CN101184789A

CN101184789A - High-molecular compound and high-molecular luminescent device using the same

Info

Publication number: CN101184789A
Application number: CNA2006800189430A
Authority: CN
Inventors: 小熊润
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2005-04-28
Filing date: 2006-04-28
Publication date: 2008-05-21
Anticipated expiration: 2026-04-28
Also published as: DE112006001016T5; WO2006118345A1; GB2440482A; GB0722483D0; KR20080013926A; CN101184789B

Abstract

High-molecular compounds characterized by having at least one residue of a compound represented by the general formula (1): (1) wherein A, B and C are each independently an optionally substituted aromatic or nonaromatic ring; Z1, Z2, Z3, Z4, and Z5 are each independently C-(Q)z or a nitrogen atom; Q is a substituent or hydrogen; z is 0 or 1; A and B may own a ring-constituent atom jointly in addition to Z5; and one or two of A, B and C are nonaromatic rings.

Description

Macromolecular compound and used its polymeric light-emitting device

Technical field

The present invention relates to macromolecular compound and used its polymeric light-emitting device.

Background technology

High-molecular weight luminescent material or charge transport material be owing to dissolve in the solvent, and can utilize coating method to form the organic layer of luminous element, therefore is carried out various researchs.As the macromolecular compound that can be used for polymeric light-emitting device electronic components such as (polymer LED) as luminescent material or charge transport material, known have a poly-fluorenes class (international disclose the 99/54385th).

But, not necessarily can gratifying level in practicality as the element function of the element of uses such as luminescent material or charge transport material with above-mentioned macromolecular compound.

For example, the polymer LED that has used above-mentioned macromolecular compound still is not a gratifying level in practicality aspect the element function such as tone of its luminous efficiency, glow color.

Summary of the invention

The objective of the invention is to, a kind of macromolecular compound that the good electronic component of element function can be provided under the situation that the material as electronic component uses is provided.

That is, the invention provides the macromolecular compound that contains with at least one of the residue of the compound of following formula (1) expression.

(formula 1)

[in the formula, A ring, B ring and C ring represent also can have substituent aromatic ring or non-aromatic ring, Z respectively independently ₁, Z ₂, Z ₃, Z ₄And Z ₅Represent C-(Q) z or nitrogen-atoms respectively independently, Q represents substituting group or hydrogen atom, and z represents 0 or 1, and the A ring also can have the Z that constitutes ring separately mutually with the B ring ₅Atom in addition, what A ring, B ring and C encircled is the non-aromatic ring below two more than one.]

Embodiment

In the formula (1), A ring, B ring and C ring represent also can have substituent aromatic ring or non-aromatic ring respectively independently.

As aromatic ring, can enumerate the material that in the ring structure, contains 4n+2 πDian Zi.Specifically, can enumerate phenyl ring, ring pentaene ring etc. in the last of the ten Heavenly stems is aromatic hydrocarbon based; Heteroaromatics such as furan nucleus, thiphene ring, pyroles, pyridine ring, pyrimidine ring, pyridazine ring.

As the non-aromatic ring, can enumerate the pentamethylene ring, the cyclopentenes ring, the cyclopentadiene ring, cyclohexane ring, cyclohexene ring, the cyclohexadiene ring, the suberane ring, the suberene ring, the cycloheptadiene ring, the cycloheptatriene ring, the cyclooctane ring, the cyclooctene ring, the cyclooctadiene ring, the cyclo-octatriene ring, the cyclooctatetraene ring, the cyclononane ring, the cyclonoene ring, the cyclonoadiene ring, ring triolefin ring in the ninth of the ten Heavenly Stems, the cyclodecane ring, the cyclodecene ring, the cyclodecadiene ring, ring triolefin ring in the last of the ten Heavenly stems, ring decatetraene ring, the cyclododecane ring, the cyclododecene ring, cyclododecane diene ring, cyclododecane triolefin ring, cyclododecane tetraene ring, cyclododecane pentaene ring, ring undecane ring, ring hendecene ring, ring undecane diene ring, ring undecane triolefin ring, ring undecane tetraene ring, ring undecane pentaene ring, ester ring type rings such as ring undecane six alkene rings; The heterocycle of non-aromatics such as pyranoid ring, thiapyran ring.

Have under the substituent situation at aromatic ring or non-aromatic ring; can enumerate alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, substituted-amino, replacement silyl, fluorine atom, acyl group, acyloxy, amide group, imide, 1 valency heterocyclic radical, carboxyl, replacement carboxyl, cyano group and nitro, more preferably alkyl, alkoxyl group, aryl, aryloxy, aralkyl, alkoxy aryl, alkylthio-aryl as substituting group.

Here, no matter alkyl is straight chain, side chain or cyclic which kind of can, carbon number is generally about 1～20, preferred carbon number 3～20, as its concrete example, can enumerate methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, hexyl, cyclohexyl, heptyl, octyl group, the 2-ethylhexyl, nonyl, decyl, 3,7-dimethyl octyl group, lauryl, trifluoromethyl, pentafluoroethyl group, perfluoro butyl, perfluoro hexyl, perfluoro capryl etc., preferred amyl group, isopentyl, hexyl, octyl group, the 2-ethylhexyl, decyl, 3,7-dimethyl octyl group.

No matter alkoxyl group is straight chain, side chain or cyclic which kind of can, carbon number is generally about 1～20, preferred carbon number 3～20, as its concrete example, can enumerate methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptan the oxygen base, octyloxy, the 2-ethyl hexyl oxy, the ninth of the ten Heavenly Stems oxygen base, the last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxy, lauryl oxygen base, trifluoromethoxy, five fluorine oxyethyl groups, the perfluor butoxy, perfluoro hexyl, perfluoro capryl, methoxymethyl oxygen base, 2-methoxy ethyl oxygen base etc., preferred pentyloxy, hexyloxy, octyloxy, the 2-ethyl hexyl oxy, the last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxy.

No matter alkylthio is straight chain, side chain or cyclic which kind of can, carbon number is generally about 1～20, preferred carbon number 3～20, as its concrete example, can enumerate methylthio group, ethylmercapto group, the rosickyite base, the iprotiazem base, butylthio, the isobutyl sulfenyl, uncle's butylthio, penta sulfenyl, own sulfenyl, the hexamethylene sulfenyl, heptan sulfenyl, hot sulfenyl, 2-ethylhexyl sulfenyl, the ninth of the ten Heavenly Stems sulfenyl, the last of the ten Heavenly stems sulfenyl, 3,7-dimethyl-octa sulfenyl, the lauryl sulfenyl, trifluoromethyl sulfenyl etc., preferred penta sulfenyl, own sulfenyl, hot sulfenyl, 2-ethylhexyl sulfenyl, the last of the ten Heavenly stems sulfenyl, 3,7-dimethyl octyl group sulfenyl.

Aryl is an atomic group of having removed 1 hydrogen atom from aromatic hydrocarbons, comprise material with condensed ring, more than 2 independently phenyl ring or condensed ring directly or by basic bonded materials such as vinylidenes.The carbon number of aryl is generally about 6～60, and is preferred 7～48, as its concrete example, can phenyl, C be shown example ₁～C ₁₂Alkoxyl phenyl (C ₁～C ₁₂The expression carbon number is 1～12.Below identical.), C ₁～C ₁₂Alkyl phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, pentafluorophenyl group etc., preferred C ₁～C ₁₂Alkoxyl phenyl, C ₁～C ₁₂Alkyl phenyl.As C ₁～C ₁₂Alkoxyl group, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy, ninth of the ten Heavenly Stems oxygen base, last of the ten Heavenly stems oxygen base, 3 specifically can example be shown, 7-dimethyl octyloxy, lauryl oxygen base etc.

As C ₁～C ₁₂Alkyl phenyl can example illustrate aminomethyl phenyl, ethylphenyl, 3,5-dimethylphenyl, propyl group phenyl,  base, methylethyl phenyl, isopropyl phenyl, butyl phenyl, isobutyl phenenyl, tert-butyl-phenyl, amyl group phenyl, isopentyl phenyl, hexyl phenyl, heptyl phenyl, octyl phenyl, nonyl phenyl, decyl phenyl, dodecylphenyl etc. specifically.

The carbon number of aryloxy is generally about 6～60, and is preferred 7～48, as its concrete example, can phenoxy group, C be shown example ₁～C ₁₂Alkoxyl group phenoxy group, C ₁～C ₁₂Alkyl phenoxy, 1-naphthyloxy, 2-naphthyloxy, pentafluorophenyl group oxygen base etc., preferred C ₁～C ₁₂Alkoxyl group phenoxy group, C ₁～C ₁₂Alkyl phenoxy.

As C ₁～C ₁₂Alkoxyl group, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy, ninth of the ten Heavenly Stems oxygen base, last of the ten Heavenly stems oxygen base, 3 specifically can example be shown, 7-dimethyl octyloxy, lauryl oxygen base etc.

As C ₁～C ₁₂Alkyl phenoxy, can methylphenoxy, ethyl phenoxy group, dimethyl phenoxy, propyl group phenoxy group, 1 be shown example specifically, 3,5-trimethylammonium phenoxy group, methylethyl phenoxy group, sec.-propyl phenoxy group, butyl phenoxy, isobutyl-phenoxy group, tertiary butyl phenoxy group, amyl group phenoxy group, isopentyl phenoxy group, hexyl phenoxy group, heptyl phenoxy group, Octylphenoxy, Nonylphenoxy, decyl phenoxy group, dodecyl phenoxy group etc.

The carbon number of arylthio is generally 3～60, as its concrete example, can phenyl sulfenyl, C be shown example ₁～C ₁₂Alkoxyl phenyl sulfenyl, C ₁～C ₁₂Alkyl phenyl sulfenyl, 1-naphthalene sulfenyl, 2-naphthalene sulfenyl, pentafluorophenyl group sulfenyl etc., preferred C ₁～C ₁₂Alkoxyl phenyl sulfenyl, C ₁～C ₁₂The alkyl phenyl sulfenyl.

The carbon number of aralkyl is generally about 7～60, and is preferred 7～48, as its concrete example, can phenyl-C be shown example ₁～C ₁₂Alkyl, C ₁～C ₁₂Alkoxyl phenyl-C ₁～C ₁₂Alkyl, C ₁～C ₁₂Alkyl phenyl-C ₁～C ₁₂Alkyl, 1-naphthyl-C ₁～C ₁₂Alkyl, 2-naphthyl-C ₁～C ₁₂Alkyl etc., preferred C ₁～C ₁₂Alkoxyl phenyl-C ₁～C ₁₂Alkyl, C ₁～C ₁₂Alkyl phenyl-C ₁～C ₁₂Alkyl.

The carbon number of alkoxy aryl is generally about 7～60, and preferred carbon number 7～48 as its concrete example, can example illustrate phenyl-C such as phenyl methoxyl group, phenyl ethoxy, phenyl butoxy, phenyl pentyloxy, phenyl hexyloxy, phenyl oxygen in heptan base, phenyl octyloxy ₁～C ₁₂Alkoxyl group, C ₁～C ₁₂Alkoxyl phenyl-C ₁～C ₁₂Alkoxyl group, C ₁～C ₁₂Alkyl phenyl-C ₁～C ₁₂Alkoxyl group, 1-naphthyl-C ₁～C ₁₂Alkoxyl group, 2-naphthyl-C ₁～C ₁₂Alkoxyl group etc., preferred C ₁～C ₁₂Alkoxyl phenyl-C ₁～C ₁₂Alkoxyl group, C ₁～C ₁₂Alkyl phenyl-C ₁～C ₁₂Alkoxyl group.

The carbon number of aromatic alkyl sulfurio is generally about 7～60, and preferred carbon number 7～48 as its concrete example, can example illustrate phenyl-C ₁～C ₁₂Alkyl sulfenyl, C ₁～C ₁₂Alkoxyl phenyl-C ₁～C ₁₂Alkyl sulfenyl, C ₁～C ₁₂Alkyl phenyl-C ₁～C ₁₂Alkyl sulfenyl, 1-naphthyl-C ₁～C ₁₂Alkyl sulfenyl, 2-naphthyl-C ₁～C ₁₂Alkyl sulfenyl etc., preferred C ₁～C ₁₂Alkoxyl phenyl-C ₁～C ₁₂Alkyl sulfenyl, C ₁～C ₁₂Alkyl phenyl-C ₁～C ₁₂The alkyl sulfenyl.

The carbon number of aromatic yl alkenyl is generally about 8～60, as its concrete example, can phenyl-C be shown example ₂～C ₁₂Alkenyl, C ₁～C ₁₂Alkoxyl phenyl-C ₂～C ₁₂Alkenyl, C ₁～C ₁₂Alkyl phenyl-C ₂～C ₁₂Alkenyl, 1-naphthyl-C ₂～C ₁₂Alkenyl, 2-naphthyl-C ₂～C ₁₂Alkenyl etc., preferred C ₁～C ₁₂Alkoxyl phenyl-C ₂～C ₁₂Alkenyl, C ₂～C ₁₂Alkyl phenyl-C ₁～C ₁₂Alkenyl.

The carbon number of aromatic yl polysulfide yl is generally about 8～60, as its concrete example, can phenyl～C be shown example ₂～C ₁₂Alkynyl, C ₁～C ₁₂Alkoxyl phenyl-C ₂～C ₁₂Alkynyl, C ₁～C ₁₂Alkyl phenyl-C ₂～C ₁₂Alkynyl, 1-naphthyl-C ₂～C ₁₂Alkynyl, 2-naphthyl-C ₂～C ₁₂Alkynyl etc., preferred C ₁～C ₁₂Alkoxyl phenyl-C ₂～C ₁₂Alkynyl, C ₁～C ₁₂Alkyl phenyl-C ₂～C ₁₂Alkynyl.

As substituted-amino, can enumerate by being selected from the amino that in alkyl, aryl, aralkyl or the 1 valency heterocyclic radical 1 or 2 groups have replaced, the heterocyclic radical of this alkyl, aryl, aralkyl or 1 valency also can substituting group.For the carbon number of substituted-amino, do not comprise this substituent carbon number, be generally about 1～60, preferred carbon number is 2～48.

Specifically, can methylamino be shown example, dimethylamino, ethylamino, diethylamino, propyl group amino, dipropyl amino, sec.-propyl amino, diisopropylaminoethyl, butyl amino, isobutylamino, tertiary butyl amino, the amyl group alkyl, hexyl amino, cyclohexyl amino, heptyl amino, octyl group amino, 2-ethylhexyl amino, nonyl amino, decyl amino, 3,7-dimethyl octyl group amino, lauryl amino, cyclopentyl amino, two cyclopentyl amino, cyclohexyl amino, dicyclohexyl amino, pyrrolidyl, piperidyl, bis trifluoromethyl aminophenyl amino, xenyl amino, C ₁～C ₁₂Alkoxyl phenyl amino, two (C ₁～C ₁₂Alkoxyl phenyl) amino, two (C ₁～C ₁₂Alkyl phenyl) amino, 1-naphthyl amino, 2-naphthyl amino, pentafluorophenyl group amino, pyridinylamino, pyridazinyl amino, pyrimidinyl-amino, pyrazinyl amino, triazyl aminophenyl-C ₁～C ₁₂Alkylamino, C ₁～C ₁₂Alkoxyl phenyl-C ₁～C ₁₂Alkylamino, C ₁～C ₁₂Alkyl phenyl-C ₁～C ₁₂Alkylamino, two (C ₁～C ₁₂Alkoxyl phenyl-C ₁～C ₁₂Alkyl) amino, two (C ₁～C ₁₂Alkyl phenyl-C ₁～C ₁₂Alkyl) amino, 1-naphthyl-C ₁～C ₁₂Alkylamino, 2-naphthyl-C ₁～C ₁₂Alkylamino etc.

As replacing silyl, can enumerate the silyl that replaces by 1,2 or 3 group that is selected from alkyl, aryl, aralkyl or the 1 valency heterocyclic radical.The carbon number that replaces silyl is generally about 1～60, and preferred carbon number is 3～48.And the heterocyclic radical of this alkyl, aryl, aralkyl or 1 valency also can have substituting group.

Specifically, can trimethyl silyl be shown example, triethylsilyl, the tripropyl silyl, the triisopropyl silyl, dimethyl sec.-propyl silyl, diethyl sec.-propyl silyl, tertiary butyl silyl dimetylsilyl, the amyl group dimetylsilyl, the hexyl dimetylsilyl, the heptyl dimetylsilyl, the octyldimethyl silyl, 2-ethylhexyl dimetylsilyl, the nonyl dimetylsilyl, the decyl dimetylsilyl, 3,7-dimethyl octyl group-dimetylsilyl, the lauryl dimethyl silyl, phenyl-C ₁～C ₁₂Alkyl silyl, C ₁～C ₁₂Alkoxyl phenyl-C ₁～C ₁₂Alkyl silyl, C ₁～C ₁₂Alkyl phenyl-C ₁～C ₁₂Alkyl silyl, 1-naphthyl-C ₁～C ₁₂Alkyl silyl, 2-naphthyl-C ₁～C ₁₂Alkyl silyl, phenyl-C ₁～C ₁₂Alkyl dimethyl silyl, triphenyl silyl, three-p-Xylol base silyl, tribenzyl silyl, xenyl methyl-silicane base, tertiary butyl xenyl silyl, 3,5-dimethylphenyl silyl etc.

The carbon number of acyl group is generally about 2～20, and preferred carbon number is 2～18, as its concrete example, can ethanoyl, propionyl, butyryl radicals, isobutyryl, valeryl, benzoyl, trifluoroacetyl group, penta fluoro benzene formyl radical etc. be shown example.

