JP4982984B2 - Polymer light emitter composition and polymer light emitting device - Google Patents

Description

  The present invention relates to a polymer light emitter composition, a polymer light emitter solution composition, and a polymer light emitting device (polymer LED) using the same.

  Unlike a low molecular weight light emitting material (high molecular weight light emitting material), which is soluble in a solvent, a light emitting layer in a light emitting element can be formed by a coating method, which meets the demand for a large area of the element. For this reason, various polymer light emitting materials have been proposed in recent years (for example, Non-Patent Document 1).

Advanced Materials Vol.12 1737-1750 (2000)

By the way, the light emitting element is desired to have high light emission efficiency, that is, high light emission luminance per current.
However, when a polymer light emitter is used, the efficiency of the device has not yet been sufficient.
An object of the present invention is to provide a polymer light-emitting composition capable of providing a light-emitting element with high efficiency when used in a light-emitting layer of a light-emitting element.

  As a result of investigations to solve the above problems, the present inventors have significantly improved efficiency when a composition containing a compound having a specific structure is used as a material of a light emitting layer of a light emitting element. The present inventors have found that a light-emitting element can be obtained, and have reached the present invention.

（Ｘは、式中の２個のベンゼン環上の４個の炭素原子と一緒になって５員環または６員環を形成するための原子または原子団を表し、Ｒ¹〜Ｒ⁴⁶はそれぞれ独立に水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、置換アミノ基、アミド基、酸イミド基、アシルオキシ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、シアノ基またはニトロ基を表す。） That is, the present invention provides a polymer light emitter composition comprising a polymer light emitter and a compound selected from the following formulas (1a) and (1b).

(X represents an atom or an atomic group for forming a 5-membered ring or a 6-membered ring together with 4 carbon atoms on two benzene rings in the formula, and R ^{1 to} R ⁴⁶ are respectively Independently hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group , Arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, cyano group Or represents a nitro group.)

  The present invention also relates to a polymer light emitter solution composition containing a solvent in addition to the polymer light emitter and the compound selected from the above formulas (1a) and (1b).

  By incorporating the light emitting polymer composition of the present invention in the light emitting layer of the light emitting device, the efficiency of the device can be increased. Therefore, the polymer LED using the polymer light emitter composition of the present invention is a curved or flat light source for backlight or illumination of a liquid crystal display, a segment type display element, a dot matrix flat panel display, etc. It can be preferably used in the apparatus.

  The compound used in the composition of the present invention is represented by the above formula (1a) or (1b).

Examples of the halogen atom in R ^{1 to} R ⁴⁶ in the formula (1a) or (1b) include fluorine, chlorine, bromine and iodine.

The alkyl group may be linear, branched or cyclic, and may have a substituent,
The total number of carbon atoms is usually about 1 to 20, and specific examples thereof include methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, and hexyl group. Cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl Group, perfluorooctyl group and the like. Examples of the substituent include halogen, oxetane group, epoxy group, oxetidinyl group, oxolidinyl group, oxolanyl group, oxanyl group, oxonanyl group, oxathiolanyl group, piperidyl group and the like.

The alkyloxy group may be linear, branched or cyclic, and may have a substituent, and the total number of carbon atoms is usually about 1 to 20, and specific examples thereof include a methoxy group, an ethoxy group, Propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy Group, decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2- A methoxyethyloxy group etc. are illustrated. Examples of the substituent include halogen, oxetane group, epoxy group, oxetidinyl group, oxolidinyl group, oxolanyl group, oxanyl group, oxonanyl group, oxathiolanyl group, piperidyl group and the like.

The alkylthio group may be linear, branched or cyclic, and may have a substituent. The total number of carbon atoms is usually about 1 to 20, and specific examples thereof include methylthio group, ethylthio group, propylthio group. Group, i-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3, Examples thereof include 7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group and the like. Examples of the substituent include halogen, oxetane group, epoxy group, oxetidinyl group, oxolidinyl group, oxolanyl group, oxanyl group, oxonanyl group, oxathiolanyl group, piperidyl group and the like.

The aryl group may have a substituent, and the total carbon number is usually about 3 to 60. Specific examples thereof include a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ are , C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl group, pentafluorophenyl group, and the like. Examples of the substituent include halogen, oxetane group, epoxy group, oxetidinyl group, oxolidinyl group, oxolanyl group, oxanyl group, oxonanyl group, oxathiolanyl group, piperidyl group and the like.

The aryloxy group may have a substituent on the aromatic ring and generally has about 3 to 60 carbon atoms. Specific examples thereof include a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group, a C Examples thereof include _{1 to} C ₁₂ alkylphenoxy groups, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group and the like. Examples of the substituent include an alkoxy group, an alkyl group, a halogen, an oxetane group, an epoxy group, an oxetidinyl group, an oxolidinyl group, an oxolanyl group, an oxanyl group, an oxonanyl group, an oxathiolanyl group, and a piperidyl group.

Arylthio group may have a substituent on the aromatic ring, the total carbon number of usually about 3 to 60, and specific examples thereof include phenylthio groups, C ₁ -C ₁₂ alkoxyphenyl-thio groups, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group and the like. Examples of the substituent include an alkoxy group, an alkyl group, a halogen, an oxetane group, an epoxy group, an oxetidinyl group, an oxolidinyl group, an oxolanyl group, an oxanyl group, an oxonanyl group, an oxathiolanyl group, and a piperidyl group.

The arylalkyl group may have a substituent, and the total number of carbon atoms is usually about 7 to 60. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkyl group and a C ₁ -C ₁₂ alkoxyphenyl. -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl group Illustrated.
Examples of the substituent include an alkoxy group, an alkyl group, a halogen, an oxetane group, an epoxy group, an oxetidinyl group, an oxolidinyl group, an oxolanyl group, an oxanyl group, an oxonanyl group, an oxathiolanyl group, and a piperidyl group.

The arylalkyloxy group may have a substituent, and the total number of carbon atoms is usually about 7 to 60. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkoxy group and a C ₁ -C ₁₂ alkoxy group. phenyl -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy group Is exemplified. Examples of the substituent include an alkoxy group, an alkyl group, a halogen, an oxetane group, an epoxy group, an oxetidinyl group, an oxolidinyl group, an oxolanyl group, an oxanyl group, an oxonanyl group, an oxathiolanyl group, and a piperidyl group.

Arylalkylthio group may have a substituent, the total carbon number of usually about 7 to 60, and specific examples thereof include a phenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio group Illustrated. Examples of the substituent include an alkoxy group, an alkyl group, a halogen, an oxetane group, an epoxy group, an oxetidinyl group, an oxolidinyl group, an oxolanyl group, an oxanyl group, an oxonanyl group, an oxathiolanyl group, and a piperidyl group.

The alkenyl group usually has about 2 to 20 carbon atoms. Specific examples thereof include a vinyl group, a 1-propylenyl group, a 2-propylenyl group, a 3-propylenyl group, a butenyl group, a pentenyl group, a hexenyl group, and a heptenyl group. Octenyl group and cyclohexenyl group.
Alkenyl groups also include alkadienyl groups such as 1,3-butadienyl groups.

  The alkynyl group usually has about 2 to 20 carbon atoms, and specific examples thereof include ethynyl group, 1-propynyl group, 2-propynyl group, butynyl group, pentynyl group, hexynyl group, heptenyl group, octynyl group, cyclohexylethynyl. Groups. In addition, the alkynyl group includes an alkydenyl group such as a 1,3-butadiynyl group.

  The arylalkenyl group usually has about 8 to 50 carbon atoms, and examples of the aryl group and alkenyl group in arylalkenyl include the same aryl groups and alkenyl groups as those described above. Specific examples thereof include 1-arylvinyl group, 2-arylvinyl group, 1-aryl-1-propylenyl group, 2-aryl-1-propylenyl group, 2-aryl-2-propylenyl group, and 3-aryl-2. -A propylenyl group etc. are mentioned. Also included are arylalkadienyl groups such as 4-aryl-1,3-butadienyl groups.

The arylalkynyl group usually has about 8 to 50 carbon atoms, and the aryl group and alkynyl group in the arylalkynyl group are the same as the above aryl group and alkynyl group, respectively. Specific examples thereof include an arylethynyl group, a 3-aryl-1-propionyl group, and a 3-aryl-2-propionyl group. Also included are arylalkadiynyl groups such as 4-aryl-1,3-butadiynyl.

  Examples of the substituted silyl group in the substituted silyloxy group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. Usually, it is about 1-60, Preferably it is C3-C30. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. Specifically, trimethylsilyloxy group, triethylsilyloxy group, tri-n-propylsilyloxy group, tri-i-propylsilyloxy group, t-butylsilyldimethylsilyloxy group, triphenylsilyloxy group, tri-p- Examples include xylylsilyloxy group, tribenzylsilyloxy group, diphenylmethylsilyloxy group, t-butyldiphenylsilyloxy group, dimethylphenylsilyloxy group and the like.

  Examples of the substituted silyl group in the substituted silylthio group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. Usually, it is about 1-60, Preferably it is C3-C30. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. Specifically, trimethylsilylthio group, triethylsilylthio group, tri-n-propylsilylthio group, tri-i-propylsilylthio group, t-butylsilyldimethylsilylthio group, triphenylsilylthio group, tri-p -Xylylsilylthio group, tribenzylsilylthio group, diphenylmethylsilylthio group, t-butyldiphenylsilylthio group, dimethylphenylsilylthio group and the like are exemplified.

The substituted silylamino group includes a silylamino group (H ₃ SiNH— or (H ₃ Si) ₂ N substituted with 1 to 6 groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. -) Is mentioned, and carbon number is 1-120 normally, Preferably it is C3-C60. The alkyl group, aryl group, arylalkyl group, and monovalent heterocyclic group may have a substituent. Specifically, trimethylsilylamino group, triethylsilylamino group, tri-n-propylsilylamino group, tri-i-propylsilylamino group, t-butylsilyldimethylsilylamino group, triphenylsilylamino group, tri-p -Xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, t-butyldiphenylsilylamino group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group, di ( Tri-n-propylsilyl) amino group, di (tri-i-propylsilyl) amino group, di (t-butylsilyldimethylsilyl) amino group, di (triphenylsilyl) amino group, di (tri-p-xylylsilyl) ) Amino group, di (tribenzylsilyl) amino group, di (di E methylpropenylmethyl silyl) amino, di (t-butyldiphenylsilyl) amino group, such as di (dimethylphenyl silyl) amino groups.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The group or the monovalent heterocyclic group may have a substituent. The number of carbon atoms is usually about 1 to 40. Specifically, methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group Group, isobutylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctyl amino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ Turkey hydroxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group, phenyl -C ₁ -C ₁₂ alkylamino groups, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino groups, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino group, 1-naphthyl-C ₁ -C ₁₂ alkylamino group, 2-naphthyl-C ₁ -C ₁₂ alkylamino group and the like.

  The amide group usually has about 2 to 20 carbon atoms. Specific examples thereof include a formamide group, an acetamide group, a propioamide group, a butyroamide group, a benzamide group, a trifluoroacetamide group, a pentafluorobenzamide group, a diformamide group, Examples include a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, a dipentafluorobenzamide group, and the like.

The acid imide group includes a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and usually has about 2 to 60 carbon atoms, preferably 2 to 20 carbon atoms. Specific examples include the following groups.

  The acyloxy group usually has about 2 to 20 carbon atoms, and specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, a trifluoroacetyloxy group, Examples thereof include a pentafluorobenzoyloxy group.

The monovalent heterocyclic group means a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 2 to 60 carbon atoms. Specifically, a thienyl group, C _{1 to} C Examples include ₁₂ alkylthienyl groups, pyrrolyl groups, furyl groups, pyridyl groups, C ₁ -C ₁₂ alkylpyridyl groups, imidazolyl groups, pyrazolyl groups, triazolyl groups, oxazolyl groups, thiazole groups, thiadiazole groups, and the like.

A heteroaryloxy group (a group represented by Q ⁴ —O—, Q ⁴ represents a monovalent heterocyclic group) usually has about 2 to 60 carbon atoms. Specific examples thereof include a thienyloxy group, C ₁ -C ₁₂ alkyl thienyl group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C ₁ -C ₁₂ alkyl pyridyl group, imidazolyloxy group, pyrazolyloxy group, triazolyl group, benzoxazolyl group, Examples include a thiazoleoxy group and a thiadiazoleoxy group.

(The .Q ⁵ represented by Q ⁵ -S- represents a monovalent heterocyclic group.) Heteroarylthio group has a carbon number in usually about 2 to 60, and specific examples thereof include thienylmercapto group, C ₁ -C ₁₂ alkyl thienylmercapto group, pyrrolyl mercapto group, a furyl mercapto group, pyridyl mercapto group, C ₁ -C ₁₂ alkyl pyridyl mercapto group, imidazolylmethyl mercapto group, a pyrazolyl mercapto group, benzotriazolyl mercapto group, oxazolyl Examples include mercapto group, thiazole mercapto group, thiadiazole mercapto group and the like.

  X represents an atom or an atomic group for forming a 5-membered ring or a 6-membered ring together with 4 carbon atoms on the 2 benzene rings in the formula (1a). Although shown below, it is not limited to these.

