CN101326214A

CN101326214A - Polymer and polymeric luminescent element employing the same

Info

Publication number: CN101326214A
Application number: CNA2006800463914A
Authority: CN
Inventors: 野口公信; 铃木智之
Original assignee: Sumitomo Chemical Co Ltd
Current assignee: Sumitomo Chemical Co Ltd
Priority date: 2005-10-07
Filing date: 2006-10-05
Publication date: 2008-12-17
Anticipated expiration: 2026-10-05
Also published as: KR20080051163A; DE112006002642T5; GB0808121D0; CN101326214B; TW200724558A; GB2452359A; GB2452359B; WO2007043439A1

Abstract

A conjugated polymer having a phenoxazine structure and a phenothiazine structure as substituents.

Description

Macromolecular compound and use the polymeric light-emitting device of this compound

Technical field

The polymeric light-emitting device (hereinafter referred to as polymer LED) that the present invention relates to macromolecular compound and use it.

Background technology

The high-molecular weight luminescent material is different with low-molecular-weight luminescent material, it dissolves in solvent, can adopt coating method to form luminescent layer in the luminous element, from this point the high-molecular weight luminescent material is being carried out various researchs, as its example, known have have the repeating unit that 2 kinds of main chains contain aromatic nucleus, have the macromolecular compound that aryl is phenyl (formula weight 77) (with reference to patent documentation 1, patent documentation 2 and patent documentation 3) as terminal group.

In addition, as the repeating unit of main chain, known have a macromolecular compound (with reference to patent documentation 4 and patent documentation 5) that contains phenoxazine-two base or thiodiphenylamine-two base.

But, above-mentioned macromolecular compound, as the luminescent material of polymer LED luminescent layer the time, characteristics such as fluorescence intensity, weather resistance are also insufficient in practicality, as the luminescent material of polymer LED luminescent layer, require to demonstrate the macromolecular compound of outstanding characteristic.

Patent documentation 1: the international brochure that discloses No. 99/54385

Patent documentation 2: the international brochure that discloses No. 01/49769

Patent documentation 3: No. 5777070 specification sheets of United States Patent (USP)

Patent documentation 4: United States Patent (USP) 2004-72989 specification sheets

Patent documentation 5: the Japanese Patent spy opens the 2004-137456 communique

Summary of the invention

The objective of the invention is to, provide a kind of luminescent material to demonstrate the macromolecular compound of outstanding characteristic as polymer LED luminescent layer.

The inventor etc. study in order to solve above-mentioned problem, found that, a kind of macromolecular compound with more than one repeating units of from the group that constitutes by the repeating unit shown in the following formula (1), selecting, wherein, have the group of from the group that constitutes by 1 valency group shown in following formula (2) or (3), selecting and show very strong fluorescence intensity as substituent macromolecular compound, luminescent material as polymer LED luminescent layer shows outstanding characteristic, so that finished the present invention.

Macromolecular compound of the present invention shows outstanding characteristic as luminescent material.Use the polymeric light-emitting device of this macromolecular compound to be high-performance, the devices such as flat light source, lithographic plate indicating meter that can be used as backlight use.In addition, macromolecular compound of the present invention can be used as laser with pigment, organic photovoltaic cell with material, the effective organic semiconductor of organic crystal, conductive membrane material.

Embodiment

Macromolecular compound of the present invention contains the repeating unit shown in more than one following formulas (1).

Promptly, the present invention relates to following above-mentioned macromolecular compound, it has the macromolecular compound of more than one repeating units of selecting from the group that is made of the repeating unit shown in the following formula (1), it is characterized in that having the group of from the group that constitutes by 1 valency group shown in following formula (2) or (3), selecting as substituting group.

-Ar ₁-(Z’)p- (1)

(at this, Ar ₁Expression arylidene, divalent heterocyclic radical or divalent aromatic series amido.Z ' expression-CR ₄=CR ₅-or-C ≡ C-.R ₄And R ₅Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group respectively independently.P represents 0 or 1.)

[changing 1]

(in the formula, A ₁Expression-O-,-S-or-C (O)-, Ar ⁰¹Directly combination of expression, arylidene, divalent heterocyclic radical or divalent aromatic series amido, R ⁰⁵And R ⁰⁷Directly combination of expression independently respectively ,-R ₁-,-O-R ₁-,-R ₁-O-,-R ₁-C (O) O-,-R ₁-OC (O)-,-R ₁-N (R ₂₀)-,-O-,-S-,-C (O) O-or-C (O)-, R ₁Expression alkylidene group or alkenylene, R ₂₀Expression hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group.Wherein, Ar ⁰¹For directly in conjunction with the time, R ⁰⁷It also is direct combination.R ⁰¹And R ⁰²Represent substituting group respectively independently.A and b represent 0 to 4 integer, a plurality of R respectively independently ⁰¹And R ⁰²Can be identical, also can be different.)

[changing 2]

(in the formula, B ₁Expression-O-,-S-or-C (O)-, Ar ⁰²Expression hydrogen atom, aryl, 1 valency heterocyclic radical or 1 valency aromatic series amido, AR ⁰³Directly combination of expression, arylidene, divalent heterocyclic radical or divalent aromatic series amido, R ⁰⁶, R ⁰⁸And R ⁰⁹Directly combination of expression independently respectively ,-R ₁-,-O-R ₁-,-R ₁-O-,-R ₁-C (O) O-,-R ₁-OC (O)-,-R ₁-N (R ₂₀)-,-O-,-S-,-C (O) O-or-C (O)-, R ₁Expression alkylidene group or alkenylene, R ₂₀Expression hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group.Wherein, Ar ⁰³For directly in conjunction with the time, R ⁰⁹It also is direct combination.R ⁰³And R ⁰⁴Represent substituting group respectively independently.C is 0 to 4 integer, and d is 0 to 3 integer.A plurality of R ⁰³And R ⁰⁴Can be identical, also can be different.)

Macromolecular compound of the present invention contains the repeating unit shown in more than one above-mentioned formulas (1).

In above-mentioned formula (1), Ar ₁Expression arylidene, divalent heterocyclic radical or divalent aromatic series amido.At this, Ar ₁Except the group shown in the group shown in the above-mentioned formula (2), the above-mentioned formula (3), can also have substituting groups such as alkyl, alkoxyl group, alkylthio, alkyl silyl, alkylamino, aryl, aryloxy, arylalkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, arylamino, 1 valency heterocyclic radical or cyano group.At Ar ₁Have under a plurality of substituent situations, they can be identical or different respectively.

In above-mentioned formula (1), arylidene is meant from aromatic hydrocarbon removes residual atomic group behind 2 hydrogen atoms, and carbon number is generally about 6～60.Do not comprise substituent carbon number in the carbon number.The aromatic hydrocarbon here comprises the structure of holding condensed ring, independently phenyl ring or 2 above condensed rings be directly or across group bonded structures such as vinylidenes.

But as arylidene illustration phenylene (for example following formula 1～3), naphthalene two bases (following formula 4～13), anthrylene (following formula 14～19), biphenylene (following formula 20～25), triphenylenyl (following formula 26～28), fused ring compound group (following formula 29～38), 1,2-toluylene-two base (following formula A～D), two stilbene-two base (following formula E and F), benzofluorene-two base (following formula G, H, I and K) etc.

[changing 3]

[changing 4]

[changing 5]

[changing 6]

[changing 7]

[changing 8]

Wherein, preferred phenylene (for example above-mentioned formula 1～3), naphthalene two bases (above-mentioned formula 4～13), anthrylene (above-mentioned formula 14～19), biphenylene (above-mentioned formula 20～25), triphenylenyl (above-mentioned formula 26～28), fused ring compound group (above-mentioned formula 29～38), 1,2-toluylene-two base (above-mentioned formula A～D), two stilbene-two base (above-mentioned formula E and F), benzofluorene-two base (above-mentioned formula G, H, I and K).

In above-mentioned formula 1～38, A～I and K, R represents the group shown in the group shown in the above-mentioned formula (2), the above-mentioned formula (3), hydrogen atom, alkyl, alkoxyl group, alkylthio, alkyl silyl, alkylamino, aryl, aryloxy, arylalkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, arylamino, 1 valency heterocyclic radical or cyano group.In the above-mentioned example, have a plurality of R, they can be identical or different.At least one is the group shown in group shown in the above-mentioned formula (2) or the above-mentioned formula (3) among the R.Wherein, do not limit the situation that has the group shown in the group shown in the above-mentioned formula (2), the above-mentioned formula (3) at the molecule chain end of high polymer main chain.

Here, as alkyl, can be in straight chain, side chain or the ring-type any, carbon number is generally about 1～20, particularly, can list methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, hexyl, cyclohexyl, heptyl, octyl group, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyl octyl group, lauryl etc., preferred amyl group, hexyl, octyl group, 2-ethylhexyl, decyl, 3,7-dimethyl octyl group.

Alkoxyl group can be any in straight chain, side chain or the ring-type, carbon number is generally about 1～20, particularly, can list 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, 3,7-dimethyl octyloxy, bay oxygen base etc., preferred pentyloxy, hexyloxy, octyloxy, 2-ethyl hexyl oxy, the last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxy.

Alkylthio can be any in straight chain, side chain or the ring-type, carbon number is generally about 1～20, particularly, can list methylthio group, ethylmercapto group, rosickyite base, iprotiazem base, butylthio, isobutyl sulfenyl, uncle's butylthio, penta sulfenyl, own sulfenyl, hexamethylene sulfenyl, heptan sulfenyl, hot sulfenyl, the own sulfenyl of 2-ethyl, ninth of the ten Heavenly Stems sulfenyl, last of the ten Heavenly stems sulfenyl, 3,7-dimethyl-octa sulfenyl, bay sulfenyl etc., preferred penta sulfenyl, own sulfenyl, hot sulfenyl, the own sulfenyl of 2-ethyl, the last of the ten Heavenly stems sulfenyl, 3,7-dimethyl-octa sulfenyl.

The alkyl silyl can be a straight chain, in side chain or the ring-type any, carbon number is generally about 1～60, particularly, can enumerate the methyl-silicane base, the ethyl silicane base, the propyl group silyl, the sec.-propyl silyl, the butyl silyl, the isobutyl-silyl, tertiary butyl silyl, the amyl group silyl, the hexyl silyl, the heptyl silyl, the octyl group silyl, 2-ethylhexyl silyl, the nonyl silyl, the decyl silyl, 3,7-dimethyl octyl group silyl, the lauryl silyl, trimethyl silyl, the ethyl dimethyl silanyl, the propyl-dimethyl silyl, the sec.-propyl dimetylsilyl, the butyl dimetylsilyl, t-butyldimethylsilyl, 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, lauryl dimethyl silyl etc., preferred amyl group silyl, the hexyl silyl, the octyl group silyl, 2-ethylhexyl silyl, the decyl silyl, 3,7-dimethyl octyl group silyl, the amyl group dimetylsilyl, the hexyl dimetylsilyl, the octyldimethyl silyl, 2-ethylhexyl-dimetylsilyl, the decyl dimetylsilyl, 3,7-dimethyl octyl group-dimetylsilyl.

Alkylamino can be a straight chain, in side chain or the ring-type any, can be alkyl monosubstituted amino and also can be dialkyl amido, carbon number is generally about 1～40, particularly, can enumerate methylamino, dimethylamino, ethylamino, diethylamino, propyl group amino, sec.-propyl amino, butyl amino, isobutylamino, tertiary butyl amino, amyl group amino, hexyl amino, cyclohexyl amino, heptyl amino, octyl group amino, 2-ethylhexyl amino, nonyl amino, decyl amino, 3,7-dimethyl octyl group amino, lauryl amino etc., preferred amyl group amino, hexyl amino, octyl group amino, 2-ethylhexyl amino, decyl amino, 3,7-dimethyl octyl group amino.

The carbon number of aryl is generally about 6～60, particularly, and can the illustration phenyl, C ₁～C ₁₂Alkoxyl phenyl (C ₁～C ₁₂The expression carbon number is 1～12.Below also identical.), C ₁～C ₁₂Alkyl phenyl, 1-naphthyl, 2-naphthyl etc., preferred C ₁～C ₁₂Alkoxyl phenyl, C ₁～C ₁₂Alkyl phenyl.

Aryloxy, carbon number are generally about 6～60, particularly, and can the illustration phenoxy group, C ₁～C ₁₂Alkoxyl group phenoxy group, C ₁～C ₁₂Alkyl phenoxy, 1-naphthyloxy, 2-naphthyloxy etc., preferred C ₁～C ₁₂Alkoxyl group phenoxy group, C ₁～C ₁₂Alkyl phenoxy.

The carbon number of aralkyl is generally about 7～60, particularly, and can illustration phenyl-C 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, particularly, and can illustration phenyl-C 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 aryl alkenyl is generally about 8～60, particularly, and can illustration phenyl-C ₂～C ₁₂Thiazolinyl, C ₁～C ₁₂Alkoxyl phenyl-C ₂～C ₁₂Thiazolinyl, C ₁～C ₁₂Alkyl phenyl-C ₂～C ₁₂Thiazolinyl, 1-naphthyl-C ₂～C ₁₂Thiazolinyl, 2-naphthyl-C ₂～C ₁₂Thiazolinyl etc., preferred C ₁～C ₁₂Alkoxyl phenyl-C ₂～C ₁₂Thiazolinyl, C ₁～C ₁₂Alkyl phenyl-C ₂～C ₁₂Thiazolinyl.

As aromatic yl polysulfide yl, carbon number is generally about 8～60, particularly, and can illustration phenyl-C 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.

The carbon number of arylamino is generally about 6～60, particularly, and can the illustration phenyl amino, diphenyl 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 etc., preferred C ₁～C ₁₂Alkyl phenyl amino, two (C ₁～C ₁₂Alkyl phenyl) amino.

1 valency heterocyclic radical is meant from heterogeneous ring compound removes atomic group remaining behind 1 hydrogen atom, and carbonatoms is generally about 4～60, particularly, and can the illustration thienyl, C ₁～C ₁₂Alkyl thienyl, pyrryl, furyl, pyridyl, C ₁～C ₁₂Alkylpyridyl etc., preferred thienyl, C ₁～C ₁₂Alkyl thienyl, pyridyl, C ₁～C ₁₂Alkylpyridyl.

At above-mentioned substituting group is to contain under the situation of group of alkyl chain, and this alkyl chain can or contain heteroatomic group by heteroatoms to interrupt.Here, but as heteroatoms illustration Sauerstoffatom, sulphur atom, nitrogen-atoms etc.As heteroatoms or contain heteroatomic group and for example can enumerate following group.

[changing 9]

At this, for example can enumerate the alkyl of Sauerstoffatom, carbon number 1～20, the aryl of carbon number 6～60,1 valency heterocyclic radical of carbon number 4～60 as R '.

In above-mentioned formula (1), the divalent heterocyclic radical is meant removes residual atomic group behind 2 hydrogen atoms from heterogeneous ring compound, and carbon number is generally about 4～60.Carbon number does not comprise substituent carbon number.

Herein, heterogeneous ring compound is meant that in the organic compound with ring type structure the element that constitutes ring is not only carbon atom, and also contains heteroatomic compounds such as aerobic, sulphur, nitrogen, phosphorus, boron in ring.For example can enumerate following material.

Contain group as heteroatomic nitrogen; Pyridine-two base (following formula 39～44), diaza phenylene (following formula 45～48), quinoline two bases (following formula 49～63), quinoxaline two bases (following formula 64～68), acridine two bases (following formula 69～72), dipyridyl two bases (following formula 73～75), phenanthroline two bases (following formula 76～78) etc.

Contain as heteroatomic silicon, nitrogen, oxygen, sulphur, selenium etc. and have fluorene structured group (following formula 79～93).

