WO2003099901A1

WO2003099901A1 - Polymer and polymeric luminescent element comprising the same

Info

Publication number: WO2003099901A1
Application number: PCT/JP2003/006578
Authority: WO
Inventors: Takanobu Noguchi; Yoshiaki Tsubata; Chizu Sekine
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2002-05-28
Filing date: 2003-05-27
Publication date: 2003-12-04
Also published as: TW200403327A; AU2003241788A1; TWI287570B

Abstract

A polymer characterized by comprising repeating units represented by the formula (1) and having a number-average molecular weight in terms of polystyrene of 103 to 108: (1) wherein Ar1 and Ar2 each represents an aromatic hydrocarbon group or heterocyclic group; one of X1 and X2 represents C(=O) or C(R1)(R2) and the other represents oxygen, sulfur, C(=O), etc.; M represents O-C(=O), C(=O)-O, oxygen, sulfur, C(=O), etc.; Z1 represents -CR=CR- or -C≡C-; and d is 0 or 1.

Description

Polymer compound and polymer light emitting device using the same

The present invention relates to a polymer compound and a polymer light-emitting device using the polymer compound (hereinafter, may be referred to as a polymer LED).

Background art

Different from low molecular weight luminescent materials, high molecular weight luminescent materials have been studied in various ways because they are soluble in solvents and can form a luminescent layer in a luminescent element by a coating method. Examples of such materials include polyphenylenevinylene derivatives , Polyfluorene derivatives, polyphenylene derivatives and the like are known.

In addition, a biphenyl derivative having a structure in which ortho-positions of aromatic rings constituting a pipenil ring are bonded to each other to form a 5- to 7-membered ring via a 1-3 atom or group of atoms. In WO 01/96454, a polymer compound represented by the following formula is disclosed.

Have been. Where A and B are ¹ B1, —S—, —NR ¹ —, — CR ¹ ! ^ ² —, —CR CRSR ⁴ —, -N ^ CR ^1- , — CR ^{1 =} CR ² —, _N = N-,-(CO). Here, it is described that this polymer compound is used as a matrix, and a metal ion is mixed with the matrix to form a light emitting layer.

Japanese Patent Application Laid-Open No. 8-81546 discloses a poly (4,5,9,10-tetrahydropyrene-1,2,7-diyl) derivative.

Disclosure of the invention

The present inventors have conducted intensive studies on a novel polymer compound that can be used as a light-emitting material. As a result, the repeating unit has two aromatic rings, and these aromatic rings are bonded by a specific bond. Polymer compound having a structure of The present invention was found to be useful and led to the present invention.

That is, the present invention relates to a polymer compound containing a repeating unit represented by the formula (1) and having a number average molecular weight of 1 × 10 ³ to 1 × 10 ⁸ in terms of polystyrene.

[Wherein, A r ¹ and A r ² each independently represent a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic group.

One of X ¹ and X ² is C (= 〇) or CiR ¹ ) (R ² ), and the other is 0, S, C (= 〇), S (= 0), S 0 ₂ , Represents S i (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (= 0) (R ⁸ ).

(Wherein, R ¹ R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, Aryl group, aryloxy group, arylthio group, arylamino group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, acyl group, acyloxy group, amide group, imino group, substituted silyl group, Represents a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group.)

M represents a group represented by the formula (2), the formula (3) or the formula (4).

One Y ¹ -Y ^2- (2)

[Wherein, Y ¹ and Y ² are each independently 0, S, C (= 〇), S (= 〇), S〇 ₂ , C (R ⁹ ) (R ¹⁰ ), S i (R ¹ Li ^{^{(R 1 2), NR 1}} 3), BCR 1 4), P (R 1 5) or? (= 〇) represents (1 ¹⁷ ;).

Where R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ Each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxy group, or an arylalkylthio group. , Arylalkylamino, acyl, acyloxy, amide, imino, substituted silyl, substituted silyloxy, substituted silylthio, substituted silylamino, monovalent heterocyclic, arylalkenyl, aryl Represents a monoluethynyl group or a cyano group. However, if Y ¹ is not C (R ⁹ MR ¹ °) or S i (R ¹¹ ) (R ^X ² ), Y ¹ and Y ² will not be the same. ]

^{^{-Y 3 = Y 4 - (3}} )

Wherein Υ ³ and Υ ⁴ each independently represent N, B, P, CiR ¹⁷ ;) or S i (R ¹⁸ ).

(Wherein, R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, Arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, acyl group, acyloxy group, amide group, imino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group Represents a monovalent heterocyclic group, arylalkenyl group, aryloxy group or cyano group.)]

— Y ⁵ — (4)

[Where Y ⁵ is 0, S, C (= 〇), S (= 〇), S〇 ₂ , CCR ¹⁹ ) (R ² ), S

^{1 (R 2 1) (R} 2 2), N (R 2 3), B (R 2 4), P (R 2 5;) or P (= 〇) (R

²⁶ ).

^{^{(Wherein, R 1 9, R 2.}} , R 2 1, R 2 2, R 2 3, R 2 4, R 2 5 and R ² ⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group, Alkoxy group, alkylthio group, alkylamino group, aryl group, aryloxy group, arylthio group, arylamino group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, acyl group, acyloxy Group, amido group, imino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, Represents a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group. )]

Z _t is one CR ^{³ 6} = CR ³ ⁷ - or - represents a C≡C-. R ^{3 6} and R ^{3 7} each independently represent a hydrogen atom, an alkyl group, Ariru group, a monovalent heterocyclic group or § cyano group. d represents 0 or 1. ]

BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, the polymer compound of the present invention and the polymer light emitting device using the same will be described in detail.

In the formula (1), Ar ¹ and Ar ² each independently represent a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic group. Both Ar ¹ and Ar ² are preferably tetravalent aromatic hydrocarbon groups, and more preferably both are monocyclic tetravalent aromatic hydrocarbon groups.

Here, the tetravalent aromatic hydrocarbon group means an atomic group obtained by removing four hydrogen atoms from a benzene ring or a condensed ring, and usually has 6 to 60, preferably 6 to 20 carbon atoms. The following compounds are exemplified. The aromatic hydrocarbon group may have a substituent, and the substituent may be a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, or an arylthio group. Group, arylamino group, arylalkyl group, arylalkoxy group, 7arylalkylthio group, arylalkylamino group, acyl group, acyloxy group, amide group, imino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, Examples thereof include a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group and a cyano group. The carbon number of the tetravalent aromatic hydrocarbon group does not include the carbon number of the substituent.

Examples of the tetravalent aromatic hydrocarbon group include the following.

Further, the tetravalent heterocyclic group refers to a remaining atomic group obtained by removing four hydrogen atoms from a heterocyclic compound, and usually has 4 to 60, preferably 4 to 20 carbon atoms. The heterocyclic group may have the same substituent as in the case of the aromatic hydrocarbon group. The carbon number of the heterocyclic group does not include the carbon number of the substituent.

Here, a heterocyclic compound refers to an organic compound having a cyclic structure in which the elements constituting the ring are not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, silicon, and selenium. In the ring. Examples of the tetravalent heterocyclic group include the following.

As a hetero atom, a nitrogen-containing tetravalent heterocyclic group; a pyridinetetrayl group (formula (16)), a diazabenzenetetrayl group (formula (17)), a quinolinetetrayl group (formula (18) ), A quinoxalinetetrayl group (the following formula (19)), an acridinetetrayl group (the following formula (20), a phenanthroline phosphorustetrayl group (the following formula (21)), and the like.

A group having a fluorene structure containing silicon, nitrogen, oxygen, sulfur, selenium, etc. as a hetero atom (the following formulas (22) and (23)).

A 5-membered heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom: (the following formula (24)) is exemplified.

A 5-membered condensed complex ring group containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom: (Formula (25) below) is exemplified.

(16)

(twenty four)

(25) In the above formula, R ′ is each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, an arylthio group. , Aryl amino group, aryl alkyl group, aryl alkoxy It represents a silyl group, an arylalkylthio group, an arylalkylamino group, an acyloxy group, an amide group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a cyano group. R "each independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, or a monovalent heterocyclic group.

X ¹ and A r ² is bonded to the adjacent position to an aromatic ring carbon of A r ^1, X ² and A r ¹ is preferably bonded to the adjacent position to an aromatic ring carbon of A r ^2.

Examples of -X ¹ -X ² -include the following.

Is preferred. One X ¹ — x ² _

Or

R

More preferably C—O— 0

— C—0—— is more preferable.

Examples of -Y ¹ -Y ² -include the following _c

R ■

Two

R '

Two

o

R-o

R 14

R 14 R ¹³ R 14 R ¹⁴ R ¹⁵ R ¹⁴ 0 II

-O-I B ■ SB-― B-I B- P- ■ BTR ¹⁶

R 15

R 15 R ¹³ R ¹⁵ OO

-O-P — S-P- — — P- — o- ■ s-f

R 11 R 11 R ⁹ R ⁹ R 16

-Si—Si C— C— Above all,

R ■

Two

o

R "R ⁹ R 13 R 11 R 11 R ¹¹ R ¹³ one Si— C— one N--c— • O-Si— — S one Si one—Si— N—

Ν

R 10 R 12 11 R 12 R 12

CRI one

Is preferred.

