TW200403327A - Polymer compound and polymer luminescent element using the same - Google Patents

Abstract

A polymer compound is provided. The polymer compound is characterized by containing one repeating unit represented by the formula (1), and having a polystyrene-reduced number average molecular weight of 103 to 108. wherein Ar1 and Ar2 each represent an aromatic hydrocarbon group or a heterocyclic group; X1 and X2 represent C(=O) or C(R1)(R2) for one, and O, S or C(=O) for another one; M represents O-C(=O), C(=O)-O, O, S, C(=O) or the like; Z1 represents-CR=CR-or-C ≡ C-; and d represents 0 or 1.

Description

200403327 Rose, description of the invention [Technical field to which the invention belongs] The present invention relates to a polymer compound and a high-light-emitting device using the polymer compound (hereinafter, also referred to as a polymer LED (light emitting diode).). [Prior art] The light emitting material of ^ 77 s is different from the low molecular weight light emitting material; the reason is that the light emitting layer using the light emitting element can be formed in the grain medium according to the coating method. On the 0th, the research on this aspect was carried out. For example, there are well-known polyphenylene oxides, polyfluorene derivatives, polyphenylene derivatives, etc. And 'about the mutual bonding between the ortho positions of the aromatic rings constituting the biphenyl ring is fixed from 1 to 3 4; ^ ", or a group of atoms and a biphenyl derivative having a structure that forms a 5 to 7 member ring — & lt A polymer compound represented by the following formula: W (World Patent) 01/96454. 1 Ding Youru

Rk

cw qing m = cR It is described here that the ancient VIII-N-, _ (C〇) ~, mixed all belong to the knife knife as a matrix (matrix), and the ions to form a light-emitting layer. In addition, Japanese Patent Laid-Open No. 8-815 tetrachloro [2,7-diyl) derivative. No MW, [Inventive Content] The inventors, etc., can use Xinlai's high score 314723 200403327 as a light-emitting material. As a result of intensive research, it was found that there are 2 fragrant clothes in Gansu Wuwu. The aromatic ring is bonded with a specific bond, and the sub-compound is suitable for the structure obtained by biting the light-emitting material to complete the present invention. The fact that 嶋 -He transmits materials and so on, that is, the present invention is related to the recurrence unit containing the formula to eliminate poverty ^ p & $ 1 (1), and the average number of workers who use ethylene to change the nose is卞] The knife is a polymer compound of U 103 to lx 108. 77

X1-X2

[In the formula, Ar1 and Ar2 are respectively 猸 ☆ Ben- / cheng is a heterocyclic group having a valence of a 4-valent aromatic hydrocarbon group independently of J. 4 χΐ and X2 indicate that either one is c (= 〇) or C (R1) (R2) and the other one is Si (R3) (R4), n (r5), B (R6), and 0, S, C (= 〇), s (= 〇), sO (R7) or P (= 0) (R8). (Where m R4, R5, R6, R7, and r8 each independently represent a nitrogen atom, a proton +, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, and an arylthio group. , Arylamino, aralkyl, arylalkoxy, aryl :): thio, aryl, amine, fluorenyl, aryloxy, giamino, imino, substituted silyl , Substituted silyloxy, substituted silylthio, substituted fluorsilylamino, monovalent heterocyclic group, arylalkenyl, arylethynyl, or cyano. ) M represents a base represented by formula (2), formula (3), or formula (4). 6 314723 200403327 [where Y1 and Y2 independently represent 0, S, c (== 〇), S ⑺, S02, C (R9) (R 丨 ο), Si (R)]) (Ri ”, N (R 丨 ”, B (R1”, p (R 〖5) or P〇〇) (R16). (Where R9, R10, Rn, Ru, R15 and r16 each independently represent a hydrogen atom, a halogen atom , Alkyl, alkoxy, alkylthio, alkylamino, aryl, aryloxy, arylthio, arylamino, aralkyl, arylcarbooxy, amine :): thiothio , Carbamoyl, acyl, acidoxy, amido, imino, substituted silyl, substituted siloxy, substituted methylsilylthio, substituted silylamino, monovalent Heterocyclyl, arylalkenyl, arylethynyl, or cyano.) However, when Y1 is other than C (R9) (Ri0), Si (RU) (R 丨 2), Y1 and γ2 are not the same.] -Υ3 = Υ4 one (3) [wherein Υ3 and Υ4 each independently represent N, B, P, C (R17) or Si (R18). (Wherein, R17 and R18 each independently represent a hydrogen atom, a halogen atom, Carbo, oxy, thio, amine, aryl, aryloxy, arylthio, arylamino, aryl :): cumyl, aryl :) : Pentyloxy, arylalkynyl, aryl :): pentylamine, aryl, oxy, S-blueamine, imide, substituted vermiculite, substituted silyloxy, substituted fluorene Ishigaki thio group, substituted silylamine group, monovalent heterocyclic group, arylalkenyl group, arylethynyl group or cyano group.)]-Y5- (4) [wherein, y) represents 0, 8 , (^ 卜 〇), 8 (two), 802, (^ (11) 9) (to 20), SURUKR22), N (R23), B (RH), P (R25), or P (= 0) (R26). 314723 7 200403327 U in Hr2G, r21'r22, r23, r24, r25 ^ r2 ^ Don't independently represent hydrogen atom, protogen +, alkyl group, alkoxy group, alkylthio group knife, burned amine Aryl, aryl, aryloxy, arylthio, arylamino, arylxyl, arylalkoxy, arylalkylthio, arylalkylamino, fluorenyl, fluorenyl, fluorenyl, Imino, substituted fluorinyl silyl, substituted silyloxy, substituted silylthio, substituted silylamino, valence heterocyclic group, arylalkenyl, arylethynyl, or cyano.)] ^ B R37 each independently represents a wind atom, an alkyl group, an aryl group, a monovalent heterocyclic group or a cyano group. D represents 0 or [Implementation [Formula] Hereinafter, the polymer compound of the present invention and a polymer light-emitting device using the polymer compound will be described in detail. In the formula (1), Ar1 and Ar2 each independently represent a tetravalent aromatic hydrocarbon group or a tetravalent heterocyclic ring. Both Ar1 and Ar2 are more preferably a 4-valent aromatic hydrocarbon group, and both are more preferably a monocyclic 4-valent aromatic hydrocarbon group. Here, a tetravalent aromatic hydrocarbon group refers to benzene. The meaning of the remaining atomic group after the ring or fused ring has been removed by 4 hydrogen atoms is usually 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms, and the following compounds can be exemplified. Here, the aromatic hydrocarbon group may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, and an arylthio group. Base, arylamino, arylalkyl, arylalkoxy, arylalkylthio, arylalkylamino, fluorenyl, fluorenyloxy, fluorenylamino, imino, substituted silyl, substituted fluorenyl Ishigamine, substituted silylthio, substituted silylamino, monovalent heterocyclic ring 8 3) 4723 200403327 group, arylalkenyl, arylethynyl or cyano. The number of carbons in the substituents is not included in the valences of valence to valence. Carbon number of the shell aromatic hydrocarbon group The 4-membered aromatic hydrocarbon group can be exemplified as follows.

In addition, the atoms gj to 20 remaining after the valence of the four valences. And in the carbon number of a heterocyclyl heterocyclyl, a phosphyl means the meaning of removing 4 hydrogen atoms from a heterocyclic compound, and the carbon number is usually 4 i 60, preferably 4 when it may have an aryl group. The same substituents. Does not include carbon number of substituents. 314723 9 200403327 In this heterocyclic compound system, the element f of nitrogen constituting the ring is not only the phosphorus of the organic compound made by A, but is only a halogen atom, but also contains oxygen, sulfur, I., Shi Xi, code in the ring. The meaning of those who are waiting for a heteroatom. -Member_ring group can be exemplified as follows: · Nitrogen-containing 4-membered heterocyclic group can be exemplified as: Hou. Definite four groups (such as the following formula (16)), two Azabenzenetetrayl (such as the following formula (17)), quinoline tetrayl (such as the following formula (18)), quinoxaline tetrayl (such as the following formula (19)), acridine tetrayl (such as the following formula ( 20)), phenanthroline tetrayl (such as the following formula (21)) and the like.

A group containing a hetero atom such as silicon, nitrogen, oxygen, sulfur, and selenium and having a europium structure (such as the following formulae (22) and (23)). Examples of the 5-membered ring heterocyclic group containing heteroatoms such as silicon, nitrogen, oxygen, sulfur, and selenium are as follows (the following formula (24)). A 5-membered ring condensed heterocyclic group containing heteroatoms such as stone, nitrogen, oxygen, sulfur, and selenium: as shown below (formula (25) below).

314723 200403327

(2 0) 11 314723 200403327

314723 200403327

(2 5) In the above formula, R '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 aromatic group Alkyl, arylalkoxy, arylalkylthio, arylalkylamino, fluorenyl, fluorenylamino, arylalkenyl, arylalkynyl, monovalent heterocyclic or cyano 314723 200403327 . Rn each independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a substituted silyl group, a fluorenyl group, or a monovalent heterocyclic group. X1 and Al · 2 are preferably bonded to adjacent positions of the aromatic ring carbon of Al, and X2 and Alm · 1 are preferably bonded to adjacent positions of the aromatic ring carbon of Ar2. -X1-X-Examples are worse than the following. _C —O—

S I OMC

OM OM OHS I one of -ϋ—Si—

6-R—B I OMC R7 _C—p—

onsMO OOP——R 1 I one OMC R11cIR-* _ 3-4 o R——si——R 1 _ RI-cIRR1 丨 C—R2 s 2 ^. 1P1c--R2 5 R—

N R11c―-r2r1 丨 c―-R2

OMC 6 R 丨

.B

R o = -sr7_p- I iric-—r2 —CIR2

R c―-r2r1 丨 c―R2

ΟΠ8ΠΟ oypIR in which 0 I one s I one

OMC I OMC s 1PIcl-- o R1 丨 c-f one R1——cl 〇 f N I -c one Si one of

π I * C ~ N— of

ii I * C-B— R1 R3 -C—Si- R1 R5 R1 R6 C—Isl— C—B— preferably 0 -X 丨 -X2- to] 4 314723 200403327 ο

II c — ο or R1

I —c— o — preferably, ο

II —c— 〇 — is better. _γΐ_γ2_ can be exemplified as follows. 314723 200403327 O II —o—c— one I one-I OMC-s oneo = 8— = c >-I OMC-ous 1 1 one 3R1 ·

