electron transport layer / cathode
• d) anode / hole transport layer / luminescent layer / electron transport layer / cathode

(The symbol "/" means that individual layers are laminated adjacent to each other. The same definition is used below.)

The Luminescent layer is a layer which is a luminescent Function has. The hole transport layer is a layer which has a function of transporting holes. The electron transport layer is a layer which has a function of transporting electrons. Note that the Electron transport layer and hole transport layer together as a charge transport layer. The number of luminescent Layers, hole transport layers and electron transport layers can each independently be 2 or more.

From the charge transport layers adjacent to an electrode are provided, the layer, which is a function of the Improving the charge injection efficiency from the electrode having, thereby effectively the operating voltage of a device is reduced, generally in particular as a charge injection layer (Hole injection layer or electron injection layer).

Farther can improve adhesion to an electrode and charge injection from the electrode to improve a charge injection layer, as mentioned above, or an insulating layer which has a thickness of 2 nm or less, adjacent to the electrode to be provided. Alternatively, to improve adhesion at the interface, preventing pollution and to other purposes a thin insulating layer between the charge transport layer and the luminescent layer are inserted become. The laminate order, number and thickness of the layers can suitable with regard to Lumineszenzeffektivität and the Life of a device can be adjusted.

• e) Anode/Ladungsinjektionsschicht/lumineszierende Schicht/Kathode
• f) Anode/lumineszierende Schicht/Ladungsinjektionsschicht/Kathode
• g) Anode/Ladungsinjektionsschicht/lumineszierende Schicht/Ladungsinjektionsschicht/Kathode
• h) Anode/Ladungsinjektionsschicht/Lochtransportschicht/lumineszierende Schicht/Kathode
• i) Anode/Lochtransportschicht/lumineszierende Schicht/Ladungsinjektionsschicht/Kathode
• j) Anode/Ladungsinjektionsschicht/Lochtransportschicht/lumineszierende Schicht/Ladungsinjektionsschicht/Kathode
• k) Anode/Ladungsinjektionsschicht/lumineszierende Schicht/Ladungstransportschicht/Kathode
• l) Anode/lumineszierende Schicht/Elektronentransportschicht/Ladungsinjektionsschicht/Kathode
• m) Anode/Ladungsinjektionsschicht/lumineszierende Schicht/Elektronentransportschicht/Ladungsinjektionsschicht/Kathode
• n) Anode/Ladungsinjektionsschicht/Lochtransportschicht/lumineszierende Schicht/Elektronentransportschicht/Kathode
• o) Anode/Lochtransportschicht/lumineszierende Schicht/Elektronentransportschicht/Ladungsinjektionsschicht/Kathode
• p) Anode/Ladungsinjektionsschicht/Lochtransportschicht/lumineszierende Schicht/Elektronentransportschicht/Ladungsinjektionsschicht/Kathode

In the present invention, examples of a polymer LED having a charge injection layer (electron injection layer and hole injection layer) include a polymer LED having a charge injection layer adjacent to a cathode; and a polymer LED having a charge injection layer adjacent to an anode. Specific examples thereof are polymer LEDs having the following structures (e) to (p).

• e) anode / charge injection layer / luminescent layer / cathode
• f) anode / luminescent layer / charge injection layer / cathode
• g) anode / charge injection layer / luminescent layer / charge injection layer / cathode
• h) anode / charge injection layer / hole transport layer / luminescent layer / cathode
• i) anode / hole transport layer / luminescent layer / charge injection layer / cathode
• j) anode / charge injection layer / hole transport layer / luminescent layer / charge injection layer / cathode
• k) anode / charge injection layer / luminescent layer / charge transport layer / cathode
• l) anode / luminescent layer / electron transport layer / charge injection layer / cathode
• m) anode / charge injection layer / luminescent layer / electron transport layer / charge injection layer / cathode
• n) anode / charge injection layer / hole transport layer / luminescent layer / electron transport layer / cathode
• o) anode / hole transport layer / luminescent layer / electron transport layer / charge injection layer / cathode
• p) anode / charge injection layer / hole transport layer / luminescent layer / electron transport layer / charge injection layer / cathode

specific Close examples of the charge injection layer a layer containing a conductive polymer; a layer between an anode and a hole transport layer is provided and contains a material which a Ionization potential, which has a mean value between that of an anode material and that of a hole transport material, which is contained in the hole transport layer is; and a layer, that between a cathode and an electron transport layer is provided and contains a material which a Has electron affinity, which is an average value between that of a cathode material and that of a Electron transport material in the electron transport layer is included, is.

When the charge injection layer contains a conductive polymer, the conductivity of the conductive polymer is preferably 10 ^-5 S / cm to 10 ³ S / cm (both inclusive). To reduce leakage current between luminescent pixels, the electrical conductivity is more preferably 10 ^-5 S / cm to 10 ² S / cm (both inclusive), and more preferably 10 ^-5 S / cm to 10 ¹ S / cm (both inclusive).

When the charge injection layer is the layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ^-5 S / cm to 10 ³ S / cm (both inclusive). In order to reduce leakage current between luminescent pixels, the electrical conductivity is preferably 10 ^-5 S / cm to 10 ² S / cm (both inclusive), and more preferably 10 ^-5 S / cm to 10 ¹ S / cm (both inclusive). In order to adjust the electrical conductivity of the conductive polymer to 10 ^-5 S / cm to 10 ³ (both inclusive), a suitable amount of ions is generally doped into the conductive polymer.

Of the Type of ion to be doped in a hole injection layer, is anion and cation for an electron injection layer. Examples of the anion include polystyrene sulfonate ions, Alkylbenzenesulfonationen and Camphersulfonationen. Examples for the cation include lithium ions, sodium ions, Potassium ions and tetrabutylammonium ions. The film thickness of the charge injection layer is, for example, 1 nm to 100 nm, and preferably 2 nm to 50 nm.

The Material used in the charge injection layer should, suitably taking into account the materials, which is used in the electrode and the adjacent layer will be elected. Close examples Polyaniline and a derivative thereof, a polyaminophen and a derivative thereof, polypyrrole and a derivative thereof, polyphenylenevinylene and a derivative thereof, polythienylenevinylene and a derivative thereof, polyquinoline and a derivative thereof, polyquinoxaline and a derivative thereof, electrically conductive polymers, such as a polymer which is an aromatic Contains amine structure in the main chain or a side chain thereof Metallophthalocyanine (eg, copper phthalocyanine) and carbon one.

The insulating layer, which has a film thickness of 2 nm or less has a function of facilitating charge injection on. Examples of the material for the insulating Layer include metal fluoride, metal oxide and organic insulating material. Examples of the polymer LED, which has an insulating layer having a film thickness of 2 nm or less, include a polymer LED which an insulating layer having a film thickness of 2 nm or less has, adjacent to a cathode, and a polymer LED, which is an insulating layer having a film thickness of 2 nm or having less, adjacent to an anode, a.

• q) Anode/isolierende Schicht mit ≤ 2 nm Dicke/lumineszierende Schicht/Kathode
• r) Anode/lumineszierende Schicht/isolierende Schicht mit < 2 nm Dicke/Kathode
• s) Anode/isolierende Schicht mit ≤ 2 nm Dicke/lumineszierende Schicht/isolierende Schicht mit ≤ 2 nm Dicke/Kathode
• t) Anode/isolierende Schicht mit ≤ 2 nm Dicke/Lochtransportschicht/lumineszierende Schicht/Kathode
• u) Anode/Lochtransportschicht/lumineszierende Schicht/isolierende Schicht mit ≤ 2 nm Dicke/Kathode
• v) Anode/isolierende Schicht mit ≤ 2 nm Dicke/Lochtransportschicht/lumineszierende Schichtisolierende Schicht mit ≤ 2 nm Dicke/Kathode
• w) Anode/isolierende Schicht mit ≤ 2 nm Dicke/lumineszierende Schicht/Elektronentransportschicht/Kathode
• x) Anode/lumineszierende Schicht/Elektronentransportschicht/isolierende Schicht mit ≤ 2 nm Dicke/Kathode
• y) Anode/isolierende Schicht mit ≤ 2 nm Dicke/lumineszierende Schicht/Elektronentransportschicht/isolierende Schicht mit ≤ 2 nm Dicke/Kathode
• z) Anode/isolierende Schicht mit ≤ 2 nm Dicke/Lochtransportschicht/lumineszierende Schicht/Elektronentransportschicht/Kathode
• aa) Anode/Lochtransportschicht/lumineszierende Schicht/Elektronentransportschicht/isolierende Schicht mit ≤ 2 nm Dicke/Kathode
• ab) Anode/isolierende Schicht mit ≤ 2 nm Dicke/Lochtransportschicht/lumineszierende Schicht/Elektronentransportschicht/isolierende Schicht mit ≤ 2 nm Dicke/Kathode

Specific examples thereof are polymer LEDs having the following structures q) to ab).