The carbon number of acyloxy is generally about 2～20, preferred carbon number is 2～18, as its concrete example, can acetoxyl group, propionyloxy, butyryl acyloxy, isobutyl acyloxy, new pentane acyloxy, benzoyloxy, trifluoroacetyl oxygen base, penta fluoro benzene methanoyl etc. be shown example.

The carbon number of amide group is generally about 2～20, preferred carbon number is 2～18, as its concrete example, can formamido-, acetamido, propionamido-, amide-based small, benzoylamino, trifluoroacetyl amido, penta fluoro benzene formamido-, diformamide base, diacetylamino, dipropyl acidamide base, two amide-based smalls, dibenzoyl amido, two trifluoroacetyl amidos, two penta fluoro benzene formamido-s etc. be shown example.

As imide, can enumerate from imide compound remove with its nitrogen-atoms bonded hydrogen atom and residue, carbon number is about 4～20, can group shown below etc. be shown example specifically.

So-called 1 valency heterocyclic radical is meant has removed remaining atomic group behind 1 hydrogen atom from heterogeneous ring compound, carbon number is generally about 4～60, is preferably 4～20.And, in the carbon number of heterocyclic radical, do not comprise substituent carbon number.Here so-called heterogeneous ring compound is meant that the central element that constitutes ring of organic compound with loop system is not only carbon atom, also contains heteroatomic compounds such as aerobic, sulphur, nitrogen, phosphorus, boron in ring.Specifically, can provide following structure.

In the above-mentioned formula, R represents hydrogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency heterocyclic radical, carboxyl, replacement carboxyl or cyano group respectively independently.

Wherein, preferred thienyl, C ₁～C ₁₂Alkylthrophene base, pyrryl, furyl, pyridyl, C ₁～C ₁₂Alkylpyridyl, piperidyl, quinolyl, isoquinolyl etc., more preferably thienyl, C ₁～C ₁₂Alkylthrophene base, pyridyl, C ₁～C ₁₂Alkylpyridyl.

Replacing carboxyl is meant by alkyl, aryl, the carboxyl that aralkyl or 1 valency heterocyclic radical have replaced, carbon number is generally about 2～60, preferred carbon number is 2～48, as its concrete example, can enumerate methoxycarbonyl, ethoxy carbonyl, propoxycarbonyl, isopropoxy carbonyl, butoxy carbonyl, isobutoxy carbonyl, tert-butoxycarbonyl, pentyloxy carbonyl, hexyloxy carbonyl, cyclohexyloxy carbonyl, heptan oxygen base carbonyl, carbonyl octyloxy, 2-ethyl hexyl oxy carbonyl, the ninth of the ten Heavenly Stems oxygen base carbonyl, the last of the ten Heavenly stems oxygen base carbonyl, 3 ,-dimethyl carbonyl octyloxy, dodecyloxy carbonyl, the trifluoromethoxy carbonyl, five fluorine ethoxy carbonyls, the perfluor butoxy carbonyl, the perfluor hexyloxy carbonyl, the perfluor carbonyl octyloxy, phenyloxycarbonyl, the naphthyloxy carbonyl, pyridyloxy carbonyl etc.And this alkyl, aryl, aralkyl or 1 valency heterocyclic radical also can have substituting group.In the carbon number that replaces carboxyl, do not comprise this substituent carbon number.

In the above-mentioned formula (1), Z ₁, Z ₂, Z ₃, Z ₄And Z ₅Independent respectively, expression C-(Q) z or nitrogen-atoms, Q represents substituting group or hydrogen atom, z represents 0 or 1.

Substituting group as Q; can enumerate alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, substituted-amino, replacement silyl, fluorine atom, acyl group, acyloxy, amide group, imide, 1 valency heterocyclic radical, carboxyl, replacement carboxyl, cyano group and nitro etc., its definition, concrete example etc. are identical with above-mentioned content.

The A ring encircles the Z that also can have formation ring separately with B ₅The atom of ring in addition, what A ring, B ring and C encircled is the non-aromatic ring below two more than one.Preferred A ring encircles except Z with B ₅Have the situation of the atom of a ring in addition.In addition, preferred non-aromatic ring is one a situation.

In addition, macromolecular compound of the present invention preferably contains the repeating unit of representing with following formula (1-1)～(1-3) as repeating unit.

Formula (1-1) formula (1-2) formula (1-3)

[in the formula, A ring, B ring and C ring represent also can have substituent aromatic ring or non-aromatic ring, Z respectively independently ₁, Z ₂, Z ₃, Z ₄And Z ₅Represent C-(Q) z or nitrogen-atoms respectively independently, Q represents substituting group or hydrogen atom, and z represents 0 or 1, and the A ring also can have Z with the B ring ₅The atom of ring in addition in addition, also can be combination between each substituting group that encircles, and formation encircles again, and what A ring, B ring, C encircled the central ring that does not have associative key (connecting bond) is the non-aromatic ring more than one.]

As the concrete example of the repeating unit of representing with formula (1-1), can enumerate

Deng and they have substituent example.

As the concrete example of the repeating unit of representing with formula (1-2), can enumerate

Deng and they have substituent example.

As the concrete example of the repeating unit of representing with formula (1-3), can enumerate

Deng and they have substituent example.

In the middle of the repeating unit by above-mentioned formula (1-1)～(1-3) expression, for the atom that constitutes A ring, B ring and C ring (so-called " constituting the atom of ring " is meant the atom of the skeleton that forms ring), except carbon atom, also can comprise atoms such as nitrogen, oxygen, sulphur, silicon, selenium, but consider that from the viewpoint of adjusting charge-transporting the atom that preferably constitutes A ring, B ring and C ring all is a carbon atom.

Consider that from the solvability that improves macromolecular compound, the viewpoint of adjustment emission wavelength, the viewpoint of adjustment charge-transporting certain that preferably A ring, B encircle, C encircles has substituting group.

In addition, consider, preferably, consider, more preferably with the structure of above-mentioned formula (1-1) expression from the viewpoint of synthetic easness with the repeating unit of the structure of above-mentioned formula (1-1), (1-2) expression from the viewpoint of charge-transporting.

In addition, the more preferably following formula of above-mentioned formula (1-1) (2-1).

Formula (2-1)

[in the formula, R ₁And R ₂Represent substituting group respectively independently, the expression of D ring also can have substituent non-aromatic ring, and a represents 0～2 integer, and b represents 0～3 integer, at R ₁And R ₂Exist respectively under a plurality of situations, they both can be identical, also can be different, and also can R ₁With R ₂Mutually combine and form ring.In addition, also can R ₁And/or R ₂Close with the D loops and form ring, Q and z represent the meaning same as described above.]

The repeating unit that comprises above-mentioned formula (2-1) is preferably with the repeating unit of following formula (3-1) expression.

Formula (3-1)

[in the formula, R ₁, R ₂, D ring, Q, z, a and b represent the meaning same as described above.]

In the middle of the repeating unit with formula (3-1) expression, consider, more preferably reach (4-4) repeating unit of expression with following formula (4-1), (4-2), (4-3) from the viewpoint of adjusting charge-transporting.

Formula (4-1) formula (4-2)

Formula (4-3) formula (4-4)

[in the formula, R _1a, R _1b, R _2a～R _2cAnd R _3a～R _3gThe expression substituting group.In the formula (4-1)～(4-3), also can R _2cWith R _3gMutually combine and form ring.In the formula (4-4), also can R _2cWith R _3gMutually combine and form ring.]

The ring that forms as mutually combining can be enumerated aromatic ring, non-aromatic ring etc., its concrete example etc. with above-mentioned in put down in writing identical.

And the unit of formula (4-1)～(4-3) is comprised in the situation of z=1 in the formula (3-1), and the unit of formula (4-4) is comprised in the situation of z=0 in the formula (3-1).

As the concrete example of the repeating unit of representing with above-mentioned formula (4-1), can enumerate

As the concrete example of the repeating unit of representing with above-mentioned formula (4-2), can enumerate

As the concrete example of the repeating unit of representing with above-mentioned formula (4-3), can enumerate

As the concrete example of the repeating unit of representing with above-mentioned formula (4-4), can enumerate

In the formula, Me represents methyl, and Et represents ethyl.

Belong to above-mentioned formula (1-1), (1-2), (1-3), (2-1), (3-1), (4-1), (4-2), (4-3) and (4-4) sum of the repeating unit of the structure of expression be generally above 100 moles below the % of 1 mole of % of sum of whole repeating units that macromolecular compound of the present invention had, above 100 moles below the % of preferred 5 moles of %.

From changing the viewpoint of emission wavelength, improve the viewpoint of luminous efficiency, improve aspect considerations such as stable on heating viewpoint, macromolecular compound of the present invention is preferably except with above-mentioned formula (1-1), (1-2), (1-3), (2-1), (3-1), (4-1), (4-2), (4-3) and (4-4) the repeating unit of expression, also contains more than a kind the multipolymer of repeating unit in addition.

As the repeating unit beyond the repeating unit that reaches (4-4) expression with above-mentioned formula (1-1), (1-2), (1-3), (2-1), (3-1), (4-1), (4-2), (4-3), the preferably repeating unit of representing with following formula (5), formula (6), formula (7) or formula (8).

-Ar ₁- (5)

-(Ar ₂-X ₁) _ff-Ar ₃- (6)

-Ar ₄-X ₂- (7)

-X ₃- (8)

In the formula, Ar ₁, Ar ₂, Ar ₃And Ar ₄Represent arylidene, divalent heterocyclic radical respectively independently or have the divalent group that metal complex is constructed.X ₁, X ₂And X ₃Difference is expression-CR independently ₉=CR ₁₀-,-C ≡ C-,-N (R ₁₁)-or-(SiR ₁₂R ₁₃) _m-.R ₉And R ₁₀Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical, carboxyl, replacement carboxyl or cyano group respectively independently.R ₁₁, R ₁₂And R ₁₃Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical, aralkyl or substituted-amino respectively independently.Ff represents 1 or 2 integer.M represents 1～12 integer.At R ₉, R ₁₀, R ₁₁, R ₁₂And R ₁₂Exist respectively under a plurality of situations, they both can be identical, also can be different.

Here said arylidene is the atomic group of having removed from aromatic hydrocarbons behind 2 hydrogen atoms, comprise atomic group with condensed ring and more than 2 independently phenyl ring or condensed ring directly or by group bonded atomic groups such as vinylidenes.Arylidene also can have substituting group.

As substituting group, can enumerate alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency heterocyclic radical, carboxyl, replacement carboxyl, cyano group.

The carbon number of removing the part behind the substituting group in the arylidene is generally about 6～60, is preferably 6～20.In addition, the substituent total carbon number that comprises of arylidene is generally about 6～100.

As arylidene, phenylene (for example formula 1～3 of figure below), naphthalene two bases (formula 4～13 of figure below), anthracene two bases (formula 14～19 of figure below), biphenyl two bases (formula 20～25 of figure below), fluorenes two bases (formula 36～38 of figure below), terphenyl two bases (formula 26～28 of figure below), fused ring compound base (formula 29～35 of figure below), vinylbenzene two bases (the formula A of figure below～D), toluylene two bases (the formula E of figure below, F) etc. can example be shown.Wherein preferred phenylene, biphenylene, fluorenes two bases, Stilbene two bases.

In addition, Ar ₁, Ar ₂, Ar ₃And Ar ₄In so-called divalent heterocyclic radical be meant and from heterogeneous ring compound, removed remaining atomic group behind 2 hydrogen atoms that this group also can have substituting group.Here said heterogeneous ring compound is meant that the central element that constitutes ring of organic compound with loop system is not only carbon atom, also comprises heteroatomic compounds such as oxygen, sulphur, nitrogen, phosphorus, boron, arsenic in ring.In the middle of the heterocyclic radical of divalent, the optimization aromatic heterocyclic radical.

The carbon number of removing the part behind the substituting group in the divalent heterocyclic radical is generally about 3～60.In addition, the substituent total carbon number that comprises of divalent heterocyclic radical is generally about 3～100.

As the divalent heterocyclic radical, for example can enumerate following group.

As heteroatoms, comprise the divalent heterocyclic radical of nitrogen: pyridine two bases (formula 39～44 of figure below), diaza phenylene (formula 45～48 of figure below), quinoline two bases (formula 49～63 of figure below), quinoxaline two bases (formula 64～68 of figure below), acridine two bases (formula 69～72 of figure below), dipyridyl two bases (formula 73～75 of figure below), phenanthroline two bases (formula 76～78 of figure below) etc.

The group (formula 79～93 of figure below) that contains silicon, nitrogen, selenium etc. as heteroatoms with fluorenes structure.

The five-ring heterocyclic radical that contains silicon, nitrogen, sulphur, selenium etc. as heteroatoms: can enumerate (formula 94～98 of figure below).

The five-ring annelated heterocycles base that contains silicon, nitrogen, selenium etc. as heteroatoms: can enumerate (formula 99～100,102～110 of figure below).

Contain the five-ring heterocyclic radical of silicon, nitrogen, sulphur, selenium etc. and be the group of dimer or oligopolymer as heteroatoms: can enumerate (formula 111～112 of figure below) at its heteroatomic α position be combined into.

Contain the five-ring heterocyclic radical of silicon, nitrogen, sulphur, selenium etc. and at its heteroatomic α position and phenyl bonded group as heteroatoms: can enumerate (formula 113～119 of figure below).

The group that phenyl, furyl, thienyl have replaced on the five-ring heterocyclic radical that contains aerobic, nitrogen, sulphur etc. as heteroatoms: can enumerate (formula 120～125 of figure below).

In addition, so-called Ar ₁, Ar ₂, Ar ₃And Ar ₄In the divalent group with metal complex structure be meant and from the organic ligand of metal complex, remove remaining divalent group behind 2 hydrogen atoms with organic ligand.

The carbon number of this organic ligand is generally about 4～60, for example can enumerate oxine and derivative thereof, benzoquinoline and derivative thereof, 2-phenylpyridine and derivative thereof, 2-phenyl benzothiazole and derivative thereof, 2-Ben base benzoxazole and derivative, porphyrin and derivative thereof etc.

In addition, as the central metal of this complex compound, for example can enumerate aluminium, zinc, beryllium, iridium, platinum, gold, europium, terbium etc.

As metal complex, can enumerate low molecular fluorescent material, as the known metal complex of phosphor material, the luminous complex compound of triplet state etc. with organic ligand.

As divalent group, specifically, can following (126～132) be shown example with metal complex structure.

In the above-mentioned formula 1～132, R represents heterocyclic radical, carboxyl, replacement carboxyl or the cyano group of hydrogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency respectively independently.In addition, the carbon atom that group had of formula 1～132 also can be substituted by nitrogen-atoms, Sauerstoffatom or sulphur atom, and hydrogen atom also can be substituted by fluorine atom.

In addition, in the middle of the repeating unit with above-mentioned formula (5), (6), (7), (8) expression, preferably with the repeating unit of following formula (9), formula (10), formula (11), formula (12), formula (13) or formula (14) expression.

[in the formula, R ₁₄Heterocyclic radical, carboxyl, replacement carboxyl or the cyano group of expression alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency.N represents 0～4 integer.There are a plurality of R ₁₄Situation under, they both can be the same or different.]

[in the formula, R ₁₅And R ₁₆Heterocyclic radical, carboxyl, replacement carboxyl or the cyano group of representing alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency respectively independently.O and p represent 0～3 integer respectively independently.There are a plurality of R ₁₅And R ₁₆Situation under, they both can be the same or different.]

[in the formula, R ₁₇And R ₂₀Heterocyclic radical, carboxyl, replacement carboxyl or the cyano group of representing alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency respectively independently.Q and r represent 0～4 integer respectively independently.R ₁₈And R ₁₉Heterocyclic radical, carboxyl, replacement carboxyl or the cyano group of representing hydrogen atom, alkyl, aryl, 1 valency respectively independently.There are a plurality of R ₁₇And R ₂₀Situation under, they both can be the same or different.]

[in the formula, R ₂₁Heterocyclic radical, carboxyl, replacement carboxyl or the cyano group of expression alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency.S represents 0～2 integer.Ar ₁₃And Ar ₁₄Represent the heterocyclic radical of arylidene, divalent respectively independently or have the divalent group that metal complex is constructed.Ss and tt represent 0 or 1 respectively independently.X ₄Expression O, S, SO, SO ₂, Se or Te.There are a plurality of R ₂₁Situation under, they both can be the same or different.]

[in the formula, R ₂₂And R ₂₅Heterocyclic radical, carboxyl, replacement carboxyl or the cyano group of representing alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency respectively independently.T and u represent 0～4 integer respectively independently.X ₅Expression O, S, SO, SO ₂, Se, Te, N-R ₂₄Or SiR ₂₅R ₂₆X ₆And X ₇Represent N or C-R respectively independently ₂₇R ₂₄, R ₂₅, R ₂₆And R ₂₇Represent hydrogen atom, alkyl, aryl, aralkyl or 1 valency heterocyclic radical respectively independently.There are a plurality of R ₂₂, R ₂₃And R ₂₇Situation under, they both can be the same or different.]

As pentacyclic example, can enumerate thiadiazoles, oxadiazole, triazole, thiophene, furans, silole etc. with the central authorities of the repeating unit of formula (11) expression.