IN one

one ί I R 丨 B 5 R1 OMC-p R9 丨 (s

11112 R—s · — R o 9, 1rr · • ilR10

3 I R1l-N R9 丨 c―1P R—

ο II R9 —c-c- R9 丨 c.Ions • p o —R1 R] UR14 R9 —U- o 9 t1R flf 15 R1 ·

OMP—1P onsMO o: I one

R 10 .i—R10 R9 丨 f: R10R9l-c · o —R1 o

11112 R—siIR R 丨 s • TTR12

3-r1in 11112 RIsi-R

14- R1IB 1 I 2 R—si—R

5 I R1-p 11-1 12 R——si——R R1 I -0-B- R1 I • S-B · r13 r14

One N one B

15IR11p i-RIB

oy Dv 4 ^ R1——B R. pI o 15I R-pIs

15I R—p 3-R1 丨 -N oy i I < 4 R—si— R 1 _ 2 R1lsi—R1 9 Rt

I10 c * — R 9-^ p—c ——R 0 = 0--RIs or less 16 314723 200403327 one Io one- s one-one 9 R_ s

o 11R r £ ic—r fl9I-C―-R1 one one l ”-u 9 I S Risi—R R——c——R | I-ons? 0I π —N— C-

11I12 R——si——R 9 R · ’i—R10

3 _ R1 丨 -N 9 R, c 丨

0 1 丨 R 11112 R—si—R I 0 11112 R—s—R I s

3 * r1in 11112 R—si—R R'lsilR1

Hi 1-1R1SI—R1 R9 丨 C-I1R r9_c-ir10 is preferred. -Y3 = Y4- can be exemplified as the following-Ν 二 Β--Ν = Ρ 一

N = C— fW -N = Si-

R 18 B = P— • B = C— B = Si— —p = c—

R 17

R 18

R 17 • P = Si-

R 18 * C = Si— R17 R18 Among them, from the viewpoint of the stability of the compound, -N = C— • B = C—

R 17 —P = C — -C = Si— R17 R18 is preferably -Y and can be exemplified as follows. 17 3I4723 200403327 〇 〇 〇 〇 One S— One C One One S One 8— II 0

~~ ^ Si 一 R22 Γ

N ΓΒ— Γ ΟΠΠΡ

6 2 • IR where:

R21 R23

II —Si— —m— In formula (1), M is -Y] -Y2-, and Y1 and Ar2 are bonded to adjacent positions of the aromatic ring carbon of Ai ", and Y2 and Ai * 1 are bonded to The adjacent position of the aromatic ring carbon of Ar2 is preferable. In the formula (1), M is -Μ ^ Υ2-, and Y1 and X2 are preferably C (20). On the combination of -Υ ^ Υ2- and-× ^ χ2-, -Υ ^ Υ2- and -Χ ^ χ2- In the repeating unit, it is preferable that the adjacent positions of the aromatic rings combine with each other to form a C2 symmetrical group, with- Υ】 -Υ2_ is 0. 丨 丨 —〇—-C- H2- is 0

II —C — 〇-better. In the present invention, the polymer compound has an inverse formula that can be expressed by formula (1). 18 314723 200403327 is a complex formula, where A! "And Aι: 2 are benzene rings, and the formula is more preferable.

[In the formula, R-, R28, R29, and R30 each independently represent a hydrogen atom M group, a halide atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an arylaryloxy group, an arylthio group, Arylamino, thio, aryl, amino, substituted, silylamino, arylalkenyl, aryl, or cyano. R27 and R28 can be connected to form a ring. Z2 represents _CR38 = Don't independently represent a hydrogen atom, an alkyl group, or 0 or 1.1. Arylalkyl, arylalkoxy, arylalkane substituted carboxyl, substituted silylthio, arylalkynyl, arylamine, A valence heterocyclic ring to form a ring, or R29 and R30 may be connected to CR: 9- or · 〇Ξ C-. R38 and R39 are aryl, 1-membered heterocyclic or cyano. e Z] means _CR36 =: (^ p37 屮 ^ ^ I R-or -c_. R36 and R37 are independent of each other without hydrogen atom, alkane,-gan dao μ standing table or 丨. Earth, earth, A monovalent heterocyclic group or a cyano group. D represents.

Zl is' CR3, r3, which is the best view ^ cool ^ the short wavelength of the luminous wavelength of the light element (blue, see, 4 is 0 (zero) is better. The halogen of the present invention; 5 workers Ding atoms can be exemplified as: fluorine, gas, desert, iodine. 314723 19 200403327 Alkyl can be any of linear, branched or cyclic, and the carbon number is usually about 1 to 20. Specific examples include: fluorenyl, Ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3, 7-dimethyloctyl, lauryl, trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, etc. Alkoxy can be any of linear, branched or cyclic Yes, the carbon number is usually about 1 to 20. Specific examples include: fluorenyloxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, third butoxy, and pentyloxy. Base, hexyloxy, cyclohexyloxy, pentyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, 3,7-dimethyloctyloxy, lauryloxy, Trifluoromethoxy, pentafluoroethoxy, perfluorobutoxy Group, perfluorohexyloxy, perfluorooctyl, fluorenyloxy, 2-methoxyethoxy, etc. The alkylthio group can be any of linear, branched, or cyclic, and the number of carbons It is usually about 1 to 20. Specific examples include: sulfanyl, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, third butylthio, pentylthio, and hexylthio. Base, cyclohexylthio, pentylthio, octylthio, 2-ethylhexylthio, nonanyl, decylthio, 3,7-dimethyloctylthio, laurylthio, trifluorosulfanyl Alkylamine group can be any of linear, branched or cyclic, it can be monoalkylamine or dialkylamine group, and the carbon number is usually about 1 to 40. Specific examples include: 曱Amine, Diamido, Ethylamino, Diethylamino, Apropylamine, Dipropylamine, Isopropylamine, Diisopropylamine, Butylamine, Isobutylamine, Tertiary Butylamine, Amylamine Base, hexylamino, cyclohexylamino, heptylamino, octylamine 20 314723 200403327, 2-ethylhexylamino, nonamino, decylamino, 3,7, dimethyloctylamine A, laurel Amino, cyclopentylamino, dicyclopentylamino, cyclohexylamino, di Hexylamino, pyrrolidinyl, piperidinyl, bistrifluoromethylamino, etc. The aryl group may have a substituent, and the carbon number is usually about 3 to 60. Specific examples include phenyl, c ^ 2 alkoxybenzene (C | ·, 2 represents a carbon number of i to 12. The same shall apply hereinafter.), CV, 2xphenyl, naphthyl, 2-naphthyl, pendantyl, etc. An aryloxy group may have on the aromatic ring Substituent 'and the carbon number is usually about 3 to 60. Specific examples include: phenoxy, c ^ 2 alkoxyphenoxy, alkphenoxy, 1-naphthyloxy, 2-naphthyloxy, penta Fluorobenzyl, etc. The arylthio group may have a substituent on the aromatic ring, and the carbon number is usually about 3 to 60. Specific examples include phenylthio, cN12 alkoxyphenylthio, and Gw alkylbenzene. Thiyl, benzonaphthyl, 2-naphthylthio, pentafluorophenylthio, and the like. The arylamine group may have a substituent on the aromatic ring, and the number of branches is usually about 3 to 60. Specific examples can be exemplified by: aniline group, diisopropyl group, C] _i2: J: endoxybenzidine, Bis ((3).] 2 alkyloxyphenyl) amino groups, bis (monoanilide) amino groups, 1-naphthylamino groups, 2-naphthylamine groups, pentafluoroaniline groups, and the like. The aryl group may have a substituent, and the number of carbon atoms is about 7 to 60. Specific examples include: phenyl-Ci 12 alkyl group, and c ^ χ Γ is called 2 垸 oxybenzyl-endyl, C, .12 phenyl-cNl2 alkyl, benzonaphthyl alkyl and the like. Carboxyl, 2-naphthyl-Cl-12 right, specific examples can be exemplified as: phenyl-c ^ 2 alkoxy, c less alkoxy C 丨 · 丨 2 alkylphenyl- (: 丨 _) 2 alkoxy Group, arylalkyloxy group may have a substituent 'and is usually 7 to 314 723 21 200403327 naphthyl-Cm2 alkoxy group, etc. The arylalkylthio group may have a substituent, and the carbon number is usually 7 to About 60, specific examples can be exemplified: phenyl-C12 alkylthio, C12 alkoxyphenyl-Cbuthio, C i. I 2thiophenyl-C ii 2thio, 1-naphthalene -C ii 2 thiol group, 2-Czechyl-Cm2 thiol group, etc. The carbon number of the arylalkylamino group is usually about 7 to 60, and specific examples can be exemplified by · Micyl-Cm2 amine group, C ^ 12 oxy 1 phenyl-Cbu phenyl amine, C! _12 phenyl phenyl- 0] ... amine amine, bis (C) _12 oxy phenyl-Cbn phenyl amine, bis (Ch12 phenyl phenyl) -Alkenyl) amine, 1-zekiyl- amine, 2-zeyl-(^ amine, etc.) The carbon number of fluorenyl is usually about 2 to 20, and specific examples include ethenyl, Propionyl, butylfluorenyl, isobutylfluorenyl, trimethylethylfluorenyl, phenylfluorenyl, trifluoroethylfluorenyl, pentafluorophenylfluorenyl, etc. The carbon number of fluorenyloxy is usually 2 to 2 About 0, specific examples are: Fluorobenzyloxy, etc. The carbon number of amidino group is usually about 2 to 20, and specific examples can be exemplified by: amidino group, acetamido group, propylamido group, butylamido group, and phenylamido group , Trifluoroacetamido, pentafluorobenzylamido, diamidoamine, diethylamidoamine, dipropylamidoamine, dibutylamidoamine, diphenylamidoamine, ditrifluoro Acetylamino, di-pentafluorobenzylamido, succinimidoimino, phthaloimino, etc. The carbon number of the imino is usually about 2 to 20, and specific examples can be exemplified as follows: Represented compound. 22 314723 200403327

Substituted silyl groups can be exemplified by: trimethylsilyl, triethylpyringyl, tri-n-propylpyringyl, triisopropylpyringyl, third butylsilyldiyl Methylsilyl, triphenylsilyl, tri-p-xylylsilyl, trimethylsilyl, diphenylmethylsilyl, third butyldiphenylsilyl, diphenyl Methylphenylsilyl and the like. Examples of substituted fluorenylsilyl groups include: trimethylsilyloxy, triethylsilyloxy, tri-n-propylsilylsilyloxy, triisopropylsilyloxy, third butylsilyldifluorenyl Silyloxy, triphenylsilyloxy, tri-p-diphenylmethylsilyl: t-peroxy, dimethylsilyloxy, diphenylmethylsilyloxy, tert-butyl Diphenylfluorenylsilyloxy, difluorenylphenylsilyloxy and the like. Examples of the substituted fluorenylsilylthio group include, for example, trifluorenylsulfanylthio group, triethylfluorenylsilylthio group, tri-n-propylsilylthio group, triisopropylfluorenylsilylthio group, and third butylphosphoranylsilyl group. Difluorenylsulfanylthio, triphenylsulfanylthio, tri-p-xylylsilylthio, tribenzylsilylthio, diphenylmethylsulfanylthio, tert-butyldiphenyl Sulfonyl sulfanyl thio, disulfonyl 314723 200403327 phenyl sulfonyl sulfanyl and the like. I. W Μ. Ψ 石 夕夕 * 月 女 基, —One ethyl substituted for arsenite amine group can be exemplified as: dioxin 〒 ^ Gly-propyl sulfonylamine silane silylamine, tri-n-propyl Methylsilylamine, one ,,