Contain 5 yuan of ring heterocyclic radicals (following formula 94～98) as heteroatomic silicon, nitrogen, oxygen, sulphur, selenium etc.

Contain 5 yuan of fused ring heterocycle bases (following formula 99～108) as heteroatomic silicon, nitrogen, oxygen, sulphur, selenium etc.

Contain as 5 yuan of ring heterocyclic radicals of heteroatomic sulphur etc. and on this heteroatomic α position bonding and become the group (following formula 109～110) of dimer or oligopolymer.

Contain as heteroatomic silicon, nitrogen, oxygen, sulphur, selenium etc. 5 yuan ring heterocyclic radicals and on this heteroatomic α position bonding phenyl groups (following formula 111～117).

[changing 10]

[changing 11]

[changing 12]

[changing 13]

[changing 14]

[changing 15]

[changing 16]

[changing 17]

[changing 18]

Wherein, preferred diphenylene-oxide-two base (above-mentioned formula 85～87), dibenzothiophene-two base (above-mentioned formula 88～90) etc.

In the above-mentioned formula 39～117, R represents implication same as described above.

In the above-mentioned formula (1), divalent aromatic series amido is meant from aromatic amine removes residual atomic group behind 2 hydrogen atoms, and carbon number is generally about 4～60, does not comprise substituent carbon number in the carbon number.Can enumerate the group shown in the following general formula (50) as the divalent aromatic amine group.

-Ar ₆-N(Ar ₅)-Ar ₇- (50)

In the formula, Ar ₆And Ar ₇Respectively independently for can have the group shown in group shown in substituent arylidene, the following general formula (4) or the following general formula (5).Ar ₅Expression can have the group shown in group shown in substituent aryl, the following general formula (6) or the following general formula (7).In addition, can also be at Ar ₆And Ar ₅Between, Ar ₅And Ar ₆Between or Ar ₆And Ar ₇Between form ring.

[changing 19]

In the formula, Ar ₈And Ar ₉Expression can have substituent arylidene independently respectively.R ₇And R ₈Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group respectively independently.L is 0 or 1.

[changing 20]

In the formula, Ar ₁₀And Ar ₁₁Expression can have substituent arylidene independently respectively.Ar ₁₂For having substituent aryl.In addition, can also be at Ar ₁₀And Ar ₁₂Between, Ar ₁₀And Ar ₁₁Between or Ar ₁₁And Ar ₁₂Between form ring.

[changing 21]

In the formula, Ar ₁₃Expression can have substituent arylidene.Ar ₁₆And Ar ₁₇Respectively independently for can have substituent aryl.In addition, can also be at Ar ₁₃And Ar ₁₆Between, Ar ₁₃And Ar ₁₇Between or Ar ₁₆And Ar ₁₇Between form ring.

[changing 22]

In the formula, Ar ₁₄Expression can have substituent arylidene.Ar ₁₅Expression can have substituent aryl.R ₁₁And R ₁₂Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group respectively independently.R is 0 or 1.

The Ar of above-mentioned formula (4) ₈And Ar ₉, formula (5) Ar ₁₀And Ar ₁₁, formula (6) Ar ₁₃And the Ar of formula (7) ₁₄Can have substituting groups such as alkyl, alkoxyl group, alkylthio, alkyl silyl, alkylamino, aryl, aryloxy, arylalkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, arylamino, 1 valency heterocyclic radical, cyano group.

In addition, the Ar of above-mentioned formula (50) ₅, above-mentioned formula (5) Ar ₁₂, above-mentioned formula (6) Ar ₁₆And Ar ₁₇, and the Ar of above-mentioned formula (7) ₁₅Can have substituting groups such as alkyl, alkoxyl group, alkylthio, alkyl silyl, alkylamino, aryl, aryloxy, arylalkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, arylamino, 1 valency heterocyclic radical, cyano group.

As divalent aromatic series amido, specifically can the following group of illustration.

[changing 23]

In above-mentioned formula 118～122, R represents implication same as described above.

In macromolecular compound of the present invention, from the fluorescence intensity or the stable on heating viewpoint of macromolecular compound, preferred arylidene is the group shown in following general formula (1-1), (1-2), (1-3), the group shown in (1-4).

[changing 24]

[in the formula, R _P1, R _Q1, R _P2, R _Q2, R _P3, R _Q3, R _P4And R _Q4Represent the group shown in the group shown in the above-mentioned formula (2), the above-mentioned formula (3), alkyl, alkoxyl group, alkylthio, alkyl silyl, alkylamino, aryl, aryloxy, arylalkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, arylamino, 1 valency heterocyclic radical or cyano group respectively independently.A is 0～3 integer, and b is 0～5 integer.At R _P1, R _Q1, R _P2, R _Q2, R _P3, R _Q3, R _P4And R _Q4Under a plurality of situations, they can be identical or different.R _W1, R _X1, R _W2, R _X2, R _W3, R _X3, R _W4And R _X4Represent hydrogen atom, alkyl, alkoxyl group, alkylthio, alkyl silyl, alkylamino, aryl, aryloxy, arylalkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, arylamino, 1 valency heterocyclic radical or cyano group respectively independently, R _W1And R _X1, R _W2And R _X2, R _W3And R _X3, R _W4And R _X4Can be bonded to each other respectively and form ring.]

In above-mentioned formula (1-1), (1-2), (1-3) reach (1-4), from viewpoints such as the solvability organic solvent, element characteristic, easy synthetic macromolecular compound or fluorescence intensity, preferred R _P1, R _Q1, R _P2, R _Q2, R _P3, R _Q3, R _P4And R _Q4Be group, alkyl, alkoxyl group, aryl, aryloxy, arylalkyl, the alkoxy aryl shown in the group shown in the above-mentioned formula (2), the above-mentioned formula (3).More preferably alkyl, alkoxyl group, aryl.

In above-mentioned formula (1-1), (1-2), (1-3) reach (1-4), from viewpoints such as the solvability organic solvent, element characteristic, easy synthetic macromolecular compound or fluorescence intensities, as R _W1, R _X1, R _W2, R _X2, R _W3, R _X3, R _W4And R _X4Be preferably alkyl, alkoxyl group, aryl, aryloxy, arylalkyl, alkoxy aryl, more preferably alkyl, aryl.

As alkyl, alkoxyl group, aryl, more specifically, can the illustration methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-, the tertiary butyl, amyl group, isopentyl, hexyl, cyclohexyl, heptyl, cyclohexyl methyl, octyl group, the 2-ethylhexyl, nonyl, decyl, 3,7-dimethyl octyl group, lauryl, trifluoromethyl, pentafluoroethyl group, perfluoro butyl, perfluoro hexyl, carbon numbers such as perfluoro capryl are generally the straight chain about 1～20, side chain or cyclic alkyl, methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptan the oxygen base, cyclohexyl methyl 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, bay oxygen base, trifluoromethoxy, five fluorine oxyethyl groups, the perfluor butoxy, perfluoro hexyl, perfluoro capryl, methoxymethyl oxygen base, carbon numbers such as 2-methoxy ethyl oxygen base are generally the alkoxyl group about 1～20, phenyl, C ₁～C ₁₂Alkoxyl phenyl, C ₁～C ₁₂Carbon numbers such as alkyl phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2-anthryl, 9-anthryl, pentafluorophenyl group be generally 6～60 about aryl etc.

At this, as C ₁～C ₁₂Alkoxyl group, particularly, can the illustration methoxyl group, oxyethyl group, propoxy-, isopropoxy, butoxy, isobutoxy, tert.-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptan oxygen base, octyloxy, 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, bay oxygen base etc. are as C ₁～C ₁₂Alkyl phenyl, particularly, can the illustration 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.

For the concrete example shown in above-mentioned formula (1-1), (1-2), (1-3) reach (1-4), as R _W1And R _X1, R _W2And R _X2, R _W3And R _X3, R _W4And R _X4Being bonded to each other respectively forms the compound that ring forms, but the following formula group of illustration (1-1-2), (1-2-2), (1-3-2) reach (1-4-2) respectively.These structures can also have substituting group.

[changing 25]

[changing 26]

[changing 27]

[changing 28]

In above-mentioned formula (1-1) and (1-2), the viewpoint that quantizes from polymer and improve stable on heating viewpoint, preferred a=b=0.

In macromolecular compound of the present invention, from the angle of easy synthon, preferably contain the compound of the group shown in formula (1-1), (1-3), (1-4), and then preferred formula (1-1).

From improving deliquescent viewpoint and the stable on heating balance of synthetic macromolecular compound organic solvent, R _W1, R _X1Be preferably alkyl, the more preferably alkyl of carbon number more than 3, more preferably more than 7, so that preferred more than 8.Most preferably being n-octyl, is the structure shown in the following formula (80).

[changing 29]

In addition, from the viewpoint of easy synthetic macromolecular compound or fluorescence intensity, the divalent heterocyclic radical is preferably the group shown in the following formula (70) especially.

[changing 30]

[in the formula, C ring and D ring are represented aromatic nucleus respectively independently.C ring and D ring can also have the substituting group of selecting from the group that is made of the group shown in the group shown in the above-mentioned formula (2), the above-mentioned formula (3), alkyl, alkoxyl group, alkylthio, alkyl silyl, alkylamino, aryl, aryloxy, arylalkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, arylamino, 1 valency heterocyclic radical and cyano group.Exist under a plurality of substituent situations, they can be identical or different.E is O or S.]

As the group shown in the above-mentioned formula (70), for example can enumerate group by any expression of following formula (2a)～(2d).

[changing 31]

(in the formula, X represents O or S, R ^aThe expression substituting group, m represents 0～5 integer independently, n represents 0～3 integer independently.There are a plurality of R ^aSituation under, they can be identical or different.)

R ^aShown substituting group with describe as the substituting group shown in the above-mentioned R, illustrative substituting group is identical.In addition, from the deliquescent angle of macromolecular compound, m is preferably 1～3 integer, and n is preferably 1 or 2.

From the viewpoint of easy synthetic macromolecular compound or fluorescence intensity, the group shown in the above-mentioned formula (2a) is preferably the group shown in the following formula (2E).

[changing 32]

[in the formula, Y represents O or S.R ^jAnd R ^kRepresent group, hydrogen atom, alkyl, alkoxyl group or the aryl shown in the group shown in the above-mentioned formula (2), the above-mentioned formula (3) respectively independently.]

In the above-mentioned formula (2E), from the viewpoint of easy synthetic macromolecular compound, R ^jAnd R ^kBe preferably identical group (promptly.Both sides are hydrogen atom, alkyl, alkoxyl group or aryl), preferred alkoxyl group.R ^jAnd R ^kShown alkyl, aryl and describe as the substituting group shown in the above-mentioned R, illustrative substituting group is identical.In addition, from the solvability of macromolecular compound or the angle of fluorescence intensity, as R ^jAnd R ^kShown alkoxyl group, be preferably butoxy, sec-butoxy, tert.-butoxy, pentyloxy, hexyloxy, heptan oxygen base, octyloxy, 2-ethyl hexyl oxy, ninth of the ten Heavenly Stems oxygen base, last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxy, bay oxygen base, and then be preferably pentyloxy, hexyloxy, octyloxy, 2-ethyl hexyl oxy, last of the ten Heavenly stems oxygen base, 3,7-dimethyl octyloxy.

As the repeating unit shown in the above-mentioned formula (70), for example can enumerate following above-claimed cpd:

[changing 33]

(in the formula, R represents the group shown in the group shown in hydrogen atom, the above-mentioned formula (2), the above-mentioned formula (3), alkyl, alkoxyl group, alkylthio, alkyl silyl, alkylamino, aryl, aryloxy, arylalkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, arylamino, 1 valency heterocyclic radical or cyano group respectively independently.), from the thermotolerance of macromolecular compound or the viewpoint of polymer quantification, be preferably as follows above-claimed cpd:

[changing 34]

(in the formula, R has implication same as described above.)。

In the above-mentioned formula, though have a plurality of R in a structural formula, they can be identical or different.In the above-mentioned formula, the group shown in the R with describe as the substituting group shown in the above-mentioned R, illustrative group is identical.

In above-mentioned formula (1), Z ' expression-C (R ₄)=C (R ₅)-or-C ≡ C-.R ₄, R ₅Be hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group independently respectively.From the viewpoint of stability preferred-C (R ₄)=C (R ₅)-.

Z ' conduct-C (R ₄)=C (R ₅)-be repeating unit, the group shown in the preferred following formula 128～135.

[changing 35]

At this, R represents implication same as described above.

P is 0 or 1.From the viewpoint of photoxidation stability, p is preferably 0.

In above-mentioned formula (2), A ₁Expression-O-,-S-or-C (O)-.

In above-mentioned formula (2), Ar ⁰¹Directly combination of expression, arylidene, divalent heterocyclic radical or divalent aromatic series amido.Arylidene, divalent heterocyclic radical or divalent aromatic amine basis representation implication same as described above.

In above-mentioned formula (2), R ⁰⁵Directly combination of expression ,-R ₁-, ^*-O-R ₁-, ^*-R ₁-O-, ^*-R ₁-C (O) O-, ^*-R ₁-OC (O)-, ^*-R ₁-N (R ₂₀)-,-O-,-S-, ^*-C (O) O-or-C (O)-(wherein, ^*Label table is shown in ^*Label side and Ar ⁰¹In conjunction with.), R ⁰⁷Directly combination of expression ,-R ₁-,-O-R ₁- ^*,-R ₁-O- ^*,-R ₁-C (O) O- ^*,-R ₁-OC (O)- ^*,-R ₁-N (R ₂₀)- ^*,-O-,-S-,-C (O) O- ^*Or-C (O)-(wherein, ^*Label table is shown in ^*Label side and Ar ⁰¹In conjunction with.), R ₁Expression alkylidene group or alkenylene.R ₂₀Expression hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group.From synthesizing or stable viewpoint R easily ⁰⁵Preferred directly combination ,-R ₁-, ^*-O-R ₁-, R ⁰⁷Preferred directly combination ,-R ₁-,-O-R ₁- ^*

In above-mentioned formula (2), R ⁰¹And R ⁰²Represent substituting group respectively independently.As substituting group, expression alkyl, alkoxyl group, alkylthio, alkyl silyl, alkylamino, aryl, aryloxy, arylalkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, arylamino, 1 valency heterocyclic radical or cyano group.

A and b are respectively 0 to 4 integer independently, a plurality of R ⁰¹And R ⁰²Can be identical or different.

As the group shown in the above-mentioned formula (2), but the concrete following group of illustration.

[changing 36]

[changing 37]

At this, R represents and R ⁰¹Identical implication.R ₁Represent implication same as described above.

In above-mentioned formula (3), B ₁Expression-O-,-S-or-C (O)-.

In above-mentioned formula (3), Ar ⁰²Expression hydrogen atom, aryl, 1 valency heterocyclic radical or 1 valency aromatic series amido.

At this, as aryl, carbon number is generally about 6～60, particularly, but illustration phenyl, C ₁～C ₁₂Alkoxyl phenyl (C ₁～C ₁₂The expression carbon number is 1～12.C below too), ₁～C ₁₂Alkyl phenyl, 1-naphthyl, 2-naphthyl etc., preferred C ₁～C ₁₂Alkoxyl phenyl, C ₁～C ₁₂Alkyl phenyl.

1 valency heterocyclic radical is meant from heterogeneous ring compound removes residual atomic group behind 1 hydrogen atom, and carbon number is generally about 2～60.

As 1 valency heterocyclic radical, for example can enumerate following group.

Contain 1 valency heterocyclic radical as heteroatomic nitrogen; Pyridyl, diaza-phenyl, quinolyl, quinoxalinyl, acridyl, bipyridine, phenanthroline-Ji etc.