式中、Ｒはそれぞれ独立にハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシルオキシ基、置換アミノ基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基または１価の複素環基を表す。Ｒ’はそれぞれ独立に水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基、ニトロ基または１価の複素環基を表す。Ｒ''はそれぞれ独立に水素原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基または１価の複素環基を表す。

In the formula, each R is independently a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, An arylalkenyl group, an arylalkynyl group, an acyloxy group, a substituted amino group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, a cyano group, or a monovalent heterocyclic group is represented. R ′ is independently hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group , Arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, nitro Represents a monovalent heterocyclic group. R '' is independently hydrogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, aryl An alkenyl group, an arylalkynyl group, an acyl group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, or a monovalent heterocyclic group is represented.

R, R ′, R ″ halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group Specific examples of arylalkenyl groups, arylalkynyl groups, substituted silyloxy groups, substituted silylthio groups, substituted silylamino groups, substituted amino groups, amide groups, acid imide groups, acyl groups, acyloxy groups, and monovalent heterocyclic groups are as follows: Examples of R ^{1 to} R ⁴⁶ in the formulas (1a) and (1b) are exemplified.

In X, —O—, —S—, —Se—, —NR ″ —, —CR′R′— or —SiR′R′— are preferable, —O—, —S—, —CR ′. R'- is more preferred.

Specific examples of the compound represented by the formula (1a) include those shown below.

Specific examples of the compound represented by the formula (1b) include those shown below.

Of the compounds of (1a) and (1b), the compound of formula (1a) is preferred from the viewpoint of solvent solubility.

  Examples of the method for synthesizing the compounds of the formulas (1a) and (1b) used in the present invention include methods such as cross-coupling between carbazole and dibromofluorene derivatives or dibromocarbazole derivatives using a palladium catalyst, or coupling by a ullmann reaction. Etc. are exemplified.

Next, the polymer light emitter used in the present invention will be described.
The polymer light emitter used in the present invention is not particularly limited, and the polystyrene-equivalent number average molecular weight is usually from 10 ³ to 10 ⁸ . The polymer light emitter used in the present invention may be a homopolymer or a copolymer.
Among the polymer light emitters used in the present invention, those which are conjugated polymer compounds are preferred. Here, the conjugated polymer compound means a polymer compound in which a delocalized π electron pair exists along the main chain skeleton of the polymer compound. As this delocalized electron, an unpaired electron or a lone electron pair may participate in resonance instead of a double bond.

As the polymer light emitter used in the present invention, for example,
Polyfluorene [e.g. Japanese Journal of Applied Physics, Vol. 30, L1941 (1991)], polyparaphenylene [e.g. Advanced Materials (Adv. Mater). 4) 36 (1992)], polyarylenes such as polypyrrole, polypyridine, polyaniline and polythiophene; polyarylene vinylenes such as polyparaphenylene vinylene and polythienylene vinylene (for example, published in WO 98/27136) Specification)
Polyphenylene sulfide, polycarbazole and the like.
[For review, for example, "Advanced Materials Vol.12 1737-1750 (2000)" and "Organic EL Display Technology Monthly Display December issue P68-73")

Of these, polyarylene polymer light emitters are preferred.
Examples of the repeating unit contained in the polyarylene polymer light emitter include an arylene group and a divalent heterocyclic group.
Here, the number of carbon atoms constituting the ring of the arylene group is usually about 6 to 60. Specific examples thereof include a phenylene group, a biphenylene group, a terphenylene group, a naphthalenediyl group, an anthracenediyl group, a phenanthrene diyl group, and a pentarange. Yl group, indenediyl group, hepterenediyl group, indacenediyl group, triphenylenediyl group, binaphthyldiyl group, phenylnaphthylenediyl group, stilbenediyl group, fluorenediyl group (for example, in the following formula (2), A = -CR 'R'-).
The number of carbon atoms constituting the ring of the divalent heterocyclic group is usually about 3 to 60. Specific examples include pyridine-diyl group, diazaphenylene group, quinolinediyl group, quinoxalinediyl group, acridinediyl group, bipyridyldiyl. A group, a phenanthrolinediyl group, and the following formula (2), A = —O—, —S—, —Se—, —NR ″ —, or —SiR′R′—.

  More preferably, it includes a repeating unit represented by the following formula (2).

（式中、Ａは、式中の２個のベンゼン環上の４個の炭素原子と一緒になって５員環または６員環を完成させるための原子または原子団を表し、Ｒ^4a、Ｒ^4b、Ｒ^4c、Ｒ^5a、Ｒ^5bおよびＲ^5cは、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基、ニトロ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アリールアルキルオキシカルボニル基、ヘテロアリールオキシカルボニル基またはカルボキシル基を表し、Ｒ^4bとＲ^4c、およびＲ^5bとＲ^5cは、それぞれ一緒になって環を形成していてもよい。）

(In the formula, A represents an atom or an atomic group for completing a 5-membered ring or a 6-membered ring together with 4 carbon atoms on the two benzene rings in the formula, R ^4a , R ^4b , R ^4c , R ^5a , R ^5b and R ^5c are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, aryl Alkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group Substituted silylthio group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroaryl Represents a thio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group or a carboxyl group, and R ^4b and R ^4c , and R ^5b and R ^5c are each taken together to form a ring May be formed.)

  Specific examples of A include those exemplified for X in formula (1a), but are not limited thereto.

In A, —O—, —S—, —Se—, —NR ″ —, —CR′R′— or —SiR′R′— are preferable, —O—, —S—, —CR ′. R'- is more preferred.

^{R 4a, R 4b, R 4c} , R 5a, halogen atom definitive ^to R ^5b and R ^5c, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group , Arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyloxy group, amide group, acid imide group, substituted amino group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic ring The group, heteroaryloxy group, heteroarylthio group, and carboxyl group are the same as described above.

The imine residue refers to an imine compound (an organic compound having —N═C— in the molecule. For example, aldimine, ketimine, and hydrogen atoms on these N are substituted with alkyl groups or the like. And a residue obtained by removing one hydrogen atom from the compound having about 2 to 20 carbon atoms. Specific examples include the following groups.

The acyl group usually has about 2 to 20 carbon atoms. Specific examples thereof include acetyl group, propionyl group, butyryl group, isobutyryl group, pivaloyl group, benzoyl group, trifluoroacetyl group, and pentafluorobenzoyl group. Illustrated.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The substituted silyl group usually has about 1 to 60 carbon atoms, and specific examples thereof include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, Diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyl butyldimethylsilyl group, a 3,7-- dimethylsilyl group, lauryldimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl -C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, Tribenzylsilyl group, diphenylmethylsilyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group, trimethoxysilyl group, triethoxysilyl group, tripropyloxysilyl group, tri-i-propylsilyl group, dimethyl-i- Examples include propylsilyl group, methyldimethoxysilyl group, ethyldimethoxysilyl group, and the like.

The alkyloxy group in the alkyloxycarbonyl group usually has about 2 to 20 carbon atoms. Specific examples thereof include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, a benzoyloxy group, Examples include a fluoroacetyloxy group and a pentafluorobenzoyloxy group.

The aryloxy group in the aryloxycarbonyl group usually has about 6 to 60 carbon atoms. Specific examples thereof include phenoxy group, C _{1 to} C ₁₂ alkoxyphenoxy group, C _{1 to} C ₁₂ alkylphenoxy group, 1 - naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group are exemplified, C ₁ -C ₁₂ alkoxy phenoxy group, a C ₁ -C ₁₂ alkylphenoxy group are preferable.

The arylalkyl group in the arylalkyloxycarbonyl group usually has about 7 to 60 carbon atoms, and specific examples thereof include a phenylmethyl group, a phenylethyl group, a phenylbutyl group, a phenylpentyl group, a phenylhexyl group, and a phenylheptyl group. group, a phenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group such as a phenyl octyl group, 1 - naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl groups and the like, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group are preferable.

The heteroaryloxy group in the heteroaryloxycarbonyl group (the group represented by Q ⁶ —O—, Q ⁶ represents a monovalent heterocyclic group) usually has about 2 to 60 carbon atoms. is thienyloxy group, C ₁ -C ₁₂ alkyl thienyl group, pyrrolyloxy group, furyloxy group, pyridyloxy group, C ₁ -C ₁₂ alkyl pyridyl group, imidazolyloxy group, pyrazolyloxy group, triazolyl group, Examples thereof include an oxazolyloxy group, a thiazoleoxy group, and a thiadiazoleoxy group. Q ⁶ is preferably a monovalent aromatic heterocyclic group.

Examples of the repeating unit represented by the above formula (2) include the following structures.

式中、ベンゼン環上の水素原子は、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アルケニル基、アルキニル基、アリールアルケニル基、アリールアルキニル基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、シアノ基、ニトロ基または１価の複素環基に置換されていてもよい。

In the formula, a hydrogen atom on the benzene ring is a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an alkenyl group, Alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group , A nitro group or a monovalent heterocyclic group may be substituted.

The polymer light emitter used in the present invention may contain, for example, a repeating unit derived from an aromatic amine in addition to an arylene group and a divalent heterocyclic group. In this case, hole injection property and transport property can be imparted.
In this case, the molar ratio of repeating units derived from an arylene group and a repeating unit consisting of a divalent heterocyclic group and an aromatic amine is usually in the range of 99: 1 to 20:80.

As the repeating unit derived from an aromatic amine, a repeating unit represented by the following formula (3) is preferable.

In the formula, Ar ⁴ , Ar ⁵ , Ar ⁶ and Ar ⁷ each independently represent an arylene group or a divalent heterocyclic group. Ar ⁸ , Ar ⁹ and Ar ¹⁰ each independently represent an aryl group or a monovalent heterocyclic group. o and p each independently represent 0 or 1, and 0 ≦ o + p ≦ 2.

Here, specific examples of the arylene group and the divalent heterocyclic group are the same as those specific examples as a repeating unit included in the polyarylene polymer light-emitting body,
Specific examples of the aryl group and the monovalent heterocyclic group are the same as those in the above formulas (1a) and (1b).

Specific examples of the repeating unit represented by the above formula (3) include the following repeating units.

  In the formula, the hydrogen atom on the aromatic ring is a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl Group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, cyano group, A substituent selected from a nitro group, a monovalent heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group and a carboxyl group It may be conversion.

  Among the repeating units represented by the above formula (3), the repeating unit represented by the following formula (4) is particularly preferable.

In the formula, Q ¹ , Q ² and Q ³ are each independently a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio Group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted Silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group or carboxyl group The table The x and y each independently represents an integer of 0 to 4. z shows the integer of 0-2. w shows the integer of 0-5.

  The polymer light emitter used in the present invention may be a random, block or graft copolymer, or a polymer having an intermediate structure thereof, for example, a random copolymer having a block property. Also good. From the viewpoint of obtaining a polymer light emitter having a high quantum yield of light emission, a random copolymer having a block property and a block or graft copolymer are preferable to a completely random copolymer. A case in which the main chain is branched and there are three or more terminal portions and dendrimers are also included.

  The terminal group of the polymer light-emitting material used in the present invention is protected with a stable group, because if the polymerization active group remains as it is, there is a possibility that the light emission characteristics and life when the device is made will be reduced. Also good. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and examples thereof include a structure in which an aryl group or a heterocyclic group is bonded via a carbon-carbon bond. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

The polymer light-emitting material used in the present invention preferably has a number average molecular weight of about 10 ³ to 10 ^{8 in} terms of polystyrene, and in particular, when the number average molecular weight is about 10 ⁴ to 10 ^{6 in} terms of polystyrene, preferable.

  In addition, since light emission from a thin film is used, a polymer light-emitting body having light emission in a solid state is preferably used.

Examples of the method for synthesizing the polymer light emitter used in the present invention include a method of polymerizing from a corresponding monomer by a Suzuki coupling reaction, a method of polymerizing by a Grignard reaction, a method of polymerizing by a Ni (0) catalyst, an oxidation of FeCl ₃ or the like. Examples include a method of polymerizing with an agent, a method of electrochemically oxidatively polymerizing, a method of decomposing an intermediate polymer having an appropriate leaving group, and the like. Among these, a method of polymerizing by Suzuki coupling reaction, a method of polymerizing by Grignard reaction, and a method of polymerizing by Ni (0) catalyst are preferable because of easy reaction control.
When a polymer light emitter is used as a light emitting material for a polymer LED, its purity affects the light emission characteristics. Therefore, the monomer before polymerization may be polymerized after being purified by methods such as distillation, sublimation purification, and recrystallization. Preferably, after the synthesis, purification treatment such as reprecipitation purification and fractionation by chromatography is preferable.

  The polymer light emitter composition of the present invention is characterized by containing a polymer light emitter and a compound of the formula (1a) or (1b), and the content of the compound of the formula (1a) or (1b) is When the polymer light emitter is 100 parts by weight, it is usually about 0.1 to 10000 parts by weight, preferably 1 to 1000 parts by weight, more preferably 5 to 500 parts by weight, and further preferably 10 to 100 parts by weight. Part.

  The polymer light emitter solution composition of the present invention is characterized by containing a polymer light emitter, the formula (1a) or (1b), and a solvent. A light emitting layer can be formed by a coating method using this solution composition. The light emitting layer produced using this solution composition usually contains the polymer light emitter composition of the present invention.

  Examples of the solvent include chloroform, methylene chloride, dichloroethane, tetrahydrofuran, toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene and the like. Although depending on the structure and molecular weight of the polymer light emitter, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

  The amount of the solvent is usually about 1000 to 100000 parts by weight with respect to 100 parts by weight of the polymer light emitter.