Base, tert-butylphosphonium silyldimethylsilylamino, diphenylsilylamino, tri-p-xylylsilylamino, trimethylsilylamine, monophenylfluorenyl Sulfasilylamino, tert-butyldiphenyl vermiculite, dimethylxylsilylamino, bis (trimethylsilyl) amino, bis (triethylsilyl) amino , Bis (tri-n-propylsilyl) amino, bis (triisopropylphosphosilyl) amino, bis (third-butylsilyldimethylsilyl) amino, bis (triphenylphosphonium) Silyl) amino, bis (tri-p-xylylsilyl) amino, bis (tri-Tylsilyl) amino, bis (diphenylmethylsilyl) amine, di (third Butyldiphenylsilyl) amino, bis (xylylsilyl) amino and the like. The 1-membered heterocyclic group refers to the atomic group remaining after removing one hydrogen atom from a heterocyclic compound. The carbon number is usually about 4 to 60. Specific examples include ·· thienyl, CU12 alkylthionine Base, pyrrolyl, furanyl, sigma-fluorenyl, C η 2 alkynyl beta ratios, sulfanyl, glutaryl, trisyl. Sit, oxazolyl, thiazolyl, thiadiazolyl. In this case, you can find this temple with Ari or Ar2 bond or ether through ether bond, thioether bond, alkyl group, amine group, alkenyl group, alkynyl group, etc. Examples of the aryl group in the arylalkenyl group and the arylethynyl group are the same as those described above. The polymer compound of the present invention has two or more kinds of complex units. The polymer compounds of the present invention may each contain a reaction represented by formula 0 and "Θ 八 u) without damaging the fluorescent light 4 ^^ 1. Α property or charge transfer 3] 4723 24 200403327, which is acceptable The tenth from the right, σσ — s other than the repetition unit shown in eight (1), the other is too early. In addition, the sum of a long period of time and the early element shown in formula (1) is more than 5 mole% of the total repetition unit, and more preferably is more than 10% by weight. Among the more suitable molecular compounds of fluorene, the repeating units shown in repeating units other than formula (1) contained in general formula (6) are as follows. —Ar3 {CR3i ^ 32, CR 10 £ ⑹ (Formula In the formula, A! Represents an aryl group or two heterocyclic groups. And R32 each independently represents a hydrogen atom +, an alkyl group, an aryl group, a " solid heterocyclic group or a cyano group. F is 0 or 1 〇). Arj in the general formula (6) is an arylene group or a divalent heterocyclic group. The A〆: has a 1 atom, a natural group, a silk group, a thio group, an amine group, a square group, a square group, Aryl sulfanyl, #arylamino, aralkyl, aralkylene, aralkylthio, aralkylamino, fluorenyl, fluorenyl, fluorenyl, imino, substituted Substituents such as silyl, substituted silyloxy, substituted silylthio, substituted fluorsilylamino, monovalent heterocyclic group, arylalkenyl, arylethyl block, or cyano.

Ar3 may be an arylene group or a divalent heterocyclic group contained in a material conventionally used as an EL (electroluminescence) light-emitting material. These materials are disclosed in, for example, W099 / 12989, WOOO / 55927, WO01 / 49769A1, WO01 / 49768A2, WO98 / 06773, US (U.S. Patent) 5,7775〇70, W099 / 543 85, WOOO / 4632, US6 , 169, 163B1, W002 / 077060. 314723 25 200403327 The arylene contains those with benzene ring and condensed ring, independent clumps or condensed rings. The two fused rings are bonded directly or through a bond such as vinylidene, usually having 6 to 60 carbon atoms. 6 to 20 are preferable, and examples thereof include phenylene (for example, the following formula (2 6)), _diyl (for the following formula (27)), anthracene (for the following formula (28)), Bis (phenylene) (the following formula (29)), tris (phenylene) (the following formula (30)), a condensed ring compound group (the following formula (3 1)), and the like. The arylene group may have a substituent. Substituents can be exemplified by: halogen atom, courtyard group, alkoxy group, :): thio group, amine group, aryl group, aryloxy group, arylthio group, arylamine group, aryl group, aryl group, oxyalkyl group Aryl, .aryl thio, aryl thio, aryl, acid oxy, acid amine, imine, vermiculite, vermiculyl oxy, methyl sulfonyl, A monovalent heterocyclic group, an aryl dilute group, an aryl ethyl block group, or a cyano group, and the carbon number of the arylene group does not include the carbon number of the substituent.

26 314723 200403327

booxbp

κ ox

K

(3 0)

(3 1)

In the present invention, a divalent heterocyclic group refers to the remaining atomic group after removing two I atoms from a heterocyclic compound, and the carbon number is usually 4 to 60, 27 314723 200403327, and 4 to 20 are used. …earth. The number of carbon atoms which may be represented by the right heterocyclic group does not include the number of carbon atoms of the substituent. Soil, and "in the base == cyclic compound [mu] means that organic compounds / forming elements in a ring structure not only contain charcoal, but also contain heteroatoms such as oxygen, sulfur, and west in the ring. ≪ Examples of the heterocyclic group of shellfish include the following:… A heterodiaceous group containing a divalent heterocyclic group of lice; examples include: pyridyldiyl (formula (32) below), diazaphenylene (formula below) (33)), quinolinediyl (the following formula 0)) toxaxanyl (the following formula (35)), acridinediyl (the following formula, bi-diphenyldiyl (the following formula ( 37)), #wroline diyl group (the following formula ⑼)), etc. A group containing heteroatoms such as silicon, nitrogen, oxygen, sulfur, and selenium and having a europium structure (the following formula (39)). Containing silicon and nitrogen Examples of 5-membered ring heterocyclic groups such as oxygen, oxygen, sulfur, and selenium are as follows: (the following formula (40)). 5-membered ring condensed heterocycles containing heteroatoms such as stone, nitrogen, oxygen, sulfur, and selenium Cyclocycline is exemplified by: (the following formula (41)), benzothiadiazole-4,7-diyl group, benzo_diazole-4,7-diyl group, etc. A 5-membered heterocyclic ring group which is bonded at the α position of its heteroatom to form a dimer or oligomer, and can be exemplified For example: (the following formula (42)). 5-membered ring heterocyclic group containing heteroatoms such as silicon, nitrogen, oxygen, sulfur, selenium, etc., and 0 of the heteroatoms; a group bonded to a phenyl group at the position: exemplified ( The following formula (4 3)). (3 2) 28 31472: 200403327

(3 6) 29 314723 200403327 (3 7) (3 8)

/ 〇〇a ό ^ ό tjJ tjl IjJ R ·· R " Rn

(3 9) Ge j I Jindou • R R1 r · 30 314723 (40) 200403327 R " /

(4 1)

q} In the formula, R ′ each independently represents a hydroxyl group, a thiol group, a sulfanyl group, an aryl group, an aryl * element atom, and a thiol group. ^ Earth alkoxyl, arylthio, and arylamino square alkylaryl groups Alkoxy, arylalkylthio, arylalkylamino, fluorenylamino, arylalkenyl, arylalkynyl, valent heterocyclic or cyano. r, separately and independently represents a hydrogen atom, an alkyl group, an aryl group, an aralkyl group, a substituted fluorsilyl group, an alkyl group, or a monovalent heterocyclic group. 31 314723 200403327 In addition, the divalent heterocyclic group may also include, for example, a triplet luminescent coordination compound and the like, and examples thereof include, for example, the divalent metal coordination compound illustrated below.

32 314723 200403327

The polymer compound of the present invention can contain repeating units other than (1) and is preferable in terms of luminous efficiency, and examples thereof include a repeating unit represented by the following formula (7). 33 314723

Ar4 ', arylene or divalent heterocyclic ^ " Al can be bonded to each other to form a% aryl group,]. R33 represents a heterocyclic group having an alkane valence of valence, and may be a group represented by the following formula: 、, 八 (8), or an integer of 1 to 4. The group represented by formula (9, heterocyclic group, may be represented by the following formula ⑻). g is an integer from 1 to 4

Ar (h ⑻ In the formula, Aι * 6 is a aryl group or a divalent fluorene ring group of 1 桷. Represents a sub group, an alkyl group, an aryl group, a monovalent heterocyclic group, earth, or the following formula (9 ), Z3.-Z4 means -CR4G = CR4 丨-or r 7 is not a ~ ^ ... Han "and r4i respectively do not have a hydrogen atom, alkyl, aryl, 1-valent # atu epithion & radical or Cyano.h is an integer of 0 $ 2.