Examples of Y ³ = Y ⁴ -include the following ₍

— Ν = Β— — Ν = Ρ 一 — N = Si

R 18

■ B = P- — B = C- -B = Si- ■ p = c- R 17 R 18 R 17

■ P = Si— — C = Si—

R 18

R ¹⁷ R ^{18 Even} from the viewpoint of compound stability

17

Is preferred.

Examples of Y ⁵ — include the following.

0 0

11 II

Above all,

preferable. t oo == In the formula (1), M is one Y ¹ -— Y ^2- , Υ ¹ and Ar ² are bonded to adjacent positions of the aromatic ring carbon of Ar ¹ , and Y ^z and A r ¹ is preferably bonded to the adjacent position of the aromatic ring carbon of Ar ² .

In the formula (1), M is preferably —Yi—Y ² —, and Y ¹ and X ² are preferably C (= 0).

In a combination of one _γ ι—γ2— and — χΐ—X, — Υ ¹ —Υ し and — X ¹ — X ² — and, in the repeating unit, the bond between the ortho positions of the aromatic ring is C 2 It is preferably a symmetric group,

One Υ ¹ — Υ ^2-

0

II

— 0 —— C

And

-X ¹ — X ^2-

0

II

― C-1 0 Is more preferable.

In the present invention, as the repeating unit represented by the formula (1) possessed by the polymer compound, Ar Ar ² is preferably a benzene ring, and more preferably a formula (5).

(Five)

^{^{Wherein, R 2 7, R 2 8}} , R 2 9 and R ^{3 0} each independently represent a hydrogen atom, water group, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, Arukirua amino group, Ariru group, Aryloxy group, arylthio group, arylamino group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, acyl group, substituted carboxyl group, substituted silylthio group, substituted silylamino group, arylalkenyl Group, arylalkynyl group, arylamino group, monovalent heterocyclic group or cyano group. It may be the R ^{2 7} and R ^{2 8} are linked form form a ring, it may also have R ^{2 9} and R ³ ° are connected to form a ring les. Z ₂ is one CR ^{³ 8} = CR ³ ⁹ - represents a or a C≡C-. R ^{3 8} and R ^{3 9} are each independently a hydrogen atom, an alkyl group, Ariru group, a monovalent heterocyclic group, or Shiano group. e indicates 0 or 1. ]

E is one CR ^{³ 6} = CR ³ ⁷ one or - represents a C≡C-. R ^{3 6} and R ³ ⁷ each independently represent a hydrogen atom, an alkyl group, Ariru group, a monovalent heterocyclic group, or Shiano group. d represents 0 or 1. In the formula (1), the ease of synthesis, from the viewpoint of stability, it is preferably an CR ^{³ 6} = CR ³ ⁷ scratch. In the formula (1), d is preferably 0 (zero) from the viewpoint of shortening the emission wavelength of the light emitting element (blueening).

In the present invention, examples of the halogen atom include fluorine, chlorine, bromine and iodine.

The alkyl group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methyl, ethyl, propyl, i-propyl, butyl, i-butyl, t-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl Group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, An example is a single fluorooctyl group.

The alkoxy group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, propyloxy, i-propyloxy, butoxy, i-butoxy, t-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy Group, 2-ethylhexyloxy group, nonyloxy group, desiloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, penfluorofluoroethoxy group, perfluorobutoxy group, perfluoro Examples include an oral hexyl group, a perfluorooctyl group, a methoxymethyloxy group, and a 2-methoxyloxy group.

The alkylthio group may be linear, branched or cyclic, and usually has about 1 to 20 carbon atoms. Specifically, methylthio, ethylthio, propylthio, i-propylthio, butylthio, i-butylthio, t-butylthio, pentylthio, hexylthio, cyclohexylthio, heptylthio, octylthio Groups, 2-ethylhexylthio, nonylthio, decylthio, 3,7-dimethyloctylthio, laurylthio, trifluoromethylthio and the like.

The alkylamino group may be linear, branched or cyclic; It may be an amino group or a dialkylamino group, and usually has about 1 to 40 carbon atoms. Specifically, methylamino group, dimethylamino group, ethylamino group, acetylamino group, propylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, t-butylamino group, pentylamino group , Hexylamino, cyclohexylamino, heptylamino, octylamino, 2-ethylhexylamino, nonylamino, decylamino, 3,7-dimethyloctylamino, laurylamino, cyclopentylamino, Examples thereof include a dicyclopentylamino group, a cyclohexylamino group, a dicyclohexylamino group, a pyrrolidyl group, a piperidyl group, and a ditrifluoromethylamino group.

The aryl group may have a substituent, and usually has about 3 to 60 carbon atoms. Specifically, a phenyl group, a ~ ₂ alkoxyphenyl group (~ ( ₁₂ indicates that the number of carbon atoms is 1 to 12; the same applies to the following.), (^ ~. ^ Alkylphenyl group, Examples thereof include 1-naphthyl group, 2-naphthyl group, penfluorofluorophenyl group and the like.

The aryloxy group may have a substituent on the aromatic ring, and usually has about 3 to 60 carbon atoms. Specifically, the phenoxy group, (^ to ( ₁₂ alkoxyphenoxy group, C ₁ , to C ₁₂ alkyl phenoxy, 11-naphthyloxy, 2-naphthyloxy, pentafluorophenyloxy and the like.

The arylthio group may have a substituent on the aromatic ring, and usually has about 3 to 60 carbon atoms. Specifically, a phenylthio group, ^ ~ (: ₁₂ alkoxy Eniruchio group, C, ~ ₂ Arukirufue two thio group, 1 one naphthylthio group, 2-naphthylthio group, a pen evening fluorophenylthio groups.

The arylamino group may have a substituent on the aromatic ring, usually has about 3 to 60 carbon atoms, and includes a phenylamino group, a diphenylamino group, and a (: ₁₂ alkoxyphenylamino group. , Di (C,-(:, _2- alkoxyphenyl) amino group, di (-dialkylphenyl) amino group, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group and the like. You. ΎThe reel alkyl group may have a substituent, and usually has about 7 to 60 carbon atoms. Specifically, phenyl — (^ to (^ alkyl group, Ci C alkoxyphenyl— to ₂ alkyl group, C, -C ₁₂ Arukirufue two Roux _1-2 alkyl group, 1-Nafuchiru ~ Ji alkyl group, 2_ naphthyl - ^ ~ (: such ₁₂ alkyl groups.

§ reel alkoxy group may have a substituent, the number of carbon atoms is usually about 7 to 60, in particular, phenyl - (^ - (alkoxy group, (^ - ₍₁₂ Arco Kishifueniru - ( ^ ~ (: ₁₂ alkoxy groups, ,, ~ (: ₁₂ alkyl phenyl-(^ ₂ alkoxy groups, 1-naphthyl-(^ ~ (: ₁₂ alkoxy groups, 2-naphthyl-C, ~ C ₁₂ alkoxy groups, etc. Is exemplified.

The arylalkylthio group may have a substituent, and usually has about 7 to 60 carbon atoms. Specifically, the phenyl-(^ to (^ alkylthio group, C _t to C ₁₂ alkoxy enyl - _1-2 alkylthio group, to c Arukirufue two Le - - ₍₁₂ alkylthio group, 1-naphthyl - (:, ~ (:, ₂ alkylthio group, 2-naphthyl - such as C i to C i ₂ alkylthio groups and the like You.

The § reel alkylamino group has a carbon number of usually 7 to about 60, specifically, phenyl - ～〇 ₁₂ alkylamino group, (^ - (- _{alkoxyphenyl-phenylalanine} over-Ji alkylamino groups, C i to C _[2 alkylphenyl - C ₁ - C, ₂ alkyl Ruamino group, di ((^ ~ § Turkey hydroxyphenyl -. ^ ~ Ji Arukiru) amino group, di (C, ~ C _[2 Arukirufue two Lou C , To C ₁₂ alkyl) amino group, 1-naphthyl to ₂ alkylamino group, 21-naphthyl (:, to (: （alkylamino group, etc.).

The acryl group usually has about 2 to 20 carbon atoms. Specifically, it is an acetyl group, a pentionyl group, a butyryl group, an isoptyryl group, a pivaloyl group, a benzoyl group, a trifluoroacetyl group, or a pentaylfuran. Orobenzoyl group and the like are exemplified.

The acyloxy group usually has about 2 to 20 carbon atoms. Specifically, it is an acetoxy group, a propionyloxy group, a petyryloxy group, an isoptyryloxy group, a piperoyloxy group, a benzoyloxy group, a trifluorofluoroacetyl group. Kishi group, pen evening Examples include a fluorobenzoyloxy group.

The amide group usually has about 2 to 20 carbon atoms.Specifically, it includes a formamide group, an acetoamide group, a propioamide group, a ptyramide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, Examples thereof include a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, a dipentafluorobenzobenzamide group, a succinimide group, and a fluorimide group.