  The polymer light emitter composition of the present invention may contain two or more polymer light emitters, and may contain two or more compounds of the formula (1a) or (1b).

  The composition of the present invention may contain a dye, a charge transport material and the like, if necessary.

The polymer LED of the present invention has a light emitting layer between electrodes composed of an anode and a cathode, and the light emitting layer contains the polymer light emitter composition of the present invention.
The polymer LED of the present invention is characterized in that it has a light emitting layer between electrodes composed of an anode and a cathode, and the light emitting layer is formed using the solution composition of the present invention.

  In addition, as the polymer LED of the present invention, a polymer LED having an electron transport layer provided between the cathode and the light emitting layer, a polymer LED having a hole transport layer provided between the anode and the light emitting layer, Examples include a polymer LED 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.

For example, the following structures a) to d) are specifically exemplified.
a) Anode / light emitting layer / cathode 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, / indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

Here, the light emitting layer is a layer having a function of emitting light, the hole transporting layer is a layer having a function of transporting holes, and the electron transporting layer is a layer having a function of transporting electrons. It is. The electron transport layer and the hole transport layer are collectively referred to as a charge transport layer.
Two or more light emitting layers, hole transport layers, and electron transport layers may be used independently.

  Further, among the charge transport layers provided adjacent to the electrodes, those having a function of improving the charge injection efficiency from the electrodes and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers). , An electron injection layer).

  Further, in order to improve adhesion with the electrode and charge injection from the electrode, the charge injection layer or an insulating layer having a thickness of 2 nm or less may be provided adjacent to the electrode, and the adhesion at the interface may be improved. In order to prevent mixing, a thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer.

  The order and number of layers to be laminated, and the thickness of each layer can be appropriately used in consideration of light emission efficiency and element lifetime.

  In the present invention, a 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 the cathode, and a charge injection layer adjacent to the anode. The provided polymer LED is mentioned.

For example, the following structures e) to p) are specifically mentioned.
e) Anode / charge injection layer / light emitting layer / cathode
f) Anode / light emitting layer / charge injection layer / cathode
g) Anode / charge injection layer / light emitting layer / charge injection layer / cathode
h) Anode / charge injection layer / hole transport layer / light emitting layer / cathode
i) Anode / hole transport layer / light emitting layer / charge injection layer / cathode
j) Anode / charge injection layer / hole transport layer / light emitting layer / charge injection layer / cathode
k) Anode / charge injection layer / light emitting layer / electron transport layer / cathode
l) Anode / light-emitting layer / electron transport layer / charge injection layer / cathode
m) Anode / charge injection layer / light emitting layer / electron transport layer / charge injection layer / cathode
n) Anode / charge injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) Anode / hole transport layer / light emitting layer / electron transport layer / charge injection layer / cathode p) Anode / charge injection layer / Hole transport layer / light emitting layer / electron transport layer / 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 provided between the anode material and the hole transport material included in the hole transport layer. A layer containing a material having an ionization potential of a value, a layer provided between a cathode and an electron transport layer, and a layer containing a material having an electron affinity of an intermediate value between the cathode material and the electron transport material contained in the electron transport layer, etc. Is exemplified.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. in order to reduce the current, more preferably less 10 ^-5 S / cm or more and 10 ² S / cm, more preferably less 10 ^-5 S / cm or more and 10 ¹ S / cm.

Usually, in order to set the electric conductivity of the conductive polymer to 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is doped with an appropriate amount of ions.

  The type 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 polystyrene sulfonate ions, alkylbenzene sulfonate ions, camphor sulfonate ions, and examples of cations include lithium ions, sodium ions, potassium ions, tetrabutylammonium ions, and the like.

  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. Polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene And derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), and carbon .

  An 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. As the polymer LED provided with the insulating layer having a thickness of 2 nm or less, the polymer LED provided with the insulating layer having a thickness of 2 nm or less adjacent to the cathode, or the insulating layer having a thickness of 2 nm or less provided adjacent to the anode. Polymer LED is mentioned.

Specific examples include the following structures q) to ab).
q) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / cathode r) Anode / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode s) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / film thickness 2 nm Insulating layer / cathode t) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / cathode
u) Anode / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode
v) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / insulating layer with a thickness of 2 nm or less / cathode
w) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / cathode
x) Anode / light-emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode
y) Anode / insulating layer with a thickness of 2 nm or less / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode
z) Anode / insulating layer with a thickness of 2 nm or less / hole transport layer / light emitting layer / electron transport layer / cathode
aa) Anode / hole transport layer / light emitting layer / electron transport layer / insulating layer with a thickness of 2 nm or less / cathode
ab) Anode / insulating layer with a thickness of 2 nm or less / hole transporting layer / light emitting layer / electron transporting layer / insulating layer with a thickness of 2 nm or less / cathode

  For example, when the light emitting layer is formed from a solution using the polymer phosphor solution composition of the present invention, it is only necessary to remove the solvent by drying after coating the solution. Even in the case of mixing, the same technique can be applied, which is very advantageous in production. As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, Application methods such as a flexographic printing method, an offset printing method, and an ink jet printing method can be used.

  As the film thickness of the light emitting layer, the optimum value varies depending on the material to be used, and it may be selected so that the drive voltage and the light emission efficiency are appropriate values. For example, the thickness is 1 nm to 1 μm, preferably 2 nm to 500 nm. More preferably, it is 5 nm-200 nm.

  In the polymer LED of the present invention, the light emitting layer may contain a light emitting material other than the polymer light emitter, and the light emitting layer containing a light emitting material other than the polymer light emitter may include the polymer light emitting. The light emitting layer including the body may be stacked.

  As the light emitting material, known materials can be used. Examples of the low molecular weight compound include naphthalene derivatives, anthracene or derivatives thereof, perylene or derivatives thereof, polymethine dyes, xanthene dyes, coumarin dyes, cyanine dyes, 8-hydroxyquinoline or metal complexes of derivatives thereof, aromatic amines, and the like. , Tetraphenylcyclopentadiene or a derivative thereof, or tetraphenylbutadiene or a derivative thereof can be used.

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

Examples of triplet light-emitting complexes include Ir (ppy) 3, Btp ₂ Ir (acac) with iridium as the central metal, PtOEP with platinum as the central metal, and Eu (TTA) 3phen with europium as the central metal. It is done.

三重項発光錯体として具体的には、例えばNature, (1998), 395, 151、Appl. Phys. Lett. (1999), 75(1), 4、Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105(Organic Light-Emitting Materials and DevicesＩＶ), 119、J. Am. Chem. Soc., (2001), 123, 4304、Appl. Phys. Lett., (1997), 71(18), 2596、Syn. Met., (1998), 94(1), 103、Syn. Met., (1999), 99(2), 1361、Adv. Mater., (1999), 11(10), 852 、Jpn.J.Appl.Phys.,34, 1883 (1995)などに記載されている。

Specific examples of triplet light emitting complexes include Nature, (1998), 395, 151, Appl. Phys. Lett. (1999), 75 (1), 4, Proc. SPIE-Int. Soc. Opt. Eng. (2001), 4105 (Organic Light-Emitting Materials and Devices IV), 119, J. Am. Chem. Soc., (2001), 123, 4304, Appl. Phys. Lett., (1997), 71 (18), 2596, Syn. Met., (1998), 94 (1), 103, Syn. Met., (1999), 99 (2), 1361, Adv. Mater., (1999), 11 (10), 852, Jpn. J. Appl. Phys., 34, 1883 (1995).

  When the polymer LED of the present invention has a hole transport layer, the hole transport material used includes polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, and a polysiloxane derivative having an aromatic amine in a side chain or a main chain. , Pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, polyaniline or derivatives thereof, polythiophene or derivatives thereof, polypyrrole or derivatives thereof, poly (p-phenylene vinylene) or derivatives thereof, or poly (2,5-thieni Lembinylene) or a derivative thereof is exemplified.

  Specifically, as the hole transport material, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, Examples described in JP-A-3-37992 and JP-A-3-152184 are exemplified.

  Among these, as a hole transport material used for the hole transport layer, polyvinyl carbazole or a derivative thereof, polysilane or a derivative thereof, a polysiloxane derivative having an aromatic amine compound group in a side chain or a main chain, polyaniline or a derivative thereof, Preferred is a polymer hole transport material such as polythiophene or a derivative thereof, poly (p-phenylene vinylene) or a derivative thereof, or poly (2,5-thienylene vinylene) or a derivative thereof, more preferably polyvinyl carbazole or a derivative thereof, Polysilane or a derivative thereof, or a polysiloxane derivative having an aromatic amine in the side chain or main chain. In the case of a low-molecular hole transport material, it is preferably used by being dispersed in a polymer binder.

  Polyvinylcarbazole or a derivative thereof is obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

  Examples of polysilane or derivatives thereof include compounds described in Chem. Rev. 89, 1359 (1989) and GB 2300196 published specification. As the synthesis method, the methods described in these can be used, but the Kipping method is particularly preferably used.

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

  Although there is no restriction | limiting in the film-forming method of a positive hole transport layer, In the low molecular hole transport material, the method by the film-forming from a mixed solution with a polymer binder is illustrated. In the case of a polymer hole transport material, a method of film formation from a solution is exemplified.

  The solvent used for film formation from a solution is not particularly limited as long as it can dissolve a hole transport material. 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; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from solution include spin coating from solution, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those showing no strong absorption against visible light are suitably used. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, and polysiloxane.

  The film thickness of the hole transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If it is too thick, the driving voltage of the element becomes high, which is not preferable. Therefore, the film thickness of the hole transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  In the polymer LED composition of the present invention, higher efficiency can be obtained by combining with a hole transport layer containing a polyamine having a repeating unit derived from an aromatic amine. As the polyamine, those containing a repeating unit represented by the formula (3) are preferable, and those containing a repeating unit represented by the formula (4) are more preferable.

  When the polymer LED of the present invention has an electron transport layer, known electron transport materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, naphthoquinone or derivatives thereof. Derivatives, anthraquinones or derivatives thereof, tetracyanoanthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanoethylene or derivatives thereof, diphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or Examples thereof include polyfluorene or a derivative thereof.

  Specifically, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-20988, JP-A-3-37992, The thing etc. which are described in the same 3-152184 gazette are illustrated.

  Of these, oxadiazole derivatives, benzoquinone or derivatives thereof, anthraquinones or derivatives thereof, or metal complexes of 8-hydroxyquinoline or derivatives thereof, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof are preferred, 2- (4-biphenylyl) -5- (4-t-butylphenyl) -1,3,4-oxadiazole, benzoquinone, anthraquinone, tris (8-quinolinol) aluminum, and polyquinoline are more preferable.

  There are no particular restrictions on the method for forming the electron transport layer, but for low molecular weight electron transport materials, vacuum deposition from powder, or by film formation from a solution or molten state, and for polymer electron transport materials, solution or Each method is exemplified by film formation from a molten state. In film formation 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 can dissolve an electron transport material and / or a 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; ketone solvents such as acetone and methyl ethyl ketone; ethyl acetate, butyl acetate, An ester solvent such as ethyl cellosolve acetate is exemplified.

  Examples of film formation methods from a solution or a molten state include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, spray coating, and screen. Coating methods such as a printing method, a flexographic printing method, an offset printing method, and an inkjet printing method can be used.

  As the polymer binder to be mixed, those not extremely disturbing charge transport are preferable, and those not strongly absorbing visible light are suitably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, or polysiloxane.

  The film thickness of the electron transport layer differs depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, at least a thickness that does not cause pinholes is required. If the thickness is too thick, the driving voltage of the element increases, which is not preferable. Therefore, the thickness of the electron transport layer is, for example, 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

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

  In the polymer LED of the present invention, it is usually preferable that at least one of an electrode composed of an anode and a cathode is transparent or translucent, and the anode side is transparent or translucent. As the material for the anode, a conductive metal oxide film, a translucent metal thin film, or the like is used. Specifically, indium oxide, zinc oxide, tin oxide, and a composite film made of conductive glass made of indium / tin / oxide (ITO), indium / zinc / oxide, etc. (NESA) Etc.), gold, platinum, silver, copper and the like are used, and ITO, indium / zinc / oxide, and tin oxide are preferable. Examples of the production method include a vacuum deposition method, a sputtering method, an ion plating method, a plating method, and the like. Further, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof may be used as the anode.

  The film thickness of the anode can be appropriately selected in consideration of light transmittance and electrical conductivity, and is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 50 nm to 500 nm. is there.

  Further, in order to facilitate charge injection on the anode, 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, or the like. A layer 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, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and their Two or more of these alloys, or an alloy of one or more of them and one or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite or graphite intercalation compound, etc. Is used. Examples of the alloy 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, and the like. The cathode may have a laminated structure of two or more layers.

  The film thickness of the cathode can be appropriately selected in consideration of electric conductivity and durability, but is, for example, 10 nm to 10 μm, preferably 20 nm to 1 μm, and more preferably 50 nm to 500 nm.

  As a method for producing the cathode, a vacuum deposition method, a sputtering method, a laminating method in which a metal thin film is thermocompression bonded, or the like is used. Further, a layer made of a conductive polymer or a layer made of a metal oxide, metal fluoride, organic insulating material or the like having an average film thickness of 2 nm or less may be provided between the cathode and the organic layer. 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 protective cover in order to protect the element from the outside.