[in the formula, R ₂₈And R ₃₃Heterocyclic radical, carboxyl, replacement carboxyl or the cyano group of representing alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency respectively independently.V and w represent 0～4 integer respectively independently.R ₂₉, R ₃₀, R ₃₁And R ₃₆Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical, carboxyl, replacement carboxyl or cyano group respectively independently.Ar ₅Represent the heterocyclic radical of arylidene, divalent or have the divalent group that metal complex is constructed.There are a plurality of R ₂₈And R ₃₃Situation under, they both can be the same or different.]

In addition, in the middle of the repeating unit with above-mentioned formula (6) expression, from the viewpoint, the viewpoint that improves luminous efficiency that change emission wavelength, improve stable on heating viewpoint and consider, preferably with the repeating unit of following formula (15) expression.

[in the formula, Ar ₆, Ar ₇, Ar ₈And Ar ₉The heterocyclic radical of representing arylidene or divalent respectively independently.Ar ₁₀, Ar ₁₁And Ar ₁₂The heterocyclic radical of representing arylidene or 1 valency respectively independently.Ar ₆, Ar ₇, Ar ₈, Ar ₉And Ar ₁₀Also can have substituting group.X and y represent 0 or 1 respectively independently.0≤x+y≤1。]

As the concrete example of the repeating unit of representing with above-mentioned formula (15), can enumerate example with following (formula 133～140) expression.

In the above-mentioned formula, R is identical with the content of above-mentioned formula 1～132.

In order to improve the solvability in solvent, preferably have the substituting group beyond the above hydrogen atom, in addition, the symmetry of shape that contains substituent repeating unit is few more good more.

In the above-mentioned formula, contain in the substituting group of alkyl,, preferably contain an above ring-type or have the alkyl of side chain in order to improve the solvability of macromolecular compound in solvent at R.

In addition, R contains in its part under the situation of aryl or heterocyclic radical in above-mentioned formula, and they also can also have more than one substituting group.

In the repeating unit with above-mentioned formula (15) expression, consider from viewpoints such as the viewpoint of regulating emission wavelength, element characteristics, preferably Ar ₆, Ar ₇, Ar ₈And Ar ₉Represent arylidene, Ar respectively independently ₁₀, Ar ₁₁And Ar ₁₂Represent aryl respectively independently.

As Ar ₆, Ar ₇, Ar ₈, preferred is the situation of unsubstituted phenylene, unsubstituted biphenyl group, unsubstituted naphthylidene, unsubstituted anthracene two bases respectively independently.

As Ar ₁₀, Ar ₁₁And Ar ₁₂, consider from the viewpoint of solvability, luminous efficiency, stability, preferably respectively independently for having substituent aryl, more preferably Ar more than 3 ₁₀, Ar ₁₁And Ar ₁₂Be to have substituent phenyl more than 3, have more than 3 substituent naphthyl or have substituent anthryl more than 3, further preferred Ar ₁₀, Ar ₁₁And Ar ₁₂For having substituent phenyl more than 3.

Wherein, Ar ₁₀, Ar ₁₁And Ar ₁₂Preferred is following formula (15-1) respectively independently.

[in the formula, Re, Rf and Rg represent alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, siloxy-, replacement siloxy-, 1 valency heterocyclic radical or halogen atom respectively independently.]

In the repeating unit with above-mentioned formula (15) expression, Ar ₇Be preferably following formula (15-2) or (15-3).

[also can have the substituting group below 4 more than 1 respectively independently with contained phenyl ring in the structure of (15-2), (15-3) expression here.These substituting groups both can be identical, also can be different.In addition, also can link and the formation ring by a plurality of substituting groups.In addition, also can be adjacent to combine other aromatic hydrocarbons ring or heterocycle with this phenyl ring.]

As repeating unit,, can enumerate example with following (formula 141～142) expression as particularly preferred concrete example with above-mentioned formula (15) expression.

[in the formula, Re～Rg is as noted above.]

In the above-mentioned formula, Re～Rg is identical with the content of above-mentioned formula 1～132.In order to improve the solvability in solvent, preferably have the substituting group beyond the above hydrogen atom, in addition, the symmetry of shape that contains substituent repeating unit is few more good more.

R contains in the substituting group of alkyl chain in the above-mentioned formula, in order to improve the solvability of macromolecular compound in solvent, preferably contains 1 above ring-type or has the alkyl chain of side chain.

In addition, R contains in its part under the situation of aryl or heterocyclic radical in above-mentioned formula, and they also can also have the substituting group more than 1.

And in the scope of not damaging the characteristics of luminescence or charge transport characteristic, macromolecular compound of the present invention also can contain with the repeating unit beyond the repeating unit of above-mentioned formula (1-1), (1-2), (1-3) and formula (5)～formula (15) expression.In addition, these repeating units or other repeating unit also can be linked by unconjugated unit, can also contain these non-conjugated parts in repeating unit.As join-together structure, structure shown below and will the structure shown below central structure that has made up more than 2 etc. can example be shown.Here, R is the group of selecting from the substituting group identical with above-mentioned substituting group, and Ar represents that carbon number is 6～60 a alkyl.

In the middle of the macromolecular compound of the present invention, the preferred compound that only constitutes by the repeating unit of above-mentioned formula (1-1) expression; And/or the compound that only constitutes by the repeating unit of (1-2) expression; And/or the compound that only constitutes by the repeating unit of (1-3) expression, in fact preferably and/or (1-2) and/or (1-3) by above-mentioned formula (1-1), with the compound that constitutes more than 1 with the repeating unit of above-mentioned formula (5)～(15) expression.

In addition, macromolecular compound of the present invention both can be random, block or graft copolymer, also can be the polymer with their intermediary structure, for example was the random copolymers that has block.Consider from the viewpoint of the high polymeric luminescent material of the quantum yield that obtains fluorescence or phosphorescence, compare, more preferably have random copolymers or the block or the graft copolymer of block with random copolymers completely.Be also included within the situation or the arborescence that have branch in the main chain and have 3 above terminal parts.

In addition, the terminal group of macromolecular compound of the present invention owing to might reduce the characteristics of luminescence or the life-span of making behind the element, therefore can be protected it with stable group when residual polymerization activity base intactly.Preferably have the structure with the conjugete structure successive conjugated link(age) of main chain, for example can example illustrate by C-C and aryl or heterocyclic radical bonded structure.The substituting group of record in the change 10 that the spy opens flat 9-45478 communique etc. specifically, can example be shown.

In the macromolecular compound of the present invention, preferably at least one side of its molecule chain end be selected from 1 valency heterocyclic radical, 1 valency aromatic series amido, by the aromatic series terminal group in heterocycle coordinated metal complex deutero-1 valency group and the aryl.This aromatic series terminal group both can be a kind, also can be more than 2 kinds.Consider from the viewpoint of fluorescent characteristic or element characteristic, preferably do not have aromatic series terminal group terminal group in addition in fact.Here, so-called molecule chain end is meant, utilizes the aromatic series terminal group of manufacture method of the present invention at the end that is present in macromolecular compound; Belong to monomeric leaving group used in the polymerization, and when polymerization, stay and be present in the leaving group of the end of macromolecular compound; Break away from debond aromatic series terminal group and bonded hydrogen atom though be present in the monomeric leaving group of deriving from of the end of macromolecular compound.In the middle of these molecule chain ends, for belonging to monomeric leaving group used in the polymerization, and when polymerization, stay and be present in the leaving group of the end of macromolecular compound, for example using monomer to make under the situation such as macromolecular compound of the present invention as raw material with halogen atom, when halogen residue when macromolecular compound is terminal, then have the tendency that fluorescent characteristic etc. reduces, therefore be preferably in the terminal leaving group of residual monomer not in fact.

In the macromolecular compound, by with at least one side of its molecule chain end be selected from 1 valency heterocyclic radical, 1 valency aromatic series amido, by the group or the aromatic series terminal group shutoff (blocking) of formula weight in the aryl more than 90 of heterocycle coordinated metal complex deutero-1 valency, just can expect to give various characteristics to macromolecular compound.Specifically, can enumerate the brightness that prolongs element and reduce the effect of needed time; Improve the effect of electric charge injection, charge-transporting, the characteristics of luminescence; Improve intermiscibility or interactional effect between multipolymer; The effect of grappling (anchor-like) etc.

As the aromatic series amido of 1 valency, can example be illustrated in 1 central structure of 2 associative keys that will have in the structure of above-mentioned formula (15) with the R shutoff.

As base, can example be illustrated in the base of above-mentioned divalent with metal complex structure 1 structure in the middle of 2 associative keys that had with the R shutoff by heterocycle coordinated metal complex deutero-1 valency.

In the middle of the aromatic series terminal group that macromolecular compound of the present invention had, at the aryl more than 90, carbon number is generally about 6～60 as formula weight.Here the formula weight of said aryl is meant, when aryl is expressed with chemical formula, for each element in this chemical formula, the value after multiply by nucleidic mass on each atoms of elements number and.

As aryl, can enumerate phenyl, naphthyl, anthryl, have the base, fused ring compound base of fluorenes structure etc.

As phenyl, for example can enumerate terminal shutoff

As naphthyl, for example can enumerate terminal shutoff

As anthryl, for example can enumerate

As the base that contains the fluorenes structure, for example can enumerate

As the fused ring compound base, for example can enumerate

As the terminal group that improves electric charge injection, charge-transporting, the aromatic series amido of the heterocyclic radical of preferred 1 valency, 1 valency, fused ring compound base, the more preferably heterocyclic radical of 1 valency, fused ring compound base.

As the terminal group that improves the characteristics of luminescence, preferred naphthyl, anthryl, fused ring compound base, by the group of heterocycle coordinated metal complex deutero-1 valency.

As having the terminal group that the brightness that prolongs element reduces the effect of needed time, preferably have substituent aryl, preferably have the phenyl of 1～3 alkyl.

As having the intermiscibility that improves between macromolecular compound or the terminal group of interactional effect, preferably has substituent aryl.In addition, by using carbon number, can play the effect of grappling at the alkyl substituted phenyl more than 6.So-called anchoring effect is meant, terminal group plays the effect of grappling to the condensation product of polymkeric substance, improves interactional effect.

As the group that improves element characteristic, preferred following structure.

R in the formula can example illustrate above-mentioned R.

The number-average molecular weight of the polystyrene conversion of macromolecular compound of the present invention is generally 10 ³～10 ⁸About, be preferably 10 ⁴～10 ⁶About.In addition, the weight-average molecular weight of polystyrene conversion is 10 ³～10 ⁸, preferred 10 ⁴～5 * 10 ⁶

As good solvent, can chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), toluene, dimethylbenzene, , tetralin, naphthalane, n-butylbenzene etc. be shown example at macromolecular compound of the present invention.Though according to the structure of macromolecular compound or molecular weight and difference can be dissolved more than the 0.1 weight % in these solvents usually.

Macromolecular compound of the present invention is compared with pairing poly-fluorene derivatives, can be luminous under short wavelength more.

Below, the manufacture method of macromolecular compound of the present invention is described.

In the middle of the macromolecular compound of the present invention, for example have with the compound of the repeating unit of formula (1-1), (1-2), (1-3) expression, can reach (16-3) by using with following formula (16-1), (16-2) as separately raw material

Formula (16-1) formula (16-2) formula (16-3)

[in the formula, A ring, B ring, C ring, Z ₁～Z ₅As previously mentioned.Y ₁, Y ₂, Y ₃, Y ₄, Y ₅And Y ₆Expression participates in the polymeric substituting group independently respectively.]

The compound of expression comes polymerization and makes.

In the middle of the compound with formula (16-1) expression, preferably with the compound of formula (17-1) expression.

Formula (17-1)

[in the formula, R ₁, R ₂, a, b, D ring, Q, z, Y ₁And Y ₂Represent the meaning same as described above.]

In the middle of the compound with formula (17-1) expression, more preferably reach (18-4) structure of expression with formula (18-1), (18-2), (18-3).

Formula (18-1) formula (18-2)

Formula (18-3) formula (18-4)

In addition, in the middle of the compound with formula (16-2) expression, preferably with the compound of formula (17-2) expression.

Formula (17-2)

[in the formula, B ring, C ring, Z ₂, Z ₃, Z ₄, Y ₃And Y ₄Represent the meaning same as described above.Z ₆, Z ₇And Z ₈Represent C-(Q) respectively independently _zOr nitrogen-atoms.Z _1a, Z _5aAnd Z ₉Represent carbon atom respectively independently.Q and z represent the meaning same as described above.R ₄The expression substituting group.E represents 0～2 integer.A plurality of R are being arranged ₄Situation under, they both can be the same or different, also can R ₄Between in conjunction with and form ring.]

In addition, in the middle of the compound with formula (16-3) expression, preferably with the compound of formula (17-3) expression.

Formula (17-3)

[in the formula, A ring, B ring, Z ₁, Z ₄, Z ₅, Y ₅And Y ₆Represent the meaning same as described above.Z ₁₀, Z ₁₁, Z ₁₂And Z ₁₃Represent C-(Q) respectively independently _zOr nitrogen-atoms.Z _2aAnd Z _3aRepresent carbon atom respectively independently.Q and z represent the meaning same as described above.R ₅The expression substituting group.F represents 0～2 integer.A plurality of R are being arranged ₅Situation under, they both can be the same or different, also can R ₅Between in conjunction with and form ring.]

In the manufacture method of the present invention, as participating in the polymeric substituting group, can enumerate halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group, sweet-smelling alkyl sulfonic acid ester group, boric acid ester group, sulfonium methyl, Phosphonium methyl, phosphoric acid ester methyl, single halogenated methyl ,-B (OH) ₂, formyl radical, cyano group, vinyl etc.

Here, as halogen atom, can enumerate fluorine atom, chlorine atom, bromine atoms, iodine atom.Consider preferred bromine atoms, iodine atom from the viewpoint that improves the polymerization degree.

As the alkylsulphonic acid ester group, can methylsulfonic acid ester group, ethyl sulfonic acid ester group, trifluoromethayl sulfonic acid ester group etc. be shown example,, can Phenylsulfonic acid ester group, tosic acid ester group etc. be shown example as the aryl sulfonic acid ester group, as the aryl sulfonic acid ester group, can benzyl sulfonate group etc. be shown example.

As the boric acid ester group, can the group of representing with following formula be shown example.

In the formula, Me represents methyl, and Et represents ethyl.

As the sulfonium methyl, can the group of representing with following formula be shown example.

-CH ₂S ⁺Me ₂X ^-、-CH ₂S ⁺Ph ₂X ^-、

(X represents halogen atom, and Ph represents phenyl.)

Make to be the Phosphonium methyl, can the group of representing with following formula be shown example.

-CH ₂P ⁺Ph ₃X ^-(X represents halogen atom.)

As the phosphoric acid ester methyl, can the group of representing with following formula be shown example.

-CH ₂PO (OR ') ₂(X represents halogen atom, R ' expression alkyl, aryl, aralkyl.)

As single halogenated methyl, can fluoro methyl, chloro methyl, bromomethyl, iodo-methyl be shown example.

Though preferred substituted is according to the kind of polyreaction and difference as participating in the polymeric substituting group, but for example under the situation of use 0 valency nickel complexes such as Yamamoto linked reaction, can enumerate halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group or sweet-smelling alkyl sulfonic acid ester group.In addition, use in Suzuki linked reaction etc. under the situation of nickel catalyzator or palladium catalyst, can enumerate alkylsulphonic acid ester group, halogen atom, boric acid ester group ,-B (OH) ₂Deng.

Particularly, the macromolecular compound with repeating unit of formula (4-1) the macromolecular compound with repeating unit of formula (4-2)～(4-4) can be used in supported palladium, platinum, rhodium, ruthenium on the activated carbon or mixed they precious metal catalyzer hydrogenation and get.

On the contrary, macromolecular compound with repeating unit of formula (4-2)～(4-4) can will have the macromolecular compound of repeating unit of formula (4-1) 2,3-two chloro-5,6-dicyano-1,4-benzoquinones (DDQ), alkaline condition get with the Tetrabutylammonium bromide oxidation down.

In addition, macromolecular compound of the present invention is under the situation with formula (1-1) or formula (1-2) or formula (1-3) repeating unit in addition, as long as 2 the substituent compounds of participation polymeric that have as formula (1-1) or formula (1-2) or formula (1-3) repeating unit are in addition coexisted and polymerization.

Except with above-mentioned formula (16-1), (16-2) or (16-3) the compound of expression, the compound with certain expression of following formula (19)～(22) can also be used as raw material.

Y ₇-Ar ₁-Y ₈ (19)

Y ₉-(Ar ₂-X ₁) _ff-Ar ₃-Y ₁₀ (20)

Y ₁₁-Ar ₄-X ₂-Y ₁₂ (21)

Y ₁₃-X ₃-Y ₁₄ (22)

[in the formula, Ar ₁, Ar ₂, Ar ₃, Ar ₄, ff, X ₁, X ₂And X ₃Same as described above.Y ₇, Y ₈, Y ₉, Y ₁₀, Y ₁₁, Y ₁₂, Y ₁₃, Y ₁₄Expression can the polymeric substituting group independently respectively.]

Can also make except with above-mentioned formula (1-1), (1-2) or (1-3) the unit of expression, have the unitary macromolecular compound of (5) more than 1, (6), (7) or (8) successively.

In addition, as with above-mentioned formula (1-1), (1-2) or (1-3) the having corresponding with above-mentioned formula (15) 2 and participate in the substituent compounds of polymeric of the repeating unit beyond the repeating unit of expression, can enumerate the compound of representing with following formula (15-7).