Contain as heteroatomic silicon, nitrogen, sulphur, selenium, oxygen etc. and have fluorene structured group (group) with the ring shown in the above-mentioned formula 79～93.

Contain 5 yuan of ring heterocyclic radicals (group) with the ring shown in the above-mentioned formula 94～98 as heteroatomic silicon, nitrogen, sulphur, selenium, oxygen etc.

Contain 5 yuan of fused ring heterocycle bases (group) with the ring shown in the above-mentioned formula 99～108 as heteroatomic silicon, nitrogen, sulphur, selenium, oxygen etc.

Contain as 5 yuan of ring heterocyclic radicals of heteroatomic sulphur etc. and on this heteroatomic α position bonding and become the group (group) of dimer or oligopolymer with the ring shown in the above-mentioned formula 109～110.

Contain as heteroatomic silicon, nitrogen, sulphur, selenium, oxygen etc. 5 yuan ring heterocyclic radicals and on this heteroatomic α position bonding phenyl groups (group) with the ring shown in the above-mentioned formula 111～117.

1 valency aromatic series amido is meant from aromatic amine removes residual atomic group behind 1 hydrogen atom, and carbon number is generally about 4～60.Do not comprise substituent carbon number in the carbon number.As the group of 1 valency aromatic series amido shown in can the following formula 123～127 of illustration.

[changing 38]

At this, R represents and R ⁰¹Identical implication.

In above-mentioned formula (3), R ⁰⁶Directly combination of expression ,-R ₁-,-O-R ₁- ^*,-R ₁-O- ^*,-R ₁-C (O) O- ^*,-R ₁-OC (O)- ^*,-R ₁-N (R ₂₀)- ^*,-O-,-S-,-C (O) O- ^*Or-C (O)-(wherein, ^*Label table is shown in ^*Label side and Ar ⁰²In conjunction with.), R ₁Expression alkylidene group or alkenylene.R ₂₀Expression hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group.From synthesizing or stable viewpoint R easily ⁰⁶Preferred directly combination ,-R ₁-,-O-R ₁- ^*

R ⁰⁸Directly combination of expression ,-R ₁-, ^*-O-R ₁-, ^*-R ₁-O-, ^*-R ₁-C (O) O-, ^*-R ₁-OC (O)-, ^*-R ₁-N (R ₂₀)-,-O-,-S-, ^*-C (O) O-or-C (O)-(wherein, ^*Label table is shown in ^*Label side and Ar ⁰³In conjunction with.), R ⁰⁹Directly combination of expression ,-R ₁-,-O-R ₁- ^*,-R ₁-O- ^*,-R ₁-C (O) O- ^*,-R ₁-OC (O)- ^*,-R ₁-N (R ₂₀)- ^*,-O-,-S-,-C (O) O- ^*Or-C (O)-(wherein, ^*Label table is shown in ^*Label side and Ar ⁰³In conjunction with.), R ₁Expression alkylidene group or alkenylene.R ₂₀Expression hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group.From synthesizing or stable viewpoint R easily ⁰⁸Preferred directly combination ,-R ₁-, ^*-O-R ₁-, R ⁰⁹Preferred directly combination ,-R ₁-,-O-R ₁- ^*

R ⁰³And R ⁰⁴Represent substituting group respectively independently.As substituting group is alkyl, alkoxyl group, alkylthio, alkyl silyl, alkylamino, aryl, aryloxy, arylalkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, arylamino, 1 valency heterocyclic radical or cyano group.

C is 0 to 4 integer, and d is 0 to 3 integer.A plurality of R ⁰³And R ⁰⁴Can be identical or different.

As the group shown in the above-mentioned formula (3), but the concrete following group of illustration.

[changing 39]

[changing 40]

[changing 41]

[changing 42]

[changing 43]

At this, R represents and R ⁰³Identical implication.R ₁Represent implication same as described above.

In macromolecular compound of the present invention,, and then preferably comprise the compound of the repeating unit shown in the following formula (30) from the viewpoint of solvability or fluorescence intensity.

-Ar ₄-(Z) _t- (30)

Ar in the above-mentioned formula (30) ₄Be arylidene, divalent heterocyclic radical or divalent aromatic series amido.As Ar ₄, can illustration and Ar ₁Identical group.Wherein, Ar ₄Do not comprise the group shown in the group shown in the above-mentioned formula (2), the above-mentioned formula (3).

In the above-mentioned formula (30), Z represents-CR ₇=CR ₈-or-C ≡ C-.R ₇And R ₈Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group respectively independently.T represents 0 or 1.From the viewpoint of stability preferred-CR ₇=CR ₈-.From the viewpoint of photoxidation stability, more preferably t is 0.

As the repeating unit shown in the formula (30), particularly, can enumerate the repeating unit of the structure described in above-mentioned formula 1 to 117, above-mentioned formula A to F, above-mentioned formula 118～122 and the above-mentioned formula 128～133.Wherein preferred phenylene (for example, above-mentioned formula 1～3), naphthalene two bases (above-mentioned formula 4～13), anthrylene (above-mentioned formula 14～19), biphenylene (above-mentioned formula 20～25), inferior terphenyl (above-mentioned formula 26～28), fused ring compound group (above-mentioned formula 29～38), diphenylene-oxide-two base (above-mentioned formula 85～87), dibenzothiophene-two base (above-mentioned formula 88～90), 1,2-toluylene-two base, 21,2-toluylene-two base, divalent aromatic series amido (above-mentioned formula 118～119 and 122) arylidene vinylidene (following formula 128～133), benzofluorene-two base (above-mentioned formula G, H, I and K) etc., wherein preferred phenylene, biphenylene, fluorenes-two base (above-mentioned formula 36～38), diphenylene-oxide-two base (above-mentioned formula 85～87), dibenzothiophene-two base (above-mentioned formula 88～90), 1,2-toluylene-two base, two stilbene-two base, benzofluorene-two base (above-mentioned formula G, H, I and K), divalent aromatic series amido.

[changing 44]

At this, R represents and described identical implication.Wherein, do not comprise the group shown in the group shown in the above-mentioned formula (2), the above-mentioned formula (3).

Macromolecular compound of the present invention can be the Ar as the above-mentioned formula (1) that constitutes its main chain ₁, its arylidene, divalent heterocyclic radical or divalent aromatic series amido substituting group, (it also can be more than 2 kinds that this substituting group can be a kind and have the compound of the group shown in group shown in 1 above-mentioned formula (2) and/or the above-mentioned formula (3) at least.), can also be that at least one side in the molecular end of this macromolecular chain has the compound of the group shown in group shown in the above-mentioned formula (2) and/or the above-mentioned formula (3) (it also can be more than 2 kinds that this substituting group can be a kind as terminal group.)。

From the viewpoint that the polymer of macromolecular compound quantizes, the Ar of above-mentioned formula (1) ₁Be preferably at least 1 material with the group shown in group shown in the above-mentioned formula (2) and/or the above-mentioned formula (3).

Also have, macromolecular compound of the present invention can also contain the repeating unit beyond the repeating unit shown in above-mentioned formula (1) and (30) under the precursor that does not damage fluorescent characteristic or charge transport characteristic, but the compound that preferably constitutes by the repeating unit shown in the formula (1) in fact, the compound that constitutes by the repeating unit shown in formula (1) and the formula (30) in fact.Repeating unit with vinylidene or non-conjugated part partly link also can, the vinylidene or the non-conjugated part that comprise them in the repeating unit also can.As the integrated structure that comprises above-mentioned non-conjugated part, can illustration structure shown below, structure that structure shown below and vinylidene are combined and the combination structure that forms more than 2 wherein etc. in structure shown below.At this, R ' is the group of selecting from the substituting group identical with above-mentioned substituting group, and Ar represents the alkyl of 6～60 of carbon numbers.

[changing 45]

With regard to macromolecular compound of the present invention, the number-average molecular weight polystyrene conversion is 10 ³～10 ⁸, be preferably 3 * 10 from the angle of film-forming properties ³～5 * 10 ⁶, more preferably 5 * 10 ³～2 * 10 ⁶, and then be preferably 1 * 10 ⁴～1 * 10 ⁶

Macromolecular compound of the present invention is preferably solid-state and has epipolic compound.And then be preferably solid-state and have fluorescence, and the number-average molecular weight polystyrene conversion is 10 ³～10 ⁸Compound.

In addition, macromolecular compound of the present invention also can have phosphorescence.

As good solvent for macromolecular compound of the present invention, but illustration chloroform, methylene dichloride, ethylene dichloride, tetrahydrofuran (THF), toluene, dimethylbenzene, mesitylene, perhydronaphthalene, n-butylbenzene etc.Different and different according to the structure of these macromolecular compounds and molecular weight, they can dissolve more than the 0.1 weight % in these solvents usually.

Macromolecular compound of the present invention can be random, block or graft copolymer, also can be to have the polymer of their intermediate structure, for example have a random copolymers of block.Consider from the viewpoint of the high macromolecular compound of the quantum yield that obtains fluorescence, compare, preferably have random copolymers or the segmented copolymer or the graft copolymer of block with random copolymers completely.Comprise also that to have side chain and terminal part on the main chain be situation or branch-shape polymer more than 3.

Then, the manufacture method to macromolecular compound of the present invention describes.

" the Ar of the repeating unit shown in the above-mentioned formula (1) ₁Has the group shown in above-mentioned formula (2) or the above-mentioned formula (3) as substituent situation (side substitution) "

Macromolecular compound of the present invention for example can be made by the compound shown in the following formula is carried out polycondensation as one of raw material.

[changing 46]

[in the formula, R represents the group shown in the group shown in the above-mentioned formula (2), the above-mentioned formula (3), hydrogen atom, alkyl, alkoxyl group, alkylthio, alkyl silyl, alkylamino, aryl, aryloxy, arylalkyl, alkoxy aryl, aryl alkenyl, aromatic yl polysulfide yl, arylamino, 1 valency heterocyclic radical or cyano group.In the above-mentioned example, have a plurality of R, but they can be identical or different.Wherein, at least one is the group shown in group shown in the above-mentioned formula (2) or the above-mentioned formula (3) among the R.D ₁And D ₂Represent halogen atom, alkylsulphonic acid ester group, aryl sulfonic acid ester group, arylalkyl sulfonic acid ester group, boric acid ester, sulfonium methyl, Phosphonium methyl, phosphonic acid ester methyl, single halogenation methyl, boronate, formyl radical, cyano methyl or vinyl respectively independently.]

At this, as the alkylsulphonic acid ester group, can illustration methanesulfonic ester group, ethane sulfonic acid ester group, trifluoromethayl sulfonic acid ester group etc., as the aryl sulfonic acid ester group, can illustration Phenylsulfonic acid ester group, tosic acid ester group etc., as the arylalkyl sulfonic acid ester group, can illustration benzyl sulfonate group etc.

As the boric acid ester group, the group shown in can the following formula of illustration.

[changing 47]

As the group of sulfonium methyl shown in can the following formula of illustration.

-CH ₂S ⁺Me ₂X ^-,-CH ₂S ⁺Ph ₂X ^-(X represents halogen atom.)

Zuo is the group of Phosphonium methyl shown in can the following formula of illustration.

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

As the group of phosphonic acid ester methyl shown in can the following formula of illustration.

-CH ₂P(O)(OR”’) ₂

(R " ' expression alkyl, aryl or arylalkyl.)

As single halogenation methyl, can the illustration fluorinated methyl, methyl chloride, Diethylaminoethyl, iodate methyl.

As the method for polycondensation, for example have under the situation of vinylidene at main chain, use other monomers as required, but illustration for example:

(1) utilizes the Wittig of the compound of compound with aldehyde radical and Ju You phosphonium salt base to react and realize polymerization;

(2) utilize and to have aldehyde radical and realize polymerization with the Wittig of the compound of phosphonium salt base reacts;

(3) utilize compound to react and realize polymerization with Heck with compound of halogen atom with vinyl;

(4) utilize the Heck of compound to react and realize polymerization with vinyl and halogen atom;

(5) utilize compound to react and realize polymerization with Horner-Wadsworth-Emmons method with compound of alkyl phosphonic acid ester group with aldehyde radical;

(6) utilize the Horner-Wadsworth-Emmons method of compound to react and realize polymerization with aldehyde radical and alkyl phosphonic acid ester group;

(7) utilize the dehydrohalogenation method of compound to react and realize polycondensation with 2 above halogenation methyl;

(8) utilize the sulfonium salt decomposition method of compound to react and realize polycondensation with 2 above sulfonium salt bases;

(9) utilize compound to react and realize polymerization with Knoevenagel with compound of acetonitrile-base with aldehyde radical;

(10) utilize the Knoevenagel of compound to react to realize the method for polymerization etc. with aldehyde radical and acetonitrile-base;

(11) utilize the McMurry of compound to react to realize the method for polymerization etc. with 2 above aldehyde radicals.

In addition, as the manufacture method of macromolecular compound of the present invention, for example, can illustration:

(12) utilize the Suzuki coupled reaction to realize the polymeric method;

(13) utilize Grignard to react and realize the polymeric method;

(14) utilize Ni (0) catalyzer to realize the polymeric method;

(15) utilize FeCl ₃Deng oxygenant realize polymeric method, electrochemically oxidative polymerization method or

(16) utilization makes and has the suitable method that breaks away from basic intermediate polymer decomposition etc.

Reaction as having used Ni (0) catalyzer can be illustrated in zero-valent nickel coordination compound { Ni (COD) ₂Existence under carry out the polymeric method.

As the zero-valent nickel coordination compound, can illustration two (1, the 5-cyclooctadiene) nickel (0), (ethylidene) two (triphenylphosphine) nickel (0), four (triphenylphosphine) nickel etc.Wherein, from versatility and cheap preferred two (1, the 5-cyclooctadiene) nickel (0) of angle.

In addition, from improving the angle of yield, preferably add neutral dentate.

At this, neutral dentate is meant not have negatively charged ion and cationic dentate, can illustration 2,2 '-bipyridine, 1,10-phenanthroline, Ya Jia Ji bisoxazoline, N, N '-nitrogenous dentates such as tetramethylethylened, tertiary phosphine dentates such as triphenylphosphine, trimethylphenyl phosphine, tributylphosphine, triple phenoxyl phosphine etc., from versatility, the cheap preferred nitrogenous dentate of angle, preferred especially 2 from the angle of hyperergy, high yield, 2 '-bipyridine.Particularly, preferably in the system that contains two (1, the 5-cyclooctadiene) nickel (0), add as 2 of neutral dentate the system of 2 '-bipyridine from improving the angle of polymer yield.

As polymer solvent, so long as do not hinder the polymeric solvent both can, there is no particular limitation, for example can enumerate acid amides series solvent, aromatic hydrocarbons series solvent, ether series solvent, ester series solvent etc.

At this, as the acid amides series solvent, for example can enumerate N, dinethylformamide, N,N-dimethylacetamide etc.

As the aromatic hydrocarbons series solvent, be the solvent that constitutes by aromatic hydrocarbon compound, for example, can enumerate, benzene,toluene,xylene, Three methyl Benzene, tetramethyl-benzene, butylbenzene, naphthalene, tetraline etc., preferred toluene, dimethylbenzene, tetraline, tetramethyl-benzene etc.

In addition, as the ether series solvent, it is the group that constitutes by the compound that forms in conjunction with alkyl with Sauerstoffatom, for example can enumerate Di Iso Propyl Ether, tetrahydrofuran (THF), 1,4-diox, diphenyl ether, glycol dimethyl ether, t-butyl methyl ether etc., preferably for macromolecular compound the tetrahydrofuran (THF), 1 of good solvent, 4-diox etc.

In addition, from improving polymerizability, deliquescent viewpoint, can also mix and use these solvents.

Polyreaction is carried out under inert gas atmospheres such as argon, nitrogen usually.