The imino group has about 2 to 20 carbon atoms, and specific examples include a compound represented by the following structural formula.

Examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tri-n-propylsilyl group, tri-i-propylsilyl group, t-butylsilyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group. And diphenylmethylsilyl, t-butyldiphenylsilyl, dimethylphenylsilyl and the like.

Examples of the substituted silyloxy group include a trimethylsilyloxy group, a triethylsilyloxy group, a tri-n-propylsilyloxy group, a tri-i-propylsilyloxy group, a t-butylsilyldimethylsilyloxy group, and a triethylsilyloxy group. Xy group, tree p-xylylsilyloxy group, tribenzylsilyloxy group, diphenylmethylsilyloxy group, t-butyldiphenylsilyloxy group, dimethylphen An example is a nilsilyloxy group.

Examples of the substituted silylthio group include trimethylsilylthio, triethylsilylthio, tri-n-propylsilylthio, tri-i-propylsilylthio, t-butylsilyldimethylsilylthio, triphenylsilylthio, triphenylsilylthio, and tri-p- Xylylsilylthio, tribenzylsilylthio, diphenylmethylsilylthio, t-butyldiphenylsilylthio, dimethylphenylsilylthio, and the like.

Examples of the substituted silylamino group include a trimethylsilylamino group, a triethylsilylamino group, a tri-n-propylsilylamino group, a trii-propylsilylamino group, a t-butylsilyldimethylsilylamino group, a triphenylsilylamino group, and a tri-silylamino group. p-xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, t-butyldiphenylsilylamino group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino Group, di (tree n-propylsilyl) amino group, di (tree i-propylsilyl) amino group, di (t-butylsilyldimethylsilyl) amino group, di (triphenylsilyl) amino group, di (tri-p-) Xylylsilyl) amino group, di (tribenzi Silyl) amino group, di (diphenyl methyl silyl) amino, di (t one heptyl diphenyl silyl) amino, such as di (dimethyl-phenylalanine silyl) Amino groups.

The monovalent heterocyclic group refers to an atomic group remaining after removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms. Specifically, a chenyl group, (^ to (: ₁₂ alkyl phenyl, pyrrolyl, furyl, pyridyl, (, to (:, ₂ alkyl pyridyl, imidazolyl, pyrazolyl, triazolyl, oxazolyl, thiazole, thiadiazole, etc.) that. these groups, ether bond, Chioe one ether bond, an alkyl group, an amino group, an alkenyl group, through an alkynyl group, may be bonded to a r ¹ or a r ^2.

Examples of the aryl group in the arylalkenyl group and the arylethynyl group include the same as the aryl group described above. The polymer compound of the present invention may contain two or more kinds of the repeating unit represented by the formula (1).

The polymer compound of the present invention may contain a repeating unit other than the repeating unit represented by the formula (1) as long as the fluorescent property and the charge transport property are not impaired. Further, the total of the repeating units represented by the formula (1) is preferably at least 5 mol% of all the repeating units, more preferably at least 10 mol%.

Preferred as the repeating unit other than (1) that can be contained in the polymer compound of the present invention is a repeating unit represented by the general formula (6).

(Wherein, A r ³ is Ariren group or a divalent heterocyclic group. R ^{3 1,} R ^{3 2} are each independently a hydrogen atom, an alkyl group, Ariru group, monovalent heterocyclic group or Shiano Represents a group, and f is 0 or 1.)

Ar ³ in the general formula (6) is an arylene group or a divalent heterocyclic group. Ar ³ represents a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxy group, Arylalkylthio group, arylalkylamino group, acyl group, acyloxy group, amido group, imino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, arylalkenyl group And a substituent such as an arylethynyl group or a cyano group.

The A r ^3, may be a conventionally Ru contained in the material that has been used as an EL luminescent material Ariren group or a divalent heterocyclic group. These materials are disclosed in, for example, W099 / 12989, WOOO / 55927, W001 / 49769AK 001 / 49768A2, W098 / 06773, US5, 777, 070, W099 / 54385, WO00 / 4632K US6, 169, 163BK W02 / 077060. It has been done.

The arylene group includes those having a benzene ring or a condensed ring, and those having two independent benzene rings or condensed rings bonded directly or via a group such as vinylene. A prime number of 6 to 60, preferably 6 to 20, a phenylene group (for example, the following formula (26)), a naphthalenediyl group (the following formula (27)), an anthracenylene group (the following formula (28)), biphen Examples include a diene group (the following formula (29)), a triene diene group (the following formula (30)), and a fused ring compound group (the following formula (31)). The arylene group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, an arylalkoxy group, and an arylalkylthio group. , Arylalkylamino, acyl, acyloxy, amido, imino, silyl, silyloxy, silylthio, silylamino, monovalent heterocyclic, arylalkenyl, arylethynyl or An example is a cyano group, and the carbon number of the arylene group does not include the carbon number of the substituent.

(26)

(27)

In the present invention, the divalent heterocyclic group refers to an atomic group obtained by removing two hydrogen atoms from a heterocyclic compound, and usually has 4 to 60, preferably 4 to 20 carbon atoms. The heterocyclic group may have a substituent, and the carbon number of the heterocyclic group does not include the carbon number of the substituent.

Here, a heterocyclic compound refers to an organic compound having a cyclic structure in which the elements constituting the ring are not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, silicon, and selenium. In the ring.

Examples of the divalent heterocyclic group include the following.

As a hetero atom, a divalent heterocyclic group containing nitrogen; a pyridinediyl group (following formula (32)), a diazaphenylene group (following formula (33)), a quinolinediyl group (following formula (34)), a quinoxaringiyl group ( The following formula (35)), an acridinediyl group (following formula (36)), a bipyridyldiyl group (following formula (37)), a phenanthine-containing lindyl group (following formula (38)), etc.

A group having a fluorene structure containing silicon, nitrogen, oxygen, sulfur, selenium and the like as a hetero atom (the following formula (39)).

A 5-membered heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium, or the like as a hetero atom is exemplified by the following formula (40).

5-membered condensed complex ring group containing silicon, nitrogen, oxygen, sulfur, selenium, etc. as a hetero atom: (the following formula (41)), benzothiadiazol-4,7-diyl group or benzoxadiazole-4, Examples thereof include a 7-diyl group.

Group which is a 5-membered heterocyclic group containing sulfur or the like as a hetero atom and is bonded at the position of the hetero atom to form a dimer or oligomer: (Formula (42) below). A 5-membered heterocyclic group containing silicon, nitrogen, oxygen, sulfur, selenium, etc. as a heteroatom and bonded to the phenyl group at the α-position of the heteroatom: (Formula (43) below). You.

(32)

(33)

(34)

(35)

Ten

(36)

Βσ

(41)

(42)

(43) In the formula, R ′ is each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamino group, an arylalkyl group, Aryl alkoxy group A arylalkylthio group, an arylalkylamino group, an acyloxy group, an amide group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a cyano group. R "independently represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, or a monovalent heterocyclic group. Further, examples of the divalent heterocyclic group include: A triplet light emitting complex is also included, and for example, a divalent metal complex group as exemplified below is exemplified.

As a repeating unit other than (1) that can be included in the polymer compound of the present invention, a repeating unit represented by the following formula (7) is preferable in terms of light emission efficiency. Ar ⁴ --N Ar ⁵ na (7)

g

33

In the R formula, Ar ⁴ and Ar ⁵ are each independently an arylene group or a divalent heterocyclic group, and Ar ⁴ and Ar ⁵ may be bonded to each other to form a ring. The R ^{3 3} represents an alkyl group, Ariru group, monovalent heterocyclic group, a group represented by the following (8) a group represented by or (9) below. g is an integer of 1-4.

Ar ° 34

(8)

h In the formula, Ar ⁶ is an arylene group or a divalent heterocyclic group. R ^{3 4} is a hydrogen atom, an alkyl group, Ariru group, a monovalent heterocyclic group or a group represented by the following formula (9). Z ₃ is one CR ⁴ . = CR ^{4 1} —or— Represents C≡C-I. R ⁴⁰ and R ⁴¹ each independently represent a hydrogen atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. h is an integer from 0 to 2.

A-(— N Ar ⁸ — R ⁴² (9)

During R ⁴³ formula, Ar ⁷ and A r ⁸ are each independently § Li one alkylene group or a divalent heterocyclic group. R ^{4 2} represents a hydrogen atom, an alkyl group, Ariru group or monovalent heterocyclic group. Further, R ^{4 3} represents an alkyl group, Ariru group or monovalent heterocyclic group. i is an integer of 1-4.

Preferred specific examples of the repeating unit represented by the formula (7) are shown below. In addition, you may have a substituent on a benzene ring or a heterocyclic group.