[in the formula, Ar ₆, Ar ₇, Ar ₈, Ar ₉, Ar ₁₀, Ar ₁₁, Ar ₁₂, x and y be same as described above.Y ₁₅And Y ₁₆Expression participates in the polymeric substituting group independently respectively.]

More preferably with the compound of formula (15-8) or formula (15-9) expression.

Formula (15-8) formula (15-9)

[in the formula, Re～Rg as previously mentioned.Y ₁₇, Y ₁₈, Y ₁₉, Y ₂₀Expression participates in the polymeric substituting group independently respectively.]

Manufacture method of the present invention can for example be used alkali or suitable catalyzer with being dissolved in as required in the organic solvent as monomeric substituent compound with a plurality of participation polycondensations specifically, carries out below the above boiling point of the fusing point of organic solvent.For example can use " organic reaction (Organic Reactions) ", the 14th volume, 270-490 page or leaf, John Wiley ﹠amp; Sons, Inc., nineteen sixty-five; " organic synthesis (Organic Syntheses) ", intersection the 6th volume (Collective VolumeVI), 407-411 page or leaf, John Wiley ﹠amp; Sons, Inc., 1988; Chemistry summary (Chem.Rev.), the 95th volume, 2475 pages (nineteen ninety-five); Organometallic chemistry magazine (J.Organomet.Chem.), the 576th volume, 147 pages (1999); The macromolecular chemistry macromole collection of essay (Makromol.Chem., Macromol.Symp.), the 12nd volume, the known method of putting down in writing during wait 229 pages (1987).

In the manufacture method of macromolecular compound of the present invention,, can use known polyreaction to make accordingly with the polymeric substituting group of the compound that participates in representing with above-mentioned formula (16-1)～(16-3) and (22)～(25) as with its polymeric method.

Generate in polymerization at macromolecular compound of the present invention under the situation of two keys, for example can enumerate the spy and open the method for putting down in writing in the flat 5-202355 communique.That is, utilize compound with formyl radical and Ju You Phosphonium methyl compound or have formyl radical with the polymerization that the Wittig of the compound of Phosphonium methyl reacts; Utilization has the compound of vinyl and the polymerization of the Heck reaction of the compound with halogen atom; Utilization has the polymerization of the dehydrohalogenation method of the compound of single halogenated methyl more than 2 or 2; Utilization has the polymerization of sulfonium salt decomposition method of the compound of 2 or 2 above sulfonium methyl; Utilization has the compound of formyl radical and the methods such as polymerization of the Knoevenagel reaction of the compound with cyano group; Utilization has the methods such as polymerization of McMurry reaction of the compound of 2 or 2 above formyl radicals.

Because of polymerization generates under the triple-linked situation, for example can utilize Heck reaction, Sonogashira reaction at macromolecular compound of the present invention in main chain.

In addition, do not generating under two keys or the triple-linked situation, for example the monomer that can routine illustrate by correspondence utilizes Suzuki linked reaction polymeric method; Utilize the method for Grignard reactive polymeric; Utilize Ni (0) complex compound polymeric method; Utilize FeCl ₃Deng oxygenant polymeric method; The method of oxypolymerization electrochemically; Perhaps utilize the method for the high molecular decomposition of intermediate etc. with suitable leaving group.

In the middle of them, owing to construct control easily, therefore preferably utilize the Wittig reaction polymerization, utilize the Heck reaction polymerization, utilize the polymerization of Knoevenagel reaction and utilize Suzuki linked reaction polymeric method, utilize the Grignard reactive polymeric method, utilize nickel 0 valency complex compound polymeric method.

In the middle of the manufacture method of the present invention, will with formula (16-1), (16-2) or (16-3) expression compound individually or be selected from in the compound of formula (19)～(22) expression at least-kind of polymerization in, the manufacture method that is preferably as follows, that is, Y ₁, Y ₂, Y ₃, Y ₄, Y ₅, Y ₆, Y ₇, Y ₈, Y ₉, Y ₁₀, Y ₁₁, Y ₁₂, Y ₁₃, Y ₁₄, Y ₁₅, Y ₁₆, Y ₁₇, Y ₁₈, Y ₁₉, Y ₂₀Be halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group or sweet-smelling alkyl sulfonic acid ester group independently respectively, in the presence of nickel 0 valency complex compound, carry out polycondensation.

As starting compound, can enumerate dihalide compound, two (alkyl sulfonic ester) compound, two (aromatic yl sulphonate) compound, two (sweet-smelling alkyl sulfonic acid ester) compound or halogen-alkylsulphonic acid ester cpds, halogen-aryl sulfonic acid ester cpds, halogen-sweet-smelling alkyl sulfonic acid ester cpds, alkyl sulfonic ester-aryl sulfonic acid ester cpds, alkyl sulfonic ester-sweet-smelling alkyl sulfonic acid ester cpds, aromatic yl sulphonate-sweet-smelling alkyl sulfonic acid ester cpds.

In addition, in the middle of the manufacture method of the present invention, will with formula (16-1), (16-2) or (16-3) expression compound individually or be selected from least a polymerization in the compound of formula (19)～(22) expression, the manufacture method that is preferably as follows, that is, Y ₁, Y ₂, Y ₃, Y ₄, Y ₅, Y ₆, Y ₇, Y ₈, Y ₉, Y ₁₀, Y ₁₁, Y ₁₂, Y ₁₃, Y ₁₄, Y ₁₅, Y ₁₆, Y ₁₇, Y ₁₈, Y ₁₉, Y ₂₀Respectively be independently halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group, sweet-smelling alkyl sulfonic acid ester group ,-B (OH) ₂Or the boric acid ester group, the sum of the mole number of halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group and sweet-smelling alkyl sulfonic acid ester group and-B (OH) ₂And the ratio of the sum of the mole number of boric acid ester group is essentially 1 (K/J is 0.7～1.2 scope usually), uses nickel or palladium catalyst to carry out polycondensation.

As the combination of concrete starting compound, can enumerate the combination of dihalide compound, two (alkyl sulfonic ester) compound, two (aromatic yl sulphonate) compound or two (sweet-smelling alkyl sulfonic acid ester) compound and hypoboric acid compound or hypoboric acid ester cpds.

In addition, can enumerate halogen-boronic acid compounds, halogen-boric acid ester compound, aromatic yl sulphonate-boronic acid compounds, alkyl sulfonic ester-boric acid ester compound, aromatic yl sulphonate-boronic acid compounds, aromatic yl sulphonate-boric acid ester compound, sweet-smelling alkyl sulfonic acid ester-boronic acid compounds, sweet-smelling alkyl sulfonic acid ester-boronic acid compounds, sweet-smelling alkyl sulfonic acid ester-boric acid ester compound.

As organic solvent, though according to used compound or reaction and difference, in general in order to suppress side reaction, used solvent is preferably implemented deoxidation treatment fully, reacts in inert atmosphere.In addition, preferably similarly carry out processed.But, the Suzuki linked reaction such with 2 phase systems water in the situation of reaction under be not so limited.

As solvent, can stable hydrocarbon such as pentane, hexane, heptane, octane, hexanaphthene be shown example; Unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, dimethylbenzene; Halogenated saturated hydrocarbon such as tetracol phenixin, chloroform, methylene dichloride, chlorobutane, n-butyl bromide, chloropentane, bromo pentane silane, chlorohexane, bromohexane, chlorine hexanaphthene, bromine hexanaphthene; Halogenation unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene, trichlorobenzene; Alcohols such as methyl alcohol, ethanol, propyl alcohol, Virahol, butanols, the trimethyl carbinol; Carboxylic-acids such as formic acid, acetate, propionic acid; Ethers such as dme, diethyl ether, methyl tertiary butyl ether, tetrahydrofuran (THF), tetrahydropyrans, dioxane; Trimethylamine 99, triethylamine, N, N, N ', amines such as N '-Tetramethyl Ethylene Diamine, pyridine; N, dinethylformamide, N,N-dimethylacetamide, N, amidess such as N-diethyl acetamide, N-methylmorpholine oxide compound can use single solvent or their mixed solvent.In the middle of them, preferred ethers, more preferably tetrahydrofuran (THF), diethyl ether.

In order to make it reaction, suitably add alkali or appropriate catalyst.They can be selected according to used reaction.This alkali or catalyzer preferably are dissolved in the used solvent of reaction fully.As method, the solution that adds alkali or catalyzer under inert atmospheres such as argon gas or nitrogen when reaction solution stirred at leisure can example be shown with alkali or catalyst mix; Perhaps in the solution of alkali or catalyzer, add the method for reaction solution on the contrary at leisure.

Macromolecular compound of the present invention is being used under the situation of polymer LED etc. because its purity exerts an influence to the performance of elements such as the characteristics of luminescence, therefore preferably with the monomer before the polymerization with the refining post polymerization of methods such as distillation, sublimation purifying, recrystallization.In addition, after polymerization, preferably carry out redeposition and make with extra care, utilize purification process such as stratographic separation.

Useful (16-1)～(16-3), (17-1)～(17-3) reaches (18-1)～(18-4) and can pass through the Y with above-mentioned formula as the raw material of macromolecular compound of the present invention ₁～Y ₆The compound of the structure that replaces with hydrogen atom carries out bromination and obtains.

Particularly, the compound utilization of the structure that the compound of the structure of formula (18-1) also can be by will having formula (18-2)～(18-4) the catalyzer hydrogenation that supported palladium, platinum, rhodium, ruthenium or mixed their precious metal on activated carbon obtains.

On the contrary, the compound with structure that the compound of the structure of formula (18-2)～(18-4) can be by will having formula (18-1) is 2,3-two chloro-5, and 6-dicyano-1,4-benzoquinones (DDQ), alkaline condition use the Tetrabutylammonium bromide oxidation to obtain down.

Below, polymer LED of the present invention is described.

The feature of polymer LED of the present invention is, between the electrode that is made of anode and negative electrode, has organic layer, and this organic layer contains macromolecular compound of the present invention.

Though organic layer no matter be luminescent layer, hole transporting layer, electron supplying layer etc. which kind of can, organic layer is preferably luminescent layer.

Here, so-called luminescent layer is meant the layer with luminous function, and so-called hole transporting layer is meant the layer with the function of carrying the hole, and so-called electron supplying layer is meant the layer of the function with conveying electronic.And, electron supplying layer and hole transporting layer are generically and collectively referred to as charge transport layer.Luminescent layer, hole transporting layer, electron supplying layer can be distinguished and use independently more than 2 layers.

At organic layer is under the situation of luminescent layer, also can also contain hole transporting material, electron transport materials or luminescent material as the luminescent layer of organic layer.Here, so-called luminous material is meant the material that demonstrates fluorescence and/or phosphorescence.

Under with macromolecular compound of the present invention and hole transporting material blended situation, with respect to this mixture integral body, the blending ratio of hole transporting material is 1wt%～80wt%, is preferably 5wt%～60wt%.Under with macromolecular compound of the present invention and electron transport materials blended situation, with respect to this mixture integral body, the blending ratio of electron transport materials is 1wt%～80wt%, is preferably 5wt%～60wt%.In addition, under with macromolecular compound of the present invention and luminescent material blended situation, with respect to this mixture integral body, the blending ratio of luminescent material is 1wt%～80wt%, is preferably 5wt%～60wt%.Under with macromolecular compound of the present invention and luminescent material, hole transporting material and/or electron transport materials blended situation, with respect to this mixture integral body, the blending ratio of luminescent material is 1wt%～50wt%, be preferably 5wt%～40wt%, hole transporting material and electron transport materials are expressed as 1wt%～50wt% with their total, be preferably 5wt%～40wt%, the content of macromolecular compound of the present invention is 99wt%～20wt%.

Institute's blended hole transporting material, electron transport materials, luminescent material can use known low molecular compound, the luminous complex compound of triplet state or macromolecular compound, but the preferred macromolecular compound that uses.Hole transporting material as macromolecular compound, electron transport materials and luminescent material can example illustrate WO99/139692, WO99/48160, GB2340304A, WO00/53656, WO01/19834, WO00/55927, GB2348316, WO00/46321, WO00/06665, WO99/54943, WO99/54385, US5777070, WO98/06773, WO97/05184, WO00/35987, WO00/53655, WO01/34722, WO99/24526, WO00/22027, WO00/22026, WO98/27136, US573636, WO98/21262, US5741921, WO97/09394, WO96/29356, WO96/10617, EP0707020, WO95/07955, Te Kaiping 2001-181618, Te Kaiping 2001-123156, Te Kaiping 2001-3045, Te Kaiping 2000-351967, Te Kaiping 2000-303066, Te Kaiping 2000-299189, Te Kaiping 2000-252065, Te Kaiping 2000-136379, Te Kaiping 2000-104057, Te Kaiping 2000-80167, Te Kaiping 10-324870, Te Kaiping 10-114891, Te Kaiping 9-111233, the poly-fluorenes of being announced among the Te Kaiping 9-45478 etc., its derivative and multipolymer, polyarylene, its derivative and multipolymer, the polyarylene vinylidene, its derivative and multipolymer, (being total to) polymkeric substance of aromatic amine and derivative thereof.

As the fluorescent material of low molecular compound, for example can use metal complex, aromatic amine, tetraphenyl cyclopentadiene or derivatives thereof or the tetraphenylbutadiene or derivatives thereof etc. of pigments such as naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine system, xanthene system, coumarin series, cyanine system, oxine or derivatives thereof.

Specifically, for example can use the spy to open the material known of putting down in writing in clear 57-51781 number, identical 59-194393 communique such as material.

As the luminous complex compound of triplet state, for example can enumerate with Ir (ppy) 3, the Btp of iridium as central metal ₂Ir (acac), with platinum as the PtOEP of central metal, with europium as Eu (TTA) 3phen of central metal etc.

As the luminous complex compound of triplet state, specifically, for example be recorded in Nature, (1998), 395,151, Appl.Phys.Lett. (1999), 75 (1), 4, Proc.SPIE-Int.Soc.Opt.Eng. (2001), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J.Am.Chem.Soc., (2001), 123,4304, Appl.Phys.Lett. (1997), 71 (18), 2596, Syn.Met., (1998), 94 (1), 103, Syn.Met., (1999), 99 (2), 1361, Adv.Mater., (1999), 11 (10), 852, Jpn.J.Appl.Phys., in 34,1883 (1995) etc.

Composition of the present invention contains at least a material and the macromolecular compound of the present invention that is selected from hole transporting material, electron transport materials, the luminescent material, can be used as luminescent material or charge transport material and uses.

This is selected from containing ratio and can determining according to purposes of at least a material in hole transporting material, electron transport materials, the luminescent material and macromolecular compound of the present invention.

As other embodiment of the present invention, can the polymeric composition that contain macromolecular compound of the present invention more than 2 kinds be shown example.

The thickness of the luminescent layer that is had as polymer LED of the present invention, optimum value be according to used material and difference, as long as so that driving voltage and luminous efficiency reach the mode of the value of appropriateness selects.For example be 1nm to 1 μ m, preferred 2nm～500nm, more preferably 5nm～200nm.

As the formation method of luminescent layer, the method by solution film forming for example can routine be shown.In the making of polymer LED, the macromolecular compound of the application of the invention, not only under situation by solution film forming, can behind this solution of coating, solvent seasoning be removed, and under the situation of having mixed charge transport material or luminescent material, also can use identical method, highly beneficial on making.

As method, can use coating methods such as spin coating method, casting (casting), micro-intaglio plate cladding process, intaglio plate cladding process, excellent cladding process, rolling method, coiling rod (wire bar) cladding process, immersion coating method, spray application method, silk screen print method, flexographic printing method, offset printing method, ink jet printing method by solution film forming.Pattern forms or the viewpoint of the multiple color of separate application is considered, print processes such as preferred silk screen print method, flexographic printing method, offset printing method, ink jet printing method from carrying out easily.

As middle solutions employed such as print processes, can use ink composite of the present invention.

As long as ink composite of the present invention contains at least a macromolecular compound of the present invention and solvent, except macromolecular compound of the present invention, can also contain additives such as hole transporting material, electron transport materials, luminescent material, stablizer in addition.

Ink composite of the present invention is aqueous when element is made, and typical situation is meant, is aqueous material normal pressure (i.e. 1 normal atmosphere), 25 ℃.

In addition, ink composite of the present invention not necessarily needs for coloured.

The ratio of the macromolecular compound of the present invention in this ink composite is that the gross weight with respect to removing this ink composite after desolvating is generally 20wt%～100wt%, is preferably 40wt%～100wt%.

In addition, the ratio of the solvent in the ink composite is 1wt%～99.9wt% with respect to the gross weight of this ink composite, is preferably 60wt%～99.9wt%, more preferably 90wt%～99.8wt%.

This ink composite (solution) though viscosity according to print process and difference, yet solution such as ink jet printing method via the situation in the blowoff under, obstruction or flight in order to prevent to spray are crooked, viscosity is preferably the scope that is in 1～20mPas at 25 ℃.