Polymerization time was generally about 0.5～100 hour, but from the angle of manufacturing cost, preferably in 30 hours.

Polymerization temperature is generally about 0～200 ℃, but from high yield, the low angle of taking, preferred 0～100 ℃ of heating.

Also have, polyreaction is usually under the inert gas atmospheres such as argon, nitrogen, carry out in the reaction system of zero-valent nickel coordination compound catalyzer non-inactivation.

As the example that in the presence of the Pd catalyzer, reacts, for example can enumerate the Suzuki coupled reaction.

As the palladium catalyst that in the Suzuki coupled reaction, uses, can the illustration palladium, palladium [four (triphenylphosphine)] coordination compound, two (tricyclohexyl phosphine) palladium coordination compound etc.

As the phosphorus dentate, can illustration triphenylphosphine, three (o-tolyl) phosphine, 1, two (diphenylphosphino) propane of 3-etc.

For example, use palladium [four (triphenylphosphine)], with inorganic alkali such as salt of wormwood, yellow soda ash, hydrated bartas, organic alkali such as triethylamine, or inorganic salt such as cesium fluoride add more than the equivalent with respect to monomer, preferably add 1～10 equivalent and react.Inorganic salt as the aqueous solution, are reacted with 2 phase systems and also can.As solvent, can illustration N, dinethylformamide, toluene, glycol dimethyl ether, tetrahydrofuran (THF) etc.Though also relevant with solvent, be adapted at using under the temperature about 50～160 ℃.Be warming up near the boiling point of solvent, also can reflux.Reaction times is about 0.2 hour to 200 hours.Also have, polyreaction is usually under the inert gas atmospheres such as argon, nitrogen, carry out in the reaction system of Pd (0) catalyzer non-inactivation.

Wherein, utilize Wittig reaction polymerization, utilize the Heck reaction polymerization, utilize the Horner-Wadsworth-Emmons method polymerization, utilize the polymerization of Knoevenagel reaction and utilize the Suzuki coupled reaction to carry out the polymeric method, utilize that the polymeric method is carried out in the Grignard reaction, (0) catalyzer carries out the polymeric method to utilize Ni, therefore control texture is preferred easily.And then, from obtaining the easy of raw material and polyreaction operation easily, more preferably utilize Ni (0) catalyzer to carry out the polymeric method.

" situation (terminal group) that has the group shown in above-mentioned formula (2) and/or the above-mentioned formula (3) at least one side of macromolecular chain " with the repeating unit shown in the above-mentioned formula (1)

Macromolecular compound of the present invention can be by method manufacturing as described below, that is: make corresponding to the monomer polymerization of more than one repeating units and had the polymkeric substance that breaks away from base endways, make this polymkeric substance and corresponding to the method for the monomer reaction of above-mentioned formula (2) and/or (3); Under coexistence has monomeric situation corresponding to above-mentioned formula (2) and/or (3), make method corresponding to the monomer polymerization of more than one repeating units etc.

Macromolecular compound of the present invention for example can be by method manufacturing as described below, that is: make more than one monomers shown in general formula (101) and/or (102), with the method for the monomer reaction shown in general formula (104) and/or (105).

Y ₁-Ar ₁-Y ₂ (101)

Y ₃-Ar ₂-Y ₄ (102)

Y ₇-E ₁ (104)

Y ₈-E ₂ (105)

(in the formula, Ar ₁And Ar ₂Represent arylidene, divalent heterocyclic radical or divalent aromatic series amido respectively independently.E ₁And E ₂The group of representing above-mentioned formula (2) and/or (3) respectively independently.Y ₁, Y ₂, Y ₃, Y ₄, Y ₇And Y ₈Expression breaks away from base independently respectively.Wherein, E ₁And E ₂Differ from one another.)

As breaking away from base, can enumerate halogen atom, alkylsulfonyloxy, aryl-sulfonyl oxygen or-B (OR ₁₁) ₂(at this, R ₁₁Be hydrogen atom or alkyl.) shown in group.

At this, as halogen atom, can enumerate chlorine atom, bromine atoms, iodine atom, preferred chlorine atom, bromine atoms, most preferably bromine atoms.For alkylsulfonyloxy, can be replaced by fluorine atom, can enumerate trifluoromethane sulfonyloxy etc.For aryl-sulfonyl oxygen, can be replaced by alkyl, can enumerate phenyl sulfonyloxy, three sulfonyloxies etc.

-B (OR ₁₁) ₂In the shown group, R ₁₁Be hydrogen atom or alkyl.Be generally about 1～20 as the alkyl carbon number, can enumerate methyl, ethyl, propyl group, butyl, hexyl, octyl group, dodecyl etc.In addition, also can link the formation ring between the alkyl.

As-B (OR ₁₁) ₂Shown group, particularly, can enumerate following group:

[changing 48]

Preferably:

[changing 49]

General formula (104) and (105) monomeric total add-on are generally 0.1～20 mole of % with respect to monomeric total add-on of general formula (101) and (102), are preferably 0.2～10 mole of %.

Manufacture method as macromolecular compound of the present invention, can illustration, for example with the monomer of above-mentioned correspondence, utilize Suzuki reaction carrying out polymeric method (Chem.Rev., the 95th volume, 2457 pages (nineteen ninety-five)), utilize Grignard reaction to carry out polymeric method (upright altogether the publication, Gao Fen Machine can roll up by material シリ one ズ the 2nd, the anti-ying of Polymer Synthesizing と (2), the 432-3 page or leaf), utilize the Yamamoto polymerization to carry out polymeric method (Prog.Polym.Sci., the 17th the volume, 1153-1205 page or leaf, 1992), utilize FeCl ₃Deng oxygenant carry out the polymeric method, with the method for electrochemically oxidative polymerization (ball Shan ， experiment Talk seat the 4th edition, 28 volumes, 339-340 page or leaf) etc.

The situation of using the Suzuki reaction is described.In this case, for example can use monomer as described below, these monomers be reacted in the presence of Pd (0) catalyzer make, above-mentioned monomer is: Y ₁And Y ₂Be independently-B (OR respectively ₁₁) ₂(at this, R ₁₁Be hydrogen atom or alkyl) shown in group, Y ₃And Y ₄Be halogen atom, alkylsulfonyloxy or aryl-sulfonyl oxygen independently respectively, Y ₇For-B (OR ₁₁) ₂(at this, R ₁₁Be hydrogen atom or alkyl) shown in group, Y ₈Monomer for halogen atom, alkylsulfonyloxy or aryl-sulfonyl oxygen.

Also have, in this case, be supplied in reaction, have 2 and break away from more than 2 kinds in the monomer of base, at least a kind for having 2-B (OR ₁₁) ₂(at this, R ₁₁Be hydrogen atom or alkyl) monomer, at least a kind for having the monomer of 2 halogen atoms, alkylsulfonyloxy or aryl-sulfonyl oxygens, in requiring so monomeric reaction, usually, make the monomer reaction shown in formula (101)～(102) about 0.2～100 hour after, in this system, add monomer (105), make its reaction about 0.5～50 hour, afterwards, monomer (104) is added in the system, make its reaction about 0.5～50 hour.

As Pd (0) catalyzer, for example, use palladium [four (triphenylphosphine)] (0), palladium acetic ester system (for example with triphenylphosphine derivative reduction palladium catalyzer system) etc., in addition, two (triphenylphosphine) palladiums (II) of dichloro etc., with inorganic alkali such as salt of wormwood, yellow soda ash, hydrated bartas, organic alkali such as triethylamine, or inorganic salt such as cesium fluoride, add more than the equivalent with respect to monomer, preferably add 1～10 equivalent and react.Inorganic salt as the aqueous solution, are reacted with 2 phase systems and also can.As solvent, can illustration N, dinethylformamide, toluene, glycol dimethyl ether, tetrahydrofuran (THF) etc.Though also relevant with solvent, be adapted at using under the temperature about 50～160 ℃.Be warming up near the boiling point of solvent, also can reflux.Reaction times is about 0.2 hour to 200 hours.Also have, polyreaction is usually under the inert gas atmospheres such as argon, nitrogen, carry out in the reaction system of Pd (0) catalyzer non-inactivation.

The situation of using three polymerizations is described.In this case, for example, use Y ₁, Y ₂, Y ₃, Y ₄, Y ₇And Y ₈Be the monomer of halogen atom, alkylsulfonyloxy or aryl-sulfonyl oxygen independently respectively, these monomers are reacted in the presence of Ni (0) coordination compound, can make polymkeric substance thus as purpose.Reaction normally reaches monomer (101), (102), (104) the whole mixing of (105) and implements.

Polymerization is to carry out in the presence of Ni (0) coordination compound (zero-valent nickel coordination compound).As nickel coordination compound, comprising: with the direct method of using of zero-valent nickel; With nickel salt is reacted in the presence of reductive agent, in system, produce zero-valent nickel, make the method for its reaction.As the zero-valent nickel coordination compound, can illustration two (1, the 5-cyclooctadiene) nickel (0), (ethylidene) two (triphenylphosphine) nickel (0), four (triphenylphosphine) nickel etc.Wherein, from versatility and cheap preferred two (1, the 5-cyclooctadiene) nickel (0) of angle.In addition, from improving the angle of yield, preferably add neutral dentate.At this, neutral dentate is meant not have negatively charged ion and cationic dentate, can illustration 2,2 '-bipyridine, 1,10-phenanthroline, Ya Jia Ji bisoxazoline, N, N '-nitrogenous dentates such as tetramethylethylened, tertiary phosphine dentates such as triphenylphosphine, trimethylphenyl phosphine, tributylphosphine, triple phenoxyl phosphine etc., from versatility, the cheap preferred nitrogenous dentate of angle, preferred especially 2 from the angle of hyperergy, high yield, 2 '-bipyridine.Particularly, preferably in the system that contains two (1, the 5-cyclooctadiene) nickel (0), add as 2 of neutral dentate the system of 2 '-bipyridine from improving the angle of polymer yield.In system, make in the method for zero-valent nickel reaction, can enumerate nickelous chloride, nickel acetate etc. as nickel salt.As reductive agent, can enumerate zinc, sodium hydroxide, hydrazine and derivative thereof, lithium aluminium hydrate etc., can use ammonium iodide, lithium iodide, potassiumiodide etc. as additive as required.As polymer solvent, so long as do not hinder the polymeric solvent both can, there is no particular limitation, but preferably contain the solvent of more than one aromatic hydrocarbons series solvents and/or ether series solvent.At this,, for example, can enumerate benzene,toluene,xylene, Three methyl Benzene, tetramethyl-benzene, butylbenzene, naphthalene, tetraline etc., preferred toluene, dimethylbenzene, tetraline, tetramethyl-benzene etc. as the aromatic hydrocarbons series solvent.In addition, as the ether series solvent, for example can enumerate Di Iso Propyl Ether, tetrahydrofuran (THF), 1,4-diox, diphenyl ether, glycol dimethyl ether, t-butyl methyl ether etc., preferably for macromolecular compound the tetrahydrofuran (THF), 1 of good solvent, 4-diox etc.Tetrahydrofuran (THF) most preferably in the solvent.In addition, from improving polymerizability, deliquescent angle, as solvent only otherwise hinder polyreaction, also can use the mixed solvent of the solvent beyond aromatic hydrocarbons series solvent and/or ether series solvent and aromatic hydrocarbons series solvent and the ether series solvent.

Operations etc. for example can be opened the method described in the 2000-44544 communique based on the spy and carry out.For the polymerization of Yamamoto, for example, polyreaction in the tetrahydrofuran solvent, under 60 ℃ of temperature, is carried out under the existence of zero-valent nickel coordination compound, neutral dentate normally in inert gas atmospheres such as argon, nitrogen.Polymerization time was generally about 0.5～100 hour, but from the angle of manufacturing cost, preferably in 10 hours.Polymerization temperature is generally about 0～200 ℃, but from high yield, the low angle of taking, preferred 20～100 ℃ of heating.

In addition, in use under the situation of property dentate, from the angle of reaction yield and cost, as its usage quantity,, be preferably about 0.5～10 mole with respect to 1 mole of zero-valent nickel coordination compound, more preferably 0.8～1.5 mole, and then be preferably 0.9～1.1 mole.

The usage quantity of zero-valent nickel coordination compound, just there is no particular limitation so long as do not hinder the amount of polyreaction, but if usage quantity is very few, the tendency of molecular weight step-down is arranged then, if usage quantity is excessive, the tendency that then has aftertreatment to become loaded down with trivial details.Therefore,, be preferably 0.1～10 mole with respect to 1 mole of monomer, more preferably 1～5 mole, and then be preferably 1.7～3.5 moles.

Produce after the macromolecular compound of the present invention, can carry out other operations such as habitual lock out operation such as acid cleaning, alkali cleaning, neutralization, water cleaning, organic solvent cleaning, redeposition, centrifugation, extraction, column chromatography analysis, purification operations, drying as required to it.

Macromolecular compound of the present invention is being used as under the situation of electronic material, its purity exerts an influence to each characteristic, therefore preferably in manufacture method of the present invention, carry out above-mentioned lock out operation, purification operations fully, remove unreacted monomer, by product, catalyst residue etc. fully.

Dry so long as under the condition of removing remaining solvent fully, carry out both can.In order to prevent the macromolecular compound sex change, preferred shading drying under inert atmosphere.In addition, preferably can not carry out drying under the temperature of thermally denature at macromolecular compound.

Macromolecular compound of the present invention can be used as luminescent material.And then, can be used as charge transport material, organic semiconductor material, optical material or be used as electro-conductive material by mixing.

＜polymeric composition 〉

Polymeric composition of the present invention comprises: solid-state and have fluorescence, and be 10 with the number-average molecular weight of polystyrene conversion ³～10 ⁸The macromolecular compound of the invention described above beyond macromolecular compound and the macromolecular compound of the invention described above.The characteristic when as long as macromolecular compound beyond the macromolecular compound of the invention described above has improved the solvability in the solvent, fluorescence intensity, life-span or brightness etc. as element etc., just there is no particular limitation, particularly, can enumerate the spy and open 2001-247861 number, spy and open 2001-507511 number, spy and open 2001-504533 number, spy and open 2001-278958 number, spy and open 2001-261796 number, spy and open the macromolecular compound described in 2001-226469 number, No. 3161058 communique of patent etc., but be not limited to this.Kind as the macromolecular compound beyond the macromolecular compound of the invention described above, can enumerate poly-fluorenes based compound, poly-fluorenes is a macromolecular compound, the polyarylene based compound, polyarylene is a macromolecular compound, the polyarylene vinylene based compound, polyarylene vinylene is a macromolecular compound, poly-1,2-diphenylethyllene based compound, poly-1,2-toluylene base system macromolecular compound, poly-1,2-diphenylethyllene vinylidene based compound, poly-1,2-diphenylethyllene vinylidene is a macromolecular compound, polypyridine two base system compounds, polypyridine two base system macromolecular compounds, alkoxyl group Polythiophene based compound, the alkoxyl group Polythiophene is a macromolecular compound etc., but is not limited to this.Wherein, preferably poly-fluorenes is that macromolecular compound, polyarylene are that macromolecular compound, polyarylene vinylene are macromolecular compound, poly-stilbene base system macromolecular compound, poly-stilbene base vinylidene macromolecular compound.

For the blended ratio, as long as the ratio of characteristic in the time of improving solvability, fluorescence intensity, life-span or brightness etc. in the solvent as element etc. just is not particularly limited, the ratio of macromolecular compound of the present invention is generally the scope of 5～95 weight % with respect to polymeric composition integral body.