• q) anode / insulating layer with ≤ 2 nm thickness / luminescent layer / cathode
• r) anode / luminescent layer / insulating layer with <2 nm thickness / cathode
• s) anode / insulating layer with ≤ 2 nm thickness / luminescent layer / insulating layer with ≤ 2 nm thickness / cathode
• t) anode / insulating layer with ≤ 2 nm thickness / hole transport layer / luminescent layer / cathode
• u) anode / hole transport layer / luminescent layer / insulating layer with ≤ 2 nm thickness / cathode
• v) anode / insulating layer with ≤ 2 nm thickness / hole transport layer / luminescent layer insulating layer with ≤ 2 nm thickness / cathode
• w) anode / insulating layer with ≤ 2 nm thickness / luminescent layer / electron transport layer / cathode
• x) anode / luminescent layer / electron transport layer / insulating layer with ≤ 2 nm thickness / cathode
• y) anode / insulating layer with ≤ 2 nm thickness / luminescent layer / electron transport layer / insulating layer with ≤ 2 nm thickness / cathode
• z) anode / insulating layer with ≤ 2 nm thickness / hole transport layer / luminescent layer / electron transport layer / cathode
• aa) anode / hole transport layer / luminescent layer / electron transport layer / insulating layer with ≤ 2 nm thickness / cathode
• ab) anode / insulating layer with ≤ 2 nm thickness / hole transport layer / luminescent layer / electron transport layer / insulating layer with ≤ 2 nm thickness / cathode

The Luminescent layer contains a polymer compound or a polymer composition according to the present invention Invention. However, the luminescent layer may be another luminescent material as a polymer compound as mentioned above. Furthermore, in a polymer LED according to the present invention, a luminescent layer, which other luminescent material than a polymer compound, such as mentioned above, with a luminescent Layer containing the polymer compound as mentioned above, contains, be laminated. As the luminescent material can a known material can be used. For example, a Low molecular weight compound, such as a naphthalene derivative, Anthracene or a derivative thereof, perylene or a derivative thereof, a pigment, e.g. As pigment on polymethine, xanthene, coumarin or Cyanine base, a metal complex of 8-hydroxyquinoline or a derivative thereof, aromatic amine, tetraphenylcyclopentadiene or a derivative or tetraphenylbutadiene or a derivative thereof.

More specifically, known luminescent materials, which may be used in e.g. JP-A-57-51781 and JP-A-59-194393 can be used.

Farther As the luminescent material, the following may be the light emitting complexes from the triplet state or derivatives thereof be used.

Furthermore, polymers containing a triplet-state light-emitting complex can be used, such as in WO 03/001616 described.

The A method of forming a film of the luminescent layer is not particularly limited. For example, a method mentioned for producing a film from a solution become.

Examples for the method of forming a film from a solution include coating methods such as a spin coating method, Casting process, micro gravure coating process, gravure coating process, Doctor blade coating method, roll coating method, wire bar coating method, Dip coating method, spray coating method, Screen printing, flexographic printing, offset printing and ink jet printing method.

Examples for a solvent for forming a film from a solution include toluene, xylene, chloroform and tetrahydrofuran.

When the film thickness of the luminescent layer varies the optimum Value of it depending on the material used shall be. The film thickness can be chosen so that the operating voltage and luminescence efficiency at appropriate Values can be obtained. The film thickness is for example 1 nm to 1 .mu.m, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

If a polymer LED according to the present invention has a hole transport layer, as an example of the hole transport material to be used, polyvinylcarbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative, which is an aromatic amine in a side chain thereof or the Main chain, a pyrazoline derivative, an arylamine derivative, a stilbene derivative, a triphenyldiamine derivative, polyaniline or a derivative thereof, polythiophene or a derivative thereof, polypyrrole or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof or poly (2,5-thienylenevinylene) or a derivative thereof become.

Specific examples of the hole transport material include those described in U.S. Pat JP-A-63-70257 . 63-175860 . 2-135359 . 2-135361 . 2-209988 . 3-37992 and 3-152184 to be discribed.

From that can act as a hole transport material in the hole transport layer is to be used, for example, preferably polymeric hole transport materials, such as polyvinylcarbazole or a derivative thereof, polysilane or a Derivative thereof, a polysiloxane derivative containing a residue of aromatic amine compound in a side chain or the main chain thereof, polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative or poly (2,5-thienylenevinylene) or a derivative thereof; and more preferably polyvinylcarbazole or a derivative thereof or polysilane or a derivative thereof, a polysiloxane derivative which a residue of an aromatic amine compound in a side chain or the main chain thereof. In the case of one It is preferred that low molecular weight hole transport material be used used by being dispersed in a polymeric binder.

The Polyvinylcarbazole or a derivative thereof may consist of a Vinyl monomer by cationic polymerization or radical Polymerization can be obtained.

Examples of the polysilane or a derivative thereof include the compounds described in U.S. Pat Chem. Rev. Vol. 89, p. 1359 (1989) and the published description of the British patent GB 2300196 to be discribed. They can be synthesized by the methods described in these documents. In particular, a kipping method is suitably used.

There a skeletal structure of siloxane virtually no transportability of holes, suitably becomes polysiloxane or a derivative thereof, which conveys a structure of the hole Low molecular weight material in a side chain or the main chain thereof has been used. In particular, polysiloxane or a derivative thereof which is an aromatic Has amine in a side chain or the main chain thereof.

One A method of forming a film of a hole transport layer is not particularly limited; however, if a hole transport material used with low molecular weight serves as an example for a method of producing a film from a Mixed solution containing a polymeric binder. When using a high molecular weight hole transport material serves as an example of a method for generating a movie from a solution.

The solvent to be used in forming a film from a solution is not particularly limited as long as it can dissolve a hole transport material. Examples of the solvent include chlorine-based solvents such as chloroform, methylene chloride and dichloroethane; Ether-based solvents such as tetrahydrofuran; Aromatic hydrocarbon-based solvents such as toluene and Xy lol; Ketone-based solvents such as acetone and methyl ethyl ketone; and ester-based solvents such as ethyl acetate and butyl acetate and ethyl cellosolve acetate.

Examples for the method of forming a film from a solution include coating methods such as a spin coating method, Casting process, micro gravure coating process, gravure coating process, Doctor blade coating method, roll coating method, wire bar coating method, Dip coating method, spray coating method, Screen printing, flexographic printing, offset printing and ink jet printing method.

When the polymeric binder to be mixed is preferably one that can not extremely block charge transport, and suitably one is used whose absorption for visible light is low. Examples of the polymeric Binders include polycarbonate, polyacrylate, polymethylacrylate, Polymethyl methacrylate, polystyrene, polyvinyl chloride and polysiloxane one.

The most suitable film thickness of a hole transport layer varies depending on the material used should, and can be chosen so that a suitable operating voltage and luminescence efficiency. The hole transport layer must have a suitable thickness, so that generation of a pinhole at least prevented. If the movie is overly thick, the operating voltage of the device decreases in unwanted Way too. Accordingly, the film thickness is the hole transport layer, for example, 1 nm to 1 micron, preferably 2 nm to 50 nm and more preferably 5 nm to 200 nm.

If a polymer LED according to the present invention has an electron transport layer can be a known electron transport material be used. As an example, a metal complex of a Oxadiazole derivative, anthraquinodimethane or a derivative thereof, benzoquinone or a derivative thereof, naphthoquinone or a derivative thereof, anthraquinone or a derivative thereof, tetracyanoanthraquinodimethane or a derivative thereof, a fluorenone derivative, diphenyldicyanoethylene or a derivative thereof, a diphenoquinone derivative or 8-hydroxyquinoline or a Derivative thereof; Polyquinoline or a derivative thereof; polyquinoxaline or a derivative thereof; or polyfluorene or a derivative thereof be used.