As solvent used in the ink composite of the present invention, can chloroform, methylene dichloride, 1, chlorine series solvents such as 2-ethylene dichloride, vinyl trichloride, chlorobenzene, orthodichlorobenzene be shown example; Ether such as tetrahydrofuran (THF), dioxane series solvent; Aromatic hydrocarbons such as toluene, dimethylbenzene series solvent; Aliphatic hydrocarbon series solvents such as hexanaphthene, methylcyclohexane, Skellysolve A, normal hexane, normal heptane, octane, positive nonane, n-decane; Ketone series solvents such as acetone, methylethylketone, pimelinketone; Ester series solvents such as ethyl acetate, butylacetate, ethyl cellosolve acetate; Ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, glycol dimethyl ether, propylene glycol, methylene diethyl ether, triglycol list ether, glycerine, 1, polyvalent alcohol and derivatives thereof such as 2-hexylene glycol; Pure series solvents such as methyl alcohol, ethanol, propyl alcohol, Virahol, hexalin; Sulfone series solvents such as methyl-sulphoxide; N-N-methyl-2-2-pyrrolidone N-, N, acid amides series solvents such as dinethylformamide.In addition, in the middle of these solvents, preferably contain more than one following organic solvents, that is, have the structure that comprises at least 1 above phenyl ring, and fusing point is below 0 ℃, boiling point is more than 100 ℃.

As solvent types, from the solvability of macromolecular compound of the present invention to organic solvent, homogeneity during film forming, viewpoints such as viscosity characteristics are considered, optimization aromatic hydrocarbon system solvent, the aliphatic hydrocarbon series solvent, the ester series solvent, the ketone series solvent, preferred toluene, dimethylbenzene, ethylbenzene, diethylbenzene, Three methyl Benzene, , n-propylbenzene, isopropyl benzene, n-butylbenzene, isobutyl-benzene, sec-butylbenzene, methyl-phenoxide, phenetole, the 1-methylnaphthalene, hexanaphthene, pimelinketone, phenylcyclohexane, bicyclohexyl, cyclohexenyl hexamethylene ketone, the n-heptyl hexanaphthene, the n-hexyl hexanaphthene, methyl benzoic acid ester, 2-propyl group pimelinketone, 2-heptanone, the 3-heptanone, dipropyl ketone, methyln-hexyl ketone, methyl n-heptyl ketone, the 2-decanone, dicyclohexyl ketone more preferably contains dimethylbenzene, methyl-phenoxide, , phenylcyclohexane, at least a in the middle of the bicyclohexyl methyl benzoic acid ester.

Consider that from viewpoints such as the viewpoint of film-forming properties or element characteristics the solvent types in the ink composite is preferably more than 2 kinds, more preferably 2～3 kinds, more preferably 2 kinds.

Contain in ink composite under the situation of 2 kinds of solvents, a kind of solvent wherein also can be solid state under 25 ℃.Consider from the viewpoint of film-forming properties, preferred a kind of solvent is that boiling point is at the solvent more than 180 ℃, another kind of solvent be boiling point at the solvent below 180 ℃, more preferably a kind of solvent be boiling point at the solvent more than 200 ℃, another kind of solvent is that boiling point is at the solvent below 180 ℃.In addition, consider from the viewpoint of viscosity, preferably in 2 kinds of solvents, under 60 ℃, all dissolve the above macromolecular compound of the present invention of 0.2wt%, preferably in a kind of solvent in the middle of 2 kinds of solvents, at 25 ℃ of macromolecular compounds of the present invention that dissolve more than the 0.2wt%.

Contain in ink composite under the situation of 3 kinds of solvents, 1～2 kind of solvent wherein also can be a solid state at 25 ℃.Consider from the viewpoint of film-forming properties, at least a solvent in the middle of preferred 3 kinds of solvents is that boiling point is at the solvent more than 180 ℃, at least a solvent is that boiling point is at the solvent below 180 ℃, more preferably at least a solvent in the middle of 3 kinds of solvents be boiling point at the solvent below 300 ℃ more than 200 ℃, at least a solvent is that boiling point is at the solvent below 180 ℃.In addition, consider from the viewpoint of viscosity, preferably in 2 kinds of solvents in the middle of 3 kinds of solvents, under 60 ℃, the above macromolecular compound of the present invention of dissolving 0.2wt% is preferably in a kind of solvent in the middle of 3 kinds of solvents, at 25 ℃ of macromolecular compounds of the present invention that dissolve more than the 0.2wt%.

In ink composite, contain under the situation of solvent more than 2 kinds, consider from the viewpoint of viscosity and film-forming properties, 40～90wt% of the weight of whole solvents that the preferred the highest solvent of boiling point is an ink composite, more preferably 50～90wt%, more preferably 65～85wt%.

As ink composite of the present invention, consider from the viewpoint of viscosity and film-forming properties, preferably the composition that constitutes by methyl-phenoxide and bicyclohexyl, the composition that constitutes by methyl-phenoxide and phenylcyclohexane, the composition that constitutes by dimethylbenzene and bicyclohexyl, the composition that constitutes by dimethylbenzene and phenylcyclohexane, the composition that constitutes by  and methyl benzoic acid ester.

Ink composite of the present invention in the middle of the additive that can contain, as hole transporting material, can enumerate Polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof, the polyorganosiloxane ramification that in side chain or main chain, has aromatic amine, pyrazoline derivative, arylamines derivative, stilbene derivative, triphenyl diamine derivative, polyaniline or derivatives thereof, Polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly-(to phenylene vinylidene) or derivatives thereof or poly-(2, the inferior thienyl vinylidene of 5-) or derivatives thereof.

As electron transport materials, can Ju Chu oxadiazole derivative, metal complex, poly quinoline or derivatives thereof, polyquinoxaline or derivatives thereof, the poly-fluorenes or derivatives thereof of anthraquinone bismethane or derivatives thereof, benzoquinones or derivatives thereof, naphthoquinones or derivatives thereof, anthraquinone or derivatives thereof, four cyano anthraquinone bismethane or derivatives thereof, fluorene derivatives, phenylbenzene dicyano ethene or derivatives thereof, phenoquinone derivative or oxine or derivatives thereof.

As luminescent material, can enumerate metal complex, aromatic amine, tetraphenyl cyclopentadiene or derivatives thereof or the tetraphenylbutadiene or derivatives thereof etc. of pigments such as naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine system, xanthene system, coumarin series, cyanine system, oxine or derivatives thereof.

Ink composite of the present invention (solution) also can contain to be useful on and regulate viscosity and/or capillary additive except macromolecular compound of the present invention.As this additive, as long as suitably be used in combination high-molecular weight macromolecular compound (thickening material) or the Weak solvent, the low-molecular-weight compound that is used to reduce viscosity that are used to improve viscosity, be used to reduce capillary tensio-active agent etc.

As above-mentioned high-molecular weight macromolecular compound, so long as with macromolecular compound of the present invention similarly be solubility in solvent, and can not hinder getting final product of luminous or charge transport.For example can use the big material of the central molecular weight of high-molecular weight polystyrene, polymethylmethacrylate or macromolecular compound of the present invention etc.Weight-average molecular weight is preferably more than 500,000, more preferably more than 1,000,000.

Also Weak solvent can be used as thickening material.That is,, just can improve viscosity by adding Weak solvent slightly with respect to the solids component in the solution.Under the situation of adding Weak solvent for this purpose, as long as in the scope that the solids component in solution can not be separated out, the kind and the addition of selective solvent get final product.

In addition, in order to improve storage stability, ink composite of the present invention (solution) can also contain antioxidant except macromolecular compound of the present invention.As antioxidant, so long as with macromolecular compound of the present invention similarly be solubility in solvent, and can not hinder the material of luminous or charge transport to get final product, can example phenol being shown is antioxidant, phosphorous antioxidant etc.

Consider that from the deliquescent viewpoint of macromolecular compound of the present invention to solvent the difference of the solubility parameter of solvent and the solubility parameter of macromolecular compound is preferably below 10, more preferably below 7.

The solubility parameter of solvent and the solubility parameter of macromolecular compound of the present invention can utilize the method for record in " solvent handbook (talk society periodical, 1976) " to try to achieve.

As polymer LED of the present invention, can enumerate at the polymer LED that is provided with electron supplying layer between negative electrode and the luminescent layer, at the polymer LED that is provided with hole transporting layer between anode and the luminescent layer, be provided with electron supplying layer between negative electrode and the luminescent layer and between anode and luminescent layer, be provided with polymer LED of hole transporting layer etc.

For example, can following structure a)～d) be shown example specifically.

A) anode/luminescent layer/negative electrode

B) anode/hole transporting layer/luminescent layer/negative electrode

C) anode/luminescent layer/electron supplying layer/negative electrode

D) anode/hole transporting layer/luminescent layer/electron supplying layer/negative electrode

(here ,/represent that each layer is adjacent to the meaning of lamination.Below identical.)

As polymer LED of the present invention, also be included in the LED that contains macromolecular compound of the present invention in hole transporting layer and/or the electron supplying layer.

Macromolecular compound of the present invention is being used under the situation of hole transporting layer, macromolecular compound of the present invention is preferably the macromolecular compound that contains the cavity conveying base, as its concrete example, can example illustrate with the multipolymer of aromatic amine, with the multipolymer of Stilbene etc.

In addition, macromolecular compound of the present invention is being used under the situation of electron supplying layer, macromolecular compound of the present invention is preferably the macromolecular compound that contains the electron transport group, as its concrete example, can example illustrate with the multipolymer of oxadiazole, with the multipolymer of triazole, with the multipolymer of quinoline, with the multipolymer of quinoxaline, with the multipolymer of diazosulfide etc.

Have under the situation of hole transporting layer at polymer LED of the present invention, as used hole transporting material, can Polyvinyl carbazole or derivatives thereof, polysilane or derivatives thereof, the polyorganosiloxane ramification that has aromatic amine in side chain or main chain, pyrazoline derivative, arylamines derivative, stilbene derivative, triphenyl diamine derivative, polyaniline or derivatives thereof, Polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly-(to phenylene vinylidene) or derivatives thereof or poly-(2, the inferior thienyl vinylidene of 5-) or derivatives thereof be shown example.

Specifically, as this hole transporting material, the spy can example be shown open clear 63-70257 communique, identical 63-175860 communique, spy and open the material put down in writing in flat 2-135359 communique, identical 2-135361 communique, identical 2-209988 communique, identical 3-37992 communique, the identical 3-152184 communique etc.

In the middle of them, as hole transporting material used in hole transporting layer, preferably polyethylene base carbazole or derivatives thereof, the polysilane or derivatives thereof, the polyorganosiloxane ramification that in side chain or main chain, has the aromatic amines compound group, the polyaniline or derivatives thereof, the Polythiophene or derivatives thereof, poly-(to phenylene vinylidene) or derivatives thereof or poly-(2, the inferior thienyl vinylidene of 5-) polymer hole transporting material such as or derivatives thereof, more preferably Polyvinyl carbazole or derivatives thereof, the polysilane or derivatives thereof, the polyorganosiloxane ramification that in side chain or main chain, has aromatic amine.

In addition, as the hole transporting material of low molecular compound, can pyrazoline derivative, arylamines derivative, stilbene derivative, triphenyl diamine derivative be shown example.Under the situation of low molecule hole transporting material, preferably it is scattered in the polymer binder and uses.

As institute's blended polymer binder, preferably can obviously not hinder the tackiness agent of charge transport, can preferably use the tackiness agent not strong in addition to the absorption of visible light.As this polymer binder, can poly-(N-vinylcarbazole), polyaniline or derivatives thereof, Polythiophene or derivatives thereof, poly-(to phenylene vinylidene) or derivatives thereof, poly-(2, the inferior thienyl vinylidene of 5-) or derivatives thereof, polycarbonate, polyacrylic ester, polymethyl acrylate, polymethylmethacrylate, polystyrene, polyvinyl chloride, polysiloxane etc. be shown example.

The Polyvinyl carbazole or derivatives thereof for example can utilize cationoid polymerisation or radical polymerization is incompatible obtains by vinyl monomer.

As the polysilane or derivatives thereof, the compound put down in writing in chemistry summary (Chem.Rev.) the 89th volume, 1359 pages (1989), the English Patent GB2300196 communique specification sheets etc. can example be shown.The method that synthetic method also can be used in them to be put down in writing, however the Kipping method especially preferably used.

Therefore the polysiloxane or derivatives thereof preferably uses the material that has the structure of above-mentioned low molecule hole transporting material in side chain or main chain owing to do not have cavity conveying basically in the siloxane backbone structure.Can example be illustrated in the material that has the aromatic amine of cavity conveying in side chain or the main chain especially.

Film forming method for hole transporting layer is not particularly limited, but if low molecule hole transporting material, and the film forming method of mixing solutions by itself and polymer binder then can example be shown.In addition if the polymer hole transporting material then can routine illustrate the method by solution film forming.

As by solvent used in the solution film forming,, just be not particularly limited so long as dissolve the solvent of hole transporting material.As this solvent, can chlorine series solvents such as chloroform, methylene dichloride, ethylene dichloride be shown example; Ether series solvents such as tetrahydrofuran (THF); Aromatic hydrocarbons such as toluene, dimethylbenzene series solvent; Ketone such as acetone, methylethylketone series solvent; Ester series solvents such as ethyl acetate, butylacetate, ethyl cellosolve acetate.

As method, can use coating methods such as spin coating method, the casting of solution, micro-intaglio plate cladding process, intaglio plate cladding process, excellent cladding process, rolling method, coiling rod cladding process, immersion coating method, spray application method, silk screen print method, flexographic printing method, offset printing method, ink jet printing method by solution film forming.

As the thickness of hole transporting layer, optimum value is according to used material and difference, as long as so that driving voltage and luminous efficiency reach the mode of the value of appropriateness selects, yet need can not produce the thickness of pin hole at least, when too thick, then the driving voltage of element uprises, thereby not ideal enough.So, as the thickness of this hole transporting layer, for example be 1nm to 1 μ m, be preferably 2nm～500nm, more preferably 5nm～200nm.

Have under the situation of electron supplying layer at polymer LED of the present invention, as used electron transport materials, can use material known, can the oxadiazole derivative be shown example, anthraquinone bismethane or derivatives thereof, the benzoquinones or derivatives thereof, the naphthoquinones or derivatives thereof, the anthraquinone or derivatives thereof, four cyano anthraquinone bismethane or derivatives thereof, fluorene derivatives, phenylbenzene dicyano ethene or derivatives thereof, the metal complex of phenoquinone derivative or oxine or derivatives thereof, the poly quinoline or derivatives thereof, the polyquinoxaline or derivatives thereof, poly-fluorenes or derivatives thereof etc.

The spy specifically, can example be shown to open clear 63-70257 communique, identical 63-175860 communique, spy and opens the material put down in writing in flat 2-135359 communique, identical 2-135361 communique, identical 2-209988 communique, identical 3-37992 communique, the identical 3-152184 communique etc.

The metal complex of You Xuan oxadiazole derivative, benzoquinones or derivatives thereof, naphthoquinones or derivatives thereof, anthraquinone or derivatives thereof or oxine or derivatives thereof, poly quinoline or derivatives thereof, polyquinoxaline or derivatives thereof, poly-fluorenes or derivatives thereof etc. in the middle of them, more preferably 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-1,3,4-oxadiazole, benzoquinones, anthraquinone, three (oxine) aluminium, poly quinoline.

One-tenth embrane method as electron supplying layer is not particularly limited, yet if low molecular electronic is carried material, then can example illustrate by the vacuum vapour deposition of powder or the film forming method that begins by solution or molten state, if the polymer electron transport materials then can example illustrate by solution or the film forming method of molten state.By solution or molten state film forming the time, also can be also with above-mentioned polymer binder.

As solvent used in the film forming by solution, so long as the solvent of dissolving electron transport materials and/or polymer binder just is not particularly limited.As this solvent, can chlorine series solvents such as chloroform, methylene dichloride, ethylene dichloride be shown example; Ether series solvents such as tetrahydrofuran (THF); Aromatic hydrocarbons such as toluene, dimethylbenzene series solvent; Ketone such as acetone, methylethylketone series solvent; Ester series solvents such as ethyl acetate, butylacetate, ethyl cellosolve acetate.

As film, can use coating methods such as spin coating method, casting, micro-intaglio plate cladding process, intaglio plate cladding process, excellent cladding process, rolling method, coiling rod cladding process, immersion coating method, spray application method, silk screen print method, flexographic printing method, offset printing method, ink jet printing method by solution or molten state.

As the thickness of electron supplying layer, optimum value is according to used material and difference, as long as so that driving voltage and luminous efficiency reach the mode of the value of appropriateness selects, yet need can not produce the thickness of pin hole at least, when too thick, then the driving voltage of element uprises, thereby not ideal enough.So, as the thickness of this electron supplying layer, for example be 1nm to 1 μ m, be preferably 2nm～500nm, more preferably 5nm～200nm.

In addition, in the middle of the charge transport layer that is adjacent to be provided with electrode, have the function of improvement from the efficient of electrode iunjected charge, and the layer with the driving voltage effect that reduces element sometimes-as property ground spy be called electric charge injection layer (hole injection layer, electron injecting layer).

In addition, inject in order to improve with the connecting airtight property of electrode or the electric charge that improves from electrode, also can be adjacent to be provided with above-mentioned electric charge injection layer or the insulation layer of thickness below 2nm with electrode, in addition, for the connecting airtight property that improves the interface or prevent to mix etc., also can insert thin buffer layer at the interface of charge transport layer or luminescent layer.

For the order of the layer of institute's lamination or the thickness of number and each layer, can consider luminous efficiency or component life and suitably use.

Macromolecular compound of the present invention also can be made organic semiconductor thin film and use as the polymer field effect transistor.As the structure of polymer field effect transistor, normally with the active coating that constitutes by polymer mutually ground connection source electrode and drain electrode are set, press from both sides then every the insulation layer that joins with active coating grid be set get final product.

The polymer field effect transistor is formed on the supporting substrate usually.As the material of supporting substrate, so long as do not hinder characteristic, just be not particularly limited as field effect transistor, can use glass substrate, flexible film substrate or plastic base.