The polymer compound of the present invention, the number average molecular weight of 10 ³ to 10 ⁸ in terms of polystyrene is there. Although the total number of the repeating structures varies depending on the repeating structures and their ratio, the total number of the repeating structures is generally preferably 5 to 100, more preferably 10 to 100 from the viewpoint of film formation. 1100,000, particularly preferably 20〜500,000. The polymer conjugate of the present invention may be a random, block or graft copolymer, or a polymer having an intermediate structure between them, for example, a random copolymer having a block property. Is also good. From the viewpoint of obtaining a polymer compound having a high fluorescence quantum yield, a random copolymer having a block property or a block copolymer or a daraft copolymer is preferable to a completely random copolymer. When the main chain is branched and has three or more terminal groups, dendrimers are also included.

The repeating unit contained in the polymer compound of the present invention may be linked by a non-conjugated unit, or the repeating unit may include a non-conjugated portion thereof. Examples of the structure for connecting the repeating units include those shown below, a combination of the following and a vinylene group, and a combination of two or more of the following c. Here, R is a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 60 carbon atoms, and a heterocyclic group having 4 to 60 carbon atoms. And Ar represents a hydrocarbon group having 6 to 60 carbon atoms.

The terminal group of the polymer compound of the present invention, if the polymerization active group remains as it is, It may be protected by a stable group, since the light-emitting characteristics and lifetime may be shortened when the temperature is reduced. Those having a continuous conjugate bond with the conjugate structure of the main chain are preferable, and examples thereof include a structure bonded to an aryl group or a heterocyclic group via a carbon-carbon bond.

Since light emission from a thin film is used, a polymer compound having fluorescence in a solid state is preferably used as the polymer compound of the present invention.

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

Next, a method for producing the polymer compound of the present invention will be described.

The polymer compound of the present invention can be produced by condensation polymerization using a compound represented by the following formula (10) as one of the raw materials.

(In the formula, Ar Ar ² XX ² and M are the same as those in the formula (1). D ¹ and D ² are each independently an octogen atom, an alkylsulfonate group, an arylsulfonate group, or an arylalkylsulfonate. Group, borate ester group, sulfonium methyl group, phosphonium methyl group, phosphonetmethyl group, monohalogenated methyl group, boric acid group, formyl group, cyanomethyl group or pinyl group.)

Examples of the alkylsulfonate group include a methanesulfonate group, an ethanesulfonate group, and a trifluoromethanesulfonate group. Examples of the arylsulfonate group include a benzenesulfonate group and a P-toluenesulfonate group. Examples of the arylalkylsulfonate group include a benzylsulfonate group.

Examples of the borate group include groups represented by the following formula.

Examples of the sulfoniummethyl group include groups represented by the following formula.

CH ₂ SMe ₂ X, —CH ₂ S Ph ₂ X (X represents a halogen atom.) Examples of the phosphonium methyl group include groups represented by the following formula.

-CH ₂ PPh ₃ X (X represents a halogen atom.)

Examples of the phosphonate methyl group include groups represented by the following formula.

-CH ₂ PO (OR '") ₂

(R ′ ″ represents an alkyl group, an aryl group or an arylalkyl group.) Examples of the monohalogenated methyl group include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group. You.

As a method of the condensation polymerization, when a vinylene group is contained in the main chain, if necessary, other monomers may be used, for example, (1) the reaction between a compound having an aldehyde group and a compound having a phosphonium base. Polymerization by Wittig reaction, [2] Polymerization by Wittig reaction of compound having aldehyde group and phosphonium base, [3] Polymerization by Heck reaction of compound having vinyl group and compound having halogen atom [4] Vinyl Polymerization of a compound having a thiol group and a halogen atom by a Heck reaction; (5) polymerization of a compound having an aldehyde group and a compound having an alkylphosphonate group by the Horner-Wadswort-Emmons method [ 6] Polymerization of a compound having an aldehyde group and an alkylphosphonate group by the Horner-Wads worth- Emmons method, [7] Compound having two or more methyl halide groups [8] Polycondensation of compounds having two or more sulfonium bases by sulfonium salt decomposition, [9] Aldehyde group Polymerization of a compound having an aldehyde group and a compound having an acetonitrile group by a Kn oven age 1 reaction (10) Examples of the method include polymerization of a compound having two or more compounds by a McMurry reaction. The polymerization of the above [1] to [11] is represented by the following formula.

[1]

^{0HC Ar-} ^CH0 + X "Ph ₃ P ⁺ H ₂ C— Ar 'CH ₂ P ⁺ Ph ₃ χ—

[2]

[3]

. Base

-Ar + Br—— Ar 'Br * ~ ~ Ar = Ar'-

Pd Cat. \

〔Four〕

„ _A _____ Base _A

Br Ar ►-"~ Ar-

Pd Cat. \ ¹ n

〔Five〕 OHC—— Ar— CHO + (RO) ₂ (0) PH ₂ C—Ar 'CH ₂ P (0) (OR) ₂

[6]

OHC—— Ar— CH ₂ P (0) (OR) ₂ ► —l— _A r-

[7]

[8]

[9]

CN

Base

OHC Ar- CHO + NCCH ₂ -Ar 'CH ₂ CN Ar- -Ar'

CN

〔Ten〕

OHC——Ar

(1 1) TiCl ₃ -Zn

OHC-Ar-1 CHO

Further, as a method for producing the polymer compound of the present invention, when there is no vinylene group in the main chain, for example, (12) polymerization by Suzuki coupling reaction, (13) polymerization by Grignard reaction how, [14] Ni (0) a method of polymerization by the catalyst, a method of polymerization with an oxidizer such as [15] FeC 1 _3, electrochemically methods oxidative polymerization, or [16] suitable leaving group Examples of the method include decomposition of an intermediate polymer having the compound.

The polymerization methods [12] to [16] are represented by the following formulas.

[12]

Br——Ar—Br + (RO) ₂ B—Ar ′ B (OR).

R = H, alkyl

〔13〕

Ni Cat.

Br Ar― gBr ► — \ ~~ Ar- n

〔14〕

Ni (0).

Br-Ar-Br Br-Ar-

[15]

Oxidative polymerization

Ύ FeC13, electrochemical

Y = S, NH

[16]

Among these, polymerization by the Wittig reaction, polymerization by the Heck reaction, polymerization by the Horner-Wads worth- Emmons method, polymerization by the Kn oeven age 1 reaction, and polymerization by the Suzuki coupling reaction The method, the method of polymerizing by a Grignard reaction, and the method of polymerizing by a Ni (0) catalyst are preferable because the structure can be easily controlled. Further, a method of polymerizing by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, and a method of polymerizing by a Ni (0) catalyst are preferable in terms of availability of raw materials and simplicity of the polymerization reaction operation.

When the polymer compound of the present invention is used as a light-emitting material for a polymer LED, the purity affects the light-emitting characteristics.Therefore, in the production method of the present invention, the above-mentioned separation operation and purification operation are sufficiently performed, and unreacted monomers, It is preferable to sufficiently remove by-products and catalyst residues.

The drying may be carried out under conditions that sufficiently remove the remaining solvent. In order to prevent deterioration of the polymer compound, it is preferable to dry the polymer compound in a light-shielded atmosphere in an inert atmosphere. In addition, it is preferable to dry the polymer compound at a temperature at which the polymer compound does not thermally deteriorate. The polymer compound of the present invention can be used as an active ingredient of a light emitting material. Further, it can be used as a charge transporting material, an organic semiconductor material, an optical material, or a conductive material by doping.

In the present invention, the polymer compound having liquid crystallinity means that a molecule containing the polymer compound exhibits a liquid crystal phase. The liquid crystal phase can be confirmed by a polarizing microscope, differential scanning calorimetry, X-ray diffraction measurement, or the like.

It is known that a compound having liquid crystallinity has optically and electrically anisotropy when oriented. (Synthetic Metals 119 (2001) 537)

As a method for aligning liquid crystals, a method generally known as a liquid crystal alignment method, for example, “Basic and Application of Liquid Crystals” (Shoichi Matsumoto, Ryo Tsunoda, Industrial Research Institute, 1991) Chapter, "Structure and Physical Properties of Ferroelectric Liquid Crystals" (Atsuo Fukuda, Hideo Takezoe, Corona, 1990) Chapter 7, "Liquid Crystals" Volume 3, Issue 1 (1999), pp. 3-16 The method described can be used. Among them, the rubbing method, the photo-alignment method, the shear stress applying method and the pull-up coating method are simple, useful and easy to use as the alignment method.

The rubbing method is a method in which the substrate surface is lightly rubbed with a cloth or the like. Glass, a polymer film, or the like can be used as the substrate. As the cloth for rubbing the substrate, cloth such as gauze polyester, cotton, nylon, or rayon can be used. Further, when an alignment film is separately formed on the substrate, the alignment performance is further improved. Here, examples of the alignment film include polyimide, polyamide, PVA, polyester, and nylon, and a commercially available alignment film for liquid crystal can also be used. The alignment film can be formed by a spin coating method or flexographic printing. The cloth used for rubbing can be appropriately selected according to the alignment film to be used.