(9) In the formulas, Ar7 and Ar8 are each independently a monovalent or divalent heterocyclic group. R42 represents a hydrogen atom, an alkyl group, a aryl group, or a monovalent heterocyclic group. In addition, trans seven represents an alkyl group, an aryl group, or a monovalent heterocyclic group .. I and I. 1 is an integer of 1 to 4. Preferred specific examples of the repeating unit ^ represented by the general formula (7) can be exemplified as shown in the figure below. Moreover, it may have a substituent on a benzene ring or a heterocyclic fluorenyl group. 314723 34 200403327

The number average molecular weight of the polymer compound of the present invention is changed from polystyrene to 35,314,723, and is 10. To 108. Although the total number of anti-y and eight structures is different due to repeated structures or proportions, p ^ & < From the perspective of ascension, the number of repeated structures is generally 5 to 100,000. 10 to 10,000 is more preferred, and 20 to 50,000 is most preferred. The polymer compound of the present invention may be a random copolymer, a block copolymer or a graft copolymer, or j may be a polymer having such an intermediate structure, such as a blocky buccal mound. Take ^ ..., gauge /, XK thing. From the viewpoint of making molecular compounds with high quantum yields of fluorescence, ^ T random copolymers or block or graft copolymers with a segmented nature are relatively complete " Early 乂 7 ^ 王 的 热Atactic copolymers are preferred. The main bond has branches and three or more 愔 J f crescents or dendrimers (den (lrimer)) are also included. The 5 molecule of the 的 molecular compound of the present invention is premature, but To be connected by a non-conjugated unit, or in a repeating unit & & > μ u + ',, ^ where f contains these non-conjugated parts. An example of the structure of a connected repeating unit is ·· Do n’t focus on one of the following, a combination of the following and a vinyl group, and a combination of two or more of the following. The R is a hydrogen atom and a carbon number.丨 $ 7 Ω + ^ u alkyl groups of 之 to 20, aryl groups of 6 to 60 carbons, and a group selected from the group consisting of hetero 俨 l- 濉% groups of 4 to 60 carbons, And Ar represents the beauty of smoke with a carbon number of 6 to 60. 314723 36 200403327 o

-S

N

RIB

I—S-R R —4—

R 1 OHC 1 '0o = c'

〇 = c c = 〇 \ / N OHC cyo OH-C〇 = q, CHO -NIR Λ-OMnc cnMO I-N onnc 1ό

〇 II —C-N-I R

——I C = C— ^ S The terminal group of the polymer compound of S Ming has the basic polymerization activity. ^ Due to the light-emitting characteristics or durable life when the device is made, it can be protected by a stable base. Those having a conjugate to the main chain and a co-light bond of fluorene are preferred, such as: via a carbon-carbon bond; "a structure bonded to a square or heterocyclic group. In addition, since the Luminescence, the eight substances of the present invention are preferably those in a solid state with fluorescence. The excellent solvent for the polymer compounds of the present invention can be exemplified by: imitation monogasmane, dichloroethane, tetrahydrofuran, formazan Benzo, xylene, trimethylbenzene, tetrahydronaphthalene, decalin, n-butylbenzene, etc. 1 varies due to the high structure and molecular weight of the child compounds, but can usually be used in these media Those that dissolve more than 0.1% by weight. ^ The "human" is based on the method for preparing the molecular compound of the present invention. The polymer compound of the present invention can be expressed as follows, as shown in (8) below. Combining bucket 314723 37 200403327 as a kind of raw material and thick polymerization, that is, 1 Γ manufacturing. X1——X2

(In the formula, Ar1, Aι, 2, X1, χ2, and ⑽ and D2 each independently represent a halogen atom, 埝: the same as 舁 formula ⑴. D1 salt group, aryl alkyl group salt group, · d μ salt group, Aryl continued acid sulfonate methyl, monohalogenated methyl, auranyl, squamyl, ethyl.) A group, methyl amidino, cyanomethyl or °: methane sulfonate, ethane Examples of the arylcontanoate group are as follows: 'Arylalkylsulfonate group may be exemplified here, and the alkanoate group may be exemplified by sulfonate group, trifluoromethanesulfonate group, etc., and benzoic acid Examples of the salt group, p-xenthionite salt, and the like include a sulfonate group and the like. The lithopentyl group can be exemplified by the following formula

OMe 〇Et i \) Me 〇et

The fluorenylmethyl group is exemplified by a group represented by the following L formula. _CH2SMe2X, -CH2SPh2X (In the formula, X represents a halogen group.) The fluorenyl group can be exemplified by a group represented by the following formula.

XH2PPh3X (In the formula, X represents a halogen shoulder.) 314723 38 200403327 The sulfonate sulfonyl group can be exemplified by the following group: -CH2P〇 (〇r " i) 2 (In the formula, R '" represents An alkyl group, an aryl group, or an aromatic group, a chlorofluorenyl group, a bromomethyl group, and an iodine monohalogenated methyl group can be exemplified by a methyl group. The method of condensation polymerization has a vinyl group on the main chain, as required Examples using other monomers include: Π] Polymerization by a Wittig reaction between a compound having an aldehyde group and a compound having a scaly salt group, and a reaction by maintaining a reaction with a compound having an acid group and a scaly salt group. Polymerization, [3] Polymerization by the Heck reaction between a compound having a vinyl group and a compound with a _ prime atom, [4] Polymerization by the hacking reaction of a Λ compound having a vinyl group and a halogen atom Polymerization '[5] by the Horner-Wadsworth-Emmons polymerization between a compound having an aldehyde group and a compound having an alkyl phosphonate group, [6] The combination of Juna and burned-based phosphonate-based compounds is O'Neal Osim's method [7]. Polycondensation by dehalogenation gas method of two or more compounds having toothed methyl groups, [8] Polycondensation by salt decomposition method of two or more compounds having a sulfonium salt group '[9] The 3-in-1 reaction of Kennefenagel (K η eveneven 1) between a compound and a compound having 3 acetonitrile groups. And other methods of polymerization such as "1" [1 1] Polymerization by McMurry reaction of two or more compounds of eight groups. As for the polymerization of [1] to [11], according to the formula It is expressed as follows: 31472 39 [1] 200403327 0HC Ar——CH0 + X * Ph3P + H2C-Ar * -CH2P + Ph3 χ *

Check

〔2〕 OHC——Ar——CH2P + Ph3 X ·

n 〔3〕

Ar — + Br—Ar · -Br- ^ -pAr Catalyst

〔4〕 Br ——Ar test -3 Palladium catalyst

η [5] 40 314723 200403327 〇HC-Ar-CH〇 + (R0) 2 (0) PH2C-Ar * -CH2P (0) (〇R) 2

CN 〔10〕 Test 〇HC——Ar——CH2CN -►

n CN 41 314723 〔11〕 200403327 OHC- • Ar-CH〇

TiCl3-Zn • Ar In addition, the method for producing the south molecular compound of the present invention, * the case where the main chain does not have an ethylidene group, can be exemplified by a method called polymerization by a Suzukl coupling reaction '[13] A method of polymerization by Grignard (-η- reaction, [14] A method of polymerization by Ni (〇) (nickel oxide) catalyst "[15] by FeCl3 (chlorination A method of polymerizing an oxidizing agent such as iron), a method of oxidative polymerization of an electrochemical formula, or a method of decomposing a polymer by an intermediate having an appropriate leaving group, and the like. [12] to [16] above The polymerization method is expressed as follows: [12] Br-Ar-Br + _ absolute catalyst (\ ^ (~ Ar-Ar '—)-" Ar-Br + (RO) 2B-Ar · -B (〇 R) 2 R is a hydrogen atom, and the base η [13]

Br-Ar-MgBr nickel catalyst n [14] Br-Ar-Br

Ni (0) 〔15〕

Cf oxidative polymerization

Y FeC13, chemical formula Y is S, NH Qian 314723 42 〔16〕 200403327

ROCO OCOR

R Thermal Decomposition->

Among these, since it is easy to control the structure, it is preferable to use polymerization by maintaining reaction, polymerization by hacking reaction, polymerization by Ona Oshos-Emmon method, and by Kennef. Polymerization of Nagel reaction and method of polymerization by Suzuki coupling reaction, method of polytheta by Gleeve reaction, and method of polymerization by Ni (0) catalyst. Furthermore, from the viewpoint of easy availability of raw materials and the convenience of polymerization reaction operation, a method of polymerization by frontal coupling reaction, a method of polymerization by Gleeve reaction, and Ni (0) are preferred. Catalyst for polymerization. When the π village's poor and bright polymer compound is used as a polymer led light-emitting material, its purity will affect the light-emitting characteristics. :: 明, in the manufacturing method, the above-mentioned separation operation is fully implemented, and the removal is precisely performed. Unreacted monomers, by-products, catalyst residues, etc. B, Mu Ri inch, as long as it can be fully removed, ^ OK. In order to prevent the conditions of the media, that is, the deterioration of the A knife compound starts from f and t, and the dry welding is performed by shading (see this, the temperature is deteriorated by the heat in an inert gas, and the m-knife compound does not cause It is better to order the dry because of anti-bubble. According to the present invention, the compound with B A knife can be used as light. Furthermore, it can also be used as the active ingredient of the raw coin # ^ ^ Materials to make the material dry, or by Doped with + conductive material, Taiyi, 〇PIng) and used as the material of the liquid crystal in the present invention; the use of raw materials. The molecular display of sub-compounds: "Sub-compounds" means high Meaning. The liquid crystal phase can be confirmed by polarized light 314723 43 200403327 ', A', and differential scanning calorimetry, X-ray diffraction measurement. It is known that a compound having a liquid crystallinity has an isotropic property of writing by aligning it. (Synthetic Metals Issue ll9, (2001), p. 537) In terms of the "direction", it can be adopted: generally known as the direction of liquid crystal, such as "basics and applications of liquid crystal" ( Co-authored by Matsumoto Masao and Ichi, published by the Industrial Survey Association, 1991) Chapter 5, "Strong. Structure and Physical Properties of Amphoteric Fluids" (Co-authored by Atsuo Fukuda and Hideaki Taketa, published by Nasha '1990) No. 7 Chapter, "Liquid Crystals", Vol. 3, No. 1 (1999-16). The methods of wiping, light-orientation, application, or lift-up are simple, useful, and easy to use as orientation methods. Use = two methods of gently wiping the surface of the substrate with cloth, etc. You can use a thin cloth or gauze or polystyrene, cotton cloth n to wipe the substrate cloth, you can use an outer orientation film, two: Second, Fen and other cloths. For example, on the substrate, another example is to support feimine, polyamidoamine HfeT, and commercially available liquid crystals (water vinyl alcohol), polyester, nylon, etc. Orientation film can also be used for evaluation. —A * Plate printing and other formation, wipe the direction plate can be spin-coated Flexible selection. Can be matched with the situation of the orientation film. Appropriate light orientation method refers to the name / UV (ultraviolet) light irradiation. $: Formed on the board (to the film, and by the function of directing polarized light. The method of light makes it Examples of the oriented film include: polyimide, polyamine, poly314723 44 200403327 vinyl cinnamate, and commercially available alignment films for liquid crystals can also be used. In the wiping method or light alignment method, the Oriented polymer materials are interposed between the substrates on which the above-mentioned treatment is performed, so that they can be oriented. At this time, the substrate must be made of a material to reach the temperature of the liquid crystal phase or isotropic phase. It can be applied to the substrate before or after the molecular material is sandwiched between the substrates. Moreover, the polymer material is coated only on the substrate subjected to the orientation treatment. Depending on the temperature on which the polymer is placed on the substrate and the temperature is higher than Tg (glass transition temperature) or can display the liquid crystal phase or isotropic phase, use the lepton "... look (d) coating in the-direction, Or prepare a solution which is dissolved in organic solvent, and can be spin-coated. Or flexographic printing method, etc. Cut the 'cross-stress application method, respectfully coexist on the production materials ^! The polymer material placed on the substrate makes the US board to one substrate' can become a liquid crystal phase or isotropic etc. Phase temperature: two-way displacement method. At this time, if the substrate is subjected to the orientation treatment described in the ::: = or the light orientation method, the substrate can be broken glass or high. The molecular film is also made of metal instead of a substrate | Kunzi. Lifting / coating method refers to the method of immersing the substrate in a polymer solution, and then k up. Use the speed and It is not particularly limited to ... a liquid organic solution, or the finishing of a substrate. 疋 It can be used to select and adjust the polymer compound ancient materials of the present invention in accordance with the orientation of the South molecule. ~~ ... In order to affect the luminous characteristics of the U, the former monomers are refined by ancient methods such as steaming halls, sublimation refining, and re-refining, and then polymerized, and ...: "Re-Sifang Fang .X is a chromatographic separation and refining 31472, 45 200403327 after synthesis. The purification process. Since the light-emitting or phosphorescent light from the thin film is used, the polymer compound of the present invention is preferably one having fluorescence or phosphorescence in a solid state. Examples of excellent solvents for the polymer compounds of the present invention include chlorine.