Field effect transistor can utilize known method, and for example special method of opening flat 5-110069 communique record is made.

In the formation active coating, with an organic solvent the high molecular way of solubility is very favorable on making, thereby preferred.As by the film that in organic solvent, has dissolved high molecular solution, can use coating methods such as spin coating method, casting, micro-intaglio plate cladding process, intaglio plate cladding process, excellent cladding process, rolling method, coiling rod cladding process, immersion coating method, spray application method, silk screen print method, flexographic printing method, offset printing method, ink jet printing method.

Preferably after making the polymer field effect transistor, the sealing polymer field effect transistor that is sealed to form.Like this, just polymer field effect transistor and atmosphere can be cut off, suppress the reduction of the characteristic of polymer field effect transistor.

As the method for sealing, the method for can enumerate the method that covers with UV cured resin, heat reactive resin or inorganic SiONx film etc., sheet glass or film being fitted with UV cured resin, heat reactive resin etc. etc.In order to carry out effectively and atmospheric partition, to make behind the polymer field effect transistor preferably not to atmospheric exposure ground (for example in the exsiccant nitrogen atmosphere, vacuum medium) and carry out operation up to sealing.

Among the present invention, as the polymer LED that is provided with electric charge injection layer (electron injecting layer, hole injection layer), can enumerate with negative electrode be adjacent to be provided with electric charge injection layer polymer LED, be adjacent to be provided with the polymer LED of electric charge injection layer with anode.

For example, can enumerate following e specifically)～p) structure.

E) anode/electric charge injection layer/luminescent layer/negative electrode

F) anode/luminescent layer/electric charge injection layer/negative electrode

G) anode/electric charge injection layer/luminescent layer/electric charge injection layer/negative electrode

H) anode/electric charge injection layer/hole transporting layer/luminescent layer/negative electrode

I) anode/hole transporting layer/luminescent layer/electric charge injection layer/negative electrode

J) anode/electric charge injection layer/hole transporting layer/luminescent layer/electric charge injection layer/negative electrode

K) anode/electric charge injection layer/luminescent layer/electron supplying layer/negative electrode

L) anode/luminescent layer/electron supplying layer/electric charge injection layer/negative electrode

M) anode/electric charge injection layer/luminescent layer/electron supplying layer/electric charge injection layer/negative electrode

N) anode/electric charge injection layer/hole transporting layer/luminescent layer/electron supplying layer/negative electrode

O) anode/hole transporting layer/luminescent layer/electron supplying layer/electric charge injection layer/negative electrode

P) anode/electric charge injection layer/hole transporting layer/luminescent layer/electron supplying layer/electric charge injection layer/negative electrode

As the concrete example of electric charge injection layer, can the layer that contain electroconductive polymer be shown example; Be located between anode and the hole transporting layer, contain the layer of material of the ionization potential of intermediary value with hole transporting material contained in anode material and the hole transporting layer; Be located between negative electrode and the electron supplying layer, contain the intermediary value with electron transport materials contained in cathode material and the electron supplying layer electron affinity material the layer etc.

Above-mentioned electric charge injection layer be contain electroconductive polymer the layer situation under, the specific conductivity of this electroconductive polymer is preferably 10 ^-5S/cm above 10 ³Below, in order to reduce the leakage current between the light emitting pixel, more preferably 10 ^-5S/cm above 10 ²Below, further preferred 10 ^-5S/cm above 10 ¹Below.

Above-mentioned electric charge injection layer be contain electroconductive polymer the layer situation under, the specific conductivity of this electroconductive polymer is preferably 10 ^-5S/cm above 10 ³Below the S/cm, in order to reduce the leakage current between the light emitting pixel, more preferably 10 ^-5S/cm above 10 ²Below the S/cm, further preferred 10 ^-5S/cm above 10 ¹Below the S/cm.

As a rule, be made as 10 for specific conductivity with this electroconductive polymer ^-5S/cm above 10 ³Below, and an amount of ion that in this electroconductive polymer, mixes.

For adulterated ionic kind, if hole injection layer then is a negatively charged ion, if electron injecting layer then is a positively charged ion.As anionic example, can polystyrolsulfon acid radical ion, benzene sulfonamide acid ion, camphorsulfonic acid radical ion etc. be shown example, as cationic example, can lithium ion, sodium ion, potassium ion, TBuA ion etc. be shown example.

As the thickness of electric charge injection layer, for example be 1nm～100nm, preferred 2nm～50nm.

Used material in the electric charge injection layer is as long as suitably select according to its relation with the material of electrode or adjacent layer, can example polyaniline and derivative, Polythiophene and derivative thereof, polypyrrole and derivative thereof, polyhenylene vinylidene and derivative thereof be shown, gather inferior thiophene vinylidene and derivative, poly quinoline and derivative thereof, polyquinoxaline and derivative thereof, contain electroconductive polymers such as polymkeric substance that aromatic amine constructs in main chain or side chain, metal phthalocyanine (copper phthalocyanine etc.), carbon etc.

The insulation layer of thickness below 2nm is to have to make electric charge inject the layer of more easy function.As the material of above-mentioned insulation layer, can enumerate metal fluoride, metal oxide, organic insulation etc.As the polymer LED that is provided with the insulation layer of thickness below 2nm, can enumerate with negative electrode and be adjacent to be provided with thickness at the polymer LED of the insulation layer below the 2nm, be adjacent to be provided with the polymer LED of the insulation layer of thickness below 2nm with anode.

Specifically, can enumerate following q)～ab) structure.

Q) the thick insulation layer/luminescent layer/negative electrode below 2nm of anode/membrane

R) insulation layer/negative electrode of anode/luminescent layer/thickness below 2nm

S) the thick insulation layer/negative electrode of insulation layer/luminescent layer/thickness below 2nm below 2nm of anode/membrane

T) the thick insulation layer/hole transporting layer/luminescent layer/negative electrode below 2nm of anode/membrane

U) insulation layer/negative electrode of anode/hole transporting layer/luminescent layer/thickness below 2nm

The v) thick insulation layer/negative electrode of insulation layer/hole transporting layer/luminescent layer/thickness below 2nm below 2nm of anode/membrane

W) the thick insulation layer/luminescent layer/electron supplying layer/negative electrode below 2nm of anode/membrane

X) insulation layer/negative electrode of anode/luminescent layer/electron supplying layer/thickness below 2nm

Y) the thick insulation layer/negative electrode of insulation layer/luminescent layer/electron supplying layer/thickness below 2nm below 2nm of anode/membrane

Z) the thick insulation layer/hole transporting layer/luminescent layer/electron supplying layer/negative electrode below 2nm of anode/membrane

Aa) insulation layer/negative electrode of anode/hole transporting layer/luminescent layer/electron supplying layer/thickness below 2nm

Ab) the thick insulation layer/negative electrode of insulation layer/hole transporting layer/luminescent layer/electron supplying layer/thickness below 2nm below 2nm of anode/membrane

Form the substrate of polymer LED of the present invention so long as the substrate that does not change gets final product in formation electrode, the organic layer of formation, for example can glass, plastics, macromolecule membrane, silicon substrate etc. be shown example.Under the situation of opaque substrate, the electrode of reverse side is preferably transparent or semitransparent.

As a rule, the anode that had of polymer LED of the present invention and at least one side of negative electrode are transparent or semitransparent.Anode side is preferably transparent or semitransparent.

As this anodic material, can use the metal oxide film of electroconductibility, translucent metallic film etc.Specifically, can use Indium sesquioxide, zinc oxide, stannic oxide and as they complex body indium tin oxide (ITO), use film (NESA etc.) that the conductive glass that is made of indium-zinc oxide etc. makes, gold, platinum, silver, copper etc., preferably ITO, indium-zinc oxide, stannic oxide.As making method, can enumerate vacuum vapour deposition, sputtering method, ion plating method, plating method etc.In addition, as this anode, also can use the organic nesa coating of polyaniline or derivatives thereof, Polythiophene or derivatives thereof etc.

The anodic thickness can consider the perviousness of light and specific conductivity and suitably select, for example be 10nm to 10 μ m, be preferably 20nm～1 μ m, more preferably 50nm～500nm.

In addition, more easy for electric charge is injected on anode, the layer that is made of phthalocyanine derivates, electroconductive polymer, carbon etc. also can be set; Or the layer of the average film thickness that constitutes by metal oxide or metal fluoride, organic insulation etc. below 2nm.

As used cathode material among the polymer LED of the present invention, the preferred little material of work function.For example can enumerate metals such as lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, aluminium, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium; And the alloy more than 2 kinds in the middle of them; Perhaps in the middle of them more than a kind with gold and silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin in the middle of the alloy more than a kind; Graphite or compound between graphite layers etc.As the example of alloy, can enumerate magnesium-silver alloys, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloys, lithium-aluminium alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminium alloy etc.Also negative electrode can be made as the stromatolithic structure more than 2 layers.

The thickness of negative electrode can consider specific conductivity or weather resistance and suitably select, for example be 10nm to 10 μ m, be preferably 20nm～1 μ m, more preferably 50nm～500nm.

As the making method of negative electrode, can use the laminating of vacuum vapour deposition, sputtering method or thermo-compressed metallic film etc.In addition; between negative electrode and organic matter layer, the layer that is made of electroconductive polymer also can be set, or the layer of the average film thickness that constitutes by metal oxide or metal fluoride, organic insulation etc. below 2nm; after negative electrode is made, the protective layer of this polymer of protection LED can be installed also.In order to use this polymer LED steadily in the long term, protective layer and/or protection outer cover preferably are installed, avoid external influence with protecting component.

As this protective layer, can use macromolecular compound, metal oxide, metal fluoride, metal boride etc.In addition,, can use sheet glass, plastic plate that low permeability rate handles etc. has been implemented on the surface as the protection outer cover, preferred use with this outer cover with heat reactive resin or light-cured resin with the device substrate applying airtight method.If use spacer block to keep the space, be easy to then prevent that element from sustaining damage.If to the rare gas element of this space nitrogen injection or argon gas and so on, then can prevent the oxidation of negative electrode, in addition, by siccative such as barium oxide is set, then can easily be suppressed at the moisture infringement element that adsorbs in the manufacturing process in this space.In the middle of them, preferably adopt any above method.

Polymer LED of the present invention can be used for flat light source, segmentation display unit, dot matrix display unit, liquid crystal indicator (for example backlight of liquid crystal indicator).

Planar luminous in order to use polymer LED of the present invention to obtain, as long as planar anode is disposed with negative electrode with overlapping.In addition, in order to obtain the luminous of pattern-like, the method for the mask of the window that is provided with pattern-like on the surface of above-mentioned planar luminous element is arranged, the organic matter layer utmost point heavy back of non-luminescent part is formed and the method that makes it non-luminous method in fact, any one party or both sides' electrode of male or female are made pattern-like.By forming pattern with the arbitrary method in them, with the On/OFF ground configuration independently of some electrode, just can obtain can display digit or literal, the simple display element of the sectional type of mark etc.In addition, in order to make the dot matrix element, as long as anode and negative electrode are all made striated and configuration orthogonally.Utilize the method for method, use colour filter or the fluorescence conversion filter of the different high molecular fluorescent body of the multiple glow color of separate application, just can realize that partial colour shows, broken colour shows.The dot matrix element both can be a passive drive, also can be with combinations such as TFT and carry out active driving.These display elements can be used as the display unit such as view finder of computer, TV, carried terminal, portable phone, navigator, pick up camera and use.

In addition, above-mentioned planar luminous element is that luminous is slim, can be used as flat light source that the backlight of liquid crystal indicator uses or planar illumination light source and uses suitably.In addition, if use flexible substrate, then also can be used as curved light source or display unit and use.

Below, provide embodiment in order in further detail the present invention to be described, yet the present invention is not limited to them.

(number-average molecular weight and weight-average molecular weight)

Here, for number-average molecular weight and weight-average molecular weight, utilize GPC (Shimadzu Seisakusho Ltd.'s system: LC-10Avp) tried to achieve the number-average molecular weight and the weight-average molecular weight of polystyrene conversion.The polymer dissolution measured in tetrahydrofuran (THF), is made it to reach the concentration of about 0.5wt%, in GPC, inject 50 μ L.The mobile phase of GPC is used tetrahydrofuran (THF), with the flow rate of 0.6mL/min.Chromatographic column is that 2 TSKgel SuperHM-H (Toso system) and 1 TSKgel SuperH2000 (Toso system) are connected in series.In detector, used differential refractive index detector (Shimadzu Seisakusho Ltd.'s system: RID-10A).

(fluorescence spectrum)

The mensuration of fluorescence spectrum is to carry out with following method.On quartz, rotate the 0.8wt% solution of coated polymer, made the film of polymkeric substance.Wavelength with 350nm excites this film, uses spectrophotofluorometer (the hole field makes made Fluorolog) to measure fluorescence spectrum.In order to obtain the relative fluorescence intensity in the film, as standard, the fluorescence spectrum integration that will draw with wave number in the spectrometry scope uses spectrophotometer (Varian corporate system Cary5E) to measure with the intensity of the Raman lines of water.Try to achieve the value after removing with the absorbancy under the excitation wavelength.

(HPLC mensuration)

Determining instrument: Agilent 1100LC

Condition determination: L-Column ODS, 5 μ m, 2.1mm * 150mm;

A liquid: acetonitrile, B liquid: THF

Gradient

B liquid:

0％(60min.)→10％up/min→100％(10min)、

Sample concentration: 5.0mg/mL (THF solution),

Injection rate: 1 μ L

Detect wavelength: 350nm

Synthesis example 1

(the 1-bromo-4-tertiary butyl-2,6-dimethyl benzene synthetic)

Under inert atmosphere, in the there-necked flask of 500ml, add acetate 225g, add the 5-tertiary butyl-m-xylene.Next after having added bromine 31.2g, reacted 3 hours down at 15～20 ℃.

Reaction solution is added in the 500ml water, filter the precipitation of separating out.Clean 2 times with 250ml water, obtained white solid 34.2g.

＜N, N '-phenylbenzene-N, N '-two (the 4-tertiary butyl-2,6-3,5-dimethylphenyl)-1,4-phenylenediamine synthetic 〉

Under inert atmosphere, in the there-necked flask of 100ml, add the dehydrated toluene 36ml outgased, add three (tertiary butyl) phosphine 0.63g.Next add three (dibenzalacetone) two palladium 0.41g, the 1-bromo-4-tertiary butyl-2,6-dimethyl benzene 9.6g, tert.-butoxy sodium 5.2g, N, N '-phenylbenzene-1 is behind the 4-phenylenediamine 4.7g, 100 ℃ of reactions 3 hours.

Reaction solution is added in the 300ml saturated aqueous common salt, is about 50 ℃ chloroform 300ml extraction with heating.Distillation is added toluene 100ml after removing and desolvating, and is heated to the solid dissolving, and behind the naturally cooling, filtering-depositing has obtained white solid 9.9g.

＜N, N '-two (4-bromophenyl)-N, N '-two (the 4-tertiary butyl-2,6-3,5-dimethylphenyl)-1,4-phenylenediamine synthetic 〉

Under inert atmosphere, in the there-necked flask of 100ml, add dehydration N, dinethylformamide 350ml, dissolving N '-phenylbenzene-N, N '-two (the 4-tertiary butyl-2,6-3,5-dimethylphenyl)-1, behind the 4-phenylenediamine 5.2g, drip N-bromine succinimide 3.5g/N in ice bath, dinethylformamide solution makes it to react diel.

In reaction solution, add entry 150ml, filter the precipitation of separating out, clean 2 times, obtained white solid 4.4g with methyl alcohol 50ml.

¹H-NMR(300MHz/THF-d8)

δ(ppm)＝1.3[s，18H]、2.0[s，12H]、6.6～6.7[d，4H]、6.8～6.9[br，4H]、7.1[s，4H]、7.2～7.3[d，4H]

MS(FD ⁺)M ⁺738

Synthesis example 2

＜N, N '-phenylbenzene-N, N '-two (the 4-tertiary butyl-2,6-3,5-dimethylphenyl)-p-diaminodiphenyl synthetic 〉

Under inert atmosphere, in the there-necked flask of 300ml, add dehydrated toluene 1660ml, add N, N '-diphenylbenzidine 275.0g, the 4-tertiary butyl-2,6-dimethyl bromobenzene 449.0g.Next after having added three (dibenzalacetone) two palladium 7.48g, tert.-butoxy sodium 196.4g, add three (tertiary butyl) phosphine 5.0g.Thereafter, 105 ℃ of reactions 7 hours.

Add toluene 2000ml in reaction solution, cerite (cerite) filters, and after filtrate usefulness 1000ml water cleaning 3 times, is concentrated into 700ml.To wherein adding toluene and methanol (1: 1) solution 1600ml, filter the crystal of separating out, use washed with methanol.Obtained white solid 479.4g.

＜N, N '-two (4-bromophenyl)-N, N '-two (the 4-tertiary butyl-2,6-3,5-dimethylphenyl)-p-diaminodiphenyl synthetic 〉

Under inert atmosphere, in the 4730g chloroform, dissolved above-mentioned N, N '-phenylbenzene-N, N '-two (the 4-tertiary butyl-2, the 6-3,5-dimethylphenyl)-p-diaminodiphenyl 472.8g after, under shading and ice bath, N-bromine succinimide 281.8g is divided into 12 parts of usefulness and added in 1 hour, reacted 3 hours.