  As the protective layer, a polymer compound, metal oxide, metal fluoride, metal boride and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a low water permeability treatment on the surface, or the like can be used, and a method of sealing the cover by bonding it to the element substrate with a heat effect resin or a photo-curing resin is preferable. Used for. If a space is maintained using a spacer, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the cathode can be prevented from being oxidized, and moisture adsorbed in the manufacturing process by installing a desiccant such as barium oxide in the space. It is easy to suppress damage to the element. Among these, it is preferable to take any one or more measures.

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

  In order to obtain planar light emission using the polymer LED of the present invention, the planar anode and cathode may be arranged so as to overlap each other. In addition, in order to obtain pattern-like light emission, a method of installing a mask provided with a pattern-like window on the surface of the planar light-emitting element, an organic material layer of a non-light-emitting portion is formed extremely thick and substantially non- There are a method of emitting light and a method of forming either one of the anode or the cathode or both electrodes in a pattern. By forming a pattern by any of these methods and arranging some electrodes so that they can be turned on / off independently, a segment type display element capable of displaying numbers, letters, simple symbols and the like can be obtained. Further, in order to obtain a dot matrix element, both the anode and the cathode may be formed in a stripe shape and arranged so as to be orthogonal to each other. Partial color display and multicolor display are possible by a method of separately coating a plurality of types of polymer light emitters having different emission colors or a method using a color filter or a light emission conversion filter. The dot matrix element can be driven passively, or can be actively driven in combination with a TFT or the like. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  Furthermore, 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.

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
Hereinafter, the number average molecular weight in terms of polystyrene was determined by SEC.
Column: TOSOH TSKgel SuperHM-H (2) + TSKgel SuperH2000 (4.6mm Id x 15cm), Detector: RI (SHIMADZU RID-10A) is used. Tetrahydrofuran (THF) was used as the mobile phase.

不活性雰囲気下で、５００ｍｌの３つ口フラスコに酢酸２２５ｇを入れ、５−ｔ−ブチル−ｍ−キシレン２４．３ｇを加えた。続いて臭素３１．２ｇを加えた後、１５〜２０℃で３時間反応させた。
反応液を水５００ｍｌに加え析出した沈殿をろ過した。水２５０ｍｌで２回洗浄し、白色の固体３４．２ｇを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ(ｐｐｍ) ＝ １．３〔ｓ，９Ｈ〕、２．４〔ｓ，６Ｈ〕、７．１〔ｓ，２Ｈ〕
ＭＳ（ＦＤ⁺）Ｍ⁺ ２４１ Synthesis example 1
<Synthesis of 4-t-butyl-2,6-dimethylbromobenzene>

Under an inert atmosphere, 225 g of acetic acid was placed in a 500 ml three-necked flask, and 24.3 g of 5-t-butyl-m-xylene was added. Then, after adding 31.2 g of bromine, it was made to react at 15-20 degreeC for 3 hours.
The reaction solution was added to 500 ml of water, and the deposited precipitate was filtered. This was washed twice with 250 ml of water to obtain 34.2 g of a white solid.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ (ppm) = 1.3 [s, 9H], 2.4 [s, 6H], 7.1 [s, 2H]
MS (FD ⁺ ) M ⁺ 241

不活性雰囲気下で、１００ｍｌの３つ口フラスコに脱気した脱水トルエン３６ｍｌを入れ、トリ（ｔ−ブチル）ホスフィン０．６３ｇを加えた。続いてトリス（ジベンジリデンアセトン）ジパラジウム０．４１ｇ、上記の４−ｔ−ブチル−２，６−ジメチルブロモベンゼン９．６ｇ、ｔ−ブトキシナトリウム５．２ｇ、Ｎ，Ｎ’−ジフェニル−１，４−フェニレンジアミン４．７ｇを加えた後、１００℃で３時間反応させた。
反応液を飽和食塩水３００ｍｌに加え、約５０℃に温めたクロロホルム３００ｍｌで抽出した。溶媒を留去した後、トルエン１００ｍｌを加えて、固体が溶解するまで加熱、放冷した後、沈殿をろ過し、白色の固体９．９ｇを得た。 Synthesis example 2
<Synthesis of N, N′-diphenyl-N, N′-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine>

Under an inert atmosphere, 36 ml of degassed dehydrated toluene was placed in a 100 ml three-necked flask, and 0.63 g of tri (t-butyl) phosphine was added. Subsequently, 0.41 g of tris (dibenzylideneacetone) dipalladium, 9.6 g of the above-mentioned 4-t-butyl-2,6-dimethylbromobenzene, 5.2 g of sodium t-butoxy, N, N′-diphenyl-1, After adding 4.7 g of 4-phenylenediamine, the mixture was reacted at 100 ° C. for 3 hours.
The reaction solution was added to 300 ml of saturated brine and extracted with 300 ml of chloroform warmed to about 50 ° C. After the solvent was distilled off, 100 ml of toluene was added, and the mixture was heated and allowed to cool until the solid was dissolved, and then the precipitate was filtered to obtain 9.9 g of a white solid.

不活性雰囲気下で、１０００ｍｌの３つ口フラスコに脱水Ｎ，Ｎ−ジメチルホルムアミド３５０ｍｌを入れ、上記のＮ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−ｔ−ブチル−２，６−ジメチルフェニル）−１，４−フェニレンジアミン５．２ｇを溶解した後、氷浴下でＮ−ブロモスクシンイミド３．５ｇ／Ｎ，Ｎ−ジメチルホルムアミド溶液を滴下し、一昼夜反応させた。
反応液に水１５０ｍｌを加え、析出した沈殿をろ過し、メタノール５０ｍｌで２回洗浄し白色の固体４．４ｇを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＴＨＦ−ｄ８）：
δ(ｐｐｍ) ＝ １．３〔ｓ，１８Ｈ〕、２．０〔ｓ，１２Ｈ〕、６．６〜６．７〔ｄ，４Ｈ〕、６．８〜６．９〔ｂｒ，４Ｈ〕、７．１〔ｓ，４Ｈ〕、７．２〜７．３〔ｄ，４Ｈ〕
ＭＳ（ＦＤ⁺）Ｍ⁺ ７３８ Synthesis example 3
<Synthesis of N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine>

Under an inert atmosphere, 350 ml of dehydrated N, N-dimethylformamide was placed in a 1000 ml three-necked flask and the above N, N′-diphenyl-N, N′-bis (4-t-butyl-2,6- After dissolving 5.2 g of (dimethylphenyl) -1,4-phenylenediamine, a 3.5 g / N, N-dimethylformamide solution of N-bromosuccinimide was added dropwise in an ice bath and allowed to react overnight.
150 ml of water was added to the reaction solution, and the deposited precipitate was filtered and washed twice with 50 ml of methanol to obtain 4.4 g of a white solid.
¹ H-NMR (300 MHz / THF-d8):
δ (ppm) = 1.3 [s, 18H], 2.0 [s, 12H], 6.6 to 6.7 [d, 4H], 6.8 to 6.9 [br, 4H], 7 .1 [s, 4H], 7.2 to 7.3 [d, 4H]
MS (FD ⁺ ) M ⁺ 738

化合物Ａ
不活性雰囲気下、３００ｍｌ三つ口フラスコに１‐ナフタレンボロン酸５．００ｇ（２９ｍｍｏｌ）、２−ブロモベンズアルデヒド６．４６ｇ（３５ｍｍｏｌ）、炭酸カリウム１０.０ｇ（７３ｍｍｏｌ）、トルエン３６ｍｌ、イオン交換水３６ｍｌを入れ、室温で撹拌しつつ２０分間アルゴンバブリングした。続いてテトラキス（トリフェニルホスフィン）パラジウム１６．８ｍｇ（０.１５ｍｍｏｌ）を入れ、さらに室温で撹拌しつつ１０分間アルゴンバブリングした。１００℃に昇温し、２５時間反応させた。室温まで冷却後、トルエンで有機層を抽出、硫酸ナトリウムで乾燥後、溶媒を留去した。トルエン：シクロヘキサン＝１：２混合溶媒を展開溶媒としたシリカゲルカラムで生成することにより、化合物Ａ５.１８ｇ（収率８６％）を白色結晶として得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ７．３９〜７．６２（ｍ、５Ｈ）、７．７０（ｍ、２Ｈ）、７．９４（ｄ、２Ｈ）、８．１２（ｄｄ、２Ｈ）、９．６３（ｓ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ２３３ Synthesis example 4
(Synthesis of Compound A)

Compound A
Under an inert atmosphere, in a 300 ml three-necked flask, 5.00 g (29 mmol) of 1-naphthaleneboronic acid, 6.46 g (35 mmol) of 2-bromobenzaldehyde, 10.0 g (73 mmol) of potassium carbonate, 36 ml of toluene, 36 ml of ion-exchanged water And argon bubbling was performed for 20 minutes with stirring at room temperature. Subsequently, 16.8 mg (0.15 mmol) of tetrakis (triphenylphosphine) palladium was added, and argon was bubbled for 10 minutes while stirring at room temperature. The temperature was raised to 100 ° C. and reacted for 25 hours. After cooling to room temperature, the organic layer was extracted with toluene, dried over sodium sulfate, and the solvent was distilled off. By producing on a silica gel column using a mixed solvent of toluene: cyclohexane = 1: 2 as a developing solvent, 5.18 g of Compound A (yield 86%) was obtained as white crystals.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 7.39-7.62 (m, 5H), 7.70 (m, 2H), 7.94 (d, 2H), 8.12 (dd, 2H), 9.63 (s, 1H)
MS (APCI (+)): (M + H) ^<+> 233

化合物Ｂ
不活性雰囲気下で３００ｍｌの三つ口フラスコに化合物Ａ８．００ｇ（３４.４ｍｍｏｌ）と脱水ＴＨＦ４６ｍｌを入れ、−７８℃まで冷却した。続いてｎ−オクチルマグネシウムブロミド（１.０ｍｏｌ／ｌＴＨＦ溶液）５２ｍｌを３０分かけて滴下した。滴下終了後０℃まで昇温し、１時間撹拌後、室温まで昇温して４５分間撹拌した。氷浴して１Ｎ塩酸２０ｍｌを加えて反応を終了させ、酢酸エチルで有機層を抽出、硫酸ナトリウムで乾燥した。溶媒を留去した後トルエン：ヘキサン＝１０：１混合溶媒を展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｂ７．６４ｇ（収率６４％）を淡黄色のオイルとして得た。ＨＰＬＣ測定では２本のピークが見られたが、ＬＣ−ＭＳ測定では同一の質量数であることから、異性体の混合物であると判断した。 Synthesis example 5
(Synthesis of Compound B)

Compound B
Under an inert atmosphere, 8.00 g (34.4 mmol) of Compound A and 46 ml of dehydrated THF were placed in a 300 ml three-necked flask and cooled to -78 ° C. Subsequently, 52 ml of n-octylmagnesium bromide (1.0 mol / l THF solution) was added dropwise over 30 minutes. After completion of dropping, the temperature was raised to 0 ° C., stirred for 1 hour, then warmed to room temperature and stirred for 45 minutes. The reaction was terminated by adding 20 ml of 1N hydrochloric acid in an ice bath, and the organic layer was extracted with ethyl acetate and dried over sodium sulfate. After distilling off the solvent, the residue was purified by a silica gel column using a mixed solvent of toluene: hexane = 10: 1 as a developing solvent to obtain 7.64 g (yield: 64%) of Compound B as a pale yellow oil. Although two peaks were observed in the HPLC measurement, they were determined to be a mixture of isomers because they were the same mass number in the LC-MS measurement.