In addition, as polymeric composition of the present invention, can enumerate and contain the composition that has substituent macromolecular compound of the present invention more than 2 kinds.As having substituent macromolecular compound of the present invention, can be with poly-fluorenes based polymer, polyarylene based polymer, polyarylene vinylene based polymer, poly-1,2-diphenylethyllene based polymer, poly-1,2-diphenylethyllene vinylidene based polymer, polypyridine two base system polymkeric substance, alkoxyl group Polythiophene based polymer, enumerate and have substituent macromolecular compound of the present invention, for polymeric composition of the present invention, can these macromolecular compounds of appropriate combination more than 2 kinds and obtain.In addition, there is no particular limitation for its cooperation ratio, but preferably make the ratio that comprises maximum macromolecular compounds in the composition, with respect to polymeric composition integral body, and in the scope of 5～90 weight %.

＜composition (fluid composition) 〉

Composition of the present invention comprises: the number-average molecular weight of the polystyrene conversion beyond the macromolecular compound of the invention described above and this macromolecular compound is 10 ³～10 ⁸Macromolecular compound.Number-average molecular weight as the polystyrene conversion beyond this macromolecular compound is 10 ³～10 ⁸Macromolecular compound, but illustration poly-(phenylene) and derivative thereof, poly-(benzofluorene) and derivative thereof, poly-(diphenylene-oxide) and derivative thereof, poly-(dibenzothiophene) and derivative thereof, poly-(carbazole) and derivative thereof, poly-(thiophene) and derivative thereof, poly-(phenylene vinylidene) and derivative thereof, poly-(fluorenes vinylidene) and derivative thereof, poly-(benzofluorene vinylidene) and derivative thereof, poly-(diphenylene-oxide vinylidene) and derivative thereof etc.Wherein, these derivatives are the compounds beyond the repeating unit shown in the above-mentioned formula (1).

Fluid composition of the present invention can be used for making luminous element or organic transistors such as polymeric light-emitting device.Fluid composition is to contain the composition that above-mentioned macromolecular compound and solvent form.In this manual, " fluid composition " be meant when making element to liquid, is meant that typically normal pressure (that is 1 normal atmosphere), 25 ℃ are down for liquid.In addition, fluid composition is called as black liquid, ink composition, solution etc. usually sometimes.

Fluid composition of the present invention except above-mentioned macromolecular compound, can also contain low molecular luminescence material, hole transporting material, electron transport materials, stablizer, be used to regulate viscosity and/or capillary additive, antioxidant etc.These any compositions can be used alone, can also be also with two or more.

The low molecular fluorescence material that can contain as fluid composition of the present invention, for example can enumerate, naphthalene derivatives, anthracene, anthracene derivant perylene perylene derivative, polymethine is a pigment, xanthene is a pigment, the coumarin series pigment, cyanine colour system pigment, the metal complex that the metal complex of oxine is had as dentate, the metal complex that the oxine derivative is had as dentate, other fluorescence metal complex, aromatic amine, the tetraphenyl cyclopentadiene, the tetraphenyl cyclobutadiene, stilbene system, siliceous fragrant family; oxazole system, furoxane, thiazole system, four arylmethanes system, thiadiazoles system, pyrazoles system, metacyclophane, the fluorescent material of low molecular compounds such as acetylene.Particularly, for example can enumerate the spy opens clear 57-51781 number, spy and opens material, the material known described in clear 59-194393 communique etc.

The hole transporting material that can contain as fluid composition of the present invention, for example, can list Polyvinyl carbazole and derivative thereof, polysilane and derivative thereof, on side chain or main chain, have polyorganosiloxane ramification, pyrazoline derivative, the arylamines derivative, 1 of aromatic amine, 2-diphenyl ethylene derivatives, triphenyl diamine derivative, polyaniline and derivative, Polythiophene and derivative thereof, polypyrrole and derivative thereof, poly-(to phenylene vinylidene) and derivative thereof, poly-(2, the inferior thienyl vinylidene of 5-) and derivative thereof etc.

The electron transport materials that can contain as fluid composition of the present invention, for example, but metal complex, poly quinoline and derivative thereof, polyquinoxaline and the derivative thereof of Lie Ju Chu oxadiazole derivative, anthraquinone bismethane and derivative, benzoquinones and derivative thereof, naphthoquinones and derivative thereof, anthraquinone and derivative thereof, four cyano anthraquinone bismethane and derivative thereof, fluorenone derivatives, phenylbenzene dicyano ethylidene and derivative thereof, connection para benzoquinone derivative or oxine and derivative thereof, poly-fluorenes and derivative thereof etc.

As the stablizer that fluid composition of the present invention can contain, for example, can enumerate phenol is antioxidant, phosphorous antioxidant etc.

Regulate viscosity and/or capillary additive as fluid composition of the present invention being used to of can containing, if will be used to improve viscosity high-molecular weight compound (tackifier) or lean solvent, be used to reduce viscosity low-molecular-weight compound, be used to reduce suitable combinations such as capillary tensio-active agent and use.

As above-mentioned high-molecular weight compound, so long as be dissolved in the solvent of fluid composition usually and the macromolecular compound that can not hinder luminous and charge transport gets final product.As the high-molecular weight compound, for example, can use high-molecular weight polystyrene, high-molecular weight polymethylmethacrylate etc.The weight-average molecular weight of the polystyrene conversion of above-mentioned high-molecular weight compounds is preferably more than 500,000, more preferably more than 1,000,000.In addition, also lean solvent can be used as tackifier.

The antioxidant that can contain as fluid composition of the present invention so long as contain at composition under the situation of solvent, is dissolved in this solvent and the antioxidant that can not hinder luminous and charge transport gets final product usually.As antioxidant, can list phenol is antioxidant, phosphorous antioxidant etc.By using antioxidant, can improve the storage stability of macromolecular material of the present invention in solvent.

Contain at fluid composition of the present invention under the situation of hole transporting material, the ratio of the hole transporting material in this fluid composition is generally 1 weight %～80 weight %, is preferably 5 weight %～60 weight %.Contain at fluid composition of the present invention under the situation of electron transport materials, the ratio of the electron transport materials in this fluid composition is generally 1 weight %～80 weight %, is preferably 5 weight %～60 weight %.

When making polymeric light-emitting device, using this fluid composition to carry out under the film forming situation, after this fluid composition of coating, only remove to desolvate and get final product by drying, in addition when hybrid charge is carried material or luminescent material, also can be suitable for identical method, so highly beneficial on making.Wherein, when drying, can be dry under the state that is warmed to about 50～150 ℃, in addition, also can be decompressed to 10 ^-3Make its drying about Pa.

Film as using fluid composition can use spin-coating method, teeming practice, nick plate coating process, notch board coating process, rod to be coated with coating processs such as method, rolling method, wire bar coating process, dip coating, spraying method, stencil printing, toppan printing, offset printing method, ink-jet printing process.

The ratio of the solvent in the fluid composition is all wts of this fluid composition relatively, is generally 1 weight %～99.9 weight %, is preferably 60 weight %～99.9 weight %, and then is preferably 90 weight %～99.8 weight %.The viscosity of fluid composition is according to print process and difference, under 25 ℃, be preferably the scope of 0.5～500mPas, under the situations of fluid composition via blowoff such as ink-jet printer method, obstruction in order to prevent to spray or crooked leap are preferably the scope of 0.5～20mPas 25 ℃ of following viscosity.

As the solvent that contains in the fluid composition, preferably can dissolve or disperse the solvent of this solvent composition in addition in this fluid composition.As this solvent, can the illustration chloroform, methylene dichloride, 1, the 2-ethylene dichloride, 1,1, the 2-trichloroethane, chlorobenzene, chlorine series solvents such as orthodichlorobenzene, ether series solvents such as tetrahydrofuran (THF) diox, toluene, dimethylbenzene, Three methyl Benzene, aromatic hydrocarbons series solvents such as mesitylene, hexanaphthene, methylcyclohexane, Skellysolve A, normal hexane, normal heptane, octane, positive nonane, aliphatic hydrocarbon series solvents such as n-decane, acetone, ethyl methyl ketone, ketone series solvents such as pimelinketone, vinyl acetic monomer, N-BUTYL ACETATE, methyl benzoate, ethyl cellosolve acetate ester series solvents such as (ethyl cellosolveacetate), ethylene glycol, ethylene glycol monobutyl ether, glycol monoethyl ether, methyl glycol, glycol dimethyl ether, propylene glycol, methylene diethyl ether, triglycol one ether, glycerine, 1, polyvalent alcohol and derivatives thereof such as 2-hexylene glycol, methyl alcohol, ethanol, propyl alcohol, Virahol, pure series solvent such as hexalin, sulfoxide series solvents such as methyl-sulphoxide, the N-N-methyl-2-2-pyrrolidone N-, N, acid amides series solvents such as dinethylformamide.In addition, these solvents can be used alone, and also can be used in combination multiple.In described solvent,, preferably contain more than one from viewpoints such as viscosity, film-forming propertiess: have the structure that contains 1 phenyl ring at least and fusing point below 0 ℃, boiling point is at the organic solvent more than 100 ℃.

As solvent types, composition beyond the solvent from fluid composition is to the solvability of organic solvent, homogeneity during film forming, viewpoints such as viscosity characteristics are set out, 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, mesitylene, n-proplbenzene, isopropyl benzene, n-butyl benzene, Isobuytel Benzene, trimethylphenylmethane, methoxybenzoyl, phenetole, the 1-methylnaphthalene, hexanaphthene, pimelinketone, phenylcyclohexane, dicyclohexyl, cyclohexenyl hexamethylene ketone, the n-heptyl hexanaphthene, the n-hexyl hexanaphthene, methyl benzoate, 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, return fragrant acyl, mesitylene, phenylcyclohexane, dicyclohexyl, at least a in the methyl benzoate.

From viewpoints such as the viewpoint of film-forming properties or element characteristics, the solvent types that contains in the fluid composition is preferably more than 2 kinds, and more preferably 2～3 kinds, and then be preferably 2 kinds.

Contain in fluid composition under the situation of 2 kinds of solvents, a kind of solvent wherein also can be solid state down at 25 ℃.From the viewpoint of film-forming properties, the boiling point of preferred a kind of solvent is more than 180 ℃, and the boiling point of another kind of solvent is less than 180 ℃, and more preferably the boiling point of a kind of solvent is more than 200 ℃, and the boiling point of another kind of solvent is less than 180 ℃.In addition, viewpoint from viscosity, under 60 ℃, be dissolved in the solvent more than preferably from fluid composition, having removed the 0.2 weight % of composition of the gained that desolvates, preferably under 25 ℃, more than having removed the 0.2 weight % of composition of the gained that desolvates, fluid composition is dissolved in a kind of solvent 2 kinds of solvents.

Contain in fluid composition under the situation of 3 kinds of solvents, 1～2 kind of solvent wherein also can be solid state down at 25 ℃.Viewpoint from film-forming properties, at least a kind of solvent in preferred 3 kinds of solvents is the solvent of boiling point more than 180 ℃, at least a solvent is the solvent of boiling point below 180 ℃, more preferably at least a kind of solvent in 3 kinds of solvents is boiling point solvent below 300 ℃ more than 200 ℃, and at least a solvent is the solvent of boiling point below 180 ℃.In addition, viewpoint from viscosity, under 60 ℃, 2 kinds of solvents that are dissolved in more than the 0.2 weight % of composition of the gained that desolvates in 3 kinds of solvents preferably from fluid composition, have been removed, preferably under 25 ℃, more than having removed the 0.2 weight % of composition of the gained that desolvates, fluid composition is dissolved in a kind of solvent 3 kinds of solvents.

In fluid composition, contain under the situation of solvent more than 2 kinds, viewpoint from viscosity and film-forming properties, the solvent that boiling point is the highest is preferably 40～90 weight % of the weight of the whole solvents that contain in the fluid composition, 50～90 weight % more preferably, and then be preferably 65～85 weight %.

-film-

Film of the present invention is described.This film is to use above-mentioned macromolecular compound to form.As the kind of film, can illustration luminous film, conductive membrane, organic semiconductor thin film etc.

From the viewpoint of the brightness of element or luminous voltage etc., the luminescent quantum yield of luminous film is preferably more than 50%, more preferably more than 60%, and then is preferably more than 70%.

The surface resistivity of conductive membrane is preferably below 1K Ω/.By the Lewis acid that in film, mixes, ionic compound etc., can improve electric conductivity.More preferably surface resistivity is 100 Ω/below the, and further preferred surface resistance is 10 Ω/below the.

For organic semiconductor thin film, a side big in electronic mobility or the hole mobility is preferably 10 ^-5Cm ²/ V/ is more than second, and more preferably 10 ^-3Cm ²/ V/ is more than second and then be preferably 10 ^-1Cm ²/ V/ is more than second.In addition, can use organic semiconductor thin film, make organic transistor.Particularly, SiO can be formed with ₂Form organic semiconductor thin film on the Si substrate Deng insulating film and gate electrode, form source electrode and drain electrode with Au, thus as organic transistor.

-organic transistor (macromolecular field effect transistor)-

Then, the macromolecular field effect transistor as a mode of organic transistor is described.

For macromolecular compound of the present invention, the material as macromolecular field effect transistor wherein is suitable as active coating.As the structure of macromolecular field effect transistor, usually, the active coating that source electrode and drain electrode contact are made of polymer and being set up, and then seize the insulation layer that contacts with active coating on both sides by the arms and gate electrode is set also can.

Macromolecular field effect transistor is formed on the supporting substrate usually.As supporting substrate, just there is no particular limitation so long as do not hinder material as the characteristic of field-effect transistor, but also can use glass substrate or flexible film substrate or plastic base.

Macromolecular field effect transistor can pass through known method, and for example the spy opens the method manufacturing described in the flat 5-110069 communique.

When forming active coating, with an organic solvent the macromolecular compound of solubility is highly beneficial on making, and is preferred therefore.As being dissolved in the macromolecular compound that makes the organic solvent solubility in the solvent and the method for the solution film forming that obtains can use spin-coating method, teeming practice, nick plate coating process, notch board coating process, rod to be coated with coating processs such as method, rolling method, wire bar coating process, dip coating, spraying method, stencil printing, toppan printing, offset printing method, ink-jet printing process.

Preferably after making macromolecular field effect transistor, the sealing macromolecular field effect transistor that is sealed to form.Thus, macromolecular field effect transistor is able to block, can suppress with atmosphere the decline of the characteristic of macromolecular field effect transistor.

As the method for sealing, can enumerate the method that covers with ultraviolet ray (UV) cured resin, heat reactive resin or inorganic SiONx film etc., with the method for applying sheet glass such as UV cured resin, heat reactive resin or film etc.Effective in order to make with atmospheric barrier effect, after making macromolecular field effect transistor, preferably do not make operation till the sealing be exposed under the state in the atmosphere (for example, the nitrogen atmosphere of drying, vacuum medium) and carry out.

-organic photovoltaic cell-

Then, organic photovoltaic cell is described.To as the organic photoelectric converter of a mode of organic photovoltaic cell, utilize photoelectric solid photo-electric conversion element to describe.

With regard to macromolecular compound of the present invention, material as organic photoelectric converter, wherein be suitable as the organic semiconductor layer of the Schottky barrier type element at the interface that utilizes organic semiconductor and metal, be suitable as the organic semiconductor layer of the pn heterojunction type element at the interface that utilizes between organic semiconductor and inorganic semiconductor or the organic semiconductor again.

And then, be suitable as electron donability polymer, electronics acceptance polymer in integral body (bulk) the heterojunction type element of the contact area that increases the donor receptor, again, be suitable as the organic photoelectric converter that uses the low molecular complex of polymer system, for example the electron donability conjugated system polymer (dispersion supporter) of the bulk heterojunction type organic photoelectric converter that forms as inferior furans (the Off ラ one レ Application) derivative of the dispersion of electron acceptor.