In reaction solution, add chloroform 1439ml, filter, the chloroformic solution of filtrate is cleaned with 5% Sulfothiorine 2159ml, distill and remove toluene, obtained white crystal.With the white crystal of gained toluene and methanol recrystallization, obtained white crystal 678.7g.

MS(APCI(+))：(M+H) ⁺815.2

Synthesizing of embodiment 1＜compd B 〉

Synthesizing of＜compd A 〉

(compd A)

In reaction vessel, add ion exchanged water 31ml, when stirring, little by little add sodium hydroxide 29g (727mmol), fully dissolving.To use argon replaces in the system, add toluene 30ml and 1,2,3,10b-tetrahydrofluoranthene 5.0g (24mmol) stirs and dissolves.Next add Tetrabutylammonium bromide 2.3g (7.3mmol) and n-octyl bromide 9.4g (48mmol), 40 ℃ of reactions 3 hours.With toluene and moisture liquid, after the organic layer extraction, use dried over sodium sulfate.Distillation by refining as the silica gel chromatography that launches solvent in order to hexane, has obtained flaxen crystal 6 .45g after removing and desolvating.

MS(APCI(+))：318([M+H] ⁺)

¹H-NMR(300MHz/CDCl ₃)δ7.69(1H，d)、7.50(1H，d)、7.40(1H，d)、7.34～7.22(3H，m)、7.03(1H，d)、3.07～2.96(1H，m)、2.77～2.70(1H，m)、2.37～2.18(2H，m)、1.95～1.74(3H，m)、1.27～1.04(11H，m)、0.84～0.69(5H，m)

(synthesizing of compd B)

(compd B)

In the reaction vessel of argon replaces, add compound A-45 .8g (18mmol) and acetate: the mixed solvent 115ml of methylene dichloride=1: 1, at room temperature stirring and dissolving.Next add tribromide benzyltrimethylammon.um 14g (36mmol), when stirring, add zinc chloride, dissolve fully until the tribromide benzyltrimethylammon.um.In with the HPCL following response, suitably add tribromide benzyltrimethylammon.um and zinc chloride.After reaction finishes, with chloroform and moisture liquid, the extraction organic layer, wash 2 times after, neutralize with wet chemical.After dried over sodium sulfate, distillation removes desolvates, in order to hexane as the silica gel chromatography that launches solvent refining after, from ethanol: recrystallization the mixed solvent of hexane=10: 1 has obtained compd B 5.08g as the powder of white.

MS(APPI(+))：476(M ⁺)

¹H-NMR(300MHz/CDCl ₃)δ7.53～7.43(4H，m)、7.33(1H，d)、2.90～2.84(2H，m)、2.33～2.22(2H，m)、2.05～1.96(1H，m)、1.83～1.64(2H，m)、1.32～1.05(13H，m)、0.85～0.81(3H，m)

Embodiment 2

(synthesizing of macromolecular compound 1)

With compd B (0.1g), 2, after 2 '-dipyridyl (0.089g) is dissolved among the tetrahydrofuran (THF) 19mL of dehydration, under nitrogen atmosphere, in this solution, add two (1, the 5-cyclooctadiene) nickel (0) { Ni (COD) ₂(0.156g), be warming up to 60 ℃, reacted 3 hours.This reaction solution is cooled to room temperature,, stirs after 1 hour, filter the precipitation of separating out, drying under reduced pressure to 25% ammoniacal liquor 1mL/ methyl alcohol 19mL/ ion exchanged water 19mL mixed solution and dripping.The output of the polymkeric substance of gained (being called macromolecular compound 1 later on) is 0.08g.In addition, the number-average molecular weight of polystyrene conversion is 2.9 * 10 ⁴, weight-average molecular weight is 6.1 * 10 ⁴

Embodiment 3

Synthesizing of＜macromolecular compound 2 〉

With compd B (0.557g), N, N '-two (4-bromophenyl)-N, N '-two (the 4-tertiary butyl-2, the 6-3,5-dimethylphenyl)-1,4-phenylenediamine (0.096g), 2,2 '-dipyridyl (0.548g) will carry out nitrogen replacement with the argon gas bubbling after being dissolved among the tetrahydrofuran (THF) 140mL of dehydration in the system.After being warming up to 60 ℃, under nitrogen atmosphere, in this solution, add two (1,5-dichloro octadiene) nickel (0) { Ni (COD) ₂(0.965g), stir, reacted 3 hours.This reaction solution is cooled to room temperature, to 25% ammoniacal liquor 5mL/ methyl alcohol 140mL/ ion exchanged water 140mL mixed solution and dripping, stirs after 1 hour, filter the precipitation of separating out, drying under reduced pressure is dissolved among the toluene 40ml.After the dissolving, add diatomite (radiolite) 1.6g, stirred 30 minutes, filter insolubles.The filtrate of gained is passed alumina column and make with extra care.Add 5.2% salt sour water 80mL then, stir after 3 hours, remove water layer.Add 4% ammoniacal liquor 80mL then, stir and remove water layer after 2 hours.Then in organic layer, add the about 80mL of ion exchanged water, stir after 1 hour, remove water layer., organic layer injected methyl alcohol 160ml, stirred 1 hour, filter the precipitation of separating out, drying under reduced pressure thereafter.The output of the polymkeric substance of gained (being called macromolecular compound 2 later on) is 0.33g.In addition, the number-average molecular weight of polystyrene conversion and weight-average molecular weight difference Mn=1.6 * 10 ⁴, Mw=8.7 * 10 ⁴

Embodiment 4

Synthesizing of＜macromolecular compound 3 〉

With compd B (0.433g), N, N '-two (4-bromophenyl)-N, N '-two (the 4-tertiary butyl-2,6-3,5-dimethylphenyl)-p-diaminodiphenyl (0.318g), 2,2 '-dipyridyl (0.548g) will carry out nitrogen replacement with the argon gas bubbling after being dissolved among the tetrahydrofuran (THF) 140mL of dehydration in the system.After being warming up to 60 ℃, under nitrogen atmosphere, in this solution, add two (1,5-dichloro octadiene) nickel (0) { Ni (COD) ₂(0.965g), stir, reacted 3 hours.This reaction solution is cooled to room temperature, to 25% ammoniacal liquor 5mL/ methyl alcohol 140mL/ ion exchanged water 140mL mixed solution and dripping, stirs after 1 hour, filter the precipitation of separating out, drying under reduced pressure is dissolved among the toluene 40ml.After the dissolving, add diatomite 1.6g, stirred 30 minutes, filter insolubles.The filtrate of gained is passed alumina column and make with extra care.Add 5.2% salt sour water 80mL then, stir after 3 hours, remove water layer.Add 4% ammoniacal liquor 80mL then, stir and remove water layer after 2 hours.Then in organic layer, add the about 80mL of ion exchanged water, stir after 1 hour, remove water layer., organic layer be injected in methyl alcohol 160ml, stirred 1 hour, filter the precipitation of separating out, drying under reduced pressure thereafter.The output of the polymkeric substance of gained (being called macromolecular compound 3 later on) is 0.46g.In addition, the number-average molecular weight of polystyrene conversion and weight-average molecular weight difference Mn=1.0 * 10 ⁴, Mw=6.1 * 10 ⁴

Embodiment 5

Synthesizing of＜macromolecular compound 4 〉

With compd B (0.588g), N, N '-two (4-bromophenyl)-N, N '-two (the 4-tertiary butyl-2,6-3,5-dimethylphenyl)-p-diaminodiphenyl (0.053g), 2,2 '-dipyridyl (0.548g) will carry out nitrogen replacement with the argon gas bubbling after being dissolved among the tetrahydrofuran (THF) 140mL of dehydration in the system.After being warming up to 60 ℃, under nitrogen atmosphere, in this solution, add two (1, the 5-cyclooctadiene) nickel (0) { Ni (COD) ₂(0.965g), stir, reacted 3 hours.This reaction solution is cooled to room temperature, to 25% ammoniacal liquor 5mL/ methyl alcohol 140mL/ ion exchanged water 140mL mixed solution and dripping, stirs after 1 hour, filter the precipitation of separating out, drying under reduced pressure is dissolved among the toluene 40ml.After the dissolving, add diatomite 1.6g, stirred 30 minutes, filter insolubles.The filtrate of gained is passed alumina column and make with extra care.Add 5.2% salt sour water 80mL then, stir after 3 hours, remove water layer.Add 4% ammoniacal liquor 80mL then, stir and remove water layer after 2 hours.Then in organic layer, add the about 80mL of ion exchanged water, stir after 1 hour, remove water layer., organic layer be injected in methyl alcohol 160ml, stirred 1 hour, filter the precipitation of separating out, drying under reduced pressure thereafter.The output of the polymkeric substance of gained (being called macromolecular compound 4 later on) is 0.31g.In addition, the number-average molecular weight of polystyrene conversion and weight-average molecular weight difference Mn=2.5 * 10 ⁴, Mw=1.2 * 10 ⁵

The making of embodiment 6＜EL element and performance 〉

(preparation of solution)

The macromolecular compound 2 that obtains in the above-mentioned explanation is dissolved in the toluene, and having made polymer concentration is the toluene solution of 1.8 weight %.

(making of EL element)

Adhered at the thickness that utilizes sputtering method with 150nm on the glass substrate of ITO film, use will gather (3,4) ethylidene dioxy thiophene/polystyrolsulfon acid (Bayer system, BaytronP AI4083) liquid that suspension liquid has filtered with 0.2 μ m membrane filter, utilize the rotation coating machine to form film with the thickness of 70nm, on hot plate with 200 ℃ of dryings 10 minutes.Then, use the toluene solution that obtains in the aforesaid operations, utilize the rotating speed film forming of rotation coating machine with 3400rpm.Thickness after the film forming is about 95nm.Then, with its 80 ℃ of dryings after 1 hour under reduced pressure, the lithium fluoride of the about 4nm of evaporation, as the calcium of the about 5nm of negative electrode evaporation, the aluminium of the about 80nm of evaporation has been made EL element then.And, arrive 1 * 10 in vacuum tightness ^-4After Pa is following, the evaporation of beginning metal.

(performance of EL element)

Apply voltage by the element to gained, the EL that has obtained having at 455nm the peak from this element is luminous.When with the EL glow color during with C.I.E. color coordinates value representation, x=0.150 then, y=0.128 demonstrates very good blueness.The luminous intensity of EL is proportional with current density basically.In addition, this element is can see luminous from 5.2V.Luminous efficiency (increase monotonously among the 0V～12V), and the value at 12V place demonstrates 1.02cd/m in the scope of being measured that applies voltage ²So higher efficient of ratio.

The making of embodiment 7＜EL element and performance 〉

(preparation of solution)

With the macromolecular compound 4 that obtains in the above-mentioned explanation with the ratio of 90 weight %, with macromolecular compound 3 with the ratio solvent of 10 weight % in toluene, having made polymer concentration is the toluene solution of 1.8 weight %.

(making of EL element)

The toluene solution that in using aforesaid operations, obtains, made EL element with the method for record among the embodiment 6 identically.And the rotating speed in the rotation coating machine of polymers soln is 3300rpm, and the thickness after the film forming of polymeric film is 95nm.

(performance of EL element)

Apply voltage by the element to gained, the EL that has obtained having at 425nm the peak from this element is luminous.When with the EL glow color during with C.I.E. color coordinates value representation, x=0.155 then, y=0.072 demonstrates very good blueness.The luminous intensity of EL is proportional with current density basically.In addition, this element is can see luminous from 5.5V.Luminous efficiency (increase monotonously among the 0V～12V), and the value at 12V place demonstrates 0.22cd/m in the scope of being measured that applies voltage ²So higher efficient of ratio.

The making of embodiment 8＜EL element and performance 〉

(preparation of solution)

The macromolecular compound 4 that obtains in the above-mentioned explanation is dissolved in the toluene, and having made polymer concentration is the toluene solution of 1.8 weight %.

(making of EL element)

The toluene solution that in using aforesaid operations, obtains, made EL element with the method for record among the embodiment 6 identically.And the rotating speed in the rotation coating machine of polymers soln is 2500rpm, and the thickness after the film forming of polymeric film is 90nm.

(performance of EL element)

Apply voltage by the element to gained, the EL that has obtained having at 425nm the peak from this element is luminous.When with the EL glow color during with C.I.E. color coordinates value representation, x=0.155 then, y=0.074 demonstrates very good blueness.The luminous intensity of EL is proportional with current density basically.In addition, this element is can see luminous from 5.8V.Luminous efficiency (increase monotonously among the 0V～12V), and the value at 12V place demonstrates 0.57cd/m in the scope of being measured that applies voltage ²So higher efficient of ratio.

Synthesizing of embodiment 9＜Compound D 〉

(synthesizing of Compound C)

(Compound C)

In reaction vessel, add ion exchanged water 31ml, when stirring-a some ground adds sodium hydroxide 29g (727mmol), dissolving fully.To use argon replaces in the system, add toluene 30ml and 1,2,3,10b-tetrahydrofluoranthene 5.0g (24mmol) stirs and dissolves.Next add Tetrabutylammonium bromide 2.3g (7.3mmol) and 2-ethylhexyl bromine 9.4g (48mmol), 40 ℃ of reactions 3 hours.With toluene and moisture liquid, after the organic layer extraction, use dried over sodium sulfate.After distillation removes and desolvates,, obtained xanchromatic oil 6.88g by refining as the silica gel chromatography that launches solvent in order to hexane.

MS(APPI(+))：318([M+H] ⁺)

¹H-NMR(300MHz/CDCl ₃)δ7.69(1H，d)、7.50(1H，d)、7.40(1H，d)、7.33～7.22(3H，m)、7.02(1H，d)、3.07～2.96(1H，m)、2.79～2.71(1H，m)、2.36～2.22(2H，m)、2.10～1.99(1H，m)、1.93～1.76(2H，m)、1.24～1.15(1H，m)、0.88～0.37(9H，m)

(synthesizing of Compound D)

(Compound D)

In the reaction vessel of argon replaces, add Compound C 6.8g (21mmol), zinc chloride 6.7g (49mmol) and acetate: the mixed solvent 134ml of methylene dichloride=1: 1, at room temperature stir.Next tribromide benzyltrimethylammon.um 18g (47mmol) is dissolved among the methylene dichloride 150ml and drips.After drip finishing, at room temperature reacted 2 hours, next 40 ℃ and 50 ℃ respectively react 30 minutes after, add chloroform and 5% aqueous solution of sodium bisulfite and stopped reaction.With chloroform and moisture liquid, the extraction organic layer, wash 2 times after, neutralize with wet chemical.After dried over sodium sulfate, distillation removes desolvates, by in order to hexane as refining 3 times of the silica gel chromatography that launches solvent, as xanchromatic oil (when placing under the room temperature white crystalsization) at leisure, obtained Compound D 1.73g.

MS(APPI(+))476(M ⁺)

¹H-NMR(300MHz/CDCl ₃)δ7.52～7.42(4H，m)、7.33(1H，d)、3.00～2.80(2H，m)、2.40～2.20(2H，m)、2.02～1.89(2H，m)、1.75～1.70(1H，m)、1.31～1.15(2H，m)、0.96～0.39(8H，m)

Embodiment 10

Synthesizing of＜macromolecular compound 5 〉

Under nitrogen atmosphere,, after 2 '-dipyridyl (0.422g) is dissolved among the tetrahydrofuran (THF) 72mL of dehydration, stirs and make it dissolving Compound D (0.476g), 2.In this solution, add two (1,5-dichloro octadiene) nickel (0) { Ni (COD) ₂(0.743g), stir, reacted 3 hours down at 60 ℃.This reaction solution is cooled to room temperature, to 25% ammoniacal liquor 4mL/ methyl alcohol 72mL/ ion exchanged water 72mL mixed solution and dripping, stirs after 1 hour, filter the precipitation of separating out, drying under reduced pressure is dissolved among the toluene 20ml.After the dissolving, add diatomite 1.6g, stirred 30 minutes, filter insolubles.The filtrate of gained is passed alumina column and make with extra care.Add 5.2% salt sour water 40mL then, stir after 3 hours, remove water layer.Add 4% ammoniacal liquor 40mL then, stir and remove water layer after 2 hours.Then in organic layer, add the about 40mL of ion exchanged water, stir after 1 hour, remove water layer., will in organic layer be injected in methyl alcohol 80ml, stirred 1 hour, filter the precipitation of separating out, drying under reduced pressure thereafter.The output of the polymkeric substance of gained (being called macromolecular compound 5 later on) is 0.17g.In addition, the number-average molecular weight of polystyrene conversion and weight-average molecular weight difference Mn=1.1 * 10 ⁵, Mw=3.2 * 10 ⁵

Comparative example 1

Synthesizing of＜macromolecular compound 6 〉

With 2,7-two bromo-9,9-dioctyl fluorene 0.22g (0.40mmol), N, N '-two (4-bromophenyl)-N, N '-two (the 4-tertiary butyl-2,6-3,5-dimethylphenyl)-1,4-phenylenediamine 0.20g (0.27mmol) and 2,2 '-dipyridyl 0.24g (1.5mmol) will use nitrogen replacement after adding reaction vessel in the reaction system.To wherein adding the tetrahydrofuran (THF) (dehydrated solvent) that outgases with the argon gas bubbling in advance.Then, in this mixing solutions, add two (1, the 5-cyclooctadiene) nickel (0) 0.42g (1.5mmol), 60 ℃ of reactions 3 hours.And reaction is carried out in nitrogen atmosphere.After the reaction, after this solution cooling, be injected in the 25% ammoniacal liquor 10mL/ methyl alcohol 120mL/ ion exchanged water 50mL mixing solutions stir about 1 hour.The precipitation that filtered and recycled generated then.Should precipitate with after the ethanol cleaning drying under reduced pressure 2 hours.Then, this resolution of precipitate in toluene 50ml, is added 1N hydrochloric acid 50mL, stirred 1 hour, remove water layer, in organic layer, add 4% ammoniacal liquor 50mL, stir and remove water layer after 1 hour.Organic layer is dripped in methyl alcohol 120mL, stirred 1 hour, filter the precipitation of separating out, drying under reduced pressure 2 hours is dissolved in the 40mL toluene., pass alumina column (alumina amount 20g) and make with extra care, the toluene solution that is reclaimed is dripped in methyl alcohol 120mL, stirred 1 hour, filter the precipitation of separating out, drying under reduced pressure 2 hours thereafter.The output of the macromolecular compound 6 of gained is 0.094g.