Specific examples of the electron transport material include those described in, e.g. JP-A-63-70257 . 63-175860 . 2-135359 . 2-135361 . 2-209988 . 3-37992 and 3-152184 to be discribed.

From that is a metal complex of an oxadiazole derivative, benzoquinone or a derivative thereof, anthraquinone or a derivative thereof or 8-hydroxyquinoline or a derivative thereof; Polyquinoline or a derivative thereof; polyquinoxaline or a derivative thereof; Polyfluorene or a derivative thereof is preferred; and 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, Anthraquinone, tris (8-quinolinol) aluminum or polyquinoline more preferred.

One Method of producing a film of an electron transport layer is not particularly limited; however, if an electron transport material used with low molecular weight serves as an example a vacuum deposition method for producing a film of powder or a method of forming a film from a solution or a molten state. If an electron transport material used with high molecular weight, serves as an example Method of producing a film from a solution or a molten state. If a movie from a solution or a molten state can be a polymeric Binders can be used in combination.

The Solvent, which when creating a film from a Solution is to be used is not particularly limited as long as it is an electron transport material and / or a polymeric Solve binder. Examples of the solvent close chlorine-based solvents, such as chloroform, Methylene chloride and dichloroethane; Ether-based solvent, such as tetrahydrofuran; Solvent based on aromatic Hydrocarbon, such as toluene and xylene; solvent ketone-based, such as acetone and methyl ethyl ketone; and solvents ester-based, such as ethyl acetate and butyl acetate and ethylcellosolve acetate, one.

Examples for the method of forming a film from a solution or a molten state, coating processes such as a spin coating method, casting method, micro gravure coating method, Gravure coating process, doctor blade application process, roll coating process, Wire bar coating method, dip coating method, spray coating method, Screen printing, flexographic printing, offset printing and ink jet printing method.

When the polymeric binder to be mixed is one preferred The charge transport can not extremely block, and will suitably one whose absorption of light is low. As a Example of the polymeric binder may include 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, polymethylacrylate, Polymethyl methacrylate, polystyrene, polyvinyl chloride or polysiloxane be used.

The most suitable film thickness of an electron transport layer varies depending on the material used should, and can be chosen so that a suitable operating voltage and luminescence efficiency. The electron transport layer must have a suitable thickness, so that generation of a pinhole at least prevented. If the movie is overly thick, the operating voltage of the device decreases in unwanted Way too. Accordingly, the film thickness is the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 50 nm and more preferably 5 nm to 200 nm.

When a substrate on which a polymer LED according to the can be produced according to the present invention, each substrate be used as long as it is not affected when electrodes and a layer of organic compound are generated become. Examples of the substrate include glass, Plastic, polymer film and silicon substrates. If an opaque Substrate used is the electrode opposite to it is arranged, preferably transparent or translucent.

in the In general, at least one of the electrodes, which consists of a Anode and a cathode exist, transparent or translucent and more preferably, the anode is transparent or translucent. As the material for the anode becomes a more conductive Metal oxide film or a thin translucent metal film used. Specific examples include indium oxide, Zinc oxide, tin oxide and an indium / tin / oxide (ITO), which is a complex from these is, and film (NESA), which is made of an electrically conductive Glass of indium / zinc / oxide and the like, gold, platinum, silver and copper was generated. Of these, ITO, indium / zinc / oxide and tin oxide preferred. Examples of the film-producing method include a vacuum deposition method, sputtering method, Ion plating method and plating method. Furthermore, can as the anode is a more transparent, more electrically conductive Film made of an organic compound such as polyaniline or a derivative thereof or a polythiophene or a derivative thereof, was made to be used. The film thickness of the anode may be appropriate considering light transmission and electrical conductivity. The film thickness is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm and more preferably 50 nm to 500 nm. In order to facilitate charge injection into the anode, can a layer consisting of a phthalocyanine derivative, electrically conductive Polymer or carbon was generated, or a layer which has an average thickness of 2 nm or less, and one of Metal oxide, metal fluoride or organic insulating material was generated.

When the material for a cathode, which is in a polymer LED be used according to the present invention is supposed to be a material that has a small work function, prefers. Examples include metals, such as lithium, sodium, potassium, rubidium, cesium, beryllium, Magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, Zinc, yttrium, indium, cerium, samarium, europium, terbium and ytterbium; Alloys selected from two or more types of metals from these, alloys were produced which consist of at least one Type of metals selected from these, and at least a type of metal selected from gold, silver, platinum, Copper, manganese, titanium, cobalt, nickel, tungsten and tin produced were; or graphite or a graphite interlayer compound one. Examples of the alloys include magnesium-silver alloy, Magnesium-indium-alloy, magnesium-aluminum-alloy, indium-silver-alloy, Lithium aluminum alloy, lithium magnesium alloy, lithium indium alloy and calcium-aluminum alloy. A laminate structure which is made of two or more layers, may be referred to as a cathode be used. The film thickness of the cathode may be appropriate below Consideration of electrical conductivity and durability are chosen. The film thickness is for example, 10 nm to 10 microns, preferably 20 nm to 1 μm and more preferably 50 nm to 500 nm.

As the film forming method for a cathode, a vacuum deposition method, sputtering method or laminate method employing thermocompression bonding of thin metal films can be used. Further, a layer formed of an electrically conductive polymer or a layer having an average thickness of 2 nm or less and formed of a metal oxide, metal fluoride or organic insulating material may be interposed between the cathode and a layer of an organic compound to be provided. Alternatively, after the cathode has been generated, a protective layer can be applied to protect the polymer LED. In order to stably use the polymer LED for a long time, a protective layer and / or a protective cover may be applied to protect the device from the outside world.

When the protective layer may be a polymer compound, metal oxide, Metal fluoride and metal boride can be used. As the protective cover can have a glass lid and a plastic lid whose surface treated to reduce water permeability, be used. A method of binding the envelope a substrate of the device with a thermosetting Resin or photohardenable resin to seal it, is suitably used. When using a spacer In order to keep a distance, it is easy to use the device to protect against being damaged. If an inert gas such as nitrogen or argon injected into the gap is oxidation of the cathode can be prevented. Furthermore is it when a desiccant, such as barium oxide, placed in the distance will, simply, suppress that water which is at Manufacturing steps, the device damages. Of these, at least one measure is preferably taken.

A polymeric luminescent device according to the The present invention can be used as a backlight for planar light sources, segment display devices, dot matrix display devices and liquid crystal devices are used.

Around a more planar light emission using a polymer LED according to the can obtain a planar Anode and a planar cathode are arranged so that they overlap each other. Furthermore, in order to obtain light emission in pattern form, there is A method of providing a mask which is a patterned one Window on the surface of the planar luminescent Device, a method of the extremely Thickly creating a layer of an organic compound which corresponds to the portion from which no light is emitted, whereby Light emission is substantially blocked, and a manufacturing process, in which either anode or cathode or both of them are shaped are that they have a pattern. A pattern is made by any one this method generates and several electrodes are arranged so that they are switched on and off independently of each other. On this way, a display device of the segment type can be obtained which are numeric characters, letters and simple symbols can show. Furthermore, to be a dot matrix device to obtain strips of anode and cathode generated and arranged so that they cross each other vertically. If a procedure of the separate Applying several types of polymer, which in different Color fluoresce, or a process in which a color filter or a conversion filter used for the light emission is used, a partial color display and multi-color display be achieved. The dot matrix device can be operated passively or can be actively operated in combination with TFT and the like become. These display devices can be used as display devices of computers, televisions, portable units, car navigation units and viewfinders used by video cameras.

Farther For example, the planar luminescent device is a luminescent one Thin film device and may suitably be considered a planar Light source for backlight of liquid crystal devices or a planar light source for illumination. In addition, if a flexible substrate is used, light sources in a curved shape and display devices be obtained in a curved shape.

Farther may be a polymer compound according to the present Invention as a pigment for lasers, a material for an organic solar battery, an organic semiconductor for an organic transistor and a material for one Thin conductive film can be used.

EXAMPLES

The The present invention will be further specifically described below Examples are described. However, the present invention is not limited to these.