The photo-alignment method is a method of forming an alignment film on a substrate and imparting an alignment function by irradiating polarized UV light or irradiating UV light obliquely. Examples of the alignment film include polyimide, polyamide, and polyvinyl cinnamate, and a commercially available alignment film for liquid crystal can also be used.

In the rubbing method or the photo-alignment method, the orientation can be achieved by sandwiching the oriented polymer material between the substrates that have been subjected to the treatment described above. At this time, it is necessary that the temperature of the substrate is a liquid crystal phase or an isotropic phase. The temperature may be set before or after the high molecular material is sandwiched between the substrates. Alternatively, the polymer material may be simply applied onto a substrate that has been subjected to an orientation treatment. To apply the polymer, place the polymer on a substrate, set it to a temperature of Tg or more, or a temperature that shows a liquid crystal phase or an isotropic phase, and coat it unidirectionally with a rod or the like, or prepare a solution dissolved in an organic solvent, The coating can be performed by a method such as spin coating or flexographic printing.

The shear stress applying method is a method in which another substrate is placed on a polymer material placed on a substrate, and the upper substrate is shifted in one direction at a temperature at which a liquid crystal phase or an isotropic phase is formed. At this time, a substrate having a higher degree of orientation can be obtained by using a substrate that has been subjected to an alignment treatment as described in the rubbing method / optical alignment method. Glass or polymer film For example, a metal rod or the like may be used instead of the substrate to be shifted by the stress.

Pull-up coating is a method of dipping a substrate in a polymer solution and lifting it up. The organic solvent used for the polymer solution and the substrate pulling speed are not particularly limited, but can be selected and adjusted according to the degree of orientation of the polymer.

When the polymer compound of the present invention is used as a light-emitting material for a polymer LED, its purity affects the light-emitting characteristics, so that the monomer before polymerization is purified and then polymerized by methods such as distillation, sublimation purification, and recrystallization. Preferably, after the synthesis, purification treatment such as reprecipitation purification and fractionation by chromatography is preferred.

Further, since light emission or phosphorescence from a thin film is used, a polymer compound having fluorescence or phosphorescence in a solid state is preferably used as the polymer compound of the present invention.

Next, the polymer LED of the present invention will be described.

The polymer LED of the present invention has a light-emitting layer between electrodes consisting of an anode and a cathode, and the light-emitting layer contains the polymer compound of the present invention.

The polymer LED of the present invention includes a polymer LED having an electron transport layer between a cathode and a light-emitting layer, a polymer LED having a hole transport layer between an anode and a light-emitting layer, Polymer LEDs in which an electron transport layer is provided between the cathode and the light emitting layer and a hole transport layer is provided between the anode and the light emitting layer are exemplified.

The polymer LED of the present invention comprises a polymer LED having a layer containing a conductive polymer adjacent to at least one electrode and the light emitting layer between the electrode and the light emitting layer; Also included are polymer LEDs in which an insulating layer having a thickness of 2 nm or less is provided adjacent to the electrode.

Specifically, the following structures a) to d) are exemplified. a) Anode Z Luminescent layer Z Cathode

b) Anode Z hole transport layer / light emitting layer / cathode

c) Anode Z light emitting layer / electron transport layer / cathode

d) Anode Z Hole transport layer / Emitting layer / Electron transport layer Cathode

(Here, “No” indicates that each layer is stacked adjacently. The same applies to the following.) Here, the light emitting layer is a layer having a light emitting function, and the hole transport layer is a hole transporting layer. It is a layer having a function of transporting, and the electron transporting layer is a layer having a function of transporting electrons. Note that the electron transport layer and the hole transport layer are collectively called a charge transport layer. Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently. Among the charge transport layers provided adjacent to the electrodes, those having the function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element include the charge injection layer (hole injection layer). Layer, electron injection layer).

Further, the above-described charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode in order to improve adhesion to the electrode and improve charge injection from the electrode. A thin buffer layer may be inserted at the interface between the charge transport layer and the light-emitting layer for the purpose of improvement and prevention of mixing.

The order and number of layers to be stacked and the thickness of each layer can be appropriately used in consideration of luminous efficiency and device life.

In the present invention, the polymer LED provided with a charge injection layer (electron injection layer, hole injection layer) includes a polymer LED provided with a charge injection layer adjacent to a cathode, and a charge injection layer adjacent to an anode. Polymer LED provided.

For example, the following structures _e ) to p) are specifically mentioned.

e) Anode / charge injection layer / emission layer / cathode

f) Anode / Emission layer Charge injection layer Z cathode

g) Anode / charge injection layer / emission layer Charge injection layer / cathode

h) Anode / charge injection layer Z hole transport layer Z light emitting layer / cathode

0 Anode / Hole transport layer Z Emission layer No charge injection layer Cathode

j) Anode / charge injection layer Z hole transport layer Z light emitting layer / charge injection layer Z cathode k) Anode / charge injection layer Light emitting layer Z charge transport layer Z cathode

1) Anode / light-emitting layer Z electron transport layer Z charge injection layer Z cathode

m) Anode / charge injection layer / emission layer / electron transport layer Z charge injection layer Z cathode

n) Anode / charge injection layer / hole transport layer / emission layer Z charge transport layer / cathode

0) Anode / Hole transport layer / Emitting layer Z Electron transport layer / Charge injection layer Z Cathode

) Anode / charge injection layer / hole transport layer Z light-emitting layer electron transport layer Z charge injection layer / cathode Specific examples of the charge injection layer include a layer containing a conductive polymer, an anode and a hole transport layer. A layer containing a material having an ionization potential of an intermediate value between the anode material and the hole transport material contained in the hole transport layer; a layer provided between the cathode and the electron transport layer; Examples include a layer containing a material having an electron affinity of an intermediate value between the electron transport material and the electron transport material contained in the electron transport layer.

When the charge injection layer is a layer containing an electric conductive polymer, the electric conductivity of the conducting polymer is preferably from 10- ⁵ SZcm than 10 ³ S / cm, the leak current between light emitting pixels to reduce the 10_ ⁵ 10, more preferably ² SZcm inclusive SZcm, 10- ⁵ S / cm or more 10 ¹ SZcm less it is more preferred.

Typically the electrical conductivity of the conducting polymer 10 ⁵ 3 / (: 111 to less than 10 ³ S / cm, a suitable amount of ions are doped into the conducting polymer.

The kind of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrenesulfonate, alkylbenzenesulfonate, camphorsulfonate, and the like.Examples of cations include lithium, sodium, potassium, and tetrabutylammonium. Is exemplified.

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

The material used for the charge injection layer may be appropriately selected in relation to the material of the electrode and the adjacent layer, such as polyaniline and its derivative, polythiophene and its derivative, polypyrrole and its derivative, polyphenylenevinylene and its derivative, Poly-Chenylene vinylene and its derivatives, Polyquinoline and its derivatives, Polyki Examples include conductive polymers such as noxaline and derivatives thereof, polymers having an aromatic amine structure in the main chain or side chain, metal phthalocyanines (eg, copper phthalocyanine), and carbon.

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

Specifically, for example, the following c! ) To ab).

Q) Anode Z Insulation layer / light-emitting layer / cathode with thickness less than 2 nm

r) Anode / Emitting layer Z Insulating layer with thickness less than 2 nm Z cathode

s) Anode Insulating layer with Z film thickness of 2 nm or less / Emitting layer Insulating layer with Z film thickness of 2 nm or less / cathode t) Anode / Insulating layer with thickness of 2 nm or less / Hole transport layer / Emitting layer / Cathode

u) Anode Z Hole transport layer Z Emitting layer Z Insulating layer with thickness of 2 nm or less Z cathode

v) Anode / insulating layer with thickness of 2 nm or less Z Hole transport layer / luminescent layer / absence of thickness of 2 nm or less) Anode Z Insulating layer with thickness of 2 nm or less Z emitting layer Z electron transporting layer

X) Anode Z Light-emitting layer Electron transport layer Insulation layer with a thickness of 2 nm or less Z cathode

y) Anode / insulating layer with thickness of 2 nm or less Z light emitting layer / electron transport layer Z insulating layer with thickness of 2 nm or less Z cathode

a) Anode / Hole transport layer / Emission layer / Electron transport layer / Cathode aa) Anode Z Hole transport layer / Z Emission layer / Z electron transport layer / Z Insulation layer with thickness of 2 nm or less Z cathode ab) Anode / insulating layer with thickness of 2 nm or less Z hole transport layer / light-emitting layer Z electron transport layer / insulating layer with thickness of 2 nm or less / cathode

The optimum value of the thickness of the light emitting layer in the polymer LED of the present invention differs depending on the material used, and may be selected so that the driving voltage and the luminous efficiency have appropriate values, for example, from 1 nm to 1 m. It is preferably from 2 nm to 500 nm, and more preferably from 5 nm to 200 nm. In the polymer LED of the present invention, a light-emitting material other than the above-mentioned polymer compound may be mixed and used in the light-emitting layer. Further, in the polymer LED of the present invention, a light emitting layer containing a light emitting material other than the polymer phosphor may be laminated with the light emitting layer containing the polymer phosphor.