Imitation, dichloromethane, dichloroethane, tetrahydrofuran, toluene, xylene, US dimethylbenzene, tetralin, decalin, n-butylbenzene, and the like. Although it differs depending on the high molecular weight, the structure of the material, or the molecular weight, it can usually be dissolved in these solvents by 0.1% by weight or more. Then, the polymer LED of the present invention will be described. The feature of Tsuki's A knife LED is that it has a light-emitting layer and a compound between electrodes formed by an anode and a cathode. The Qiyou layer 3 contains the polymer of the present invention. For the polymer LED of the present invention, a polymer coffee having an electron transport layer disposed between the step aurora layers can be mentioned: a hole transport is provided between the heart =. Polymer LED with two layers, an electron transport layer is provided between the first two cathode layers; Wait. In the polymer LED of the present invention, a layer is provided adjacent to the electrode between one layer: eight to ... an electrode ... a polymer having at least a layer of conductive polymer adjacent to the electrode and the film factory "&Quot; Polymer LEDs with ... following insulating layers are also provided between the light-emitting layers. 'M shows the following a) U) structure. A) 1% pole / light-emitting layer / cathode 314723 46 b) Anode / hole transport layer / light emitting layer / cathode c) anode / light emitting layer / electron transport layer / cathode d) anode / hole transport layer / light emitting layer / electron transport layer / cathode (here, / § number indicates each The meaning is the same.). The layers are adjacent to each other and are laminated. The following is here. The light-emitting layer refers to the layer that has the function of transporting holes ... =, and the function of transporting electrons by holes. , !! The transport layer refers to the object as a charge transport layer. 'Sub-transport layer and hole-transport layer total * The light-emitting layer and the hole are trapped above the __ layer. The transport-layer and the electron-transport layer can be used independently. 2: The charge transfer provided adjacent to the electrode is well documented. Those who have the effect of charge implantation from the electrode are generally special ~ The driving element of the low element is the implantation layer.) The twist is the electrical implantation layer (hole implantation layer, electrons, and 'for the improvement of the improvement of the implantation of the electrode and the electrode, can be connected with the electricity:; :: : Adhesive or the charge layer from the electrode or the thickness of 2 or less. Set the charge implantability or prevent the incorporation of rain, etc. * Y ', also to improve the interface's close adhesion ^ ， 可 ， 恭 * Into a thin buffer layer. Interpolation of the transport layer or the light-emitting layer = the order or number of laminated layers, and the thickness of each layer can be considered as appropriate or under the durability of the component. Use. Inshore: 'Mid-month. There is a charge implantation layer (electron implantation layer, hole implantation ... South molecular LED can be exemplified as: adjacent to the cathode and provided with electricity 314723 47 200403327 He implantation layer Polymer LED and polymer LED adjacent to the anode and provided with a charge implantation layer. For example, the following can be specifically mentioned: e) to p). E) Anode / charge implantation layer / light emitting layer / Cathode f) anode / light-emitting layer / charge-implanted layer / cathode g) anode / charge-implanted layer / light-emitting layer / charge-implanted layer / cathode h) electrode / electrical Charge implantation layer / hole transfer layer / light emitting layer / cathode 0 anode / hole transport layer / light emitting layer / charge implant layer / cathode J) anode / charge implant layer / air six pass wheel child implant layer / Cathode wood-wrapped implant layer / Light-emitting layer / Charge transport layer / Cathode U Anode / Light-emitting layer / Electron transport layer / Charge implant layer / Cathode m) Anode / Charge implant layer / Light-emitting layer / Electronic ™ layer / Electricity implantation thickness / Insurance s) Anode / Charge-implanted sound / a IW pole 0) Anodizing, Γ Transport layer / Light-emitting layer / Charge transport layer / Cathode 17 28 Knowledge layer / Light-emitting layer / Electronic transmission P) Supporting / Thousand and Four Ding 1 Tracing layer / Er Ho implant layer / Cathode pole / -Electro He implant layer / Hole transfer layer / Luminous implant layer / Cathode electric sensor layer / Charge charge implant A specific example of the layer-into-layer can be exemplified as: "containing layer '· via the anode and hole transport · u knife

Between the t-layers, there is a layer containing a material with an ion potential of the right masculine U, two M, known as the intermediate value of the material; between the ion layers, there is a ^^ f pole and electron transmission轮 # There is an electron affinity in the middle of the dagger pole material and the human M + transfer material in the electron transport unit ... the electrons in the layer 3, the layer of the material of the affinity unit, etc. As mentioned above, when the charge implantation layer contains a layer of snow gas that conducts an electric polymer, and a layer of a π knife, the guide "preferably is above." 〇3S / cm 3) 4723 48 200403327 " ~ p In order to reduce the leakage between the light-emitting pixels # 10'5S / cm. When the pen is ventilated, it is preferably below 80-S / cm, more preferably below inflammation. It is 100S / cm or more and 10iS. / cm I ", in order to make the conductive polymer Tai々 ^ S / cm ^, l α; < the milk-conducting conductivity is made 10- ^ up to S / Cm, the guide two secret ancient 乂 (doPe ) It is suitable for doping Tianshang Zongzi in the same molecule. The type of ions to be doped, such as the Department ~ If the electrons are X Θ, the implanted layer is anion, and the Er implanted layer is cation. Examples of vinyl sulfonate ions, "stone m" can be exemplified, such as · polyphenylene oxide / wooden slate acid, and photographic examples can be exemplified-^ ^ month end luteal ions, etc. Examples are not as good as lithium ion, sodium ion, etc. The film thickness of the potassium ion and tetrabutylammonium ion-implanted charge layer may be, for example, 2 to 50 nm. m to lOOmn, and it is preferred because the material of the charge implantation layer, the material, and the relationship between the electrode or the adjacent layer are appropriately selected, that is, biological and public. 8 3 Gan / a example is not as good as ... polyaniline and its derivative χκ_% and its bamboo creatures, polyethene · B Gan and its nail organisms, polyphenylene sene and its derivatives, polythiophene smoke Gan /,, T 〇 cloth and its derivatives, polyquinine and its derivatives, polyquinoxaline and hydrazone — # > "He Biao, a polymer containing a square amine structure on the main chain or branch chain Etc., etc.), carbon, etc. ¥ ... molecules, metal phthalocyanines (copper film thickness 2_ or less, an insulating layer that has an easy to implant charge charge: Examples include: metal fluorides, mongolian oxides, and organic insulating materials & Shiki 5 and 咼 molecule leds with an electrical edge layer of 朕 2nm thick and below can be exemplified. A polymer LED with an insulating layer having a thickness of 2 nm or less is arranged adjacent to the electrodes 314723 49 200403327, and a polymer LED having an insulating layer with a thickness of 2 nm or less is provided adjacent to the anode. Specific examples include the following: From ... to ab). Q) anode / insulating layer / film thickness below 2nm / cathode 0 anode / emissive layer / insulating layer / cathode below 2nm s) Electrode / insulating layer of a thickness of 2nm or less / light emitting layer / thickness of 2nm or less of the insulating layer / cathode

t) Anode / Insulation layer / Hole transport layer / Light emitting layer / Cathode below 2nm u) Anode / Hole transport layer / Emitting layer / Insulation layer / Cathode below 2_α v) Anode / Thickness below 2nm Insulation layer / hole transport layer / light-emitting layer / insulation layer with a thickness of less than 2nm / cathode forward / insulation layer / light-emitting layer / electron transport layer / cathode cathode / light-emitting layer / electron transport layer / Insulating layer with a thickness of less than 2nm / Cathode y) Anode / Insulating layer with a thickness of less than 2nm / Emitting layer / Electron transport layer / Insulating layer with a thickness of less than 2nm / Cathode Z) Anode / Insulating layer with a thickness of less than 2nm / Hole transport layer / Light emitting layer / Electric transport layer / Cathode aa) Anode / Hole transport layer / Light emitting layer / Electron transport layer / Insulation layer with thickness less than 2nm / Cathode ab)% Insulation layer with skin thickness less than 2nm / Hole transport layer / Light-emitting layer / Electron transfer layer / Insulation layer with a thickness of less than 2nm / Cathode The film thickness of the light-emitting layer in the polymer LED of the present invention is different due to the material used. The driving voltage and the luminous efficiency can be selected as appropriate values, but for example, it is from nm to I. This is 314723 50 200403327. Of 2nm to 500nm, 200nm to 5nm is better. 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, the "light-emitting layer containing a light-emitting material other than the above-mentioned polymer phosphor" may be laminated to include the above-mentioned polymer phosphor and a light-emitting layer. A known material can be used for this luminescent material. Among the low-molecular compounds, for example, Tsai derivatives, anthracene or its derivatives, can be used! (Perylene) or its bamboo organisms, pigments such as 4々 甲 川 (ρ 〇1 ymethine) system, X anthene system, cumalin system, cyanine system, etc. Metal complexes of oxoline or its derivatives, aromatic amines, tetraphenylcyclopentadiene or its derivatives, or tetrabenzyl butadiene or its derivatives. Specifically, those skilled in the art can be used, for example, as described in Japanese Patent Application Laid-Open No. Sho 57_5 丨 78 No. 1 and 5 9-1 943 93. The method for forming a light-emitting layer is not specified, but a method using a film from a solution can be exemplified. From the film forming method of the solution, spin coating method, washing molding 4, micro gravure coating method, gravure coating method, insert coating method, roll coating method: ¾, wire rod coating method can be used. , Dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, t ink printing method and other coating methods. ~~~ The hole transporting materials used in the history of Kangan / Hakucho, Shiten 4 can be exemplified by: Wanru · Polyvinylcarbazole or its derivative, Shixiyao or its derivative, in a branched chain. Main — A polysiloxane derivative with square amines on the main chain, pyrazoline derivatives, monoamines, StUbene derivatives, dibenzylamine derivatives, pentamine, ♦ + Amine or its derivative, polythiophene or 31472 51 200403327 derivative, polypyrrole or its derivative, or poly (2,5-thiophene A double phenylene vinylene) or its derivative in these, : Ethyl or its derivatives. Lixing Biotechnology / * 'Vinyl carbazole or its derivatives, polysilane or any other organism, presenting on the branch or main chain, P-copper extraction —, polyethoxylates with a private amine compound base Any organism, polybenzylamine or its derivative # ^ A ^ r, χ to phenphene or its derivative, poly (p-benzylidene) or its derivative,. Ge 苴 derivative β γ second time yong (2,5-thienyl vinylene) taste * * Gan, good transmission material is more 'Polyvinyl carbazole or its derivative, polysilane ^ ^, Biosynthetic derivatives, polysiloxane derivatives with well-known amines on the side chain or main chain .. S! F ^ ^ is best. Low-molecular hole-transporting materials 枓: used to disperse in polymer binding Polyvinylcarbazole or a derivative thereof, which is prepared by cationic polymerization or radical polymerization: ... ethylene monomers can be exemplified by t ^ & · Di Yi Juan, published on the title page (1989), compounds described in British Patent gb23001i96, etc. Synthetic methods can also be used in these methods. The methods already included, but the Qiping method is most applicable The polylithic yakiniku or its derivative is suitable for those who have the above-mentioned low-molecular vacancies on the branch or main chain due to the benefits of the * hole transport properties in the oxidative structure of the oxidized stone. In particular, for example, an aromatic amine having a hole-transporting property in a branch or a main bond can be exemplified. The film-forming method of the transfer layer is not particularly limited, but in the case of low-molecular hole-transporting materials, it can be exemplified by: a method of forming a film from a combination of a polymer binder and a liquid. The hole transfer wheel material can be exemplified by the method of forming a film from a solution. 314723 52 200403327 From the solution used for film formation from a solution, i is not particularly limited. The solvent can be exemplified as ^ Empty = Chlorine: Chlorine solvents such as alkane, dichloroethane, etc .; Ethers such as tetrahydrofuran-aromatic hydrocarbon solvents such as methylben, dimethylbenzyl, propane, methyl :, dione ketone solvents, acetic acid Ethyl acetate, soil S are equivalent vinegar-based solvents. M ... based-cellulose acetic acid can be made from solution by spin-coating gravure coating method, strip coating dipping coating method, spray coating from / valley For the film formation method, cloth method, casting method, micro gravure coating method, cloth coating method, wire rod coating method, cloth method, screen printing method, flexographic printing method, and offset printing method can be used. Coating method such as coating. The polymer binder mixed with the WP brush does not excessively hinder the charge.