One Polystyrene reduced number average molecular weight and a Polystyrene reduced weight average molecular weight by gel permeation chromatography (GPC: LC-10Avp by Shimadzu Corporation) using tetrahydrofuran as a solvent as a number average molecular weight and a weight average molecular weight.

example 1

<synthesis of monomer (1)>

Synthesis Example (1)

und Phenoxazin (2,56 g) wurden in o-Dichlorbenzol (60 g) gelöst. Zu dieser Lösung wurde eine 40%ige wässrige Natriumhydroxidlösung gegeben und dann wurde Benzyltriethylammoniumchlorid (3,2 g) zugegeben. Die Reaktion wurde 25 Stunden lang bei 105°C durchgeführt. Man beachte, dass die Reaktion unter einer Stickstoffgasatmosphäre durchgeführt wurde.A compound (A) (5.0 g), which is listed below:

and phenoxazine (2.56 g) were dissolved in o-dichlorobenzene (60 g). To this solution was added a 40% aqueous sodium hydroxide solution and then benzyltriethylammonium chloride (3.2 g) was added. The reaction was carried out at 105 ° C for 25 hours. Note that the reaction was conducted under a nitrogen gas atmosphere.

After the end of the reaction, the solution was cooled and allowed to stand still, and then the upper layer which had separated was recovered. After the solution was washed with demineralized water, the solvent was distilled off under reduced pressure. Then, toluene (40 g) was added to the solution. After filtration, the solution was passed through a column filled with alumina to purify it. The solvent was distilled off from the resulting solution under reduced pressure and dried under reduced pressure to obtain 2.0 g of the monomer (1) shown below.
[H-NMR: solvent CDCl _3; 1.5 ~ 1.8 ppm (6H); 3.4 ~ 3.6 ppm (2H); 3.9 ~ 4.1 ppm (2H); 6.4 ~ 7.4 ppm (11H)]

<synthesis of polymer compound 1>

After this 2,7-dibromo-9,9-dioctylfluorene (1.18 g) and 2,7-dibromo-9,9-diisopentylfluorene (0.26 g), the above-mentioned monomer (1) (0.12 g) and 2,2'-bipyridyl (1.4 g) were fed to a reaction vessel were, the atmosphere of the reaction system was against Replaced nitrogen gas. To this was added 80 g of tetrahydrofuran (dried solvent), which previously by means of bubbling had been degassed from argon gas given. The following became to the mixed solution 2.5 g bis (1,5-cyclooctadiene) nickel (0) and the reaction was allowed to proceed at room temperature for 14 hours carried out. Note that the reaction is under one Nitrogen gas atmosphere was performed.

To the end of the reaction was a mixed solution of methanol (120 ml) / demineralized water (120 ml) to the solution and stirred for about 1 hour. The rainfall, which had formed was collected by filtration. following The precipitate was dried under reduced pressure and in Toluene dissolved. After the toluene solution is filtered was to remove insoluble substance was passed the toluene solution through a column, which filled with alumina to clean it.

Next, the toluene solution was washed with about 5% ammonia water, allowed to stand still and separated. Thereafter, the toluene solution was recovered. Subsequently, the toluene solution was washed with demineralized water, allowed to stand still and separated, and then the toluene solution was recovered. The toluene solution was then poured into methanol, producing a reprecipitate has been.

The generated precipitate was collected and dried under reduced pressure, whereby a polymer (0.48 g) was obtained. This polymer is referred to as polymer compound 1. The polystyrene-reduced weight-average molecular weight of polymer compound 1 thus obtained was 1.0 × 10 ⁵ and the polystyrene-reduced number average molecular weight thereof was 4.1 × 10 ⁴ .

The Structures of repeating units, which are in polymer compound 1 and estimated from the fed materials were are as follows. The molar ratio of repetitive Unit A: repeating unit B: repeating unit C, which is estimated from the feed materials was 72/18/10.

Example 2

<synthesis of polymer compound 2>

das Monomer (1) (0,19 g) und 2,2'-Bipyridyl (0,7 g) wurden in einen Reaktionsbehälter eingespeist und die Atmosphäre des Reaktionssystems wurde gegen Stickstoffgas ausgetauscht. Zu diesem wurden 50 g Tetrahydrofuran (getrocknetes Lösungsmittel), welches zuvor mittels Durchperlen von Argongas entgast worden war, gegeben. Nachfolgend wurden zu dem Lösungsgemisch 1,24 g Bis(1,5-cyclooctadien)nickel(0) gegeben und die Reaktion wurde 32 Stunden lang bei Zimmertemperatur durchgeführt. Man beachte, dass die Reaktion unter einer Stickstoffgasatmosphäre durchgeführt wurde.A monomer (2) (0.61 g) represented by the following formula:

the monomer (1) (0.19 g) and 2,2'-bipyridyl (0.7 g) were fed into a reaction vessel, and the atmosphere of the reaction system was exchanged with nitrogen gas. To this was added 50 g of tetrahydrofuran (dried solvent), which had been previously degassed by bubbling argon gas. Subsequently, to the mixed solution was added 1.24 g of bis (1,5-cyclooctadiene) nickel (0), and the reaction was carried out at room temperature for 32 hours. Note that the reaction was conducted under a nitrogen gas atmosphere.

To the end of the reaction was a mixed solution of methanol (40 ml) / demineralized water (40 ml) to the solution and the mixture was stirred for about 1 hour. The precipitate that formed was filtered off collected. Subsequently, the precipitate was under reduced Dried and dissolved in toluene. After the toluene solution filtered to remove insoluble matter, the toluene solution was passed through a column, which was filled with alumina to clean it. Next, after the toluene solution with washed about 5% ammonia water, allowed to stand still and had been separated, the toluene solution recovered. Subsequently, the toluene solution with demineralized Washed water, left to stand still and separated and then The toluene solution was recovered. The toluene solution was then poured into methanol, creating a reprecipitate was generated.

The generated precipitate was collected and dried under reduced pressure, whereby a polymer (0.11 g) was obtained. This polymer is referred to as polymer compound 2. The polystyrene-reduced weight-average molecular weight of polymer compound 2 thus obtained was 7.5 × 10 ^4, and the polystyrene-reduced number average molecular weight thereof was 1.4 × 10 ⁴ .

The structures of repeating units contained in polymer compound 2 and from the materials fed in are as follows. The molar ratio of repeating unit D: repeating unit E and estimated from the feed materials is 70/30.

Comparative Example 1

<synthesis of polymer compound 3>

und 2,2'-Bipyridyl (0.56 g) wurden in ein Reaktionsgefäß eingespeist und dann wurde die Atmosphäre des Reaktionssystems gegen Stickstoffgas ausgetauscht. Zu diesem wurden 60 g Tetrahydrofuran (getrocknetes Lösungsmittel), welches zuvor mittels Durchperlen von Argongas entgast worden war, gegeben. Nachfolgend wurden zu dem Lösungsgemisch 1,0 g Bis(1,5-cyclooctadien)nickel(0) gegeben und die Reaktion wurde 4 Stunden lang bei 60°C durchgeführt. Man beachte, dass die Reaktion unter einer Stickstoffgasatmosphäre durchgeführt wurde.2,7-dibromo-9,9-dioctylfluorene (0.59g), 2,7-dibromo-9,9-diisopentylfluorene (0.13g), a monomer (3) (0.071g), which is represented by the following Formula is shown:

and 2,2'-bipyridyl (0.56 g) were fed into a reaction vessel, and then the atmosphere of the reaction system was exchanged with nitrogen gas. To this was added 60 g of tetrahydrofuran (dried solvent), which had previously been degassed by bubbling argon gas. Subsequently, to the mixed solution was added 1.0 g of bis (1,5-cyclooctadiene) nickel (0), and the reaction was carried out at 60 ° C for 4 hours. Note that the reaction was conducted under a nitrogen gas atmosphere.

To At the end of the reaction, the solution was cooled and a mixed solution of methanol (40 ml) / demineralized Water (40 ml) was poured into the solution and about 1 Stirred for an hour. The precipitate that formed was collected by filtration. Subsequently, the precipitation dried under reduced pressure and dissolved in toluene. After the toluene solution had been filtered to insoluble To remove substance, the toluene solution was replaced by a Pillar passed, which filled with alumina was to cleanse her. Next, after the Toluene solution with an about 1N aqueous hydrochloric acid solution washed, left to stand still and had been separated Recovered toluene solution. Then the toluene solution became washed with about 5% ammonia water, left to stand still and separated. Thereafter, the toluene solution was recovered. Subsequently, the toluene solution with demineralized Washed water, left to stand still and separated and then The toluene solution was recovered. The toluene solution was then poured into methanol, creating a reprecipitate was generated.