As the light emitting material, known materials can be used. Examples of low molecular compounds include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine-based, xanthene-based, coumarin-based, and cyanine-based dyes, metal complexes of 8-hydroxyquinoline or its derivatives, and aromatics. For example, amine, tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.

Specifically, known materials such as those described in, for example, JP-A-57-51781 and JP-A-59-194393 can be used.

There is no limitation on the method of forming the light emitting layer, but a method of forming a film from a solution is exemplified. Spin coating, casting, microgravure coating, gravure coating, vacuum coating, roll coating, wire coating, bar coating, dip coating, spray coating, screen coating, etc. A coating method such as a printing method, a flexographic printing method, an offset printing method, and an ink jet printing method can be used.

When the polymer LED of the present invention has a hole transport layer, the hole transport material used may be polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, or a polymer having an aromatic amine in the side chain or main chain. Siloxane derivative, pyrazoline derivative, arylamine derivative, stilbene derivative, triphenyldiamine derivative, polyaniline or its derivative, polythiophene or its derivative, polypyrrole or its derivative, poly (p-phenylenevinylene) or its Derivatives or poly (2,5-Chenylene vinylene) or derivatives thereof are exemplified.

Among them, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane having an aromatic amine compound group in a side chain or a main chain. Polymeric hole transport materials such as sun derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, poly (p-phenylenevinylene) or derivatives thereof, or poly (2,5-chenylenevinylene) or derivatives thereof Preferred are polypinylcarbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low-molecular-weight hole transport material, it is preferable to use it by dispersing it in a high-molecular binder.

Polyvinyl carbazole or a derivative thereof can be obtained, for example, from a vinyl monomer by force polymerization or radical polymerization.

As polysilanes or derivatives thereof, Chemical 'Review (Chem. Rev.), Vol. 89, pp. 139 (1989), UK Patent GB 2 301 196 Compounds described in this document are exemplified. The synthesis methods described above can be used for the synthesis method, but the Kipping method is particularly preferably used.

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

There is no limitation on the method of forming the hole transport layer, but for the low molecular weight hole transport material, a method of forming a film from a mixed solution with a polymer binder is exemplified. In the case of a polymer hole transporting material, a method of forming a film from a solution is exemplified.

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

As a method of film formation from a solution, spin coating from a solution, casting method, microgravure coating method, gravure coating method, vacuum coating method, roll coating method Coating methods such as wire printing, wire coating, dip coating, spray coating, screen printing, flexographic printing, offset printing, and ink jet printing can be used.

As the polymer binder to be mixed, those which do not extremely inhibit charge transport are preferable, and those which do not strongly absorb visible light are preferably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, and the like.

The optimal value of the thickness of the hole transport layer depends on the material used, and may be selected so that the driving voltage and the luminous efficiency are at appropriate values, but at least a thickness that does not cause pinholes is necessary. If the thickness is too large, the driving voltage of the device becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, from l nm to it m, preferably from 2 nm to 500 nm, and more preferably from 5 nm to 200 nm.

When the polymer LED of the present invention has an electron transporting layer, known electron transporting materials can be used, such as oxadiazole derivative, anthraquinodimethane or its derivative, benzoquinone or its derivative, naphthoquinone or its derivative. A derivative, anthraquinone or a derivative thereof, tetrathrananoanthraquinodimethane or a derivative thereof, a fluorenone derivative, diphenyldicyanoethylene or a derivative thereof, a diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or a derivative thereof; Examples thereof include polyquinoline or a derivative thereof, polyquinoxaline or a derivative thereof, and polyfluorene or a derivative thereof. Of these, oxadiazole derivatives, benzoquinone or its derivatives, anthraquinone or its derivatives, or metal complexes of 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoxaline or its derivatives, and polyfluorene or its derivatives are preferred. , 2- (4-biphenyl) _5 _ (4-t-butylphenyl) _ 1,3,4-oxaziazol, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum Polyquinoline is more preferred.

There is no particular limitation on the method for forming the electron transport layer, but for low-molecular-weight electron transport materials, vacuum deposition from powder or film formation from a solution or molten state is used. Alternatively, a method of forming a film from a molten state is exemplified. When forming a film from a solution or a molten state, a polymer binder may be used in combination.

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

Spin coating, casting, microgravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, dip coating, and spraying can be used as a film forming method from a solution or molten state. Coating methods such as a coating method, a screen printing method, a flexographic printing method, an offset printing method, and an ink jet printing method can be used.

As the polymer binder to be mixed, those that do not extremely inhibit charge transport are preferable, and those that do not strongly absorb visible light are preferably used. Examples of the polymer binder include poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, and poly (2,5-chenylenevinylene). Or a derivative thereof, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, or polysiloxane.

The optimum value of the thickness of the electron transporting layer depends on the material used, and may be selected so that the driving voltage and the luminous efficiency are appropriate. However, at least a thickness that does not cause pinholes is necessary. Yes, if it is too thick, the driving voltage of the Not good. Therefore, the thickness of the electron transport layer is, for example, from 1 nm to 1 / m, preferably from 2 nm to 500 nm, and more preferably from 5 nm to 200 nm.

The substrate on which the polymer LED of the present invention is formed may be any substrate as long as it does not change when an electrode is formed and an organic layer is formed.Examples include a glass, plastic, polymer film, and silicon substrate. You. In the case of an opaque substrate, the opposite electrode is preferably transparent or translucent.

In the present invention, it is preferable that at least one of the electrodes including the anode and the cathode is transparent or translucent, and the anode side is transparent or translucent.

As a material of the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, a film formed using a conductive glass made of indium oxide, zinc oxide, tin oxide, or a complex thereof, such as indium tin oxide (ITO), indium zinc zinc oxide, or the like ( NESA, etc.), gold, platinum, silver, copper, etc., and ITO, indium-zinc oxide, and tin oxide are preferable. Examples of the manufacturing method include a vacuum evaporation method, a sputtering method, an ion plating method, and a plating method. An organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.

The thickness of the anode can be appropriately selected in consideration of light transmittance and electric conductivity, and is, for example, from 10 nm to 10 m, and preferably from 20 nm to 1 m. More preferably, it is 50 nm to 500 nm.

In addition, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or an average film thickness of 2 nm or less made of a metal oxide, a metal fluoride, an organic insulating material, etc., on the anode to facilitate charge injection. May be provided.

As a material of the cathode used in the polymer LED of the present invention, a material having a small work function is preferable. For example, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium , Samarium, europium, terbium, ytterbium, etc., and two or more of them, or one or more of them, and gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin An alloy with one or more of the above, graphite, an interlayer compound of graphite, or the like is used. Examples of alloys include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, calcium-aluminum alloy, etc. Can be The cathode may have a laminated structure of two or more layers. The thickness of the cathode can be appropriately selected in consideration of electrical conductivity and durability. For example, the thickness is from 10 nm to 10 m, preferably from 20 nm to: Lim. More preferably, it is 50 nm to 50 O nm.

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

As the protective layer, a polymer compound, a metal oxide, a metal fluoride, a metal boride and the like can be used. Further, as the protective cover, a glass plate, a plastic plate whose surface has been subjected to a low-permeability treatment, or the like can be used. The method is preferably used. If a space is maintained using a spacer, it is easy to prevent the element from being damaged.

. By enclosing an inert gas such as nitrogen or argon in the space, it is possible to prevent oxidation of the cathode, and by installing a desiccant such as oxidized barium in the space, it is adsorbed in the manufacturing process. It becomes easy to suppress the moisture from giving damage to the element. It is preferable to take one or more of these measures.

A charge transport layer and a light emitting layer between the anode and the cathode, A polymer LED in which the load transport layer contains the polymer compound of the present invention is also possible.

The polymer light emitting device of the present invention can be used as a planar light source, a segment display device, a dot matrix display device, and a backlight of a liquid crystal display device.

In order to obtain planar light emission using the polymer LED of the present invention, a planar anode and a planar cathode may be arranged so as to overlap. Further, in order to obtain patterned light emission, a method in which a mask having a patterned window provided on the surface of the planar light emitting element is provided. There is a method of emitting light, a method of forming either the anode or the cathode, or both electrodes in a pattern. A segment-type display element that can display numbers, letters, simple symbols, etc. by forming a pattern by any of these methods and arranging several electrodes so that they can be independently turned on and off Is obtained. Further, in order to form a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged orthogonally. A partial color display or a multicolor display can be achieved by a method in which a plurality of types of polymer phosphors having different emission colors are separately applied, or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively or may be driven actively in combination with TFT or the like. These display elements can be used as display devices such as computers, televisions, mobile terminals, mobile phones, power navigation systems, and video camera viewfinders. Further, the planar light emitting element is a self-luminous thin type, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can be used as a curved light source or display device.

Hereinafter, examples will be shown in order to explain the present invention in further detail, but the present invention is not limited to these.

Here, as for the average molecular weight, the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC) using tetrahydrofuran as a solvent.