化合物Ｃ
不活性雰囲気下、５００ｍｌ三つ口フラスコに化合物Ｂ（異性体の混合物）５.００ｇ（１４.４ｍｍｏｌ）と脱水ジクロロメタン７４ｍｌを入れ、室温で撹拌、溶解させた。続いて、三フッ化ホウ素のエーテラート錯体を室温で１時間かけて滴下し、的か終了後室温で４時間撹拌した。撹拌しながらエタノール１２５ｍｌをゆっくりと加え、発熱がおさまったらクロロホルムで有機層を抽出、２回水洗し、硫酸マグネシウムで乾燥した。溶媒を留去後、ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｃ３．２２ｇ（収率６８％）を無色のオイルとして得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．９０（ｔ、３Ｈ）、１．０３〜１．２６（ｍ、１４Ｈ）、２．１３（ｍ、２Ｈ）、４．０５（ｔ、１Ｈ）、７．３５（ｄｄ、１Ｈ）、７．４６〜７．５０（ｍ、２Ｈ）、７．５９〜７．６５（ｍ、３Ｈ）、７．８２（ｄ、１Ｈ）、７．９４（ｄ、１Ｈ）、８．３５（ｄ、１Ｈ）、８．７５（ｄ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ３２９ Synthesis Example 6
(Synthesis of Compound C)

Compound C
Under an inert atmosphere, 5.00 g (14.4 mmol) of Compound B (mixture of isomers) and 74 ml of dehydrated dichloromethane were placed in a 500 ml three-necked flask and stirred and dissolved at room temperature. Subsequently, boron ether trifluoride etherate complex was added dropwise at room temperature over 1 hour, and after completion, the mixture was stirred at room temperature for 4 hours. While stirring, 125 ml of ethanol was slowly added. When the exotherm subsided, the organic layer was extracted with chloroform, washed twice with water, and dried over magnesium sulfate. After distilling off the solvent, the residue was purified by a silica gel column using hexane as a developing solvent to obtain 3.22 g (yield 68%) of Compound C as a colorless oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.90 (t, 3H), 1.03-1.26 (m, 14H), 2.13 (m, 2H), 4.05 (t, 1H), 7.35 (dd, 1H), 7 .46-7.50 (m, 2H), 7.59-7.65 (m, 3H), 7.82 (d, 1H), 7.94 (d, 1H), 8.35 (d, 1H) ), 8.75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 329

化合物Ｄ
不活性雰囲気下２００ｍｌ三つ口フラスコにイオン交換水２０ｍｌをいれ、撹拌しながら水酸化ナトリウム１８．９ｇ（０.４７ｍｏｌ）を少量ずつ加え、溶解させた。水溶液が室温まで冷却した後、トルエン２０ｍｌ、化合物Ｃ５.１７ｇ（１５.７ｍｍｏｌ）、臭化トリブチルアンモニウム１．５２ｇ（４.７２ｍｍｏｌ）を加え、５０℃に昇温した。臭化ｎ−オクチルを滴下し、滴下終了後５０℃で９時間反応させた。反応終了後トルエンで有機層を抽出し、２回水洗し、硫酸ナトリウムで乾燥した。ヘキサンを展開溶媒とするシリカゲルカラムで精製することにより、化合物Ｄ５．１３ｇ（収率７４％）を黄色のオイルとして得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．５２（ｍ、２Ｈ）、０．７９（ｔ、６Ｈ）、１．００〜１．２０（ｍ、２２Ｈ）、２．０５（ｔ、４Ｈ）、７．３４（ｄ、１Ｈ）、７．４０〜７．５３（ｍ、２Ｈ）、７．６３（ｍ、３Ｈ）、７．８３（ｄ、１Ｈ）、７．９４（ｄ、１Ｈ）、８．３１（ｄ、１Ｈ）、８．７５（ｄ、１Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ４４１ Synthesis example 7
(Synthesis of Compound D)

Compound D
Under an inert atmosphere, 20 ml of ion-exchanged water was placed in a 200 ml three-necked flask, and 18.9 g (0.47 mol) of sodium hydroxide was added little by little with stirring to dissolve. After the aqueous solution was cooled to room temperature, 20 ml of toluene, 5.17 g (15.7 mmol) of Compound C and 1.52 g (4.72 mmol) of tributylammonium bromide were added, and the temperature was raised to 50 ° C. N-Octyl bromide was added dropwise, and after completion of the addition, the mixture was reacted at 50 ° C. for 9 hours. After completion of the reaction, the organic layer was extracted with toluene, washed twice with water, and dried over sodium sulfate. Purification by a silica gel column using hexane as a developing solvent gave 5.13 g (yield 74%) of Compound D as a yellow oil.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.52 (m, 2H), 0.79 (t, 6H), 1.00-1.20 (m, 22H), 2.05 (t, 4H), 7.34 (d, 1H), 7 40 to 7.53 (m, 2H), 7.63 (m, 3H), 7.83 (d, 1H), 7.94 (d, 1H), 8.31 (d, 1H), 8. 75 (d, 1H)
MS (APCI (+)): (M + H) ^<+> 441

化合物Ｅ
空気雰囲気下、５０ｍｌの三つ口フラスコに化合物Ｄ４．００ｇ（９．０８ｍｍｏｌ）と酢酸：ジクロロメタン＝１：１混合溶媒５７ｍｌを入れ、室温で撹拌、溶解させた。続いて三臭化ベンジルトリメチルアンモニウム７．７９ｇ（２０．０ｍｍｏｌ）を加えて撹拌しつつ、塩化亜鉛を三臭化ベンジルトリメチルアンモニウムが完溶するまで加えた。室温で２０時間撹拌後、５％亜硫酸水素ナトリウム水溶液１０ｍｌを加えて反応を停止し、クロロホルムで有機層を抽出、炭酸カリウム水溶液で２回洗浄し、硫酸ナトリウムで乾燥した。ヘキサンを展開溶媒とするフラッシュカラムで２回精製した後、エタノール：ヘキサン＝１：１、続いて１０：１混合溶媒で再結晶することにより、化合物Ｅ４．１３ｇ（収率７６％）を白色結晶として得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．６０（ｍ、２Ｈ）、０．９１（ｔ、６Ｈ）、１．０１〜１．３８（ｍ、２２Ｈ）、２．０９（ｔ、４Ｈ）、７．６２〜７．７５（ｍ、３Ｈ）、７．８９（ｓ、１Ｈ）、８．２０（ｄ、１Ｈ）、８．４７（ｄ、１Ｈ）、８．７２（ｄ、１Ｈ）
ＭＳ（ＡＰＰＩ（＋））：（Ｍ＋Ｈ）⁺ ５９８ Synthesis Example 8
(Synthesis of Compound E)

Compound E
Under an air atmosphere, 4.00 g (9.08 mmol) of Compound D and 57 ml of a mixed solvent of acetic acid: dichloromethane = 1: 1 were placed in a 50 ml three-necked flask, and the mixture was stirred and dissolved at room temperature. Subsequently, 7.79 g (20.0 mmol) of benzyltrimethylammonium tribromide was added and stirred, and zinc chloride was added until benzyltribromide tribromide was completely dissolved. After stirring at room temperature for 20 hours, the reaction was stopped by adding 10 ml of 5% aqueous sodium bisulfite solution, and the organic layer was extracted with chloroform, washed twice with aqueous potassium carbonate solution, and dried over sodium sulfate. After purification twice with a flash column using hexane as a developing solvent, 4.13 g (yield 76%) of Compound E was obtained as white crystals by recrystallization with ethanol: hexane = 1: 1, followed by a 10: 1 mixed solvent. Got as.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.60 (m, 2H), 0.91 (t, 6H), 1.01-1.38 (m, 22H), 2.09 (t, 4H), 7.62-7.75 (m, 3H), 7.89 (s, 1H), 8.20 (d, 1H), 8.47 (d, 1H), 8.72 (d, 1H)
MS (APPI (+)): (M + H) ^<+> 598

100 mLの三口フラスコにPd(OAc)2 (123 mg, 0.54 mmol)、P(t-Bu)₃・HBF₄ (476 mg, 16.4 mmol)、Cs₂CO₃ (2.67 g, 82.1 mmol)を秤り取り、アルゴン雰囲気にした。
脱水キシレン (50 mL)をシリンジで導入し、室温で２時間撹拌した。カルバゾール(2.74 g, 16.4 mmol)、2,7-dibromo-9,9-di-n-octylfluorene (3g, 5.47 mmol)をフラスコ内に加え、120℃で８時間加熱した。
反応終了後、反応液を室温まで冷却してから固体をろ別した。ろ液を濃縮乾固し、シリカゲルクロマトグラフィーで精製｛展開溶媒：CHCl3/hexane (1:3, v/v)｝することにより、白色のフィルム状固体として化合物Ｆ (2.9 g,74.4%)を得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ０．７９〜０．８９（ｍ、１０Ｈ）、１．１５〜１．２７（ｍ、２０Ｈ）、２．０１〜２．０７（ｍ、４Ｈ）、７．３０〜７．３５（ｍ、４Ｈ）、７．４１〜７．４９（ｍ、８Ｈ）、７．５９〜７．６２（ｍ、４Ｈ）、７．９８（ｄ、J = 7.5 Hz、１Ｈ）、８．１９（ｄ、J = 8.4 Hz、４Ｈ）
ＭＳ（ＡＰＣＩ（＋））：（Ｍ＋Ｈ）⁺ ７２１ Synthesis Example of Compound F

Three-necked flask 100 mL Pd (OAc) 2 ( 123 mg, 0.54 mmol), P (t-Bu) 3 · HBF 4 (476 mg, 16.4 mmol), Cs 2 CO 3 (2.67 g, 82.1 mmol) the balance To an argon atmosphere.
Dehydrated xylene (50 mL) was introduced with a syringe and stirred at room temperature for 2 hours. Carbazole (2.74 g, 16.4 mmol) and 2,7-dibromo-9,9-di-n-octylfluorene (3 g, 5.47 mmol) were added to the flask and heated at 120 ° C. for 8 hours.
After completion of the reaction, the reaction solution was cooled to room temperature, and the solid was filtered off. The filtrate was concentrated to dryness and purified by silica gel chromatography {developing solvent: CHCl3 / hexane (1: 3, v / v)} to give compound F (2.9 g, 74.4%) as a white film-like solid. Obtained.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ 0.79 to 0.89 (m, 10H), 1.15 to 1.27 (m, 20H), 2.01 to 2.07 (m, 4H), 7.30 to 7.35 (m, 4H) ), 7.41-7.49 (m, 8H), 7.59-7.62 (m, 4H), 7.98 (d, J = 7.5 Hz, 1H), 8.19 (d, J = 8.4 Hz, 4H)
MS (APCI (+)): (M + H) ^<+> 721

Synthesis Example 9
<Synthesis of Polymer Compound 1>
Compound E (8.0 g) and 2,2′-bipyridyl (5.9 g) were dissolved in 300 mL of dehydrated tetrahydrofuran, and then bubbled with nitrogen to purge the system with nitrogen. In a nitrogen atmosphere, the temperature of the solution was raised to 60 ° C., bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (10.4 g, 0.038 mol) was added, and the reaction was performed for 5 hours. I let you. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 40 mL / methanol 300 mL / ion exchanged water 300 mL and stirred for 30 minutes, and then the deposited precipitate was filtered. Air dried. Then, after dissolving in 400 mL of toluene, filtration is performed, the filtrate is purified through an alumina column, about 300 mL of 1N hydrochloric acid is added and stirred for 3 hours, the aqueous layer is removed, and about 300 mL of 4% aqueous ammonia is added to the organic layer. In addition, the aqueous layer was removed after stirring for 2 hours. About 300 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. About 100 mL of methanol was added dropwise to the organic layer, stirred for 1 hour, and allowed to stand, and then the supernatant was removed by decantation. The obtained precipitate was dissolved in 100 mL of toluene, dropped into about 200 mL of methanol, stirred for 1 hour, filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer was 4.1 g (hereinafter referred to as polymer compound 1). The average molecular weight and weight average molecular weight in terms of polystyrene of the polymer compound 1 were Mn = 1.5 × 10 ⁵ and Mw = 2.7 × 10 ⁵ (mobile phase: tetrahydrofuran), respectively.

Synthesis Example 10
<Synthesis of Polymer Compound 2>
Compound E (0.65 g), N, N′-bis (4-bromophenyl) -N, N′-bis (4-t-butyl-2,6-dimethylphenyl) -1,4-phenylenediamine (0 .34 g) and 2,2′-bipyridyl (0.58 g) were dissolved in 100 mL of dehydrated tetrahydrofuran, and the inside of the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (1.0 g) was added to this solution, the temperature was raised to 60 ° C., and the reaction was continued for 3 hours with stirring. I let you. After the reaction, this reaction solution is cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 10 mL / methanol about 100 mL / ion exchange water about 100 mL, and stirred for 1 hour, and then the deposited precipitate is filtered. The solution was dried under reduced pressure for 3 hours, and then dissolved in 50 mL of toluene, followed by filtration. The filtrate was purified through an alumina column, added with about 50 mL of 4% aqueous ammonia, stirred for 2 hours, and then the aqueous layer was removed. About 50 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. The organic layer was dropped into about 100 mL of methanol, stirred for 1 hour, and allowed to stand, and then the supernatant was removed by decantation. The obtained precipitate was dissolved in 50 mL of toluene, dropped into about 200 mL of methanol, stirred for 1 hour, filtered and dried under reduced pressure for 2 hours. The yield of the obtained copolymer was 390 mg (hereinafter referred to as polymer compound 2). The average molecular weight and weight average molecular weight in terms of polystyrene of the polymer compound 2 were Mn = 1.6 × 10 ⁴ and Mw = 7.4 × 10 ⁴ (mobile phase: tetrahydrofuran), respectively.