The number-average molecular weight of the polystyrene conversion of macromolecular compound 6 is 2.0 * 10 ⁴, the polystyrene conversion weight-average molecular weight is 1.1 * 10 ⁵

The making of comparative example 2＜EL element and performance 〉

(preparation of solution)

The macromolecular compound 6 that obtains in the above-mentioned explanation is dissolved in the chloroform, and having made polymer concentration is the chloroformic solution of 1.8 weight %.

(making of EL element)

Adhered at the thickness that utilizes sputtering method with 150nm on the glass substrate of ITO film, use will gather solution (the Bayer system of (ethylidene dioxy thiophene)/polystyrolsulfon acid, BaytronP), utilize the thickness film forming of rotation coating machine with 50nm, on hot plate with 200 ℃ of dryings 10 minutes.Then, use the above-mentioned chloroformic solution of preparing, utilize the rotating speed film forming of rotation coating machine with 2500rpm.Thickness is about 100nm.Then, with its 80 ℃ of dryings after 1 hour under reduced pressure, as cathode buffer layer, the LiF of the about 4nm of evaporation, as the calcium of the about 5nm of negative electrode evaporation, the aluminium of the about 80nm of evaporation has been made EL element then.And, arrive 1 * 10 in vacuum tightness ^-4After Pa is following, the evaporation of beginning metal.

(performance of EL element)

Apply voltage by the element to gained, the EL that has obtained having at 448nm the peak is luminous.When with the EL glow color during with C.I.E. color coordinates value representation, x=0.155 then, y=0.133.This element demonstrates maximum luminous efficiency at about 10V, and its value is 0.14cd/A.

When macromolecular compound of the present invention uses at the material as electronic component, can provide element function good electronic component.

Macromolecular compound of the present invention as a rule sends fluorescence or phosphorescence under solid state, can be used as polymeric luminescent material (high-molecular weight luminescent material) and use.

In addition, this macromolecular compound has the excellent electric charge transportation performance, can be used as polymer LED and uses suitably with material or charge transport material.The polymer LED that has used this polymeric luminescent material is can be with the high performance polymer LED of low voltage, high-level efficiency driving.So this polymer LED can be used for the backlight liquid crystal display lamp ideally, as devices such as illuminating curved surface shape or plane light source, the display element of sectional type, the flat-panel monitors of dot matrix.

In addition, macromolecular compound of the present invention also can be used as laser apparatus and uses with material with pigment, the organic solar batteries conductive film with the effective organic semiconductor of material, organic crystal, conductive membrane, organic semiconductor thin film etc.

In addition, can also use as the luminous thin-film material that sends fluorescence or phosphorescence.

Claims

1. a macromolecular compound is characterized in that, contains at least a with the residue of the compound of following formula (1) expression,

(formula 1)

In the formula, A ring, B ring and C ring represent also can have substituent aromatic ring or non-aromatic ring, Z respectively independently ₁, Z ₂, Z ₃, Z ₄And Z ₅Represent C-(Q) z or nitrogen-atoms respectively independently, Q represents substituting group or hydrogen atom, and z represents 0 or 1, and the A ring encircles the Z that also can have formation ring separately with B ₅Atom in addition, what A ring, B ring and C encircled is the non-aromatic ring below two more than one.

2. a macromolecular compound is characterized in that, contain with following formula (1-1), (1-2) or (1-3) repeating unit of expression,

Formula (1-1) formula (1-2) formula (1-3)

In the formula, A ring, B ring and C ring represent also can have substituent aromatic ring or non-aromatic ring, Z respectively independently ₁, Z ₂, Z ₃, Z ₄And Z ₅Represent C-(Q) respectively independently _zOr nitrogen-atoms, Q represents substituting group or hydrogen atom, and z represents 0 or 1, and the A ring also can have Z with the B ring ₅The atom of ring in addition in addition, also can be combination between each substituting group that encircles, and formation encircles again, and what A ring, B ring, C encircled the central ring that does not have associative key is the non-aromatic ring more than one.

3. macromolecular compound according to claim 1 and 2 is characterized in that, the atom that constitutes the ring of A ring, B ring and C ring all is a carbon atom.

4. according to claim 2 or 3 described macromolecular compounds, it is characterized in that the repeating unit of representing with above-mentioned formula (1-1) is the repeating unit of representing with following formula (2-1),

Formula (2-1)

In the formula, R ₁And R ₂Represent substituting group respectively independently, the expression of D ring also can have substituent non-aromatic ring, and a represents 0～2 integer, and b represents 0～3 integer, at R ₁And R ₂Exist respectively under a plurality of situations, they both can be identical, also can be different, and also can R ₁With R ₂Mutually combine and form ring.In addition, also can R ₁And/or R ₂Close with the D loops and form ring, Q and z represent implication same as described above.

5. according to claim 2 or 3 described macromolecular compounds, it is characterized in that the repeating unit of representing with above-mentioned formula (2-1) is the repeating unit of representing with following formula (3-1),

Formula (3-1)

In the formula, R ₁, R ₂, D ring, Q, z, a and b represent implication same as described above.

6. macromolecular compound according to claim 5 is characterized in that, is with following formula (4-1), (4-2), (4-3) or (4-4) repeating unit of expression with the repeating unit of formula (3-1) expression,

Formula (4-1) formula (4-2)

Formula (4-3) formula (4-4)

In the formula, R _1a, R _1b, R _2a～R _2cAnd R _3a～R _3gRepresent hydrogen atom or substituting group respectively independently, in the formula (4-1)～(4-3), also can R _2cWith R _3gMutually combine and form ring, in the formula (4-4), also can R _2cWith R _3eMutually combine and form ring.

7. according to any described macromolecular compound in the claim 1～6, it is characterized in that, also contain repeating unit with following formula (5), formula (6), formula (7) or formula (8) expression,

-Ar ₁- (5)

-(Ar ₂-X ₁) _ff-Ar ₃- (6)

-Ar ₄-X ₂- (7)

-X ₃- (8)

In the formula, Ar ₁, Ar ₂, Ar ₃And Ar ₄Represent arylidene, divalent heterocyclic radical respectively independently or have the divalent group that metal complex is constructed, X ₁, X ₂And X ₃Difference is expression-CR independently ₉=CR ₁₀-,-C ≡ C-,-N (R ₁₁)-or-(SiR ₁₂R ₁₃) _m-, R ₉And R ₁₀Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical, carboxyl, replacement carboxyl or cyano group respectively independently, R ₁₁, R ₁₂And R ₁₃Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical, aralkyl or substituted-amino respectively independently, ff represents 1 or 2, and m represents 1～12 integer, at R ₉, R ₁₀, R ₁₁, R ₁₂And R ₁₃Exist respectively under a plurality of situations, they both can be identical, also can be different.

8. according to any described macromolecular compound in the claim 1～6, it is characterized in that, also contain repeating unit with following formula (9), (10), (11), (12), (13) or (14) expression,

In the formula, R ₁₄Heterocyclic radical, carboxyl, replacement carboxyl, cyano group or the nitro of expression alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency; n represents 0～4 integer, has a plurality of R ₁₄Situation under, they both can be the same or different;

In the formula, R ₁₅And R ₁₆Heterocyclic radical, carboxyl, replacement carboxyl, cyano group or the nitro of representing alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency respectively independently; o and p represent 0～3 integer respectively independently, have a plurality of R ₁₅And R ₁₆Situation under, they both can be the same or different;

In the formula, R ₁₇And R ₂₀Heterocyclic radical, carboxyl, replacement carboxyl, cyano group or the nitro of representing alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency respectively independently; q and r represent 0～4 integer, R respectively independently ₁₈And R ₁₉Represent heterocyclic radical, carboxyl, replacement carboxyl or the cyano group of hydrogen atom, alkyl, aryl, 1 valency respectively independently, have a plurality of R ₁₇And R ₂₀Situation under, they both can be the same or different;

In the formula, R ₂₁Heterocyclic radical, carboxyl, replacement carboxyl, cyano group or the nitro of expression alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency, s represents 0～2 integer.Ar ₁₃And Ar ₁₄Represent the heterocyclic radical of arylidene, divalent respectively independently or have the divalent group that metal complex is constructed, ss and tt represent 0 or 1 respectively independently, X ₄Expression O, S, SO, SO ₂, Se or Te, have a plurality of R ₂₁Situation under, they both can be the same or different,

In the formula, R ₂₂And R ₂₃Heterocyclic radical, carboxyl, replacement carboxyl, cyano group or the nitro of representing alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency respectively independently; t and u represent 0～4 integer, X respectively independently ₅Expression O, S, SO ₂, Se, Te, N-R ₂₄Or SiR ₂₅R ₂₆, X ₆And X ₇Represent N or C-R respectively independently ₂₇, R ₂₄, R ₂₅, R ₂₆And R ₂₇Represent hydrogen atom, alkyl, aryl, aralkyl or 1 valency heterocyclic radical respectively independently, have a plurality of R ₂₅, R ₂₆And R ₂₇Situation under, they both can be the same or different,

In the formula, R ₂₈And R ₃₃Heterocyclic radical, carboxyl, replacement carboxyl, cyano group or the nitro of representing alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, alkoxy aryl, alkylthio-aryl, aromatic yl alkenyl, aromatic yl polysulfide yl, amino, substituted-amino, silyl, replacement silyl, halogen atom, acyl group, acyloxy, imines residue, amide group, imide, 1 valency respectively independently; v and w represent 0～4 integer, R respectively independently ₂₉, R ₃₀, R ₃₁And R ₃₂Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical, carboxyl, replacement carboxyl or cyano group respectively independently, Ar ₅Represent arylidene, divalent heterocyclic radical or have the divalent group that metal complex is constructed, have a plurality of R ₂₈And R ₃₃Situation under, they both can be the same or different.

9. according to any described macromolecular compound in the claim 1～6, it is characterized in that, also contain repeating unit with following formula (15) expression,

In the formula, Ar ₆, Ar ₇, Ar ₈And Ar ₉Represent arylidene or divalent heterocyclic radical respectively independently, Ar ₁₀, Ar ₁₁And Ar ₁₂The heterocyclic radical of representing arylidene or 1 valency respectively independently, Ar ₆, Ar ₇, Ar ₈, Ar ₉And Ar ₁₀Also can have substituting group, x and y represent 0 or 1,0≤x+y≤1 respectively independently.

10. the manufacture method of any described macromolecular compound in the claim 1～9 is characterized in that, as raw material, use at least with following formula (16-1), (16-2) or (16-3) compound polymerization of expression,

Formula (16-1) formula (16-2) formula (16-3)

In the formula, A ring, B ring, C ring, Z ₁～Z ₅As previously mentioned, Y ₁, Y ₂, Y ₃, Y ₄, Y ₅And Y ₆Expression participates in the polymeric substituting group independently respectively.

11. manufacture method according to claim 10 is characterized in that, the compound of representing with following formula (16-1) is the compound of representing with following formula (17-1),

In the formula, R ₁, R ₂, a, b, D ring, Q, z, Y ₁And Y ₂Represent implication same as described above.

12. manufacture method according to claim 11 is characterized in that, is with following formula (18-1), (18-2), (18-3) or (18-4) compound of expression with the compound of following formula (17-1) expression,

Formula (18-1) formula (18-2)

Formula (18-3) formula (18-4)

R in the formula _1a, R _1b, R _2a～R _2c, R _3a～R _3g, Y ₁And Y ₂Represent implication same as described above.

13. manufacture method according to claim 10 is characterized in that, the compound of representing with above-mentioned formula (16-2) is the compound of representing with following formula (17-2),

Formula (17-2)

In the formula, B ring, C ring, Z ₂, Z ₃, Z ₄, Y ₃And Y ₄Represent implication same as described above, Z ₆, Z ₇And Z ₈Represent C-(Q) respectively independently _zOr nitrogen-atoms, Z _1a, Z _5aAnd Z ₉Represent carbon atom respectively independently, Q and z represent implication same as described above, R ₄The expression substituting group, e represents 0～2 integer, and a plurality of R are being arranged ₄Situation under, they both can be the same or different, also can R ₄Between in conjunction with and form ring.

14. manufacture method according to claim 10 is characterized in that, the compound of representing with above-mentioned formula (16-3) is the compound of representing with following formula (17-3),

Formula (17-3)

In the formula, A ring, B ring, Z ₁, Z ₄, Z ₅, Y ₅And Y ₆Represent implication same as described above, Z ₁₀, Z ₁₁, Z ₁₂, and Z ₁₃Represent C-(Q) respectively independently _zOr nitrogen-atoms, Z _2aAnd Z _3aRepresent carbon atom respectively independently, Q and z represent implication same as described above, R ₅The expression substituting group, f represents 0～2 integer, and a plurality of R are being arranged ₅Situation under, they both can be the same or different, also can R ₅Between in conjunction with and form ring.

15. according to any described manufacture method in the claim 10～14, it is characterized in that, except with above-mentioned formula (16-1), (16-2) or (16-3) the compound of expression, will use and polymerization as raw material with the compound of any one expression in following formula (19)～(22)

Y ₇-Ar ₁-Y ₈ (19)

Y ₉-(Ar ₂-X ₁) _ff-Ar ₃-Y ₁₀ (20)

Y ₁₁-Ar ₄-X ₂-Y ₁₂ (21)

Y ₁₃-X ₃-Y ₁₄ (22)

In the formula, Ar ₁, Ar ₂, Ar ₃, Ar ₄, ff, X ₁, X ₂And X ₃Represent implication same as described above, Y ₇, Y ₈, Y ₉, Y ₁₀, Y ₁₁, Y ₁₂, Y ₁₃, Y ₁₄Expression participates in the polymeric substituting group independently respectively.

16. according to any described manufacture method in the claim 10～15, it is characterized in that, will with formula (16-1), (16-2) or (16-3) expression compound individually or be selected from least a polymerization in the compound of formula (19)～(22) expression Y ₁, Y ₂, Y ₃, Y ₄, Y ₅, Y ₆, Y ₇, Y ₈, Y ₉, Y ₁₀, Y ₁₁, Y ₁₂, Y ₁₃And Y ₁₄Be halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group or sweet-smelling alkyl sulfonic acid ester group independently respectively, in the presence of nickel 0 valency complex compound, carry out polycondensation.

17. according to any described manufacture method in the claim 10～15, it is characterized in that, will be selected from formula (16-1), (16-2) or (16-3) individually at least a in the compound of expression or be selected from least a polymerization in the compound of formula (19)～(22) expression Y ₁, Y ₂, Y ₃, Y ₄, Y ₅, Y ₆, Y ₇, Y ₈, Y ₉, Y ₁₀, Y ₁₁, Y ₁₂, Y ₁₃And Y ₁₄Respectively be independently halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group, sweet-smelling alkyl sulfonic acid ester group ,-B (OH) ₂Or the boric acid ester group, the sum of the mole number of halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group and sweet-smelling alkyl sulfonic acid ester group and-B (OH) ₂And the ratio of the sum of the mole number of boric acid ester group is essentially 1, uses nickel or palladium catalyst to carry out polycondensation.

18. more than one state the compound of formula (17-1) expression.

19. the compound that more than one are stated formula (18-1), (18-2), (18-3) or (18-4) represent.

20. the compound that more than one are stated formula (16-2) or (16-3) represent.

21. the compound that more than one are stated formula (17-2) or (17-3) represent.

22. a composition is characterized in that, contains any described macromolecular compound at least a material that is selected from hole transporting material, electron transport materials and the luminescent material and the claim 1～9.

23. an ink composite is characterized in that, contains any described macromolecular compound and solvent in the claim 1～9.

24. ink composite according to claim 23 is characterized in that, viscosity is 1～20mPas at 25 ℃.

25. luminous film that contains any described macromolecular compound in the claim 1～9.

26. conductive membrane that contains any described macromolecular compound in the claim 1～9.

27. organic semiconductor thin film that contains any described macromolecular compound in the claim 1～9.

28. a polymeric light-emitting device is characterized in that, has organic layer between the electrode that is made of anode and negative electrode, this organic layer contains any described macromolecular compound in the claim 1～9.

29. polymeric light-emitting device according to claim 28 is characterized in that, organic layer is a luminescent layer.

30. polymeric light-emitting device according to claim 29 is characterized in that, luminescent layer also contains hole transporting material, electron transport materials or luminescent material.

31. a flat light source is characterized in that, contains any described polymeric light-emitting device in the claim 28～30.

32. a segmentation display unit is characterized in that, contains any described polymeric light-emitting device in the claim 28～30.

33. a dot matrix display unit is characterized in that, contains any described polymeric light-emitting device in the claim 28～30.

34. a liquid crystal indicator is characterized in that, contains any described polymeric light-emitting device in the claim 28～30.