As the structure of organic photoelectric converter, for example in pn heterojunction type element, the ohmic properties electrode is set, for example on ITO, form the p type semiconductor layer, and then stacked n type semiconductor layer, the ohmic properties electrode is set thereon both can.

Organic photoelectric converter is formed on the supporting substrate usually.As supporting substrate, just there is no particular limitation so long as do not hinder material as the characteristic of organic photoelectric converter, but also can use glass substrate or flexible film substrate or plastic base.

Organic photoelectric converter can pass through known method, Synth.Met. for example, method described in 102,982 (1999) or Science, the method manufacturing described in 270,1789 (1995).

-polymeric light-emitting device (polymer LED)-

Under with the situation of macromolecular compound of the present invention,,, be preferably solid state and have fluorescence or the compound of phosphorescence therefore as macromolecular compound of the present invention owing to the luminous or phosphorescence that is used to from film as the luminescent material of polymer LED.

The feature of polymer LED of the present invention is, has luminescent layer between the electrode that is made of anode and negative electrode, contains polymeric composition of the present invention in this luminescent layer.

Also comprise among the polymer LED of the present invention: between at least one side's electrode and luminescent layer, the polymeric light-emitting device of the layer that comprises electroconductive polymer is set in abutting connection with this electrode; Between at least one side's electrode and luminescent layer, the polymeric light-emitting device of the insulation layer of average film thickness below 2nm is set in abutting connection with this electrode.

In addition, as polymer LED of the present invention, can list the polymer LED that electron supplying layer is set between negative electrode and luminescent layer, the polymer LED of hole transporting layer is set between anode and luminescent layer, electron supplying layer is being set between negative electrode and the luminescent layer and polymer LED of hole transporting layer etc. is set between anode and luminescent layer.

As the structure of polymer LED of the present invention, can list following structure a)～d) particularly.

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

(herein, "/" represents that each layer is adjacent to carry out stacked.Below identical.)

Herein, luminescent layer is meant the layer with lighting function, and hole transporting layer is meant the layer with the function of carrying the hole, and electron supplying layer is meant the layer of the function with conveying electronic.Also have, electron supplying layer and hole transporting layer are referred to as charge transport layer.Luminescent layer, hole transporting layer, electron supplying layer also can use more than 2 layers independently of one another.

In addition, in the charge transport layer of the adjacent setting of electrode, for having the function of improving the electric charge injection efficiency of coming self-electrode, layer, be referred to as electric charge injection layer (hole injection layer, electron injecting layer) sometimes especially with the effect that reduces element drives voltage.

And then, in order to improve with the adaptation of electrode and to improve the electric charge injection efficiency of coming self-electrode, can be adjacent to be provided with above-mentioned electric charge injection layer or the insulation layer below the thickness 2nm with electrode, in addition, for the adaptation that improves the interface with prevent to mix etc., also can insert thin insulation layer at the interface of charge transport layer and luminescent layer.About stacked layer order and the thickness of quantity and each layer, can use aptly according to luminous efficiency and component life.

In the present invention, as the polymer LED that is provided with electric charge injection layer (electron injecting layer, hole injection layer), can list 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 list following e particularly)～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 list the layer that contains electroconductive polymer; The layer that is provided with between anode and hole transporting layer, contain a kind of material as described below, the ionization potential energy that this material had are about the intermediate value of anode material and the hole transporting material that contained in hole transporting layer; The layer that is provided with between negative electrode and electron supplying layer, contain a kind of material as described below, the electron affinity that this material had are about the intermediate value of cathode material and the electron transport materials that contained in electron supplying layer.

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 is above and 10 ³Below the S/cm, in order to reduce the leakage current between light-emitting pixels, more preferably 10 ^-5S/cm is above and 10 ²Below the S/cm, more preferably 10 ^-5S/cm is above and 10 ¹Below the S/cm.For the specific conductivity that makes this electroconductive polymer is 10 ^-5S/cm is above and 10 ³Below the S/cm, an amount of ion generally can mix in this electroconductive polymer.

Adulterated ionic kind is if hole injection layer then is a negatively charged ion; If electron injecting layer then is a positively charged ion.As anionic example, can list polystyrolsulfon acid ion, benzene sulfonamide acid ion, camphorsulfonic acid ion etc.; As cationic example, can list lithium ion, sodium ion, potassium ion, TBuA ion etc.As the thickness of electric charge injection layer, be 1nm～100nm for example, be preferably 2nm～50nm.

The material that uses in the electric charge injection layer, if according to and the material of electrode or adjacent layer between relation select aptly, can list polyaniline and derivative thereof, Polythiophene and derivative thereof, polypyrrole and derivative thereof, polyphenylene vinylene and derivative thereof, gather inferior thienyl vinylidene and derivative, poly quinoline and derivative thereof, polyquinoxaline and derivative thereof, on main chain or side chain, contain the electroconductive polymer, metal phthalocyanine (copper phthalocyanine etc.), carbon of the polymkeric substance etc. of aromatic amine structure etc.

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

For example can list following q particularly)～ab) structure.

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

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

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

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

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

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

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

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

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

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

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

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

Luminescent layer contains macromolecular compound of the present invention or polymeric composition, but also can mix the luminescent material beyond the above-mentioned macromolecular compound and use in luminescent layer.In addition, in polymer LED of the present invention, the luminescent layer that contains above-mentioned macromolecular compound luminescent material in addition also can be stacked with the luminescent layer that contains above-mentioned macromolecular compound.As this luminescent material, can use material known.As this luminescent material, can use material known.For low molecular compound, for example can use, naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine system, xanthene system, coumarin series, cyanine are metal complex, aromatic amine, tetraphenyl cyclopentadiene or derivatives thereof or the tetraphenylbutadiene or derivatives thereof etc. of isochrome prime system, oxine or derivatives thereof.

For example can use particularly and specially to open clear 57-51781 number, spy and open the known luminescent materials of putting down in writing in the clear 59-194393 communique such as luminescent material.

And then, as this luminescent material, can use the luminous coordination compound or derivatives thereof of following triplet state etc.

[changing 50]

[changing 51]

[changing 52]

In addition, for example can use macromolecular compound described in the WO03/001616, that contain the luminous coordination compound of triplet state etc.

There is no particular limitation for the film of luminescent layer, for example can the illustration utilization by the method for solution film forming.

As method, can use spin-coating method, teeming practice, nick plate coating process, notch board coating process, rod to be coated with coating processs such as method, rolling method, wire bar coating process, dip coating, spraying method, stencil printing, toppan printing, offset printing method, ink-jet printing process by solution film forming.

As the solvent that in film forming, uses by solution, but illustration toluene, dimethylbenzene, chloroform, tetrahydrofuran (THF).

As the thickness of luminescent layer, according to employed material difference, optimum value difference, as long as select according to the condition that can make driving voltage and luminous efficiency reach the value of appropriateness, for example can be 1nm～1 μ m, be preferably 2nm～500nm, more preferably 5nm～200nm.

Have under the situation of hole transporting layer at polymer LED of the present invention, as employed hole transporting material, can list the Polyvinyl carbazole or derivatives thereof, the polysilane or derivatives thereof, the polyorganosiloxane ramification that on side chain or main chain, has aromatic amine, pyrazoline derivative, the arylamines derivative, 1, the 2-diphenyl ethylene derivatives, the triphenyl diamine derivative, the polyaniline or derivatives thereof, the Polythiophene or derivatives thereof, the polypyrrole or derivatives thereof, poly-(to phenylene vinylidene) or derivatives thereof, perhaps poly-(2, the inferior thienyl vinylidene of 5-) or derivatives thereof etc.

Particularly, as this hole transporting material, can list the spy and open clear 63-70257 communique, spy and open clear 63-175860 communique, spy and open flat 2-135359 communique, spy and open flat 2-135361 communique, spy and open that flat 2-209988 communique, spy are opened flat 3-37992 communique, the spy opens material of putting down in writing in the flat 3-152184 communique etc.

Wherein, as the hole transporting material that is used for hole transporting layer, be preferably the Polyvinyl carbazole or derivatives thereof, the polysilane or derivatives thereof, the polyorganosiloxane ramification that on side chain or main chain, has aromatic amines compound, the polyaniline or derivatives thereof, the Polythiophene or derivatives thereof, poly-(to phenylene vinylidene) or derivatives thereof, perhaps gather (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 on side chain or main chain, has aromatic amine.Under the situation of low molecule hole transporting material, it is scattered in the polymer binder uses.

The Polyvinyl carbazole or derivatives thereof can be by for example carrying out cationoid polymerisation or the incompatible acquisition of radical polymerization by vinyl monomer.

As the polysilane or derivatives thereof, can list in Chem.Rev., the 89th volume, 1359 pages (1989); The compound of putting down in writing in the English Patent GB2300196 prospectus etc.Synthetic method also can adopt the method for putting down in writing in these documents, especially preferably adopts the Kipping method.

Therefore the polysiloxane or derivatives thereof preferably uses the polymkeric substance that has the structure of above-mentioned low molecule hole transporting material on side chain or main chain owing to almost do not have cavity conveying in the siloxane backbone structure.

Especially, can list the polymkeric substance of the structure of the aromatic amine that on side chain or main chain, has cavity conveying.

The film of hole transporting layer is not particularly limited, and for low molecule hole transporting material, can list by the mixing solutions with polymer binder and carry out film forming method.In addition, for the polymer hole transporting material, can list by solution and carry out film forming method.

As the solvent that is used for solution film forming,, just be not particularly limited so long as can make hole transporting material dissolved solvent.As this solvent, can list chlorine series solvents such as chloroform, methylene dichloride, ethylene dichloride; Ether series solvents such as tetrahydrofuran (THF); Aromatic hydrocarbons such as toluene, dimethylbenzene series solvent; Ketone such as acetone, ethyl methyl ketone series solvent; Ester series solvents such as ethyl acetate, butylacetate, ethyl cellosolve acetate.

As institute's blended polymer binder, preferably can obviously not suppress the tackiness agent of charge transport, and preferred the use can the powerful tackiness agent that absorbs to visible light.As this polymer binder, can list polycarbonate, polyacrylic ester, polymethyl acrylate, polymethylmethacrylate, polystyrene, polyvinyl chloride, polysiloxane etc.

Thickness as hole transporting layer, according to employed material difference, the optimum value difference, as long as select according to the condition that can make driving voltage and luminous efficiency reach the value of appropriateness, must be the thickness that pin hole can not take place at least, if but thickness is excessive, the driving voltage of element is improved, therefore bad.Therefore, as the thickness of this hole transporting layer, can be preferably 2nm～500nm, more preferably 5nm～200nm for for example 1nm～1 μ m.

Have under the situation of electron supplying layer at polymer LED of the present invention, as employed electron transport materials, can use material known, but Lie Ju Chu oxadiazole derivative, 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, fluorenone derivatives, phenylbenzene dicyano ethylidene or derivatives thereof, connection para benzoquinone derivative, the perhaps metal complex of oxine or derivatives thereof, the poly quinoline or derivatives thereof, the polyquinoxaline or derivatives thereof, poly-fluorenes or derivatives thereof etc.

Can list particularly and open clear 63-70257 communique, spy the spy and open clear 63-175860 communique, spy and open flat 2-135359 communique, spy and open flat 2-135361 communique, spy and open that flat 2-209988 communique, spy are opened flat 3-37992 communique, the spy opens material of putting down in writing in the flat 3-152184 communique etc.

The wherein metal complex of You Xuan oxadiazole derivative, benzoquinones 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, 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, and carries material for low molecular electronic, can list by the vacuum vapour deposition of powder or by solution or molten state and carry out film forming method; For the polymer electron transport materials, can list by solution or molten state and carry out film forming method.When carrying out film forming, also can merge the use polymer binder by solution or molten state.

Carry out film forming solvent as being used for by solution, so long as electron transport materials and/or polymer binder dissolved solvent just can be not particularly limited.As this solvent, can list chlorine series solvents such as chloroform, methylene dichloride, ethylene dichloride; Ether series solvents such as tetrahydrofuran (THF); Aromatic hydrocarbons such as toluene, dimethylbenzene series solvent; Ketone such as acetone, ethyl methyl ketone series solvent; Ester series solvents such as ethyl acetate, butylacetate, ethyl cellosolve acetate.

As carrying out film forming method, can use spin-coating method, teeming practice, nick plate coating process, notch board coating process, rod to be coated with coating processs such as method, rolling method, wire bar coating process, dip coating, spraying method, stencil printing, toppan printing, offset printing method, ink-jet printing process by solution or molten state.

As being used for the blended polymer binder, preferably can not suppress the tackiness agent of charge transport significantly, and preferred the use can the powerful tackiness agent that absorbs to visible light.As this polymer binder, can list 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 or polysiloxane etc.

Thickness as electron supplying layer, according to employed material difference, the optimum value difference, as long as select according to the condition that can make driving voltage and luminous efficiency reach the value of appropriateness, but must be the thickness that pin hole can not take place at least, if thickness is excessive, the driving voltage of element is improved, therefore bad.Therefore,, can be for example 1nm～1 μ m, be preferably 2nm～500nm, more preferably 5nm～200nm as the thickness of this electron supplying layer.

Be used to form the substrate of polymer LED of the present invention, as long as, can list for example glass, plastics, macromolecule membrane, silicon substrate etc. at the substrate that forms electrode, can not change when forming organic layer.Under the situation of opaque substrate, preferably its counter-electrodes is transparent or semitransparent.

Among the polymer LED of the present invention, usually, at least one side of the electrode that is made of anode and negative electrode is transparent or semitransparent, and anode side is preferably transparent or semitransparent.As anode material, can use the metal oxide film of electroconductibility, translucent metallic film etc.Particularly, can use those by Indium sesquioxide, zinc oxide, stannic oxide and belong to film (NESA etc.) that the conductive glass of the formations such as indium-tin-oxide (ITO), indium-zinc oxide of their complex body makes and gold, platinum, silver, copper etc., preferred ITO, indium-zinc oxide, stannic oxide.As making method, can list vacuum vapour deposition, sputtering method, ion plating method, electrochemical plating etc.In addition, as this anode, can use organic nesa coating of polyaniline or derivatives thereof, Polythiophene or derivatives thereof etc.For the anodic thickness, can suit to select according to the perviousness and the specific conductivity of light, for example can be 10nm～10 μ m, be preferably 20nm～1 μ m, more preferably 50nm～500nm.In addition, easier for electric charge is injected, can layer that be made of phthalocyanine derivates, electroconductive polymer, carbon etc. or the layer below the average film thickness 2nm that is made of metal oxide, metal fluoride, organic insulation etc. be set on the anode.

As the cathode material that uses among the polymer LED of the present invention, the preferred little material of work function.For example can use, metal such as lithium, sodium, potassium, rubidium, caesium, beryllium, magnesium, calcium, strontium, barium, aluminium, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium and by their central alloys that forms more than 2 kinds or by they central more than a kind with gold and silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin in alloy, graphite or the compound between graphite layers etc. that form more than a kind.As the example of alloy, can list 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 formed stepped construction more than 2 layers.For the thickness of negative electrode, can suit to select according to specific conductivity and weather resistance, for example can be 10nm～10 μ m, be preferably 20nm～1 μ m, more preferably 50nm～500nm.

As the making method of negative electrode, can adopt vacuum vapour deposition, sputtering method or with laminating of metallic film hot pressing etc.In addition; can be between negative electrode and organic matter layer; layer that setting is made of electroconductive polymer or the layer below the average film thickness 2nm that constitutes by metal oxide, metal fluoride, organic insulation etc.; after making negative electrode, also can be provided for protecting the protective layer of this polymer LED.In order to use this polymer LED steadily in the long term, and, protective layer and/or protective guard are set preferably for from the outer protection element.