50 mLの三口フラスコにPd(OAc)2 (0.007g, 0.03 mmol)、カルバゾール(0.75g, 4.5mmol)、2,7-ジブロモ-9,9-ジ-シクロヘキシルメチルフルオレン (0.77g, 1.5mmol)、K2CO3(1.24g、９mmol)、を仕込み減圧でアルゴン置換を３度行った。次に脱水トルエン(１６mL)をシリンジで加え再度減圧でアルゴン置換を行った。このマスを70〜75℃に加熱し(t-Bu)P (0.015ｇ、0.075mmolを加え昇温し105〜107℃で9時間加熱攪拌した。反応終了後、反応液を室温まで冷却し固体をろ別し た。濾紙上の残滓をクロロホルム(50mL)で洗浄し濾液を濃縮乾固した。シリカゲルクロマトグラフィーで精製｛展開媒：クロロホルム/ヘキサン(1:10, v/v)、0.1％トリエチルアミン添加｝することにより、白色の固体として化合物Ｇ(0.6ｇ、 収率 59.2％)を得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ０．７４７（ｍ、６Ｈ）、０．９３４（ｍ、６Ｈ）、１．１６５（ｍ、４Ｈ）、１．４５９（ｍ、６Ｈ）、１．９８３（ｄ、４Ｈ）、７．３８２（ｍ、１２Ｈ）、７．５８３（ｍ、４Ｈ）、８．００６（ｍ、２Ｈ）、８．１８７（ｄ、４Ｈ）
Synthesis Example 11
Synthesis of Compound G

Pd (OAc) 2 (0.007g, 0.03mmol), carbazole (0.75g, 4.5mmol), 2,7-dibromo-9,9-dicyclohexylmethylfluorene (0.77g, 1.5mmol) in a 50 mL three-necked flask , K2CO3 (1.24 g, 9 mmol) was charged, and argon substitution was performed three times under reduced pressure. Next, dehydrated toluene (16 mL) was added with a syringe, and argon substitution was performed again under reduced pressure. The mass was heated to 70 to 75 ° C., (t-Bu) P (0.015 g, 0.075 mmol was added, the temperature was raised, and the mixture was heated and stirred for 9 hours at 105 to 107 ° C. After completion of the reaction, the reaction solution was cooled to room temperature and solid. The residue on the filter paper was washed with chloroform (50 mL), and the filtrate was concentrated to dryness and purified by silica gel chromatography {developing medium: chloroform / hexane (1:10, v / v), 0.1% triethylamine Compound G (0.6 g, yield 59.2%) was obtained as a white solid.
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.747 (m, 6H), 0.934 (m, 6H), 1.165 (m, 4H), 1.259 (m, 6H), 1.983 (d, 4H), 7.382 (m , 12H), 7.583 (m, 4H), 8.006 (m, 2H), 8.187 (d, 4H)

化合物Ｈ

化合物Ｈの前駆体

50 mLの三口フラスコにPd(OAc)2 (0.007g, 0.03 mmol)、カルバゾール(0.80g, 4.8mmol)、 特願2003-343244の記載に従って合成した上記前駆体 (0.77g, 1.6mmol)、 K2CO3(1.33g、９.6mmol)、を仕込み減圧でアルゴン置換を３度行った。次に脱水トルエン(１６mL)をシリンジで加え再度減圧でアルゴン置換を行った。このマスを70〜75℃に加熱し(t-Bu)P(0.016ｇ、0.08mmol)を加え昇温し105〜107℃で6時間加熱攪拌した。反応終了後、反応液を室温まで冷却し固体をろ別した。濾紙上の残滓をクロロホルム(50mL)で洗浄し濾液を濃縮乾固した。シリカゲルクロマトグラフィーで精製｛展開溶媒：クロ ロホルム/ヘキサン (1:10, v/v)、0.1％トリエチルアミン添加｝することにより白色の固体1.05gを得た。この白色個体にメタノール30gを加え30分還流攪拌し室温へ冷却後濾過しケーキをメタノール20mL洗浄した。80℃で減圧乾燥し化合物Ｈ (0.87ｇ、収率 82.8％)を得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ０．８８２（ｍ、１２Ｈ）、１．４０７（ｍ、６Ｈ）、１．９９２（ｍ、４Ｈ）、７．５９７（ｍ、１６Ｈ）、８．０６９（ｍ、２Ｈ）、８．１７４（ｍ、４Ｈ）
Synthesis Example 12
Synthesis of Compound H

Compound H

Compound H precursor

In a 50 mL three-necked flask, Pd (OAc) 2 (0.007 g, 0.03 mmol), carbazole (0.80 g, 4.8 mmol), the precursor synthesized as described in Japanese Patent Application 2003-343244 (0.77 g, 1.6 mmol), K2CO3 (1.33 g, 9.6 mmol) was charged, and argon substitution was performed three times under reduced pressure. Next, dehydrated toluene (16 mL) was added with a syringe, and argon substitution was performed again under reduced pressure. The mass was heated to 70 to 75 ° C., (t-Bu) P (0.016 g, 0.08 mmol) was added, the temperature was raised, and the mixture was heated and stirred at 105 to 107 ° C. for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature and the solid was filtered off. The residue on the filter paper was washed with chloroform (50 mL), and the filtrate was concentrated to dryness. Purification by silica gel chromatography {developing solvent: chloroform / hexane (1:10, v / v), addition of 0.1% triethylamine} gave 1.05 g of a white solid. To this white solid, 30 g of methanol was added, stirred under reflux for 30 minutes, cooled to room temperature, filtered, and the cake was washed with 20 mL of methanol. Drying under reduced pressure at 80 ° C. gave Compound H (0.87 g, yield 82.8%).
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.882 (m, 12H), 1.407 (m, 6H), 1.992 (m, 4H), 7.597 (m, 16H), 8.069 (m, 2H), 8.174 (m 4H)

化合物Ｉの前駆体

500 mLの三口フラスコにNaOH( 48.0g、1.2mol)、水(89.1)gを仕込みNaOHを溶解した。50℃に調温後2,7-ジブロモフル オレン（12.96g、40mmol)、トルエン(74.8g)、テトラ-n-ブチルアンモニウムブロミド(7.74g,24mmol)を仕込んだ。
攪拌下1-クロロ-3-メチル-2-ブテン(12.55g、120mmol)を52〜55℃で４０分で滴下した。その後50〜55℃で3 時間攪拌した。反応終了後室温まで冷却しトルエン(50mL)を加え水層を分離した。油層を水(100mL)で４回洗浄した後濃縮し19.0gの
固形物を得た。この固形物をエタノール(57g)に80℃で溶解、5℃以下で析出結晶を濾過、エタノール(30mL)で洗浄した後乾燥し乾燥ケーキ15.3gを得た。ケーキ／ヘキサン／エタノール=1／0.5／1.5(重量比)で更に２回再結晶を行ったのち乾燥し白色の前駆体(10.3ｇ、収率 55.9％)を得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ１．４２（ｓ、６Ｈ）、１．４８（ｓ、６Ｈ）、２．５２５（ｄ、４Ｈ）、４．６２５（ｔ、２Ｈ）、７．４６５（ｍ、６Ｈ）

（2）化合物Ｉの合成

化合物Ｉ

Pd(OAc)2(0.045g, 0.2 mmol)、カルバゾール(5.02g, 30mmol)、 前駆体 (4.60g, 10mmol)、K2CO3(8.29g、60mmol)を仕込み減圧でアルゴン置換を３度行った。次に脱水トルエン(50mL)をシリンジで加え再度減圧でアルゴン置換を行った。
このマスを70〜75℃に加熱し(t-Bu)P(0.10ｇ、0.5mmol)を加え昇温し105〜107℃で11時間加熱攪拌した。反応終了後、反応液を室温まで冷却し固体をろ別した。濾紙上の残滓をクロロホルム(100mL)で洗浄し濾液を濃縮乾固し固形分(8.6g)を得た。
固形分／クロロホルム／エタノール=1／5／5（重量比)の条件で再結晶を行い乾燥ケーキ(6.04g)を得た。
シリカゲルクロマトグラフィーで精製｛展開溶媒：クロロホルム/ヘキサン (1:10, v/v)、0.1％トリエチルアミン添加｝することにより白色の固体(6.00)gを得た。更に、白色個体／クロロホルム／ヘキサン=1／3／10（重量比）の 条件で再結晶を2回行い80℃で減圧乾燥し化合物Ｉ(5.10ｇ、収率 80.5％)を得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ１．５１３（ｓ、６Ｈ）、１．５５１（ｓ、６Ｈ）、２．７３０（ｍ、４Ｈ）、４．８１８（ｍ、２Ｈ）、７．３１４（ｍ、４H）、７．４４６（ｍ、８Ｈ）、７．５８６（ｍ、４H）、７．９７６（ｄ、２Ｈ）、８．１８５（ｄ、４H）
Synthesis Example 13
Synthesis of Compound I (1) Synthesis of precursor

Precursor of Compound I

NaOH (48.0 g, 1.2 mol) and water (89.1) g were charged into a 500 mL three-necked flask to dissolve NaOH. After adjusting the temperature to 50 ° C., 2,7-dibromofluorene (12.96 g, 40 mmol), toluene (74.8 g), and tetra-n-butylammonium bromide (7.74 g, 24 mmol) were charged.
With stirring, 1-chloro-3-methyl-2-butene (12.55 g, 120 mmol) was added dropwise at 52-55 ° C. over 40 minutes. Thereafter, the mixture was stirred at 50 to 55 ° C. for 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, toluene (50 mL) was added, and the aqueous layer was separated. The oil layer was washed 4 times with water (100 mL) and concentrated to 19.0 g
A solid was obtained. This solid was dissolved in ethanol (57 g) at 80 ° C., and the precipitated crystals were filtered at 5 ° C. or less, washed with ethanol (30 mL) and dried to obtain 15.3 g of a dry cake. The crystal was further recrystallized twice with cake / hexane / ethanol = 1 / 0.5 / 1.5 (weight ratio) and then dried to obtain a white precursor (10.3 g, yield 55.9%).
¹ H-NMR (300 MHz / CDCl ₃ ):
δ1.42 (s, 6H), 1.48 (s, 6H), 2.525 (d, 4H), 4.625 (t, 2H), 7.465 (m, 6H)

(2) Synthesis of Compound I

Compound I

Pd (OAc) 2 (0.045 g, 0.2 mmol), carbazole (5.02 g, 30 mmol), precursor (4.60 g, 10 mmol), K2CO3 (8.29 g, 60 mmol) were charged, and argon substitution was performed three times under reduced pressure. Next, dehydrated toluene (50 mL) was added with a syringe, and argon substitution was performed again under reduced pressure.
The mass was heated to 70 to 75 ° C., (t-Bu) P (0.10 g, 0.5 mmol) was added, the temperature was raised, and the mixture was heated and stirred at 105 to 107 ° C. for 11 hours. After completion of the reaction, the reaction solution was cooled to room temperature and the solid was filtered off. The residue on the filter paper was washed with chloroform (100 mL), and the filtrate was concentrated to dryness to obtain a solid (8.6 g).
Recrystallization was performed under the conditions of solid content / chloroform / ethanol = 1/5/5 (weight ratio) to obtain a dry cake (6.04 g).
Purification by silica gel chromatography {developing solvent: chloroform / hexane (1:10, v / v), addition of 0.1% triethylamine} gave white solid (6.00) g. Further, recrystallization was carried out twice under the conditions of white solid / chloroform / hexane = 1/3/10 (weight ratio), and dried under reduced pressure at 80 ° C. to obtain Compound I (5.10 g, yield 80.5%).
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 1.513 (s, 6H), 1.551 (s, 6H), 2.730 (m, 4H), 4.818 (m, 2H), 7.314 (m, 4H), 7.446 (m) 8H), 7.586 (m, 4H), 7.976 (d, 2H), 8.185 (d, 4H)

化合物Ｊの前駆体
500 mLの三口フラスコにNaOH( 48.0g、1.2mol)、水(89.1)gを仕込みNaOHを溶解した。50℃に調温後2,7-ジブロモフル オレン（12.96g、40mmol)、トルエン(64.8g)、テトラ-n-ブチルアンモニウムブロミド(7.74g,24mmol)を仕込んだ。
攪拌下エチルブロミド(6.54g、60mmol)を52〜55℃で30分で滴下した。その後50〜55℃で7時間攪拌した。反応終了後室温まで冷却しトルエン(50mL)を加え水層を分離した。油層を水(100mL)で４回洗浄した後濃縮し15.2gの 固形物を得た。この固形物をエタノール(45g)で75〜80℃で1時間洗浄し、室温に冷却後濾過、エタノール(30mL)で洗浄した。乾燥し乾燥ケーキ(15.2)gを得た。ケーキ／クロロホルム／ヘキサン=1／2／4(重量比)で更に3回再結晶を行ったのち乾燥し白色の前駆体 (4.90ｇ、収率 32.2％)を得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ０．３１７（ｔ、６Ｈ）、１．９９１（ｑ、４Ｈ）、７．４９３（ｍ、６Ｈ）

（2）化合物Ｊの合成

化合物Ｊ

Pd(OAc)2(0.045g, 0.2 mmol)、カルバゾール(5.02g, 30mmol)、 前駆体 (3.80g, 10mmol)、K2CO3(8.29g、60mmol)を仕込み減圧でアルゴン置換を３度行った。次に脱水トルエン40mLをシリンジで加え再度減圧でアルゴン置換を行った。このマスを70〜75℃に加熱し(t-Bu)P(0.10ｇ、0.5mmol)を加え昇温し105〜107℃で10.5時間加熱攪拌した。反応終了後、反応液を室温まで冷却し固体をろ別した。濾紙上の残滓をクロロホルム(150mL)で洗浄し濾液を濃縮乾固し固形分(6.85g)た。
固形分／クロロホルム／エタノール=1／5／5（重量比）の条件で再結晶を行い乾燥ケーキ(5.45g)を得た。 このケーキを クロロホルム(24g)に溶解しヘキサン(36g)を加えて再結晶を行い乾燥ケーキ(5.00g)を得た。シリカゲルクロマトグフィー で精製｛展開溶媒：クロロホルム/ヘキサン (1:5, v/v)、0.1％トリエチルアミン添加｝することにより白色の固(5.00g)を得た。更に、白色個体をクロロホルム(24g)に溶解しヘキサン(36g)を加えて再結晶を行い化合物Ｊ(4.55ｇ、収82.4％)を得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ０．５５９（ｔ、６Ｈ）、２．１０１（ｍ、４Ｈ）、７．３３４（ｍ、４Ｈ）、７．４５６（ｍ、８Ｈ）、７．５９４（ｍ、４H）、８．０８７（ｄ、２Ｈ）、８．１８５（ｄ、４H）
Synthesis Example 14
Synthesis of Compound J (1) Synthesis of precursor