The generated precipitate was collected and dried under reduced pressure to give a polymer (0.29 g). This polymer is referred to as polymer compound 3. The polystyrene-reduced weight-average molecular weight of polymer compound 3 thus obtained was 4.2 × 10 ⁵ and the polystyrene-reduced number average molecular weight thereof was 8.9 × 10 ⁴ .

The structures of the repeating units contained in polymer compound 3 and estimated from the materials fed are as follows. The molar ratio of reho unit F: repeating unit G: repeating unit H, which was estimated from the feed materials, is 72/18/10.

Comparative Example 2

<synthesis of polymer compound 4>

The Monomer (2) (0.61 g), monomer (3) (0.21 g) and 2,2'-bipyridyl (0.56 g) was fed to a reaction vessel and then the atmosphere of the reaction system was against Replaced nitrogen gas. To this was added 60 g of tetrahydrofuran (dried solvent), which previously by means of bubbling had been degassed from argon gas given. The following became 1.0 g of bis (1,5-cyclooctadiene) nickel (0) is added to the mixed solution and the reaction was carried out at room temperature for 40 hours. Note that the reaction is under a nitrogen gas atmosphere was carried out.

To the end of the reaction was a mixed solution of methanol (40 ml) / demineralized water (40 ml) in the solution poured and stirred for about 1 hour. The rainfall, which had formed was then collected by filtration. Subsequently, the precipitate was dried under reduced pressure and dissolved in toluene. After the toluene solution filtered to remove insoluble matter, the toluene solution was passed through a column, which was filled with alumina to clean it. Next, after the toluene solution was washed with about 1N aqueous hydrochloric acid solution washed, left to stand still and had been separated Recovered toluene solution. Then the toluene solution became washed with about 5% ammonia water, left to stand still and separated. Thereafter, the toluene solution was recovered. Subsequently, the toluene solution with demineralized Washed water, left to stand still and separated and then The toluene solution was recovered. The toluene solution was then poured into methanol, creating a reprecipitate was generated.

The generated precipitate was collected and dried under reduced pressure, whereby a polymer (0.35 g) was obtained. This polymer is referred to as polymer compound 4. The polystyrene-reduced weight-average molecular weight of polymer compound 4 thus obtained was 7.2 × 10 ⁴ and the polystyrene-reduced number average molecular weight thereof was 2.0 × 10 ⁴ .

The Structures of repeating units, which are in polymer compound 4 are estimated and estimated from the input materials were are as follows. The molar ratio of repetitive Unit M: repeating unit N, which is fed from the Materials was estimated to be 70/30.

Example 3

<synthesis of monomer (4)>

Synthesis Example (2)

und Phenoxazin (2,7 g) wurden in o-Dichlorbenzol (60 g) gelöst. Zu dieser Lösung wurde eine 40%ige wässrige Natriumhydroxidlösung gegeben und dann wurde Benzyltriethylammoniumchlorid (3,2 g) zugegeben. Die Reaktion wurde 25 Stunden lang bei 105°C durchgeführt. Man beachte, dass die Reaktion in einer Stickstoffgasatmosphäre durchgeführt wurde.The following compound (C) (7.4 g):

and phenoxazine (2.7 g) were dissolved in o-dichlorobenzene (60 g). To this solution was added a 40% aqueous sodium hydroxide solution and then benzyltriethylammonium chloride (3.2 g) was added. The reaction was carried out at 105 ° C for 25 hours. Note that the reaction was carried out in a nitrogen gas atmosphere.

After the end of the reaction, the solution was cooled, allowed to stand still and separated, and then the upper layer was recovered. Subsequently, the solution was washed with demineralized water and the solvent was distilled off under reduced pressure. Then, toluene (40 g) was added to the solution. After filtration, the solution was passed through a column filled with alumina to purify it. The solvent was then distilled off under reduced pressure. The resulting precipitate was washed with methanol and dried under reduced pressure to obtain 2.7 g of monomer (4) shown below.
[H-NMR: solvent CDCl _3; 1.5 ~ 1.9 ppm (6H); 3.4 ~ 3.6 ppm (2H); 3.8 ~ 4.0 ppm (2H); 6.4 ~ 7.4 ppm (12H)]

<synthesis of polymer compound 5>

The Monomer (2) (0.79 g), monomer (4) (0.064 g) and 2,2'-bipyridyl (0.56 g) was fed to a reaction vessel and then the atmosphere of the reaction system was against Replaced nitrogen gas. To this was added 60 g of tetrahydrofuran (dried solvent), which previously by means of bubbling had been degassed from argon gas given. The following became 1.0 g of bis (1,5-cyclooctadiene) nickel (0) is added to the mixed solution and the reaction was carried out at 60 ° C for 4 hours. Note that the reaction is under a nitrogen gas atmosphere was carried out.

To At the end of the reaction, the solution was cooled. A mixed solution of methanol (40 ml) / demineralized Water (40 ml) was poured into the solution and about 1 Stirred for an hour. The precipitate that formed was collected by filtration. Subsequently, the precipitation dried under reduced pressure and dissolved in toluene. After the toluene solution had been filtered to insoluble To remove substance, the toluene solution was replaced by a Pillar passed, which filled with alumina was to cleanse her. Next was the toluene solution with an about 1N aqueous hydrochloric acid solution washed, left to stand still and separated. After that, the Recovered toluene solution. Then the toluene solution became washed with about 5% ammonia water, left to stand still and separated. Thereafter, the toluene solution was recovered. Subsequently, the toluene solution with demineralized Washed water, left to stand still and separated and then The toluene solution was recovered. The toluene solution was then poured into methanol, creating a reprecipitate was generated.

The generated precipitate was collected and dried under reduced pressure to give a polymer (0.14 g). This polymer is referred to as polymer compound 5. The polystyrene reduced weight average molecular weight of polymer compound 5 thus obtained was 2.5 × 10 ⁴ and the polystyrene reduced number average molecular weight thereof was 1.8 × 10 ⁴ .

The Structures of the repeating unit and the terminal group, which are contained in polymer compound 5 and fed from the Materials were estimated are as follows. The molar ratio of repeating unit A ': terminal group B', which was estimated from the fed materials is 90/10.

Example 4

<synthesis of monomer (5)>

Synthesis Example (3)

wurde in N,N-Dimethylformamid (100 g) gelöst. Die Lösung wurde auf Eis gekühlt und dann wurde eine Lösung von N-Bromsuccinimid (1,62 g), gelöst in N,N-Dimethylformamid (50 g), welche zuvor hergestellt worden war, etwa 80 Minuten lang zugetropft.The following compound (D) (3.15 g)

was dissolved in N, N-dimethylformamide (100 g). The solution was cooled on ice and then a solution of N-bromosuccinimide (1.62 g) dissolved in N, N-dimethylformamide (50 g) previously prepared was added dropwise for about 80 minutes.

following after dropping, the reaction became 0 to 5 ° C for 4 hours carried out. Then, the temperature of the reaction solution became raised to room temperature and the reaction was overnight carried out continuously at room temperature. Note, that the reaction is carried out under a nitrogen gas atmosphere has been.

After the end of the reaction, demineralized water was added to the reaction solution and washed. The solvent was distilled off from the solution under reduced pressure. After toluene was added to the generated precipitate and dissolved, the toluene solution was filtered to remove insoluble matter. The solution was passed through a column filled with alumina to clean it. After the solvent was evaporated under reduced pressure, the residue was then dried under reduced pressure to obtain the following monomer (5) (2.0 g).
[H-NMR: solvent CDCl _3; 0.9 ~ 1.0 ppm (3H); 1.3 ~ 1.7 ppm (4H); 2.6 ~ 2.7 ppm (2H); 5.7 ~ 6.0 ppm (2H); 6.5 ~ 6.8 (5H, 7.1 ~ 7.4 (4H))

<synthesis of polymer compound 6>

The Monomer (2) (0.79 g), monomer (5) (0.059 g) and 2,2'-bipyridyl (0.56 g) was fed to a reaction vessel and then the atmosphere of the reaction system was against Replaced nitrogen gas. To this was added 60 g of tetrahydrofuran (dried solvent), which previously by means of bubbling had been degassed from argon gas given. The following became the mixed solution 1.0 g bis (1,5-cyclooctadiene) nickel (0) and the reaction was at 60 ° C for 4 hours carried out. Note that the reaction is under one Nitrogen gas atmosphere was performed.