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. is implemented on the surface, can adopt the method that this protective guard is fit together and seals with heat effect resin or photo-curable resin and device substrate as protective guard.If use dividing plate to keep the space, can prevent easily that then element from sustaining damage.If in this space, enclose inert gasses such as nitrogen or argon gas, then can prevent the oxidation of negative electrode, and then can easily be suppressed at the infringement that the moisture that adsorbs in the manufacturing process brings element in this space by siccative such as barium oxide are set.Wherein, preferably adopt any scheme more than a kind.

The back of the body illuminator that polymer LED of the present invention can be used as flat light source, segmentation display unit, dot matrix display unit, liquid crystal indicator waits and uses.

Planar luminous in order to use polymer LED of the present invention to obtain, as long as planar anode and negative electrode are disposed overlappingly.In addition, luminous in order to obtain pattern-like, following several method is arranged: the method that a kind of template of the window that has formed pattern form is set on the surface of above-mentioned planar luminous element; Form the organic matter layer of very thick non-luminescent part, thereby make its in fact non-luminous method; The either party of male or female or both sides' electrode is formed the method for pattern-like.According to any method in these methods, by forming pattern and several electrodes being disposed according to carrying out open/close mode independently, promptly can obtain can display digit or the display element of the sectional type of literal, simple symbol etc.And then, in order to make the dot matrix element, as long as anode and negative electrode are all formed ribbon and be configured with making its square crossing.By the method that the polymeric luminescent material that multiple illuminant colour is different separately is coated with, perhaps use the method for colour filter or use fluorescence transcoding filter device, all can reach the purpose that partial colour shows, broken colour shows.The dot matrix element can passive drive, also can carry out active driving with combinations such as TFT.These display elements can be used as the display unit of the view finder of computer, TV, mobile termination, mobile telephone, on-vehicle navigation apparatus (camavigation), pick up camera etc. and use.

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

In addition, macromolecular compound of the present invention can be as laser with pigment, organic photovoltaic cell with material, effective organic semiconductor, the conductive membrane material of organic crystal.

Embodiment

Embodiment is shown below, so that illustrate in greater detail the present invention, but the present invention is not subjected to the qualification of these embodiment.

At this, for number-average molecular weight and weight-average molecular weight, be solvent with the tetrahydrofuran (THF), utilize gel permeation chromatography (GPC) (Shimadzu Seisakusho Ltd.: LC-10Avp), obtain the number-average molecular weight and the weight-average molecular weight of polystyrene conversion.

Implement sharp 1

Synthesizing of＜monomer (1) 〉

Synthesis example (1)

With following compound (A):

[changing 53]

5.0g He phenoxazine 2.56g is dissolved in the o-dichlorobenzene of 60g.After in this solution, adding 40% aqueous sodium hydroxide solution, add benzyltriethylammoinium chloride 3.2g, reacted 25 hours down at 105 ℃.Also have, reaction is carried out under nitrogen atmosphere.

After the reaction, cool off this solution, leave standstill then, separatory reclaims the upper strata.Then, clean this solution with ion exchanged water after, heat up in a steamer under the decompression and desolvate.Then, add 40g toluene, after filtering, make this solution, make with extra care by being filled with the post of aluminum oxide to this solution.From this solution, under reduced pressure heat up in a steamer and desolvate, carry out drying under reduced pressure then, thereby obtain the following monomer of 2.0g (1).

[H-NMR: solvent C DCl3; 1.5～1.8ppm (6H), 3.4～3.6ppm (2H), 3.9～4.1ppm (2H), 6.4～7.4ppm (11H)]

[changing 54]

Synthesizing of＜macromolecular compound 1 〉

In reaction vessel, add 2,7-two bromo-9,9-dioctyl fluorene 1.18g, 2,7-two bromo-9,9-diisoamyl fluorenes 0.26g, described monomer (1) 0.12g and 2,2 '-bipyridine 1.4g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 80g through the degassing.Then, add two (1, the 5-cyclooctadiene) nickel (0) 2.5g in this mixing solutions, reaction is 14 hours under the room temperature.Also have, reaction is carried out under nitrogen atmosphere.

After the reaction, in this solution, inject methyl alcohol 120ml/ ion exchanged water 120ml mixing solutions, stir about 1 hour.Then, the precipitation that generates is reclaimed after filtration.Then, should precipitate drying under reduced pressure after, be dissolved in the toluene.Filter this toluene solution, remove insolubles after, make this toluene solution by being filled with the post of aluminum oxide, make with extra care thus.

Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with about 5% ammoniacal liquor.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with ion exchanged water.Then, this toluene solution is injected in the methyl alcohol, makes it generate the redeposition thing.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.48g.This polymkeric substance is called macromolecular compound 1.The polystyrene conversion weight-average molecular weight of the macromolecular compound 1 that obtains is 1.0 * 10 ⁵, number-average molecular weight is 4.1 * 10 ⁴

As described below by the structure of adding the repeating unit that comprises in the macromolecular compound 1 of inferring, be repeating unit A/ repeating unit B/ repeating unit C=72/18/10 by adding the mol ratio of inferring.

[changing 55]

Repeating unit A repeating unit B repeating unit C

Embodiment 2

Synthesizing of＜macromolecular compound 2 〉

In reaction vessel, add following structural formula:

[changing 56]

Shown monomer (2) 0.61g, described monomer (1) 0.19g and 2,2 '-bipyridine 0.7g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 50g through the degassing.Then, add two (1, the 5-cyclooctadiene) nickel (0) 1.24g in this mixing solutions, reaction is 32 hours under the room temperature.Also have, reaction is carried out under nitrogen atmosphere.

After the reaction, in this solution, inject methyl alcohol 40ml/ ion exchanged water 40ml mixing solutions, stir about 1 hour.Then, the precipitation that generates is reclaimed after filtration.Then, should precipitate drying under reduced pressure after, be dissolved in the toluene.Filter this toluene solution, remove insolubles after, make this toluene solution by being filled with the post of aluminum oxide, make with extra care thus.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.11g.This polymkeric substance is called macromolecular compound 2.The polystyrene conversion weight-average molecular weight of the macromolecular compound 2 that obtains is 7.5 * 10 ⁴, number-average molecular weight is 1.4 * 10 ⁴

As described below by the structure of adding the repeating unit that comprises in the macromolecular compound 2 of inferring, be repeating unit D/ repeating unit E=70/30 by adding the mol ratio of inferring.

[changing 57]

Repeating unit D repeating unit E

Comparative example 1

Synthesizing of＜macromolecular compound 3 〉

In reaction vessel, add 2,7-two bromo-9,9-dioctyl fluorene 0.59g, 2,7-two bromo-9,9-diisoamyl fluorenes 0.13g, following structural formula:

[changing 58]

Shown monomer (3) 0.071g and 2,2 '-bipyridine 0.56g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 60g through the degassing.Then, in this mixing solutions, add two (1, the 5-cyclooctadiene) nickel (0) 1.0g, reacted 4 hours down at 60 ℃.Also have, reaction is carried out under nitrogen atmosphere.

After the reaction, cool off this solution, in this solution, inject methyl alcohol 40ml/ ion exchanged water 40ml mixing solutions afterwards, stir about 1 hour.Then, the precipitation that generates is reclaimed after filtration.Then, should precipitate drying under reduced pressure after, be dissolved in the toluene.Filter this toluene solution, remove insolubles after, make this toluene solution by being filled with the post of aluminum oxide, make with extra care thus.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with 1 equivalent aqueous hydrochloric acid.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with about 5% ammoniacal liquor.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with ion exchanged water.Then, this toluene solution is injected in the methyl alcohol, makes it generate the redeposition thing.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.29g.This polymkeric substance is called macromolecular compound 3.The polystyrene conversion weight-average molecular weight of the macromolecular compound 3 that obtains is 4.2 * 10 ⁵, number-average molecular weight is 8.9 * 10 ⁴

As described below by the structure of adding the repeating unit that comprises in the macromolecular compound 3 of inferring, be repeating unit F/ repeating unit G/ repeating unit H=72/18/10 by adding the mol ratio of inferring.

[changing 59]

Repeating unit F repeating unit G repeating unit H

Comparative example 2

Synthesizing of＜macromolecular compound 4 〉

In reaction vessel, add described monomer (2) 0.61g, described monomer (3) 0.21g and 2,2 '-bipyridine 0.56g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 60g through the degassing.Then, in this mixing solutions, add two (1, the 5-cyclooctadiene) nickel (0) 1.0g, at room temperature reacted 40 hours.Also have, reaction is carried out under nitrogen atmosphere.

After the reaction, in this solution, inject methyl alcohol 40ml/ ion exchanged water 40ml mixing solutions, stir about 1 hour.Then, the precipitation that generates is reclaimed after filtration.Then, should precipitate drying under reduced pressure after, be dissolved in the toluene.Filter this toluene solution, remove insolubles after, make this toluene solution by being filled with the post of aluminum oxide, make with extra care thus.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with 1 equivalent aqueous hydrochloric acid.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with about 5% ammoniacal liquor.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with ion exchanged water.Then, this toluene solution is injected in the methyl alcohol, makes it generate the redeposition thing.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.35g.This polymkeric substance is called macromolecular compound 4.The polystyrene conversion weight-average molecular weight of the macromolecular compound 4 that obtains is 7.2 * 10 ⁴, number-average molecular weight is 2.0 * 10 ⁴

As described below by the structure of adding the repeating unit that comprises in the macromolecular compound 4 of inferring, be repeating unit M/ repeating unit N=70/30 by adding the mol ratio of inferring.

[changing 60]

Repeating unit M repeating unit N

Synthesis example (2)

With following compound (C):

[changing 61]

7.4g He phenoxazine 2.7g is dissolved in the o-dichlorobenzene of 60g.After in this solution, adding 40% aqueous sodium hydroxide solution, add benzyltriethylammoinium chloride 3.2g, reacted 25 hours down at 105 ℃.Also have, reaction is carried out under nitrogen atmosphere.

After the reaction, cool off this solution, leave standstill then, separatory reclaims the upper strata.Then, clean this solution with ion exchanged water after, heat up in a steamer under the decompression and desolvate.Then, add 40g toluene, filter to this solution.Make this solution by being filled with the post of aluminum oxide, make with extra care, heat up in a steamer under the decompression and desolvate.Then,, carry out drying under reduced pressure then, thereby obtain the following monomer of 2.7g (4) with the precipitation that washed with methanol obtains.

[H-NMR: solvent C DCl3; 1.5～1.9ppm (6H), 3.4～3.6ppm (2H), 3.8～4.0ppm (2H), 6.4～7.4ppm (12H)]

[changing 62]

Synthesizing of＜macromolecular compound 5 〉

In reaction vessel, add described monomer (2) 0.79g, described monomer (4) 0.064g and 2,2 '-bipyridine 0.56g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 60g through the degassing.Then, in this mixing solutions, add two (1, the 5-cyclooctadiene) nickel (0) 1.0g, reacted 4 hours down at 60 ℃.Also have, reaction is carried out under nitrogen atmosphere.

After the reaction, cool off this solution, in this solution, inject methyl alcohol 40ml/ ion exchanged water 40ml mixing solutions, stir about 1 hour.Then, the precipitation that generates is reclaimed after filtration.Then, should precipitate drying under reduced pressure after, be dissolved in the toluene.Filter this toluene solution, remove insolubles after, make this toluene solution by being filled with the post of aluminum oxide, make with extra care thus.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with 1 equivalent aqueous hydrochloric acid.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with about 5% ammoniacal liquor.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with ion exchanged water.Then, this toluene solution is injected in the methyl alcohol, makes it generate the redeposition thing.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.14g.This polymkeric substance is called macromolecular compound 5.The polystyrene conversion weight-average molecular weight of the macromolecular compound 5 that obtains is 2.5 * 10 ⁴, number-average molecular weight is 1.8 * 10 ⁴

Structure by the repeating unit that comprises in the macromolecular compound 5 that adds deduction, end is as described below, is repeating unit A '/terminal group B '=90/10 by adding the mol ratio of inferring.

[changing 63]

Repeating unit A ' terminal group B '

Embodiment 4

Synthesizing of＜monomer (5) 〉

Synthesis example (3)

With following compound (D):

[changing 64]

3.15g be dissolved in N, among the dinethylformamide 100g.Behind ice-cooled this solution, in this solution, in advance N-bromosuccinimide 1.62g is dissolved in N, the solution that forms among the dinethylformamide 50g through dropping in about 80 minutes.

After the dropping, then reacted 4 hours down at 0～5 ℃.Then, this reaction soln is warming up to room temperature, then at room temperature reacts a night.Also have, reaction is carried out under nitrogen atmosphere.

After the reaction, in this reaction soln, add ion exchanged water, after the cleaning, under reduced pressure heat up in a steamer from this solution and to desolvate.Then, in the precipitation that obtains, add toluene, after the dissolving, filter this toluene solution, remove insolubles.Then, make this toluene solution, make with extra care by being filled with the post of aluminum oxide.From this solution under reduced pressure heat up in a steamer desolvate after, drying under reduced pressure obtains following monomer (5) 2.0g.

[H-NMR: solvent C DCl3; 0.9～1.0ppm (3H), 1.3～1.7ppm (4H), 2.6～2.7ppm (2H), 5.7～6.0ppm (2H), 6.5～6.8 (5H, 7.1～7.4 (4H))]

[changing 65]

Synthesizing of＜macromolecular compound 6 〉

In reaction vessel, add described monomer (2) 0.79g, described monomer (5) 0.059g and 2,2 '-bipyridine 0.56g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 60g through the degassing.Then, in this mixing solutions, add two (1, the 5-cyclooctadiene) nickel (0) 1.0g, reacted 4 hours down at 60 ℃.Also have, reaction is carried out under nitrogen atmosphere.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.20g.This polymkeric substance is called macromolecular compound 6.The polystyrene conversion weight-average molecular weight of the macromolecular compound 6 that obtains is 2.5 * 10 ⁴, number-average molecular weight is 1.6 * 10 ⁴

Structure by the repeating unit that comprises in the macromolecular compound 6 that adds deduction, end is as described below, is repeating unit C '/terminal group D '=90/10 by adding the mol ratio of inferring.

[changing 66]

Repeating unit C ' terminal group D '

Comparative example 3

Synthesizing of＜macromolecular compound 7 〉

In reaction vessel, add described monomer (2) 0.79g, described monomer (3) 0.071g and 2,2 '-bipyridine 0.56g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 60g through the degassing.Then, in this mixing solutions, add two (1, the 5-cyclooctadiene) nickel (0) 1.0g, reacted 4 hours down at 60 ℃.Also have, reaction is carried out under nitrogen atmosphere.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.29g.This polymkeric substance is called macromolecular compound 7.The polystyrene conversion weight-average molecular weight of the macromolecular compound 7 that obtains is 1.0 * 10 ⁵, number-average molecular weight is 4.4 * 10 ⁴

The repeat unit structure that comprises in the macromolecular compound 7 of inferring is as described below by adding, and is repeating unit E '/repeating unit F '=90/10 by adding the mol ratio of inferring.

[changing 67]

Repeating unit E ' repeating unit F '

Embodiment 5

Synthesizing of＜macromolecular compound 8 〉

In reaction vessel, add described monomer (5) 0.059g, 2,7-two bromo-9,9-dioctyl fluorene 0.59g, 2,7-two bromo-9,9-diisoamyl fluorenes 0.13g and 2,2 '-bipyridine 0.56g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 60g through the degassing.Then, add two (1, the 5-cyclooctadiene) nickel (0) 1.0g in this mixing solutions, 60 ℃ were reacted 4 hours down.Also have, reaction is carried out under nitrogen atmosphere.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.20g.This polymkeric substance is called macromolecular compound 8.The polystyrene conversion weight-average molecular weight of the macromolecular compound 8 that obtains is 3.2 * 10 ⁴, number-average molecular weight is 1.6 * 10 ⁴

The repeating unit, the terminal group structure that comprise in the macromolecular compound 8 of inferring are as described below by adding, and are repeating unit A by adding the mol ratio of inferring "/repeating unit B "/terminal group C "=72/18/10.