Compound J precursor
NaOH (48.0 g, 1.2 mol) and water (89.1) g were charged into a 500 mL three-necked flask to dissolve NaOH. After adjusting the temperature to 50 ° C., 2,7-dibromofluorene (12.96 g, 40 mmol), toluene (64.8 g), and tetra-n-butylammonium bromide (7.74 g, 24 mmol) were charged.
Ethyl bromide (6.54 g, 60 mmol) was added dropwise at 52-55 ° C. over 30 minutes with stirring. Then, it stirred at 50-55 degreeC for 7 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, toluene (50 mL) was added, and the aqueous layer was separated. The oil layer was washed 4 times with water (100 mL) and then concentrated to obtain 15.2 g of a solid. This solid was washed with ethanol (45 g) at 75-80 ° C. for 1 hour, cooled to room temperature, filtered, and washed with ethanol (30 mL). The dried cake (15.2) g was obtained by drying. The crystal was recrystallized three more times with cake / chloroform / hexane = 1/2/4 (weight ratio) and then dried to obtain a white precursor (4.90 g, yield 32.2%).
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.317 (t, 6H), 1.991 (q, 4H), 7.493 (m, 6H)

(2) Synthesis of Compound J

Compound J

Pd (OAc) 2 (0.045 g, 0.2 mmol), carbazole (5.02 g, 30 mmol), precursor (3.80 g, 10 mmol), K2CO3 (8.29 g, 60 mmol) were charged, and argon substitution was performed three times under reduced pressure. Next, 40 mL of dehydrated toluene was added with a syringe, and argon substitution was performed again under reduced pressure. The mass was heated to 70 to 75 ° C., (t-Bu) P (0.10 g, 0.5 mmol) was added, the temperature was raised, and the mixture was heated and stirred at 105 to 107 ° C. for 10.5 hours. After completion of the reaction, the reaction solution was cooled to room temperature and the solid was filtered off. The residue on the filter paper was washed with chloroform (150 mL), and the filtrate was concentrated to dryness to obtain a solid (6.85 g).
Recrystallization was performed under the conditions of solid content / chloroform / ethanol = 1/5/5 (weight ratio) to obtain a dry cake (5.45 g). This cake was dissolved in chloroform (24 g), hexane (36 g) was added and recrystallized to obtain a dry cake (5.00 g). Purification by silica gel chromatography {developing solvent: chloroform / hexane (1: 5, v / v), 0.1% triethylamine added} gave a white solid (5.00 g). Further, the white solid was dissolved in chloroform (24 g), hexane (36 g) was added and recrystallized to obtain Compound J (4.55 g, yield 82.4%).
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.559 (t, 6H), 2.101 (m, 4H), 7.334 (m, 4H), 7.456 (m, 8H), 7.594 (m, 4H), 8.087 (d 2H), 8.185 (d, 4H)

オキセタンユニット

アルゴン置換した1ｌ三つ口フラスコにイオン交換水１６３ｍｌを入れ、水酸化ナトリウム８５．２ｇ（２．１３ｍｏｌ）を少量ずつ加えて撹拌、溶解させた。続いて臭化テトラブチルアンモニウム１２．５ｇ（０．０４ｍｏｌ）、を入れ、３−エチル−３−オキセタンメタノール１５ｇ（０．１３ｍｏｌ）、１，６−ジブロモヘキサン９４．５ｇ（０．３９ｍｏｌ）、およびヘキサン１２８ｍｌを加え、室温で９時間反応後、８０℃に昇温して１時間反応させた。室温まで冷却後、ヘキサンで有機層を抽出、硫酸ナトリウムで乾燥後、溶媒を留去した。減圧蒸留で精製することにより、無色透明なオイル状のオキセタンユニット３２．４ｇを得た

（１）前駆体の合成

化合物Ｋの前駆体
200 mLの三口フラスコにNaOH( 12.0g、0.3mol)、水(22.3)gを仕込みNaOHを溶解した。50℃に調温後2,7-ジブロモフル オレン（3.24g、10mmol)、トルエン(13.9g)、テトラ-n-ブチルアンモニウムブロミド(0.97g,3mmol)を仕込んだ。
攪拌下上記オキセタンユニット(6.98g、25mmol)をトルエン(7.0g)に溶解した液を52〜55℃で25分で滴下した。その後50〜55℃で8時間攪拌した。反応終了後室温 まで冷却しトルエン(100mL)を加え水層を分離した。油層を水(50mL)で４回洗浄した後濃
縮し9.0gの粘稠な油状物(一部結晶化)を得た。このマスにメタノール(20g)を加え結晶を濾別した。濾液を濃縮し粘稠な油 状物(9.0g)を得た。シリカゲルクロマトグフィーで精製｛展開溶媒：クロロホルム/ヘキサン (1:1, v/v)、0.1％トリエチルアミン添加｝を３回繰り返すことにより前駆体(1.82g、収率 25.2%)を得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ０.５９４（ｍ、４Ｈ）、０．８５０（ｔ、６Ｈ）、１．０９６（ｍ、８Ｈ）、１．３８０（ｍ、４H）、１．６９３（ｍ、４H）、１．９１４（ｍ、４H）、３．３３２（ｔ、４H）、３．４５８（ｓ、４H）、４．３２６（ｄ、４H）、４．４０８（ｄ、４H）、７．４８６（ｍ、６H）

（2）化合物Ｋの合成

化合物Ｋ

Pd(OAc)2(0.007g, 0.03 mmol)、カルバゾール(0.75g, 4.5mmol)、前駆体 (1.08g, 1.5mmol)、K2CO3(1.24g、9mmol)を仕込み減圧でアルゴン置換を３度行った。次に脱水トルエン(16mL)をシリンジで加え再度減圧でアルゴン置換を行った。
このマスを70〜75℃に加熱し(t-Bu)P(0.015ｇ、0.075mmol)を加え昇温し105〜107℃で6時間加熱攪拌した。反応終了後、反応液を室温まで冷却し固体をろ別した。濾紙上の残滓をクロロホルム(50mL)で洗浄し濾液を濃縮乾固し固形分(1.95g)を 得た。シリカゲルクロマトグフィーで2回精製｛展開溶媒：クロロホルム/ヘキサン (1:2, v/v)、0.1％トリエチルアミンを添加｝することにより樹脂状個体の化合物Ｋ(0．92g、収率68.6%)を得た。
¹Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ₃）：
δ０．８０９（ｔ、４Ｈ）、０．９０１（ｍ、６Ｈ）、１．１９４（ｍ、８Ｈ）、１．４４６（ｍ、４Ｈ）、１．６５８（ｍ、４H）、２．０８９（ｍ、４Ｈ）、３．３３８（ｔ、４H）、３．４４２（ｓ、４H）、４．２９９（ｄ、４H）、４．３６７（ｄ、４H）、７．３６６（ｍ、４H）、７．４５６（ｍ、８H）、７．６０８（ｍ、４H）、７．９９２（ｄ、２H）、８．１８７（ｄ、４H）
Synthesis Example 15
Synthesis of Compound K Synthesis of Oxetane Unit

Oxetane unit

163 ml of ion-exchanged water was placed in a 1 l three-neck flask purged with argon, and 85.2 g (2.13 mol) of sodium hydroxide was added little by little to stir and dissolve. Subsequently, 12.5 g (0.04 mol) of tetrabutylammonium bromide was added, 15 g (0.13 mol) of 3-ethyl-3-oxetanemethanol, 94.5 g (0.39 mol) of 1,6-dibromohexane, and After adding 128 ml of hexane and reacting at room temperature for 9 hours, the temperature was raised to 80 ° C. and reacted for 1 hour. After cooling to room temperature, the organic layer was extracted with hexane, dried over sodium sulfate, and the solvent was distilled off. Purification by vacuum distillation gave 32.4 g of a colorless and transparent oily oxetane unit.

(1) Synthesis of precursor

Compound K precursor
NaOH (12.0 g, 0.3 mol) and water (22.3) g were charged into a 200 mL three-necked flask to dissolve NaOH. After adjusting the temperature to 50 ° C., 2,7-dibromofluorene (3.24 g, 10 mmol), toluene (13.9 g), and tetra-n-butylammonium bromide (0.97 g, 3 mmol) were charged.
Under stirring, a solution prepared by dissolving the oxetane unit (6.98 g, 25 mmol) in toluene (7.0 g) was added dropwise at 52 to 55 ° C. over 25 minutes. Thereafter, the mixture was stirred at 50 to 55 ° C. for 8 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, toluene (100 mL) was added, and the aqueous layer was separated. The oil layer is washed 4 times with water (50 mL) and concentrated
Shrinking to obtain 9.0 g of a viscous oil (partially crystallized). Methanol (20 g) was added to the mass and the crystals were separated by filtration. The filtrate was concentrated to obtain a viscous oil (9.0 g). Purification by silica gel chromatography {developing solvent: chloroform / hexane (1: 1, v / v), 0.1% triethylamine added} was repeated 3 times to obtain a precursor (1.82 g, yield 25.2%).
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.594 (m, 4H), 0.850 (t, 6H), 1.096 (m, 8H), 1.380 (m, 4H), 1.663 (m, 4H), 1.914 (m) 4H), 3.332 (t, 4H), 3.458 (s, 4H), 4.326 (d, 4H), 4.408 (d, 4H), 7.486 (m, 6H)

(2) Synthesis of compound K

Compound K

Pd (OAc) 2 (0.007 g, 0.03 mmol), carbazole (0.75 g, 4.5 mmol), precursor (1.08 g, 1.5 mmol), K2CO3 (1.24 g, 9 mmol) were charged, and argon substitution was performed three times under reduced pressure. . Next, dehydrated toluene (16 mL) was added with a syringe, and argon substitution was performed again under reduced pressure.
The mass was heated to 70 to 75 ° C., (t-Bu) P (0.015 g, 0.075 mmol) was added, the temperature was raised, and the mixture was heated and stirred at 105 to 107 ° C. for 6 hours. After completion of the reaction, the reaction solution was cooled to room temperature and the solid was filtered off. The residue on the filter paper was washed with chloroform (50 mL), and the filtrate was concentrated to dryness to obtain a solid (1.95 g). Purified twice with silica gel chromatography {Developing solvent: chloroform / hexane (1: 2, v / v), 0.1% triethylamine added} to obtain resinous solid compound K (0.92 g, yield 68.6%) Obtained.
¹ H-NMR (270 MHz / CDCl ₃ ):
δ 0.809 (t, 4H), 0.901 (m, 6H), 1.194 (m, 8H), 1.446 (m, 4H), 1.658 (m, 4H), 2.089 (m 4H), 3.338 (t, 4H), 3.442 (s, 4H), 4.299 (d, 4H), 4.367 (d, 4H), 7.366 (m, 4H), 7 .456 (m, 8H), 7.608 (m, 4H), 7.992 (d, 2H), 8.187 (d, 4H)

不活性雰囲気下で、５００ｍｌの３つ口フラスコに酢酸２２５ｇを入れ、５−ｔ−ブチル−ｍ−キシレン２４．３ｇを加えた。続いて臭素３１．２ｇを加えた後、１５〜２０℃で３時間反応させた。
反応液を水５００ｍｌに加え析出した沈殿をろ過した。水２５０ｍｌで２回洗浄し、白色の固体３４．２ｇを得た。
¹Ｈ−ＮＭＲ（３００ＭＨｚ／ＣＤＣｌ₃）：
δ(ｐｐｍ) ＝ １．３〔ｓ，９Ｈ〕、２．４〔ｓ，６Ｈ〕、７．１〔ｓ，２Ｈ〕
ＭＳ（ＦＤ⁺）Ｍ⁺ ２４１ Synthesis Example 16
<Synthesis of 4-t-butyl-2,6-dimethylbromobenzene>

Under an inert atmosphere, 225 g of acetic acid was placed in a 500 ml three-necked flask, and 24.3 g of 5-t-butyl-m-xylene was added. Then, after adding 31.2 g of bromine, it was made to react at 15-20 degreeC for 3 hours.
The reaction solution was added to 500 ml of water, and the deposited precipitate was filtered. This was washed twice with 250 ml of water to obtain 34.2 g of a white solid.
¹ H-NMR (300 MHz / CDCl ₃ ):
δ (ppm) = 1.3 [s, 9H], 2.4 [s, 6H], 7.1 [s, 2H]
MS (FD ⁺ ) M ⁺ 241

不活性雰囲気下で、３００ｍｌの３つ口フラスコに脱気した脱水トルエン１６６０ｍｌを入れ、Ｎ，Ｎ’−ジフェニルベンジジン２７５．０ｇ、４−ｔ−ブチル−２，６−ジメチルブロモベンゼン４４９．０ｇを加えた。続いてトリス（ジベンジリデンアセトン）ジパラジウム７．４８ｇ、ｔ−ブトキシナトリウム１９６．４ｇ、を加えた後、トリ（ｔ−ブチル）ホスフィン５．０ｇを加えた。その後、１０５℃で７時間反応させた。
反応液にトルエン２０００ｍｌを加え、セライト濾過し、濾液を水１０００ｍｌで３回洗浄した後、７００ｍｌまで濃縮した。これにトルエン／メタノール（１：１）溶液１６００ｍｌを加え、析出した結晶を濾過し、メタノールで洗浄した。白色の固体４７９．４ｇを得た。 Synthesis Example 17
<Synthesis of N, N'-diphenyl-N, N'-bis (4-tert-butyl-2,6-dimethylphenyl) -benzidine>

In an inert atmosphere, 1660 ml of degassed toluene was put into a 300 ml three-necked flask, and 275.0 g of N, N′-diphenylbenzidine and 449.0 g of 4-t-butyl-2,6-dimethylbromobenzene were added. added. Subsequently, 7.48 g of tris (dibenzylideneacetone) dipalladium and 196.4 g of sodium t-butoxy were added, and 5.0 g of tri (t-butyl) phosphine was added. Then, it was made to react at 105 degreeC for 7 hours.
Toluene (2000 ml) was added to the reaction mixture, and the mixture was filtered through Celite. The filtrate was washed with 1000 ml of water three times and then concentrated to 700 ml. To this was added 1600 ml of a toluene / methanol (1: 1) solution, and the precipitated crystals were filtered and washed with methanol. 479.4 g of a white solid was obtained.