Example 1 <Synthesis of Monomer 1>'Reaction of 25 g of ellagic acid, 221 g of 1-bromo_3,7-dimethyloctane and 60 g of potassium carbonate in 100 g of 450 g of N, N-dimethylformamide for 28 hours I let it. After the reaction solution was cooled and allowed to stand, it separated into two layers. Next, the upper layer was recovered. The collected solution was washed with ion-exchanged water. Washing was repeated until the washing water became neutral. Next, the oil layer was dried under reduced pressure, and then unreacted using a silica gel column with a fluid phase of toluene Z hexane = 1 to 1, unreacted 1-bromo-3,7-dimethyloctane and tetraalkoxy-substituted ellagic acid After removal of the compound, the dialkoxy-substituted product was fractionated with a liquid-phase chromatoform. After distilling out the solvent from the fractionated solution under reduced pressure, the solvent was dried under reduced pressure to obtain 6.5 g of a dialkoxy-substituted product. The obtained dialkoxy-substituted product was found to be 2,7 based on the chemical shift of proton NMR and the reactivity between the hydroxyl groups at the 2,7,3,8 positions and 1_bromo-3,7-dimethyloctane. —Dihydroxy— 3,8-di (3,7-dimethyloctyloxy) _ [1] benzopyrano [5,4,3-cde] [1] Benzopyran was estimated to be 5,10-dione.

The resulting compound is called monomer 1.

0.59 g of trifluoromethanesulfonic acid ester of monomer 1 obtained by reacting monomer 1 with trifluoromethanesulfonic anhydride and ethylene glycol 9,9-dioctyl-2,7-fluoreneborate 0.37 g of monoester and 1 g of potassium carbonate were dissolved in 20 g of toluene and 20 g of ion-exchanged water, followed by bubbling with nitrogen gas to replace the inside of the system with nitrogen gas. To this solution was added a solution prepared by dissolving 0.02 g of a palladium catalyst {Pd (PPh3) 4} in 1 ml of toluene degassed by previously doubling with nitrogen gas. After stirring at room temperature for 10 minutes, the mixture was reacted at 100 ×: for 5 hours. The reaction was performed in a nitrogen atmosphere.

After the reaction solution was cooled, toluene was added thereto, and the mixture was separated to collect a toluene layer. The toluene solution was washed with 1N hydrochloric acid, further washed with 2% aqueous ammonia, and finally washed with ion-exchanged water. This toluene solution is filled with alumina After purification by passing through a column, the toluene solution was poured into methanol and purified by reprecipitation. After collecting the resulting precipitate, the precipitate was dried under reduced pressure to obtain 0.3 g of a polymer. The obtained polymer is called polymer compound 1.

The number average molecular weight in terms of polystyrene of the polymer compound 1, 2. a 0X 10 ^4, weight average molecular weight, 5 was 6 X 10 ^4. The structure of the repeating unit contained in the polymer compound 1 estimated from the preparation is shown below.

Example 2

0.63 g of trifluoromethanesulfonic acid ester of monomer 1 obtained by reacting monomer 1 obtained in Example 1 with trifluoromethanesulfonic anhydride and 2,2 ′ · bipyridyl 0 28 g was dissolved in 30 g of tetrahydrofuran (dehydrated), and the system was purged with nitrogen gas by purging with nitrogen gas. To this solution was added 0.5 g of bis (1,5-cyclohexene) nickel (0) {Ni (C0D) 2}, and the mixture was stirred at room temperature for about 10 minutes, heated, and reacted at 60 for 3 hours. did. The reaction was performed in a nitrogen atmosphere.

After the reaction solution was cooled, a mixed solution of 25% ammonia water 10 ml methanol 100 ml / ion exchanged water 200 ml was added, and the mixture was stirred for about 1 hour. This solution was allowed to stand at room temperature overnight, and the generated precipitate was collected by filtration. Next, the precipitate was dried and dissolved in toluene. After removing insolubles by filtration, the solution was purified by passing through a column filled with alumina. Next, the solution was poured into methanol and purified by reprecipitation. The generated precipitate After being collected and washed with ethanol, it was dried under reduced pressure to obtain 02 g of a polymer. The obtained polymer is called polymer compound 2.

The polystyrene equivalent number average molecular weight of the polymer compound 2 was 4.5 × 10 ^3, and the weight average molecular weight was 7.2 × 10 ³ . The structure of the repeating unit contained in the polymer compound 2 estimated from the preparation is shown below.

As a result of observing the polymer compound 2 under crossed Nicols using a polarizing microscope, it was confirmed from the texture that the polymer compound 2 was a liquid crystal.

Example 3

0.63 g of trifluoromethanesulfonic acid ester of monomer 1 obtained by reacting monomer 1 obtained in Example 1 with trifluoromethanesulfonic anhydride and NN—bis (4-bromophenyl) 1 NN '1 bis- (4-n-butylphenyl) — Dissolve 0.23 g of 1,4-phenylenediamine and 0.39 g of 2,2 bipyridyl in 30 g of tetrahydrofuran (dehydrated) The system was purged with nitrogen gas by publishing with gas. To this solution was added 0.7 g of bis (15-cyclooctadiene) nickel (0) {Ni (C0D) 2}, and the mixture was stirred at room temperature for about 10 minutes. Reacted for hours. The reaction was performed in a nitrogen atmosphere.

After cooling the reaction solution, a mixed solution of 25% ammonia water 10 ml methanol 100 m 1Z ion-exchanged water 200 ml was added and stirred for about 1 hour. This solution was allowed to stand at room temperature overnight, and the generated precipitate was collected by filtration. Next, the precipitate was dried and dissolved in toluene. Removal by filtering insolubles After that, the solution was purified by passing through a column filled with alumina. Next, the solution was poured into methanol and purified by reprecipitation. The generated precipitate was collected, washed with ethanol, and dried under reduced pressure to obtain 0.03 g of a polymer. The obtained polymer is called polymer compound 3.

The polystyrene reduced number average molecular weight of the polymer compound 3 was 5.3 × 10 ^3, and the weight average molecular weight was 1.2 × 10 ⁴ . The structure of the repeating unit contained in the polymer compound 3 estimated from the preparation is shown below.

Example 4

Trifluoromethanesulfonic acid ester of monomer 1 obtained by reacting monomer 1 obtained in Example 1 with trifluoromethanesulfonic anhydride 0.258 and 14 dibu-mole 25-bis (37-Dimethyloctyloxy) After dissolving 0.66 g of benzene and 0.61 g of 22 viviridyl in 40 g of tetrahydrofuran (dehydrated), bubbling with nitrogen gas was performed, and the inside of the system was purged with nitrogen gas. Replaced. To this solution was added bis (15-cyclooctadiene) nickel (0) {Ni (C0D) 2} 1.1 g Was added and reacted at room temperature for 24 hours. The reaction was performed in a nitrogen atmosphere.

Next, to this reaction solution, a mixed solution of 25% ammonia water 10 ml / methanol 30 ml 1 Zion exchanged water 6 Oml was added and stirred for about 1 hour. The solution was allowed to stand at room temperature overnight, and the generated precipitate was collected by filtration. Next, the precipitate was dried and dissolved in toluene. Insolubles were removed by filtration. Next, this solution was washed with 1N hydrochloric acid and separated, and then the toluene layer was washed with about 2.5% ammonia water. After separation, the toluene layer was washed with ion-exchanged water. Next, the obtained toluene solution was poured into methanol and purified by reprecipitation. The resulting precipitate was collected, washed with ethanol, and dried under reduced pressure to obtain 05 g of a polymer. The obtained polymer is called polymer compound 4.

The number average molecular weight in terms of polystyrene of the polymer compound 4, 4. 7X Ri 10 ³ der, weight average molecular weight was 7. 0X 10 ^3. The structure of the repeating unit contained in the polymer compound 4 estimated from the preparation is shown below.

Example 5

The monomer 1 obtained in Example 1 was reacted with trifluoromethanesulfonic acid anhydride. 0.25 g of the trifluoromethanesulfonic acid ester of the monomer 1 obtained by the above method and 0.72 g of the 3,7-dibutene-mo 2,8-dioctyloxydibenzothiophene and 2,2′-biviridyl 0 55 g was dissolved in 40 g of tetrahydrofuran (dehydrated), and the system was purged with nitrogen gas to replace the inside of the system with nitrogen gas. To this solution, 1.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (C0D) 2} was added and reacted at room temperature for 24 hours. The reaction was performed in a nitrogen atmosphere.

Next, a mixed solution of 25% ammonia water, 10 ml of methanol, 30 ml of methanol / 60 ml of ion-exchanged water was added to the reaction solution, and the mixture was stirred for about 1 hour. The solution was allowed to stand at room temperature overnight, and the generated precipitate was collected by filtration. Next, the precipitate was dried and dissolved in toluene. Insolubles were removed by filtration. Next, this solution was washed with 1 N hydrochloric acid. After liquid separation, the toluene layer was washed with about 2.5% ammonia water. After liquid separation, the toluene layer was washed with ion-exchanged water. Next, the obtained toluene solution was poured into methanol and purified by reprecipitation. The resulting precipitate was collected, washed with ethanol, and dried under reduced pressure to obtain 0.05 g of a polymer. The obtained polymer is called polymer compound 5.