It is suitable if the absorption of visible light is not too strong. The ancient eight L mixture can be exemplified by: polycarbonate, polyacrylate = knife ^ ^ κ T-based acrylic cool,: fluorenyl methyl propyl 1 stylene, polyvinyl chloride, poly, cavity! The optimal value of the film thickness of the transport layer will vary depending on the materials used. 'As long as the appropriate values are set according to the driving voltage and luminous efficiency, you Huanyang will only need to avoid the occurrence of pinhole thickness. -Unfavorable pressure increase. Therefore, the thickness of the hole-transporting acoustic driving layer is preferably from 1 nm to ⑽ ', preferably from 2 nm to 500 nm, and more preferably from 5 nm to 200 tens. For example, when the polymer LED of the present invention has an electron transfer layer, a conventional electron transfer material can be used. Zanyan line, Anthracene 314723 53 200403327 Burnt or its derivatives, Stupid or its derivatives, Naphthoquinone or its derivatives, Anthracene or its derivatives, Tetracyanoanthracene or its derivatives Compounds, hydrazine derivatives, diphenyl dicyanoethylene or its derivatives, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or its derivatives, polyquinolines or its derivatives, Polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof. Where 'from ^ — Tu Ho Sheng Milk + Ribei Tou Ho Wang Dui /, Enbei or its derivatives, or 8-Metal complexes based on Kirin or its derivatives, polyquinoline or its derivatives It is preferred that the compound, polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof, and 2- (4-biphenyl) -5- (4-third butylphenyl) -1,3, Diazine, benzoquinone, anthraquinone, ginseng (8-quinolinol) aluminum, and polyquinoline are more preferred. The film-forming method of the electron transport layer is not particularly limited, but examples of the low-molecular electron-transport material include a vacuum deposition method made of powder, or a film formation method made of gluten solution or molten state, and An example of a high-molecular electron-transporting material is a method of forming a film from a solution or a molten state. A composition made from a solution or a molten state. "Solution, transmission material, and / or polymer used for film formation from the solution of 1 Khan's molecular adhesion from solution." As long as it can dissolve electrons, it can be exemplified by: chloroform, dichloromethane, erbium #inchbe Restriction: Ether solvents such as hydrogen furan; chlorine solvents such as toluene and dioxane; ketone solvents equivalent to tetraacetone and methyl ethyl formamidine—aromatic hydrocarbon solvents such as methylbenzyl; Ester solvents such as methyl lysin, acetic acid, etc., acetic acid, acetic acid, butyl acetate, etc .: film formation from cereal or molten state ~ main molding method, micro gravure coating, and de-twistable Application: spin coating *, gravure coating. Wide < cloth method, ballast coating 314723 200403327 method, roll coating method, screen printing method coating method. Wire rod coating method, dipping The coating method, spray-cold cloth printing method, offset printing method, puppet master, and printing method are two-phase adhesives. For example, those who do not excessively hinder charge transport are taken as examples. Those whose absorption is not too strong are applicable. Take molecules Adhesives such as: willow-ethylene diene), polyaniline or its derivatives, polyaniline or its derivatives, poly (p-phenylene diene) ) Or its derivatives j "5-thienyl vinylene) or its derivatives: vinegar, polymethacrylic acid, γ-methyl acetic acid, polyacrylic acid, polyethylenic acid, vinyl acetate, polyethylen, Or polysiloxane. The film thickness of the electron transfer layer is 1 g, # Μ ^ Same, as long as the material selected for the driving power = Γ / Γ is not factory-strengthened: pinhole ", if it is too thick, the driving power of the component to U & quot 7 'The film thickness of the electron transport layer is, for example, preferably from 1 nm to 12 to 500 axes. The substrate with the right ED is the polymer τ p pole of the present invention with 5 to fine surfaces, As long as it is not a π 成, plastic, high score m "b" when forming a layer of organic matter, and can be exemplified as "+"., Silicon substrate, etc. For opaque substrates, this = 3 is transparent or translucent. An electrode made of bright or opaque & anode and cathode is at least -square ^, and the anode side is transparent or translucent. The anode is better than π% of people. Metal beta team, conductive metal oxide film for alpha wood, semi-transparent-r medium temple. Carcass e • Indium oxide, zinc oxide, tin oxide 314723 55 200403321 made from the sum of 4 ... u bismuth indium. Tin. Oxide (ιτο), indium. Zinc, emulsion Guiding Ming, silver, steel, etc., film (NESA, etc.) or gold made of joints, can be produced by the following methods: = T0, indium, zinc, oxide, and tin oxide. Law. + Two-deposition method, sputtering method, ion plating method, electroplating • ‘The anode may also be’ p m and its derivatives 箄 ># ^ Use polyaniline or its derivative, polythiophene, or an organic transparent conductive film. The thickness of the anode can be selected, but for example, A ..., tooth permeability and electrical conductivity, it is appropriate to select Feng 10nm to 10 ~ 50nm to m, and preferably 20nm to 1 // m, 芏 50 0 nm is more preferable. In addition, on the anode, a layer made of a compound or metal can be provided for the purpose of implanting a phthalocyanine derivative and a conductive charge of eight lines: or a layer made of carbon or a metal oxide or less Of layers. A material having an average film thickness of 2 nm made of a bar material or the like is preferably a material having a small polymer LEd according to the present invention. The cathode material that can be used for the field has a work function,-, J is used for example: magnesium, calcium, gill, barium, aluminum, sharp, vanadium, ':, sodium, potassium, thallium, planer, beryllium, Metals such as ytterbium and food, and their equivalents, zinc, yttrium, indium, osmium, ytterbium, osmium, " more than gold, silver, starting, pin, 2: alloys with more than weight, or their equivalent t 1 Kinds of alloys, graphite or graphite layer I, titanium, cobalt, nickel, tungsten, magnesium-silver alloys in tin, magnesium-indium alloys, magnesium-aluminum eight compounds, and the like. Examples of alloys ...

Gold, lithium-magnesium alloy, lithium-indium alloy, S-gold, indium-silver alloy, lithium-aluminum have a laminated structure of two or more layers, Xinlu alloy, and the like. The thickness of the cathode can be made. The choice of A can be considered, but for example, it is 100nm to】 :: wide conductivity or durability, and A ni is appropriately selected, preferably 20nm to} am, 314723 56 200403327, 50nm to 500nm. For the better. The manufacturing method of the cathode can be: vacuum, lamination method of thermal compression bonding of metal thin films, and the like. ^ The plating method and the organic material layer are provided with a conductive polymer, a layer that can be formed on the cathode, or a metal oxide or a metal chaotic compound, and an organic insulation with τ ^ ^ ^ 4 Takenizumi's average film thickness is 2nm