[changing 68]

Repeating unit A " repeating unit B " terminal group C "

Embodiment 6

Synthesizing of＜macromolecular compound 9 〉

In reaction vessel, add following structural formula:

[changing 69]

Shown monomer (6) 0.81g, described monomer (5) 0.059g and 2,2 '-bipyridine 0.58g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 60g through the degassing.Then, in this mixing solutions, add two (1, the 5-cyclooctadiene) nickel (0) 1.0g, at room temperature reacted 23 hours.Also have, reaction is carried out under nitrogen atmosphere.

After the reaction, in this solution, inject methyl alcohol 40ml/ ion exchanged water 40ml mixing solutions, stir about 1 hour.Then, the precipitation that generates is reclaimed after filtration.Then, should precipitate drying under reduced pressure after, be dissolved in the toluene.Filter this toluene solution, remove insolubles after, clean this toluene solution with about 5% aqueous acetic acid, leave standstill, separatory, reclaim toluene solution then.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with 4% ammoniacal liquor.Then, clean this toluene solution, leave standstill, separatory, reclaim toluene solution then with ion exchanged water.Then, this toluene solution is injected in the methyl alcohol, makes it generate the redeposition thing.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.31g.This polymkeric substance is called macromolecular compound 9.The polystyrene conversion weight-average molecular weight of the macromolecular compound 9 that obtains is 2.9 * 10 ⁴, number-average molecular weight is 1.5 * 10 ⁴

Structure by the repeating unit that comprises in the macromolecular compound 9 that adds deduction, end is as described below, is repeating unit D by adding the mol ratio of inferring "/terminal group E "=90/10.

[changing 70]

Repeating unit D " terminal group E "

Embodiment 7

Synthesizing of＜macromolecular compound 10 〉

In reaction vessel, add described monomer (6) 0.81g, described monomer (1) 0.063g and 2,2 '-bipyridine 0.58g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 60g through the degassing.Then, add two (1, the 5-cyclooctadiene) nickel (0) 1.0g in this mixing solutions, reaction is 23 hours under the room temperature.Also have, reaction is carried out under nitrogen atmosphere.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.40g.This polymkeric substance is called macromolecular compound 10.The polystyrene conversion weight-average molecular weight of the macromolecular compound 10 that obtains is 1.4 * 10 ⁵, number-average molecular weight is 4.7 * 10 ⁴

As described below by the structure of adding the repeating unit that comprises in the macromolecular compound 10 of inferring, be repeating unit F by adding the mol ratio of inferring "/repeating unit G "=90/10.

[changing 71]

Repeating unit F " repeating unit G "

Embodiment 8

Synthesizing of＜monomer (7) 〉

Synthesis example 4

With above-claimed cpd (A) 5.0g He phenoxazine 2.8g be dissolved in the o-dichlorobenzene of 60g.After in this solution, adding 40% aqueous sodium hydroxide solution, add benzyltriethylammoinium chloride 3.2g, reacted 25 hours down at 105 ℃.Also have, reaction is carried out under nitrogen atmosphere.

After the reaction, cool off this solution, leave standstill then, separatory reclaims the upper strata.Then, clean this solution with ion exchanged water after, heat up in a steamer under the decompression and desolvate.Then, add 40g toluene, after filtering, make this solution, make with extra care by being filled with the post of aluminum oxide to this solution.From this solution, under reduced pressure heat up in a steamer and desolvate, obtain the 2.0g precipitation.Then, with refining this precipitation of silicagel column (toluene/hexane=2/8 mixed solvent) 1.5g.Solution from branch is got under reduced pressure heats up in a steamer and desolvates, and carries out drying under reduced pressure then, thereby obtains the following monomer of 0.9g (7).

[H-NMR: solvent C DCl3; 1.5～2.0ppm (6H), 3.8～4.0ppm (4H), 6.7～7.3ppm (11H)]

[changing 72]

Synthesizing of＜macromolecular compound 11 〉

In reaction vessel, add described monomer (6) 0.72g, described monomer (7) 0.13g and 2,2 '-bipyridine 0.56g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 60g through the degassing.Then, add two (1, the 5-cyclooctadiene) nickel (0) 1.0g in this mixing solutions, reaction is 23 hours under the room temperature.Also have, reaction is carried out under nitrogen atmosphere.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.34g.This polymkeric substance is called macromolecular compound 11.The polystyrene conversion weight-average molecular weight of the macromolecular compound 11 that obtains is 4.9 * 10 ⁴, number-average molecular weight is 2.5 * 10 ⁴

As described below by the structure of adding the repeating unit that comprises in the macromolecular compound 11 of inferring, be repeating unit H by adding the mol ratio of inferring " '/repeating unit I " '=80/20.

[changing 73]

Repeating unit H " ' repeating unit I " '

Embodiment 9

Synthesizing of＜macromolecular compound 12 〉

In reaction vessel, add described monomer (2) 0.70g, described monomer (7) 0.13g and 2,2 '-bipyridine 0.56g, then, in the nitrogen replacement reaction system.Therein, froth with argon gas in advance, add tetrahydrofuran (THF) (dehydrated solvent) 60g through the degassing.Then, add two (1, the 5-cyclooctadiene) nickel (0) 1.0g in this mixing solutions, reaction is 23 hours under the room temperature.Also have, reaction is carried out under nitrogen atmosphere.

Then, reclaim the precipitation that generates, should precipitate drying under reduced pressure, obtain polymkeric substance 0.21g.This polymkeric substance is called macromolecular compound 12.The polystyrene conversion weight-average molecular weight of the macromolecular compound 12 that obtains is 3.0 * 10 ⁴, number-average molecular weight is 6.3 * 10 ³

As described below by the structure of adding the repeating unit that comprises in the macromolecular compound 12 of inferring, be repeating unit J by adding the mol ratio of inferring " '/repeating unit K " '=80/20.

[changing 74]

Repeating unit J " ' repeating unit K " '

Embodiment 10

The fluorescent characteristic evaluation of＜macromolecular compound 〉

The 0.8wt% toluene solution of macromolecular compound is spun on the quartz plate and makes the film of macromolecular compound.Use spectrophotofluorometer (JOBINYVON-SPEX corporate system Fluorolog), under excitation wavelength 350nm, measure the fluorescence spectrum of this film.In order to obtain relative fluorescence intensity to film, intensity with the Raman lines of water is benchmark, obtain the value that obtains with the removal value as described below of the absorbancy under the excitation wavelength of using spectrophotometer (Varian corporate system Cary5E) to measure, this value is carried out the value that integration obtains for the fluorescence spectrum that will draw wave number in measurement range.

The measurement result of fluorescence peak wavelength and fluorescence intensity is shown in table 1.The fluorescence intensity of macromolecular compound 1 that contains side chain radical of the present invention is compared with macromolecular compound the last 3 of containing the phenoxazine ring in the macromolecular chain.In addition, contain the fluorescence intensity of macromolecular compound 2 of side chain radical of the present invention compared with the macromolecular compound semi-finals that contains the phenoxazine ring in the macromolecular chain.

Contain the macromolecular compound 5 of terminal group of the present invention and 6 fluorescence intensity compared with macromolecular compound the last 7 of containing the phenoxazine ring in the macromolecular chain.

The fluorescence intensity of macromolecular compound 8 that contains terminal group of the present invention is compared with macromolecular compound the last 3 of containing the phenoxazine ring in the macromolecular chain.

[table 1]

Table 1

Embodiment 11

The evaluation of＜element characteristic 〉

Have utilizing sputtering method on the glass substrate of ITO film of about 150nm thickness, use poly-(ethylene oxidation of thiophene)/polystyrolsulfon acid solution (bayer company, BaytronP), utilize spin-coating method, with the thickness film forming of about 50nm, on hot-plate, drying is 10 minutes under about 200 ℃.Then, use the formulated toluene solution of mode that becomes about 1.5wt% with 3: 7 (weight ratio) mixtures of macromolecular compound 1 and macromolecular compound 2, utilize spin-coating method, with the rotating speed film forming of 1500rpm.And then, with it decompression, 80 ℃ down after dry 1 hour, the about 4nm of evaporation lithium fluoride, as negative electrode, the calcium of the about 20nm of evaporation is followed the aluminium of the about 50nm of evaporation, thereby the making EL element.Also have, when vacuum tightness reaches 1 * 10 ^-4When pa is following, the evaporation of beginning metal.By applying voltage to the element that obtains, it is luminous to obtain blue EL.

Utilizability on the industry

In the luminescent layer of macromolecule LED, when macromolecular compound of the present invention is used as luminescent material, The good drawing property of its macromolecule LED. Thereby this macromolecule LED is preferred for the back of the body of liquid crystal display Light modulation or as illuminating curved surface shape or plane light source, the display element of sectional type. Dot matrix The devices such as flat-panel monitor. In addition, macromolecular compound of the present invention can be used as laser with pigment, Organic photovoltaic cell is with material, effective organic semiconductor, the conductive membrane material of organic crystal.

Claims

1. macromolecular compound, it has more than one repeating units of selecting from the group that is made of the repeating unit shown in the following formula (1), it is characterized in that,

Have the group of from the group that constitutes by 1 valency group shown in following formula (2) or the formula (3), selecting as substituting group,

-Ar ₁-(Z’)p- (1)

At this, Ar ₁Expression arylidene, divalent heterocyclic radical or divalent aromatic series amido, Z ' expression-CR ₄=CR ₅-or-C ≡ C-, R ₄And R ₅Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group respectively independently, P represents 0 or 1,

[changing 1]

In the formula, A ₁Expression-O-,-S-or-C (O)-, Ar ⁰¹Directly combination of expression, arylidene, divalent heterocyclic radical or divalent aromatic series amido, R ⁰⁵And R ⁰⁴Directly combination of expression independently respectively ,-R ₁-,-O-R ₁-,-R ₁-O-,-R ₁-C (O) O-,-R ₁-OC (O)-,-R ₁-N (R ₂₀)-,-O-,-S-,-C (O) O-or-C (O)-, R ₁Expression alkylidene group or alkenylene, wherein, Ar ⁰¹Under direct bonded situation, R ⁰⁷Also be direct combination, R ₂₀Expression hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group, R ⁰¹And R ⁰²Represent substituting group respectively independently, a and b are respectively 0 to 4 integer independently, a plurality of R ⁰¹And R ⁰²Can be identical, also can be different,

[changing 2]

In the formula, B ₁Expression-O-,-S-or-C (O)-, Ar ⁰²Expression hydrogen atom, aryl, 1 valency heterocyclic radical or 1 valency aromatic series amido, Ar ⁰³Directly combination of expression, arylidene, divalent heterocyclic radical or divalent aromatic series amido, R ⁰⁶, R ⁰⁸And R ⁰⁹Directly combination of expression independently respectively ,-R ₁-,-O-R ₁-,-R ₁-O-,-R ₁-C (O) O-,-R ₁-OC (O)-,-R ₁-N (R ₂₀)-,-O-,-S-,-C (O) O-or-C (O)-, R ₁Expression alkylidene group or alkenylene, R ₂₀Expression hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group, wherein, Ar ⁰³Under direct bonded situation, R ⁰⁹Also be direct combination, R ⁰³And R ⁰⁴Represent substituting group respectively independently, c is 0 to 4 integer, and d is 0 to 3 integer, a plurality of R ⁰³And R ⁰⁴Can be identical, also can be different.

2. macromolecular compound according to claim 1, wherein,

The Ar of above-mentioned formula (1) ₁At least has the group shown in the above-mentioned formula (2).

3. macromolecular compound according to claim 1, wherein,

The Ar of above-mentioned formula (1) ₁At least has the group shown in the above-mentioned formula (3).

4. macromolecular compound according to claim 1, wherein,

At least one side of the molecule chain end of macromolecular chain has the group shown in the above-mentioned formula (2).

5. macromolecular compound according to claim 1, wherein,

At least one side of the molecule chain end of macromolecular chain has the group shown in the above-mentioned formula (3).

6. according to any described macromolecular compound in the claim 1～5, wherein,

And then contain the repeating unit shown in the following formula (30),

-Ar ₄-(Z) _t- (30)

At this, Ar ₄Expression can have substituent arylidene, can have substituent divalent heterocyclic radical maybe can have substituent divalent aromatic series amido, wherein, does not comprise above-mentioned formula (2) and above-mentioned formula (3) in the substituting group, and Z represents-CR ₇=CR ₈-or-C ≡ C-, R ₇And R ₈Represent hydrogen atom, alkyl, aryl, 1 valency heterocyclic radical or cyano group respectively independently, t represents 0 or 1.

7. according to any described macromolecular compound in the claim 1～6, wherein,

The number-average molecular weight of polystyrene conversion is 10 ³～10 ⁸

8. according to any described macromolecular compound in the claim 1～6, wherein,

Described macromolecular compound is solid state and has fluorescence.

9. according to any described macromolecular compound in the claim 1～6, wherein,

Described macromolecular compound is solid state and has fluorescence, and the number-average molecular weight of polystyrene conversion is 10 ³～10 ⁸

10. according to any described macromolecular compound in the claim 1～6, wherein,

Described macromolecular compound is solid state and has phosphorescence.

11. a polymeric composition is characterized in that,

Comprise: the number-average molecular weight of polystyrene conversion is 10 ³～10 ⁸, solid state and have fluorescence, and do not have the macromolecular compound of above-mentioned formula (2) and above-mentioned formula (3) as substituting group; Form with any described macromolecular compound in the claim 1～10.

12. a polymeric light-emitting device is characterized in that,

Have luminescent layer between the electrode that is made of anode and negative electrode, this luminescent layer contains any described macromolecular compound in the claim 1～10.

13. a polymeric light-emitting device is characterized in that,

Have luminescent layer between the electrode that is made of anode and negative electrode, this luminescent layer contains the described polymeric composition of claim 11.

14. according to claim 12 or 13 described polymeric light-emitting devices, wherein,

Between at least one side's electrode and luminescent layer, the layer that comprises electroconductive polymer is set in abutting connection with this electrode.

15. according to any described polymeric light-emitting device in the claim 12～14, wherein,

Between at least one side's electrode and luminescent layer, the insulation layer of average film thickness below 2nm is set in abutting connection with this electrode.

16. according to any described polymeric light-emitting device in the claim 12～15, wherein,

Between negative electrode and luminescent layer, electron supplying layer is set in abutting connection with this luminescent layer.

17. according to any described polymeric light-emitting device in the claim 12～16, wherein,

Between anode and luminescent layer, hole transporting layer is set in abutting connection with this luminescent layer.

18. according to any described polymeric light-emitting device in the claim 12～17, wherein,

Between negative electrode and luminescent layer, electron supplying layer is set in abutting connection with this luminescent layer; And

19. a flat light source is characterized in that,

Comprise: any described polymeric light-emitting device in the claim 12～18.

20. a segmentation display unit is characterized in that,

Comprise: any described polymeric light-emitting device in the claim 12～18.

21. a dot matrix display unit is characterized in that,

Comprise: any described polymeric light-emitting device in the claim 12～18.

22. a liquid crystal indicator is characterized in that,

With any described polymeric light-emitting device in the claim 12～18 as backlight.

23. a liquid composite is characterized in that,

Comprise: any described macromolecular compound in the claim 1～10.

24. a film is characterized in that,

Comprise: any described macromolecular compound in the claim 1～10.

25. a transistor is characterized in that,

Comprise: any described macromolecular compound in the claim 1～10.

26. a solar cell is characterized in that,

Comprise: any described macromolecular compound in the claim 1～10.