The number average molecular weight in terms of polystyrene of the polymer compound 5, 1. 0X 10 ⁴ der is, weight average molecular weight was 1. 8X 10 ^4. The structure of the repeating unit contained in the polymer compound 5 estimated from the preparation is shown below.

0

Example 6

0.25 g of trifluoromethanesulfonic acid ester of Monomer 1 obtained by reacting Monomer 1 obtained in Example 1 with trifluoromethanesulfonic anhydride and 3,7-dibutanol , 8-Dioctyloxydibenzothiophene 0.45 g with N, N, 1-bis- (4-bromophenyl) -1-N, N, 1-bis- (2,6-dimethyl-1-4-1tert-butylphenyl) -1 1 After dissolving 0.33 g of 4-phenylenediamine and 0.55 g of 2,2'-bipyridyl in 40 g of tetrahydrofuran (dehydrated), bubbling with nitrogen gas was performed to replace the inside of the system with nitrogen gas. To this solution, 1.0 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (C0D) 2} was added, and reacted at room temperature for 40 hours. The reaction was performed in a nitrogen atmosphere.

Next, a mixed solution of 50 ml of methanol and 50 ml of Z ion-exchanged water was added to the reaction solution, followed by stirring for about 1 hour. This solution was allowed to stand at room temperature overnight, and the generated precipitate was collected by filtration. Next, this precipitate was dried and then dissolved in toluene. After removing insolubles by filtration, the solution was purified by passing through a column filled with alumina. Next, this solution was poured into methanol and purified by reprecipitation. After collecting the formed precipitate and washing with ethanol, Was dried under reduced pressure to obtain 0.35 g of a polymer. The obtained polymer is called polymer compound 6.

The polystyrene reduced number average molecular weight of the polymer compound 6 was 1.5 × 10 ^4, and the weight average molecular weight was 2.8 × 10 ⁴ . The structure of the repeating unit contained in the polymer compound 6 estimated from the preparation is shown below.

Example 7

The polymer compound 16 could be easily dissolved in black hole form. The 0.2% chloroform solution was spin-coated on a quartz plate to form a polymer thin film. The UV-visible absorption spectrum and the fluorescence spectrum of this thin film were used for Shimadzu Corporation, respectively. The measurement was performed using an automatic recording spectrophotometer UV 365 manufactured by Hitachi, Ltd. and a fluorescence spectrophotometer 850 manufactured by Hitachi, Ltd.

Table 1 shows the fluorescence peak wavelengths and relative intensities of polymer compounds 1 to 6. Polymer compound Fluorescent peak wavelength (nm) Fluorescent intensity (a.u.)

1 438 6. 7

2 428 1.2

3 598 0.01

4 437 2.8

5 442 0.7

6 531 0.07 Example 8

A glass substrate on which an IT〇 film with a thickness of 150 nm is applied by the sputter method is spin-coated with a solution of poly (ethylenedioxythiophene) / polystyrenesulfonic acid (Baytron, Baytron) to a thickness of 50 nm. And dried on a hot plate at 120 for 5 minutes. Next, a film having a thickness of 70 nm was formed by spin coating using a 1.5 wt% benzene solution of the polymer compound 1. After drying at 80 ° C for 1 hour under reduced pressure, about 4 nm of lithium fluoride was deposited, about 20 nm of calcium was deposited as a cathode, and then about 50 nm of aluminum was deposited as a polymer. An LED was fabricated. The degree of vacuum at the time of vapor deposition was 1 to 8 × 10 ¹⁶ To rr. By applying a voltage to the obtained device, EL light emission from polymer compound 1 was obtained. The emission start voltage was about 7.6 V, the emission efficiency was about 0.14 cdZA at maximum, and the maximum luminance was about 100 cd / m2. The EL peak wavelength almost coincided with the fluorescence peak wavelength of the polymer compound 1 thin film, and EL emission from the polymer compound 1 was confirmed.

Industrial applicability The polymer compound of the present invention can be used as a light emitting material. Therefore, the polymer compound can be used for a polymer LED. The polymer LED can be preferably used as a planar light source as a backlight, or a device such as a flat panel display.

Claims

The scope of the claims

1. A polymer compound comprising a repeating unit represented by the formula (1) and having a polystyrene equivalent number average molecular weight of 10 ³ to 10 ⁸ .

X ¹ and X ^2, either one is C (= 0) or CiR ¹⁾ (R ^2), the other is 0, S, C (= 0 ), S (= 〇), S0 _2, S i (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (= 0) (R ⁸ ).

(Wherein, RR ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are each independently a hydrogen atom, an octogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group) Group, aryloxy group, arylthio group, arylamino group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, acyl group, acyloxy group, amido group, imino group, Represents a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group.)

-Y ¹ -Y ^2- (2)

[Wherein, Y ¹ and Y ² are each independently o, s, c (= 〇), s (= o), so ₂

, C (R ⁹ R ¹ ), S i (R ¹ (R ^{1 2} ), NCR ¹³ ), BCR ¹⁴ ), P (R ¹⁵ ) or Ρ (= 0) (Ι ^ ⁶ ) (Wherein, R ⁹ , R ¹ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group , Alkylthio, alkylamino, aryl, aryloxy, arylthio, arylamino, arylalkyl, arylalkoxy, arylalkylthio, arylalkylamino, acyl, acyloxy, Amide group, imino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, aryl alkenyl group, aryl ethynyl group or cyano group. However, Y ¹ is ^{^{C (R 9) (R X}} 0), otherwise ^{^{^{S i (R 1 1 R 1}}} 2), Y 1 and Y ² do not represent the same. ]

One ^{^{Υ 3 = Υ 4 - (3}} )

[Wherein, Υ ³ and Υ ⁴ are each independently N, B, P, C (R ^{X 7} ) or S i (R ¹⁸ )

(Wherein R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, an arylthio group, Arylamino group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, acyl group, acyloxy group, amide group, imino group, substituted silyl group, substituted silyloxy group, substituted silylthio Group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group. ]

One Y ⁵ — (4)

[Where Y ⁵ is 0, S, C (= 0), S (= 〇), S〇 ₂ , C iR ¹⁹ ) (R ^{2 0} ) S

^{1 (R 2 1) (R} 2 2), N (R 2 3), B (R 2 4), P (R 2 5;) or P (= 〇) (R

2 6)

^{^{(Wherein, R 1 9, R 2 0}} , R 2 1, R 2 2, R 2 3, R 2 4, R 2 5 and R ² ⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group, Alkoxy group, alkylthio group, alkylamino group, aryl group, aryloxy group, arylthio group, arylamino group, arylalkyl group, arylalkoxy group, arylalkylthio group, arylalkylamino group, acyl group, acyloxy group, Represents an amide group, an imino group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a monovalent heterocyclic group, an arylalkenyl group, an arylethynyl group or a cyano group. ). ]

Represents —CR ^{3 6} = CR ^{3 7} or —C≡C—. R ^{3 6} and R ³ ⁷ each independently represent a hydrogen atom, an alkyl group, Ariru group, a monovalent heterocyclic group, or Shiano group. d represents 0 or 1. ]

2. The polymer compound according to claim 1, wherein in the formula (1), M is represented by the formula (2).

3. In the formula (1), X ¹ and Ar ² are bonded to the aromatic ring carbon of Ar ¹ , X ² and Ar ¹ are bonded to the aromatic ring carbon of Ar ² , billing Y ¹ and a r ² is adjacent position fc bonds of the aromatic ring-carbon of a r ^1, Y ² and a r ^1, characterized in that the bonded at the adjacent position to an aromatic ring carbon of a r ² Item 4. The polymer compound according to Item 2.

4. The polymer compound according to claim 1, wherein Ar ¹ and Ar ² in the formula (1) are benzene rings.

5. The polymer compound according to claim 2, wherein in the formula (1), Y ¹ and X ² are C (= 〇).

6. In the formula (1), Y ¹ and X ² are C (= 〇), and Y ² and X ¹ are 〇 (oxygen atom). Or the polymer compound according to 5.

7. The polymer compound according to any one of claims 1 to 6, wherein the total of the repeating units represented by the formula (1) is 10 mol% or more of all the repeating units.

8. The polymer compound according to any one of claims 1 to 7, which has liquid crystallinity.

9. The polymer compound according to any one of claims 1 to 7, which has fluorescence in a solid state.

10. A polymer electronic device comprising the polymer compound according to claim 1.

11. A light-emitting layer is provided between the electrodes consisting of the anode and the cathode, wherein the light-emitting layer is defined in claims 1 to A polymer light-emitting device comprising the polymer compound according to any one of claims 9 to 13.

12. A planar light source comprising the polymer light-emitting device according to claim 11.

13. A segment table comprising the polymer light-emitting device according to claim 11.

14. A dot matrix display device comprising the polymer light-emitting device according to claim 11.

15. A backlight, wherein the polymer light-emitting device according to claim 11 is used as a backlight.