The lower layer 'or after the cathode is fabricated, a protective layer for protecting the polymer LED is attached. In order to use the polymer coffee stably for a long time, it is better to attach a protective layer and / or a protective cover to the outer county m. The protective layer may be made of a polymer compound, a metal oxide, a metal fluoride, a metal boride, or the like. ^ ^ You can also use a thin glass cover and a plastic plate with a low water permeability treatment on the surface, and use a thermal effect resin or light-curing resin to hold the cover close to it. The method of k μ + 4 i for attaching a substrate is applicable. When spacers are used to maintain space, it is easy to prevent damage to the components. Eight, if an inert gas such as nitrogen or argon is enclosed in the space, the oxidation of the cathode can be prevented. If a desiccant such as barium oxide is provided in the space, the adsorption during the manufacturing process can be easily suppressed Damage to components caused by water. It is better to take any one or more of these measures. In addition, a charge transport layer and a light coil layer are provided between the electrodes formed by the anode and the cathode, and the charge transport layer may also contain a polymer LED of the polymer compound of the present invention. The europium molecular light emitting device of the present invention can be used as a back light of a planar light source, a segment display device, a dot matrix display device, and a liquid crystal display device. If the polymer LED of the present invention is used to obtain a planar light emission 31723 200403327, 'the planar anode and the cathode can be arranged in an overlapping manner to obtain a pattern (-)-shaped light emission, then: 在: in the front plane '' The first method is to set a mask with a patterned window hole on the surface. / The organic material layer of the non-light emitting part is formed to be extremely thick so as to be substantially non-^ = 2. Either the anode or the cathode or both electrodes are formed into a pattern according to the independent party; follow any of these methods to form a diagram Type, and several electrode characters are configured to be 0N / 0FF (on / off), and a segment type display element that can display numbers, texts, and simple marks can be made. When the dot matrix element is clicked again, it is… as: it can be arranged in such a way that it can intersect vertically. By applying a plurality of types of hair) = coating method of the same macromolecules, or turning _ ... . Method, which can achieve partial color display, multi-color: No. The dot matrix element can also be passively driven. D. Active-g (common TFT) is used for active driving. These display elements' can be used as head units of computers, televisions, mobile phones, car navigation cards, viewfinders of video cameras, and the like. ^ Furthermore, 4 planar light-emitting elements-a thin type of self-generating light, which can be applied to liquid crystal display light sources ^ clothing, moonlight use a flat light source or as a plane ', and, such as A flexible substrate can also be used as a curved light source or display device. In the following, examples are described in order to explain the present invention in more detail, but the present invention is not limited to these examples. In it, Pingtu A. The knife uses tetrahydrofuran as a solvent, and the number average molecular weight of polystyrene based on the method of gel permeation (314723 58 200403327 μ) (GPC) is used throughout Example 1 & lt Synthesis of monomer 1> 25 g of ellagic acid, 22 g of dimethyl octane bromide, and 60 g of potassium carbonate were added to 45,0 g of dimethylformamide. = Reaction at 28 ° C for 28 hours. After cooling the reaction solution, it was allowed to stand. As a result, the second layer was separated, and then the upper layer was recovered. The recovered solution was washed with ion-exchanged water. Wash repeatedly until the washing water becomes neutral. Next, the oil layer was dried under reduced pressure, and then, using a silica gel column, the unreacted p-bromo-3,7-di? After removal of the tetraalkoxy substitutes of octane and ellagic acid, # the mobile phase is used to remove the dialkoxy substitutes by knife cutting. Dry 'to obtain 6.5 g of dialkoxy substitution. Observation of the obtained dialkoxy substituents from the chemical shifts of the nucleus resonance spectrum (NMR) of the shellfish and the reactivity between the-and 3,8 radicals and i-Mo_3,7_dimethyloctane As a result, it is presumed to be 2,7-diademyl-3,8-bis (3,7_diamidyloctyloxyΗι] benzoxan [5,4,3-cde] [l] benzopyridine Those who are ano-dione. The obtained chemical is referred to as monomer 1. < Synthesis of molecular compound 1 > The monomer obtained by reacting monomer 1 with trifluoromethanesulfonic anhydride. 0.59g of sour vinegar and 9,9_dioctyl_2,7_nuthiprate ethylene glycol 0.17g, and potassium carbonate lg, dissolved in 20g of toluene and ion-exchanged water 2〇§ Zhongjiao was boiled in nitrogen # for nitrogen exchange in the system. To this solution was added 0.02g of palladium catalyst {Pd (PPh3) 4} dissolved in degassed tritium which was previously bubbled with nitrogen 314723 59 200403327 The solution in 1 ml of benzene. Yu ,, and ^ ^, and stir for 10 minutes under the dish, then carry out the reaction at 100 ° C for 5 hours. Force; Ren Guangye, 'The reaction is carried out in a nitrogen environment. After the reaction solution was cooled, add a Koben to Table Shitian # 1, and After closing Yue benzene layer. When using a hydrochloric acid wash in degrees Shibo sent without lean A / Yin Yue present this bath, then 2% ammonium

Rinse with water, and finally use the ion $$ k, Jie W T and change the water again. This toluene solution was passed through a column filled with alumina to remove the fines. After the face & w # was cloaked, this toluene solution was poured into methanol and then sank; refined. The solute and the precipitate produced were recovered; after lx, the polymer was dried under reduced pressure to obtain 0.3 g of polymer. The obtained octanoate hydration% was polymer compound 1. Macromolecular compound 1: ^ 7. Knee her μ ♦ The number of sacrifice is different. The average molecular weight is 2.0 X 104 'and the weight average score + the estimated molecular compound of the South]. From the repeating unit contained in σ1 Of the structure.

< Synthesis of polymer compound 2 > The following is obtained from Feeding Example 2 by reacting the monomer 1 obtained in Example 1 with chlorinated methanesulfonic anhydride | Difluoropyrrolite succinic acid S of body 1 is 0.63 g and 2,2 bipyridine. 〇.28g was dissolved in tetrahydrofuran (dehydrated) 3〇ζ, German, gas # + ^ thousand ^ boil in the lice, nitrogen exchange within the system. To this solution was added bis (1,5 • cyclooctane dilute) (COD), 5 g was taken out, it was searched at room temperature for ⑺ minutes, and the temperature was raised. The reaction was performed at 314723 60 200403327 C for 3 hours. Here, the reaction was performed in a nitrogen atmosphere. After cooling the reaction solution, 25 ° / was added. Ammonia water 100m / methanol 100ml / ion-exchanged water 200m mixed solution, and stirred for about 1 hour. This solution was allowed to stand overnight at room temperature and then filtered to recover the formed precipitate. Then, this Shen Dian was dried and dissolved in toluene. After filtration to remove insoluble matter, the solution was purified by passing it through a column filled with oxide. Then, this solution was refined by Shen Dian. The resulting Shen Dian was washed with ethanol, and then dried under reduced pressure to obtain a polymer Q Q2g. The obtained polymer is referred to as polymer compound 2. The polystyrene-equivalent number average molecular weight of the door knives & products 2 was 4.5X 103 'and the weight average molecular weight was 7.2x103. The structure of the repeating unit contained in the polymer compound 2 estimated from the feed is shown below. In addition, a polarizing microscope was used to observe the results of the polymer compound 2 under orthogonal polarized light (crOssnicOi), and from the structure (howl), it was confirmed that the polymer molecule 2 was a liquid crystal.

〇 II

Example 3 < Synthesis of polymer compound 3 >

Monomer N, N-bis (4-bromobenzyl) -N, N 'obtained by reacting monomer 1 obtained in Example 1 with difluoropyrene tartaric acid ester 0.63 g of trifluoromethanesulfonic anhydride 314723 61 200403327 and (4-n-butylphenylbenzene, mg of biphenylene diamine, and bipyridine 0.8-decomposition in 30 g of tetrahydrofuran (dehydrated), boiling in nitrogen, and carried out; r, The nitrogen inside was changed. To this solution was added bis (丄, 5 · cyclooctadiene) {Ni (COD) 2} 0.7g, and the mixture was heated at room temperature for 10 minutes and heated at 60 ° C. The reaction was continued for 3 hours. Here, the reaction was performed in a nitrogen atmosphere.

After cooling the reaction solution, a mixed solution of 25% ammonia water 10rnl / methanol 100ml / ion-exchanged water 200ml was added and stirred for about 1 hour. This solution was allowed to stand at room temperature for a while, and then filtered to recover the formed precipitate. Next, this precipitate was dried and then dissolved in toluene. After filtering to remove insoluble matter, this solution was purified by passing it through a column filled with alumina. Next, this solution was poured into methanol and then precipitated and purified. The resulting precipitate was recovered, washed with formazan, and dried under reduced pressure to obtain a polymer 〇3§. This polymer is referred to as polymer compound 3. The polymer compound 3 has a number-average molecular weight in terms of polyethylene of 5 · 3χ 10, and a weight-average molecular weight is! 2χ 104. The structure of the repeating unit contained in the polymer compound 3 estimated from the feed is shown below. 314723 62 200403327

Xia _ Example 4 < Synthesis of Polymer Compound 4 > The monomer 1 obtained in Example 1 was reacted with trifluoropine sulfonic anhydride, trifluoromethanesulfonate 0.25 g and 1, 4- 0.66 g of dibromo-2,5-bis (3 7-difluorenyloctyloxy) benzene and 61 g of 2,2, -bibipyridine were dissolved in 40 g of tetrahydrofuran (anhydrous) and then boiled in nitrogen Perform nitrogen exchange in the system. To the solution was added bis (1,5-cyclooctadiene) nickel (〇) {Ni (COD) 2} 1.1 g, and the mixture was reacted at room temperature for 24 hours. Here, the reaction was performed under a nitrogen atmosphere. Next, to this reaction solution, a mixed solution of 25% ammonia water 10ml / methanol 30ml / ion parent exchange water 60ml was added and mixed for about 1 hour. This solution was allowed to stand at room temperature overnight and then filtered to recover the formed precipitate. Then, this Shen Dian was dried and dissolved in Jiaben. Filter to remove insolubles. Next, the solution was washed with 1 equivalent concentration of hydrochloric acid and separated. Then, the solution was washed with about 63 314723 200403327 2.5% ammonia water, and the methylbenzene layer was separated, and then the benzene layer was separated. Next, the obtained toluene solution was poured into methanol and washed with water. The resulting precipitate was recovered, and the resulting mixture was refined with a nail bucket ... μ. Human 丄 卞 'first / yin bian, after decompression and dry release, ~ all compounds were obtained. The polymer obtained is referred to as a high-w polymer compound 4 of the polymer compound 4. ,. ^ The average number of fine-to-different numbers is 4.07 × 10, and the weight-average molecular weight is 70 × 10. The estimated polymer compound for the contents is 4 _ & not drawn from the feed 5 Early Wu structure. C —〇