After the end of the reaction, the solution was cooled. A mixed solution of methanol (40 ml) / demineralized water (40 ml) was poured into the solution and stirred for about 1 hour. The Never The precipitate that formed was collected by filtration. Subsequently, the precipitate was dried under reduced pressure and dissolved in toluene. After the toluene solution was filtered to remove insoluble matter, the toluene solution was passed through a column filled with alumina to purify it. Next, the toluene solution was washed with an about 1N hydrochloric acid aqueous solution, allowed to stand still and separated. Thereafter, the toluene solution was recovered. Then, the toluene solution was washed with about 5% ammonia water, allowed to stand still and separated. Thereafter, the toluene solution was recovered. Subsequently, the toluene solution was washed with demineralized water, allowed to stand still and separated, and then the toluene solution was recovered. The toluene solution was then poured into methanol to produce a reprecipitate.

The generated precipitate was collected and dried under reduced pressure, whereby a polymer (0.20 g) was obtained. This polymer is referred to as polymer compound 6. The polystyrene reduced weight average molecular weight of polymer compound 6 thus obtained was 2.5 × 10 ⁴ and the polystyrene reduced number average molecular weight thereof was 1.6 × 10 ⁴ .

The Structures of the repeating unit and the terminal group, which are contained in polymer compound 6 and fed from the Materials were estimated are as follows. The molar ratio of repeating unit C ': terminal group D', which was estimated from the fed materials is 90/10.

Comparative Example 3

<synthesis of polymer compound 7>

The Monomer (2) (0.79 g), monomer (3) (0.071 g) and 2,2'-bipyridyl (0.56 g) was fed to a reaction vessel and then the atmosphere of the reaction system was against Replaced nitrogen gas. To this was added 60 g of tetrahydrofuran (dried solvent), which previously by means of bubbling had been degassed from argon gas given. The following became the mixed solution 1.0 g bis (1,5-cyclooctadiene) nickel (0) and the reaction was at 60 ° C for 4 hours carried out. Note that the reaction is under one Nitrogen gas atmosphere was performed.

To At the end of the reaction, the solution was cooled. Then, a mixed solution of methanol (40 ml) / demineralized Water (40 ml) poured into the solution and about 1 hour stirred for a long time. The precipitate that had formed was collected by filtration. Subsequently, the precipitation was below dried under reduced pressure and dissolved in toluene. After this the toluene solution had been filtered to insoluble To remove substance, the toluene solution was replaced by a Pillar passed, which filled with alumina was to cleanse her. Next was the toluene solution with an approximately 1 N aqueous hydrochloric acid solution washed, left to stand still and separated. After that, the Recovered toluene solution. Then the toluene solution became washed with about 5% ammonia water, left to stand still and separated. Thereafter, the toluene solution was recovered. Subsequently, the toluene solution with demineralized Washed water, left to stand still and separated and then The toluene solution was recovered. The toluene solution was then poured into methanol, creating a reprecipitate was generated.

The generated precipitate was collected and dried under reduced pressure to give a polymer (0.29 g). This polymer is referred to as polymer compound 7. The polystyrene-reduced weight-average molecular weight of Polymer compound 7 thus obtained was 1.0 × 10 ⁵ and the polystyrene-reduced number average molecular weight thereof was 4.4 × 10 ⁴ .

The Structures of repeating units, which are in polymer compound 7 are estimated and estimated from the input materials were are as follows. The molar ratio of repetitive Unit E ': repeating unit F', which is fed from the Materials was estimated to be 90/10.

Example 5

<synthesis of polymer compound 8>

The Monomer (5) (0.059 g), 2,7-dibromo-9,9-dioctylfluorene (0.59 g), 2,7-dibromo-9,9-diisopentylfluorene (0.13 g) and 2,2'-bipyridyl (0.56 g) were fed to a reaction vessel and then the atmosphere of the reaction system was against Replaced nitrogen gas. To this was added 60 g of tetrahydrofuran (dried solvent), which previously by means of bubbling had been degassed from argon gas given. The following became the mixed solution 1.0 g bis (1,5-cyclooctadiene) nickel (0) and the reaction was at 60 ° C for 4 hours carried out. Note that the reaction is under one Nitrogen gas atmosphere was performed.

To At the end of the reaction, the solution was cooled and a mixed solution of methanol (40 ml) / demineralized Water (40 ml) was poured into the solution and about 1 Stirred for an hour. The precipitate that formed was collected by filtration. Subsequently, the precipitation dried under reduced pressure and dissolved in toluene. After the toluene solution had been filtered to insoluble To remove substance, the toluene solution was replaced by a Pillar passed, which filled with alumina was to cleanse her. Next, after the Toluene solution with an about 1N aqueous hydrochloric acid solution washed, left to stand still and had been separated Recovered toluene solution. Then the toluene solution became washed with about 5% ammonia water, left to stand still and separated. Thereafter, the toluene solution was recovered. Subsequently, the toluene solution with demineralized Washed water, left to stand still and separated and then The toluene solution was recovered. The toluene solution was then poured into methanol, creating a reprecipitate was generated.

The generated precipitate was collected and dried under reduced pressure, whereby a polymer (0.20 g) was obtained. This polymer is referred to as polymer compound 8. The polystyrene-reduced weight-average molecular weight of polymer compound 8 thus obtained was 3.2 × 10 ^4, and the polystyrene-reduced number average molecular weight thereof was 1.6 × 10 ⁴ .

The Structures of repeating units and terminal ones Group, which are contained in polymer compound 8 and from the fed materials are estimated as follows. The molar ratio of repeating unit A '': repeating unit B '': terminal group C '', which consists of was estimated from the fed materials is 72/18/10.

Example 6

<synthesis of polymer compound 9>

das Monomer (5) (0,059 g) und 2,2'-Bipyridyl (0,58 g) wurden in ein Reaktionsgefäß eingespeist und dann wurde die Atmosphäre des Reaktionssystems gegen Stickstoffgas ausgetauscht. Zu diesem wurden 60 g Tetrahydrofuran (getrocknetes Lösungsmittel), welches zuvor mittels Durchperlen von Argongas entgast worden war, gegeben. Nachfolgend wurden zu dem Lösungsgemisch 1,0 g Bis(1,5-cyclooctadien)nickel(0) gegeben und die Reaktion wurde 23 Stunden lang bei Zimmertemperatur durchgeführt. Man beachte, dass die Reaktion unter einer Stickstoffgasatmosphäre durchgeführt wurde.The monomer (6) (0.81 g) represented by the following formula:

the monomer (5) (0.059 g) and 2,2'-bipyridyl (0.58 g) were fed to a reaction vessel, and then the atmosphere of the reaction system was exchanged for nitrogen gas. To this was added 60 g of tetrahydrofuran (dried solvent), which had previously been degassed by bubbling argon gas. Subsequently, to the mixed solution was added 1.0 g of bis (1,5-cyclooctadiene) nickel (0), and the reaction was carried out at room temperature for 23 hours. Note that the reaction was conducted under a nitrogen gas atmosphere.

To the end of the reaction was a mixed solution of methanol (40 ml) / demineralized water (40 ml) in the solution poured and stirred for about 1 hour. The rainfall, which had formed was collected by filtration. following The precipitate was dried under reduced pressure and in Toluene dissolved. The toluene solution was filtered, to remove insoluble substance. Thereafter, the toluene solution became with an approximately 5% aqueous acetic acid solution washed, left to stand still and separated. After that, the Recovered toluene solution. Then the toluene solution became washed with 4% ammonia water, left to stand still and separated. Thereafter, the toluene solution was recovered. following the toluene solution was washed with demineralised water, left to stand still and separated and then the toluene solution recovered. The toluene solution was then poured into methanol cast, creating a republication.

The generated precipitate was collected and dried under reduced pressure, whereby a polymer (0.31 g) was obtained. This polymer is referred to as polymer compound 9. The polystyrene-reduced weight-average molecular weight of polymer compound 9 thus obtained was 2.9 × 10 ⁴ and the polystyrene-reduced number average molecular weight thereof was 1.5 × 10 ⁴ .

The Structures of the repeating unit and the terminal group, which are contained in polymer compound 9 and fed from the Materials were estimated are as follows. The molar ratio of repeating unit D ": terminal group E", which was estimated from the fed materials is 90/10.