/ oci〇H 21

^ 2lC10O Ο——c

II ο pc 10 ^ 21 〇0 Example 5 < Synthesis of South molecular compound 5 > The monomer obtained in Example 1 丨 was antiparalyzed with trifluoromethanesulfonic anhydride "^ Leaflet 1 of trifluoromethanesulfonate. .25 g and 0.72 g of 3,7-dibromo-2,8-difluorene & Tyldibenzothiophene and 0.55 g of 2,2, -bibipyridine were dissolved in four air blows. South (dehydrated ) After 40 g, boil in nitrogen to perform nitrogen exchange in the system. Add bis (1,5-cyclooctane dilute) to the solution (〇) {N i (C〇D) 2} 1 · Q α & 'The reaction was carried out at room temperature for 24 hours. Here, the reaction was carried out in a nitrogen atmosphere. 64 314723 200403327 Next' To this reaction solution, 25% ammonia water was added 〇ιιιη 1 / methanol 30ml / water was changed by the father-in-law 6 The solution was mixed with 0 m 1 and allowed to stir for about 1 hour. The solution was allowed to stand at room temperature overnight and then filtered to recover the resulting precipitate. Then, the precipitate was dried and 'dissolved in toluene. Filtered to remove insoluble matter Next, the solution was washed with 1% strength hydrochloric acid and separated, and then the solution was washed with about 2.5% ammonia water. After the solution was separated, the toluene layer was washed with ion exchange water. Next, the obtained toluene solution was poured into methyl alcohol and then precipitated and purified. The resulting Shen Dian was recovered, washed with methanol, and then dried under reduced pressure to obtain 0.05 g of a polymer. This obtained One percent of the polymer is south molecular compound 5. The polymer of the polymer compound 5! The number average molecular weight of Hiromoto Ethylene is 1. 0x104, and the weight average molecular weight is 1.8x104. The following indicates from the feed The structure of the repetitive unit contained in the presumed southern molecular compound $% 5. h21c10o

o op 21 Η ον ο chno

Example 6 < Synthesis of high molecular compound 6 > The monomer obtained in Example 1 obtained from the reaction of fluoromethanesulfonic acid anhydride with 314723 65 200403327 0.25g of trifluoromethanesulfonate of body 1 and 3,7-dibromo -2,8-dioctyloxydibenzothiophene 0.45g and N, N, bis (4 "bromophenyl) -N, N, -bis (2,6-difluorenyl tert-butylphenyl) ) 0.33 g of 1,4-phenylenediamine and 0.5 5 g of 2,2, -dioxine were dissolved in 40 g of tetrahydrofuran (dehydrated), and then boiled in nitrogen to perform nitrogen exchange in the system. To this solution, bis (1,5-cyclooctenene) nickel (〇) {Ni (COD) 2} 1.0 g was added and reacted at room temperature for 40 hours. Here, the reaction was performed under a nitrogen atmosphere. Next, a mixed solution of methanol [Om] " ion-exchanged water " was added to the reaction solution, and stirred for about 1 hour. This solution was allowed to stand at room temperature overnight and then filtered to return to your office & + 丄 Dissolved in Jiaben: Shen Shen. Then, after this Shen Dian was dried, there was a solution of oxides and two removals: after dissolving the dissolved matter, the solution was filled by precipitation to refine it. With "Moon Clothes." Next, this solution was poured into methanol and then added to recover the resulting precipitate. After drying under reduced pressure using Γ 舻, soil, ^, and ethanol, the mixture was cleaned, and then passed through a cloud of 0.35 g. Put this y molecule on compound 6. The polymer served by the dagger is called high. The polystyrene of molecular compound 6 is replaced by 工 104, and what is the weight average molecular weight? δχ, "The number average molecular weight is the estimated ancient-. The following indicates from the feed] asked the molecular compound 6 contained in the structure of bang bang early. 314723 66 200403327

h17c8o oc8h17 0-N—H3C CH3 h3c, τ 1 t-C4H9 Example 7 < Measurement of absorption spectrum and fluorescence spectrum > Polymer compounds 1 to 6 are easily dissolved in chloroform. A 0.2% chloroform solution was spin-coated on a quartz plate to make a polymer film. A UV spectrophotometer UV3 65 manufactured by Shimadzu Corporation and a fluorescent spectrophotometer 850 manufactured by Hitachi, Ltd. were used to measure the ultraviolet visible absorption spectrum and fluorescence chromatography of the film. Table 1 shows the fluorescence peak wavelengths and relative intensities of the polymer compounds 1 to 6. 67 314723 200403327 Table 1 Polymer compound 1 2 3 4 5 6 ijfe Example 8 Peak light wavelength (nm) 438 428 598 437 442 531 Fluorescence intensity (au) 6.7 1.2 0.01 2.8 0.7 0.07 ;

Spin-coating using a solution of poly (vinyl dithiophene) / polystyrene acid (Bayer) on a glass-breaking substrate with an IT0 film adhered to a thickness of 150 nm by a sputtering method (Bayer) The cloth method was formed into a film having a thickness of 50 nm. The hot plate was dried at mt: 5 minutes. Next, a 1.5 wt.% Toluene solution of polymer compound 1 was used to form a film according to the thickness of the melons by a spin coating method. Furthermore, after drying under reduced pressure for 1 hour, Dunhuazhong was deposited to a thickness of about 4 nm, and then the cathode was deposited to a thickness of about ①, and then, to a thickness of about 50 nm to produce a polymer coffee. True during deposition *: =: 1〇, _. A voltage was applied to the obtained element, that is, EL emission of 7 M knife compound 1. The light emission starting voltage is about :: V (volt) 'and the light emitting efficiency is about one A, ... =, 100 sc / m2. Yau [Peak wavelength and high molecular weight ....., light bee value wavelength is slightly ... and it has been confirmed that the fluorescent film EL of the bound film ° emits light. [Industrial Applicability] Light materials for trowel compound 1. Thus. The molecular LED is applicable to the polymer compound of the present invention, and the polymer compound can be used as a polymer LED. 314723 68 200403327 Suitable for devices such as flat light sources and flat panel displays that are backlights. 69 314723

Claims (1)

The scope of the patent is a high-molecular compound, 1 i ^ 5 /, the demolition is: containing the formula (U & early Wu, and the repeated conversion of stupid ethylene is not repeated χ1 #t thousand average molecules $ 10, 10. 8, X--X2 At1 is * Αγ2 Z i (i) [wherein Ar1 and Ar2 are heterocyclic groups of 4 or 4 valences; do not independently represent a 4-membered aromatic hydrocarbon group and X represents that either party is C (= 〇) or (^ (RJhR2), and the other 〇, s, c (= 〇), si (= 〇), s〇2, Si (R3) (R4), n (r5), B (P6), P (R7), or P (= 〇) ( r8); (wherein R1, R2, R3, R4, r5, r6, R7, and r8 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an amine group, an aryl group, Aryloxy, arylthio, arylamino, arylthio, arylalkoxy, arylalkylthio, arylalkylamino, fluorenyl, fluorenyl, fluorenyl, imino, substituted曱 silyl, substituted silyloxy, substituted silylthio, substituted silylamino, monovalent heterocyclic group, arylalkenyl, arylethynyl, or cyano) M represents formula (2), formula (3 ) Or a group represented by formula (4); W a (2) [wherein Υ1 and Υ2 each independently represent 0, s, C (= 〇), =, S〇2, C (R9) (R1G), Si (Rn) (R) 2), N (R13), B (R14), P (R15) or P (= 0) (Ri6), 314660 70 200403327 (where R9, R10, Rn, R12, R13 , R14 R15 and R] 6 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkyl * thio group, an alkylamino group, an aryl group, an aryloxy group, an arylthio group, an arylamine group, an aryl group, and an aromatic group. Alkylalkoxy, arylalkylthio, arylalkylamino, fluorenyl, fluorenyl, fluorenyl, imino, substituted fluorsilyl, substituted silyloxy, substituted silylthio, Substituted silylamino, monovalent heterocyclic group, arylalkenyl, arylethynyl or cyano), but γΐ is other than C (R9) (R1 ()), Si (Rn) (R12) 'Υ1 Not the same as Υ2] etc. -Y3 = Y4- (3) '[where Υ3 and Υ4 independently represent N, B, P, C (R17) or Si (R18), (where R17 and R18 are respectively 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 arylamine group, an aryl group, an aryl group, an aryl group, or an aryl group Burning thio, 'aryl burning amine, donkey, acidoxy, acid amine, imine, substituted silyl, substituted fluorin silyloxy, substituted silylthio, substituted # 曱 石 夕 烧Amino group, monovalent heterocyclic group Arylalkenyl, arylethenyl, or cyano)] -γ5- (4) [wherein Υ) represents 0, S, C (= 0), s (= 0), so 2, C (R) 9 ) (R2〇), Si (R21) (R22), N (R23), B (R24), P (R25), or P (= 0) (R26) '(where R is 9, R20, R2) , R22, R23, r24, r25 and R20 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkyl group, 314660 71 200403327 an alkylthio group, an amino group, an aryl group, an aryloxy group, an arylthio group, an arylamine Aryl, aralkyl, arylalkoxy, arylalkylthio, arylalkylamino, fluorenyl, fluorenyloxy, fluorenylamino, imino, substituted fluorinated silyl, substituted methacrylate (Oxyl, substituted methanthoxythio, substituted vermiculite amine, monovalent heterocyclic group, arylalkenyl, arylethynyl, or cyano)] Z, represents -CR36 = CR37- or -Ce C-, R36 and R37 are independent It represents a wind atom, an alkyl group, an aryl group, a valence heterocyclic group or a cyano group, and d represents 0 or 1]. 2. The polymer compound according to item i in the patent application range, wherein M is represented by formula (2). ^ τ Orbital π target circumference, η Ganchu, in the formula α, and Ar2 is bonded to the adjacent ring of aromatic ring carbon, ΐ: Γ: * A1 · 2 aromatic ring Adjacent positions of carbon, ... Adjacent position of aromatic ring carbon of bond 2 ^ tArI, Υ2 and ^ series bonds, 0 are adjacent positions of aromatic ring carbon of Ar-. 4.: =: Scope item 〖2 」, Nanbezi compound, in which‘ in formula ’’ a Page 1 of 5. If the scope of patent application is r-benzene ring. Compound, its order, in the formula ，, the polymerization of the 4th item of Ym brother ", the scope of the patent 2: and the item x! (C-0). A polymer compound in which 'is in the formula 及 and the term χ? Γ is the term, and γ and X1 are 0 (oxygen atom). It is (〇〇). 7. If the patent scope of the patent application is 1 item, it makes the total number of repeating units shown in the macromolecularization 0 of any one of the formulas be the total repeating 314660 72 200403327 units. Above 0 mole%. 8. The polymer compound according to any one of claims 1 to 7 of the scope of application for a patent, wherein the polymer compound is liquid crystalline. 9. The polymer compound according to any one of claims 1 to 7 of the scope of application for a patent, wherein the polymer compound has fluorescence in a solid state. 1 〇 · A polymer electronic component, which is characterized in that it contains a polymer compound in the scope of claims 1 to 9 of the patent application. 11. A polymer light-emitting device, characterized in that it has a light-emitting layer between electrodes formed by an anode and a cathode, and the light-emitting layer contains a polymer compound according to any one of claims 1 to 9 of the patent application range. 12 · —A planar light source, which is characterized in that it contains a polymer light emitting element according to item 11 of the scope of patent application. 1 3 · —Segment display device, which is characterized in that it contains a polymer light-emitting element according to item 11 of the scope of patent application. 14. A dot matrix display device, which is characterized in that it contains a polymer light-emitting element according to item 11 of the scope of patent application. 1 5 · A liquid crystal display device, characterized in that a polymer light emitting element according to item 11 of the patent application scope is used as a backlight. 314660 200403327 * 指定, designated representative map: no representative map in this case (I) The designated representative map in this case is: (). (II) Brief description of the representative symbols of the components in this representative figure: ^ φ 捌, if there is a chemical formula in this case, please disclose the chemical formula that can best show the characteristics of the invention: X1-X2 4 314723