Example 7

<synthesis of polymer compound 10>

The Monomer (6) (0.81 g), monomer (1) (0.063 g) and 2,2'-bipyridyl (0.58 g) was fed to a reaction vessel and then the atmosphere of the reaction system was against Replaced nitrogen gas. To this was added 60 g of tetrahydrofuran (dried solvent), which previously by means of bubbling had been degassed from argon gas given. The following became the mixed solution 1.0 g bis (1,5-cyclooctadiene) nickel (0) and the reaction was carried out at room temperature for 23 hours. Note that the reaction is under a nitrogen gas atmosphere was carried out.

To the end of the reaction was a mixed solution of methanol (40 ml) / demineralized water (40 ml) in the solution poured and stirred for about 1 hour. The rainfall, which had formed was collected by filtration. following The precipitate was dried under reduced pressure and in Toluene dissolved. The toluene solution was filtered, to remove insoluble substance. Thereafter, the toluene solution became with an approximately 5% aqueous acetic acid solution washed, left to stand still and separated. After that, the Recovered toluene solution. Then the toluene solution became washed with 4% ammonia water, left to stand still and separated. Thereafter, the toluene solution was recovered. following the toluene solution was washed with demineralised water, left to stand still and separated and then the toluene solution recovered. The toluene solution was then poured into methanol cast, creating a republication.

The generated precipitate was collected and dried under reduced pressure to give a polymer (0.40 g). This polymer is referred to as polymer compound 10. The polystyrene-reduced weight-average molecular weight of polymer compound 10 thus obtained was 1.4 × 10 ⁵ and the polystyrene-reduced number average molecular weight thereof was 4.7 × 10 ⁴ .

The Structures of repeating units, which are in polymer compound 10 are estimated and estimated from the input materials were are as follows. The molar ratio of repetitive Unit F '': repeating unit G '', which is fed from the Materials was estimated to be 90/10.

Example 8

<synthesis of monomer (7)>

Synthesis Example 4

The Compound (A) (5.0 g) and phenothiazine (2.8 g) were dissolved in o-dichlorobenzene (60 g) solved. To this solution was a 40% aqueous sodium hydroxide solution and then Benzyltriethylammonium chloride (3.2g) was added. The reaction was carried out at 105 ° C for 25 hours. Note that the reaction is under a nitrogen gas atmosphere was carried out.

After the end of the reaction, the solution was cooled, allowed to stand still. Then, the upper layer which had separated was recovered. Subsequently, the solution was washed with demineralized water and the solvent was distilled off under reduced pressure. Then, toluene (40 g) was added to the solution. After filtration, the solution was passed through a column filled with alumina to purify it. The solvent was distilled off from the resulting solution under reduced pressure, whereby a precipitate (2.0 g) was obtained. Subsequently, the precipitate (1.5 g) was purified by silica gel column chromatography (solvent mixture of toluene / hexane = 2/8). The solvent was distilled off from an aliquoted solution under reduced pressure and dried under reduced pressure, whereby the following monomer (7) (0.9 g) was obtained.
[H-NMR: solvent CDCl _3; 1.5 ~ 2.0 ppm (6H); 3.8 ~ 4.0 ppm (4H); 6.7 ~ 7.3 ppm (11H)]

<synthesis of polymer compound 11>

The Monomer (6) (0.72 g), monomer (7) (0.13 g) and 2,2'-bipyridyl (0.56 g) was fed to a reaction vessel and then the atmosphere of the reaction system was against Replaced nitrogen gas. To this was added 60 g of tetrahydrofuran (dried solvent), which previously by means of bubbling had been degassed from argon gas given. The following became the mixed solution 1.0 g bis (1,5-cyclooctadiene) nickel (0) and the reaction was carried out at room temperature for 23 hours. Note that the reaction is under a nitrogen gas atmosphere was carried out.

After completion of the reaction, a mixed solution of methanol (40 ml) / demineralized water (40 ml) was poured into the solution and stirred for about 1 hour. The precipitate that formed was collected by filtration. Subsequently, the precipitate was dried under reduced pressure and dissolved in toluene. The toluene solution was filtered to remove insoluble matter. Thereafter, the toluene solution was washed with about 5% aqueous acetic acid solution, allowed to stand still and separated. Then, the toluene solution was recovered. Thereafter, the toluene solution was washed with 4% ammonia water, allowed to stand still and separated. Then, the toluene solution was recovered. Subsequently, the toluene solution was washed with demineralized water, allowed to stand still and separated, and then the toluene solution was recovered. The toluene solution was then poured into methanol to produce a reprecipitate.

The generated precipitate was collected and dried under reduced pressure, whereby a polymer (0.34 g) was obtained. This polymer is referred to as polymer compound II. The polystyrene-reduced weight-average molecular weight of polymer compound 11 thus obtained was 4.9 × 10 ⁴ and the polystyrene-reduced number average molecular weight thereof was 2.5 × 10 ⁴ .

The Structures of repeating units, which are in polymer compound 11 are estimated and estimated from the input materials were are as follows. The molar ratio of repetitive Unit H '' ': repeating unit I' '', which fed from the Materials was estimated to be 80/20.

Example 9

<synthesis of polymer compound 12>

The Monomer (2) (0.70 g), monomer (7) (0.13 g) and 2,2'-bipyridyl (0.56 g) was fed to a reaction vessel and then the atmosphere of the reaction system was against Replaced nitrogen gas. To this was added 60 g of tetrahydrofuran (dried solvent), which previously by means of bubbling had been degassed from argon gas given. The following became the mixed solution 1.0 g bis (1,5-cyclooctadiene) nickel (0) and the reaction was carried out at room temperature for 23 hours. Note that the reaction is under a nitrogen gas atmosphere was carried out.

To the end of the reaction was a mixed solution of methanol (40 ml) / demineralized water (40 ml) in the solution poured and stirred for about 1 hour. The rainfall, which had formed was collected by filtration.

following The precipitate was dried under reduced pressure and in Toluene dissolved. The toluene solution was filtered, to remove insoluble substance. Thereafter, the toluene solution became with an approximately 5% aqueous acetic acid solution washed, left to stand still and separated. After that, the Recovered toluene solution. Then the toluene solution became washed with 4% ammonia water, left to stand still and separated. Thereafter, the toluene solution was recovered. following the toluene solution was washed with demineralised water, left to stand still and separated and then the toluene solution recovered. The toluene solution was then poured into methanol cast, creating a republication.

The generated precipitate was collected and dried under reduced pressure, whereby a polymer (0.21 g) was obtained. This polymer is referred to as polymer compound 12. The polystyrene reduced weight average molecular weight of polymer compound 12 thus obtained was 3.0 × 10 ⁴ and the polystyrene reduced number average molecular weight thereof was 6.3 × 10 ³ .

The Structures of repeating units, which are in polymer compound 12 are estimated and estimated from the input materials were are as follows. The molar ratio of repetitive Unit J '' ': repeating unit K' '', which is fed from the Materials was estimated to be 80/20.

Example 10

<evaluation the fluorescence property of the polymer compound>

A 0.8 wt .-% toluene solution of a polymer compound was coated by spin coating on a quartz plate, whereby a thin film of the polymer compound was prepared. The fluorescence spectrum of the thin film was determined by a Fluorospectrophotometer (Fluorolog, manufactured by Jobinyvon-Spex) obtained at an excitation wavelength of 350 nm. A relative fluorescence intensity of the thin film was obtained by taking the integral value (which by integrating of the fluorescence spectrum, which is against the wavelength was plotted over the measuring range of the spectrum was based on the intensity of the Raman line of water as a reference) by absorbance, which is measured by a spectrophotometer (Cary 5E, manufactured by Varian) at the excitation wavelength was measured, was shared.

The Measurement results for the fluorescence peak wavelength and fluorescence intensity are listed in Table 1. The fluorescence intensity of polymer compound 1, which contained a side chain group according to the present invention Invention was stronger than that of a polymer compound 3, which had a Phenoxazinring in the polymer chain. The Fluorescence intensity of polymer compound 2, which is a Side chain group contained, according to the present Invention was stronger than that of a polymer compound 4, which had a phenoxazine ring in the polymer chain.

The Values for the fluorescence intensity of polymer compounds 5 and 6, which contained a terminal group according to the present invention, were stronger than those of Polymer compound 7, which contains a phenoxazine ring in the polymer chain had.

The fluorescence intensity of polymer compound 8 containing a terminal group according to the present invention was stronger than that of polymer compound 3 which had a phenoxazine ring in the polymer chain. [Table 1] Table 1 Peak wavelength and fluorescence intensity (relative value) of the polymer compound polymer compound Fluorescence peak wavelength (nm) Fluorescence intensity (relative value) 1 423 8.3 2 433 5.1 3 458 4.2 4 474 3.0 5 414 6.4 6 456 6.4 7 468 3.9 8th 454 8.5 9 465 12.4 10 450 12.8 11 449 12.9 12 415 3.3

Example 11

<evaluation of characteristics of the device>

On a glass substrate having an ITO film of about 150 nm in thickness produced by sputtering, a solution of poly (ethylenedioxythiophene) / polystyrenesulfonate (Baytron P, manufactured by Bayer) was spin-coated to form a film of about 50 nm thickness is generated. The film is dried for 10 minutes on a hot plate at about 200 ° C. Subsequently, a toluene solution prepared to contain a mixture of Polymer Compound 1 and Polymer Compound 2 (3: 7 by weight) at a concentration of about 1.5% is spin-coated at a speed of 1500 rpm, whereby Film is produced. The resulting film is dried at 80 ° C for one hour under reduced pressure. Thereafter, lithium fluoride is deposited to a thickness of about 4 nm. Around calcium is deposited to about 20 nm thickness and then aluminum is deposited to a thickness of about 50 nm as a cathode. In this way, an EL device is manufactured. Note that, after the vacuum had 1 × 10 ^-4 Pa or less is achieved, the deposition of a metal was initiated. When voltage is applied to the obtained device, blue EL is emitted.

INDUSTRIAL APPLICABILITY

If a polymer compound according to the present invention Invention as a luminescent material for a luminescent Layer of a polymer LED is used, shows the polymer LED excellent properties. Accordingly, the Polymer LED preferably used in curved and planar light sources which can be used as backlight or lighting for serve a liquid crystal display, and in devices, such as a segment-type display device and a dot matrix flat-panel display device, be used. In addition, a polymer compound according to the present invention as a dye for lasers, a material for an organic solar battery, an organic semiconductor for an organic transistor and a material for a thin conductive Film to be used.

SUMMARY

One conjugated polymer having a phenoxazine structure and a phenothiazine structure as a substituent.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

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Claims (26)

A polymer compound containing at least one type of repeating unit selected from the group consisting of repeating units represented by the following formula (1), characterized by having a substituent selected from the group consisting of the monovalent radicals represented by the following formula (2) or (3), -Ar ₁ - (Z ') p- (1) wherein Ar _{1 represents} an arylene radical, a divalent heterocyclic radical or a divalent aromatic amine radical; Z 'is -CR ₄ = CR ₅ - or -C≡C-; Each of R ₄ and R ₅ independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group; and p is 0 or 1,

wherein A _{1 is} -O-, -S- or -C (O) -; Ar ⁰¹ represents a direct bond, an arylene group, a divalent heterocyclic group or a divalent aromatic amine group; R ⁰⁵ and R ^{07 are} each independently a direct bond, -R ₁ -, -OR ₁ -, -R ₁ -O-, -R ₁ -C (O) O-, -R ₁ -OC (O) -, R _{1 is} -N (R ₂₀ ) -, -O-, -S-, -C (O) O- or -C (O) -; R _{1 is} an alkylene radical or an alkenylene radical, provided that when Ar ^{01 is} a direct bond, R ^{07 is} also a direct bond; R _{20 represents} a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group; R ⁰¹ and R ^{02 are} each independently a substituent; a and b are each independently an integer of 0 to 4; and a plurality of substituents represented by R ⁰¹ and R ^{02 may} be the same or different,

wherein B _{1 is} -O-, -S- or -C (O) -; Ar ^{02 represents} a hydrogen atom, an aryl group, a monovalent heterocyclic group or a monovalent aromatic amine group; Ar ^{03 represents} a direct bond, an arylene radical, a divalent heterocyclic radical or a divalent aromatic amine radical; R ⁰⁶ , R ⁰⁸ and R ^{09 are} each independently a direct bond, -R ₁ -, -OR ₁ -, -R ₁ -O-, -R ₁ -C (O) O-, -R ₁ -OC (O ) -, -R ₁ -N (R ₂₀ ) -, -O-, -S-, -C (O) O- or -C (O) - stand; R _{1 is} an alkylene radical or an alkenylene radical, R _{20 is} a hydrogen atom, an alkyl radical, an aryl radical, a monovalent heterocyclic radical or a cyano group, with the proviso that when Ar ^{03 is} a direct bond, R ^{09 is} also a direct Bond is; R ⁰³ and R ^{04 are} each independently a substituent; c is an integer of 0 to 4; d is an integer from 0 to 3; and a plurality of substituents represented by R ⁰³ and R ^{04 may} be the same or different. A polymer compound according to claim 1, wherein Ar _{1 of} the above-mentioned formula (1) has at least one of the groups represented by the above-mentioned formula (2). A polymer compound according to claim 1, wherein Ar _{1 of} the above-mentioned formula (1) has at least one of the groups represented by the above-mentioned formula (3). A polymer compound according to claim 1, wherein at least one of the molecular chain ends of the polymer compound has a radical which is represented by the above-mentioned formula (2) is reproduced. A polymer compound according to claim 1, wherein at least one of the molecular chain ends of the polymer compound has a radical which is represented by the above-mentioned formula (3) is reproduced. A polymer compound according to any one of claims 1 to 5, further comprising a repeating unit represented by the following formula (30) -Ar ₄ - (Z) _t - (30) wherein Ar _{4 is} an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a divalent aromatic amine group which may have a substituent, provided that none of those represented by the above-mentioned formulas (2) and (3) in which substituents are included; Z is -CR ₇ = CR ₈ - or -C≡C-; Each of R ₇ and R ₈ independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group; and t is 0 or 1. A polymer compound according to any one of claims 1 to 6, which has a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁸ . Polymer compound according to one of the claims 1 to 6, which is fluorescent in a solid state. A polymer compound according to any one of claims 1 to 6, which is fluorescent in a solid state and has a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁸ . Polymer compound according to one of the claims 1 to 6, which is phosphorescent in a solid state. Polymer composition characterized in that it comprises the polymer compound having a polystyrene reduced number average molecular weight of 10 ³ to 10 ⁸ which is fluorescent in a solid state which does not contain any of the radicals represented by the aforementioned formulas (2) and ( 3) as having a substituent, and the compound according to any one of claims 1 to 10. Polymer luminescent device, which is a luminescent layer between electrodes, consisting of an anode and a cathode, comprises, characterized the luminescent layer is a polymer compound according to of claims 1 to 10 contains. Polymer luminescent device, which is a luminescent layer between electrodes, consisting of an anode and a cathode, comprises, characterized in that the luminescent layer is a polymer compound according to claim 11 contains. A polymeric luminescent device according to claim 12 or 13, which is a layer that is a conductive polymer between at least one of the electrodes and the luminescent Layer and adjacent to the electrode contains, provides. Polymer luminescent device according to a of claims 12 to 14, which is an insulating layer, which has an average film thickness of 2 nm or less between at least one of the electrodes and the luminescent layer and adjacent to the electrode. Polymer luminescent device according to a of claims 12 to 15, which is an electron transport layer between the cathode and a luminescent layer and adjacent to the luminescent layer. Polymer luminescent device according to a of claims 12 to 16, which a hole transport layer between the anode and the luminescent layer and adjacent to the luminescent layer. Polymer luminescent device according to a of claims 12 to 17, which is an electron transport layer between the cathode and the luminescent layer and adjacent to the luminescent layer and a hole transport layer between the anode and the luminescent layer and adjacent to the luminescent layer. Planar light source, characterized in that a polymeric luminescent device according to any one of claims 12 to 18. Segment display device, characterized in that it comprises a polymeric luminescent device according to one of the Claims 12 to 18 comprises. Dot matrix display device, characterized in that it comprises a polymeric luminescent device according to one of the Claims 12 to 18 comprises. Liquid crystal display device, characterized characterized in that it is a polymeric luminescent device according to one of claims 12 to 18 as a backlight used. Solution composition, characterized in that they are the polymer compound according to claims 1 to 10 includes. Thin film, characterized in that it comprises the polymer compound of claims 1 to 10. Transistor, characterized in that it the A polymer compound according to claims 1 to 10. Solar battery, characterized in that it the polymer compound according to claims 1 to 10.