不活性雰囲気下で、クロロホルム４７３０ｇに、上記Ｎ，Ｎ’−ジフェニル−Ｎ，Ｎ’−ビス（４−ｔ‐ブチル−２，６−ジメチルフェニル）−ベンジジン４７２．８ｇを溶解した後、遮光および氷浴下でＮ−ブロモスクシンイミド２８１．８ｇを１２分割で１時間かけて仕込み、３時間反応させた。
クロロホルム１４３９ｍｌを反応液に加え、濾過し、濾液のクロロホルム溶液を５％チオ硫酸ナトリウム２１５９ｍｌで洗浄し、トルエンを溶媒留去して白色結晶を得た。得られた白色結晶をトルエン／エタノールで再結晶し、白色結晶６７８．７ｇを得た。 Synthesis Example 18
<Synthesis of N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -benzidine>

In an inert atmosphere, 472.8 g of N, N′-diphenyl-N, N′-bis (4-t-butyl-2,6-dimethylphenyl) -benzidine was dissolved in 4730 g of chloroform, In an ice bath, 281.8 g of N-bromosuccinimide was charged in 12 portions over 1 hour and reacted for 3 hours.
Chloroform 1439 ml was added to the reaction solution, followed by filtration. The chloroform solution of the filtrate was washed with 2159 ml of 5% sodium thiosulfate, and toluene was distilled off to obtain white crystals. The obtained white crystals were recrystallized with toluene / ethanol to obtain 678.7 g of white crystals.

Synthesis Example 19
<Synthesis of Polymer Compound 3>
Compound E (5.25 g), N, N′-bis (4-bromophenyl) -N, N′-bis (4-tert-butyl-2,6-dimethylphenyl) -benzidine (3.06 g) and 2 2,2′-bipyridyl (5.3 g) was dissolved in 226 mL of dehydrated tetrahydrofuran, and the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (9.30 g) was added to this solution, the temperature was raised to 60 ° C., and the reaction was continued for 3 hours with stirring. I let you. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 45 mL / methanol about 230 mL / ion exchanged water about 230 mL and stirred for 1 hour, and then the deposited precipitate was filtered. And then dried under reduced pressure for 2 hours, then dissolved in 400 mL of toluene and filtered. The filtrate was purified through an alumina column, added with about 400 ml of 5.2% hydrochloric acid and stirred for 3 hours, and then the aqueous layer was removed. did. Next, about 400 mL of 4% aqueous ammonia was added, and after stirring for 2 hours, the aqueous layer was removed. Further, about 400 mL of ion exchange water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. 80 ml of toluene was added to the organic layer, and the precipitate deposited by decantation was collected and dissolved in 200 ml of toluene. Then, this was dropped into about 600 ml of methanol and stirred for 1 hour, and the deposited precipitate was filtered for 2 hours. Dry under reduced pressure. The yield of the obtained copolymer (hereinafter referred to as polymer compound 3) was 4.25 g. The number average molecular weight and weight average molecular weight in terms of polystyrene were Mn = 2.5 × 10 ⁴ and Mw = 8.0 × 10 ⁵ (mobile phase: tetrahydrofuran), respectively.

窒素雰囲気下で、１ｌの３つ口フラスコに３，６−ジブロモカルバゾール９３．４ｇ、４−ジメチルアミノピリジン１．７６ｇを加え次に脱水テトラヒドロフラン４６７ｍｌを加え溶解した。 ジ-t-ブチルジカ−ボネ−ト６９．０ｇを滴下ロ−トに秤り取り水冷下２０〜２３℃で１．５時間かけ滴下した。同温度で１時間攪拌した。反応液を１ｌナス型フラスコに移し減圧下６０℃でエバポレ−タでテトラヒドロフランを留去した。濃縮途中で結晶が析出した。次に７０℃、３ｍｍHgで結晶を乾燥し１２２．４ｇの粗ケ−キを得た。粗ケ−キにエタノ−ル２５０ｇを加え還流下１時間攪拌し室温まで冷却後濾過した。ウエットケ−キをエタノ−ル１５０ｇで２回洗浄した。このウエットケ−キにエタノ−ル２５０ｇを加え粗ケ−キと同じ精製操作を再度行った後８０℃、３ｍｍＨｇで乾燥した。僅かに黄色を帯びた乾燥ケ−キ１１７．９ｇを得た。

１Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ3）：
δ(ｐｐｍ) ＝ １．７５〔ｓ，９Ｈ〕、７．５７〔ｄ，２Ｈ〕、８．０３〔ｓ，２Ｈ〕、８．１６〔ｄ，２Ｈ〕 Synthesis Example 20
<Protection of amino group of 3,6-dibromocarbazole>

Under a nitrogen atmosphere, 93.4 g of 3,6-dibromocarbazole and 1.76 g of 4-dimethylaminopyridine were added to a 1 l three-necked flask and then dissolved in 467 ml of dehydrated tetrahydrofuran. 69.0 g of di-t-butyl dicarbonate was weighed into a dropping funnel and added dropwise at 20-23 ° C. for 1.5 hours under water cooling. Stir at the same temperature for 1 hour. The reaction solution was transferred to a 1 l eggplant type flask, and tetrahydrofuran was distilled off with an evaporator at 60 ° C. under reduced pressure. Crystals precipitated during the concentration. Next, the crystals were dried at 70 ° C. and 3 mmHg to obtain 122.4 g of a crude cake. 250 g of ethanol was added to the crude cake, stirred for 1 hour under reflux, cooled to room temperature, and filtered. The wet cake was washed twice with 150 g of ethanol. 250 g of ethanol was added to the wet cake, and the same purification operation as that of the crude cake was performed again, followed by drying at 80 ° C. and 3 mmHg. 117.9 g of a slightly yellowish dry cake was obtained.

1H-NMR (270 MHz / CDCl3):
δ (ppm) = 1.75 [s, 9H], 7.57 [d, 2H], 8.03 [s, 2H], 8.16 [d, 2H]

アルゴン雰囲気下で、５００ｍｌの３つ口フラスコに合成例２０で合成したBoc体２５．５ｇ、炭酸カリウム４１．５ｇ、ｎ−ブチルボロン酸１４．７ｇ、イオン交換水９６．７ｇ、トルエン１５３ｇを加えた。室温下フラスコを４０ｍｍＨｇまで減圧にしアルゴンで復圧する操作を３回繰り返しフラスコ内をアルゴン置換した。６５℃まで昇温しテトラキス（トリフェニルホスフィン）パラジウム（０）０．３５ｇを加えた。次にトリ-t-ブチルホスフィンの１０％トルエン溶液２．７ｍｌをシリンジで量りとり加えた。昇温し８４〜８５℃で３．５時間還流下反応させた。反応終了後６５℃まで冷却し分液ロ−トに反応液を移し水層を分離した。６０〜６５℃に保温したイオン交換水１００ｍｌで油層を２回洗浄した。中間層が生成したのため同温度で１０％食塩水１００ｍｌで再度洗浄した。油層を室温まで冷却し無水硫酸ナトリウムを適量加え２０〜２３℃で脱水した。
油層を濾別後濾紙上の無水硫酸ナトリウムを５０ｍｌのトルエンで洗浄した。濾洗液をエバポレ−タで濃縮し最終７０℃、３ｍｍＨｇで乾個した。オレンジ色のBoc体結晶２３．４ｇを得た。
アルゴン雰囲気下で、１ｌの３つ口フラスコにBoc体結晶２３．４ｇ、テトラブチルアンモニウムフロリドの1mol/Lテトラヒドロフラン溶液４９４ｍｌを加えた。昇温し還流下６６時間反応させた。室温に冷却後反応マスを１ｌナス型フラスコに移し減圧下６０℃でエバポレ−タで濃縮し濃縮物２２８．１ｇを得た。濃縮物にイオン交換水５００ｍｌを加え１ｌ分液ロ−トに移しクロロホルム２００ｍｌで２回抽出した。クロロホルム層を１ｌナス型フラスコに移し減圧下６０℃でエバポレ−タで濃縮し濃縮物６１．５ｇを得た。シリカゲルクロマトグラフィ−[展開溶媒：クロロホルム/ヘキサン＝１/６(V/V)、トリエチルアミン０．１％添加]で精製し白色ケ−キ１３．４ｇを得た。

１Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ3）：
δ(ｐｐｍ) ＝ ０．９５〔ｔ，６Ｈ〕、１．４０〔ｍ，４Ｈ〕、１．６９〔ｍ、４H〕、２．７７〔ｔ、４Ｈ〕、７．２５〔ｍ，４Ｈ〕、７．８５〔ｍ，３Ｈ〕
Synthesis Example 21
<Synthesis of 3,6-di-n-butylcarbazole>

Under an argon atmosphere, 25.5 g of the Boc compound synthesized in Synthesis Example 20, 41.5 g of potassium carbonate, 14.7 g of n-butylboronic acid, 96.7 g of ion-exchanged water, and 153 g of toluene were added to a 500 ml three-necked flask. . The operation of depressurizing the flask to 40 mmHg at room temperature and restoring the pressure with argon was repeated three times, and the atmosphere in the flask was replaced with argon. The temperature was raised to 65 ° C., and 0.35 g of tetrakis (triphenylphosphine) palladium (0) was added. Next, 2.7 ml of a 10% toluene solution of tri-t-butylphosphine was weighed and added with a syringe. The temperature was raised, and the reaction was carried out under reflux at 84 to 85 ° C. for 3.5 hours. After completion of the reaction, the mixture was cooled to 65 ° C., transferred to a separatory funnel, and the aqueous layer was separated. The oil layer was washed twice with 100 ml of ion-exchanged water kept at 60 to 65 ° C. Since an intermediate layer was formed, it was washed again with 100 ml of 10% brine at the same temperature. The oil layer was cooled to room temperature, added with an appropriate amount of anhydrous sodium sulfate, and dehydrated at 20-23 ° C.
After the oil layer was filtered off, anhydrous sodium sulfate on the filter paper was washed with 50 ml of toluene. The filtrate was concentrated with an evaporator and dried at 70 ° C. and 3 mmHg. 23.4 g of orange Boc crystals were obtained.
Under an argon atmosphere, 23.4 g of Boc crystals and 494 ml of a 1 mol / L tetrahydrofuran solution of tetrabutylammonium fluoride were added to a 1 l three-necked flask. The temperature was raised and reacted for 66 hours under reflux. After cooling to room temperature, the reaction mass was transferred to a 1 L eggplant-shaped flask and concentrated under reduced pressure at 60 ° C. with an evaporator to obtain 228.1 g of a concentrate. To the concentrate was added 500 ml of ion exchange water, transferred to a 1 l separatory funnel, and extracted twice with 200 ml of chloroform. The chloroform layer was transferred to a 1 L eggplant-shaped flask and concentrated with an evaporator at 60 ° C. under reduced pressure to obtain 61.5 g of a concentrate. Purification by silica gel chromatography [developing solvent: chloroform / hexane = 1/6 (V / V), triethylamine 0.1% added] gave 13.4 g of a white cake.

1H-NMR (270 MHz / CDCl3):
δ (ppm) = 0.95 [t, 6H], 1.40 [m, 4H], 1.69 [m, 4H], 2.77 [t, 4H], 7.25 [m, 4H], 7.85 [m, 3H]

２ｌの３つ口フラスコに４、４´-ジヨ−ドビフェニル９７．４ｇ、炭酸カリウム６６．３ｇ、カルバゾ−ル１３．４ｇ、酢酸パラジウム０．３６ｇ、脱水トルエン７８０ｇを加えた。フラスコを４０ｍｍHｇまで減圧にしアルゴンで復圧する操作を３回繰り返しアルゴン置換した。７０〜７５℃まで昇温しトリ（ｔ−ブチル）ホスフィンの１０％トルエン溶液１１．６ｍｌをシリンジで量り取りフラスコに加えた。１０５〜１０７℃に昇温し還流下１６時間反応させた。反応マスを室温に冷却後濾過しケ−キをトルエン１００ｍｌで洗浄した。濾過ビンを変え次にイオン交換水１５０ｍｌで３回洗浄した。ケ−キを５００ｍｌナス型フラスコに移し８０℃、３ｍｍＨｇで乾燥し個体５２．９ｇを得た。別途濾洗液を５００ｍｌナス型フラスコで濃縮し最終８０℃、３ｍｍＨｇで乾個し固体４１．４ｇを得た。この個体にトルエン２００ｇを加え還流下溶解した後室温まで冷却し結晶を析出させた。結晶を濾過しトルエン１００ｍｌで洗浄後８０℃、３ｍｍＨｇで乾燥し２４．９ｇの結晶を得た。個体５２．９ｇと結晶２４．９ｇを合わせシリカゲルクロマトグラフィ−[展開溶媒：クロロホルム/ヘキサン＝１/５(V/V)、トリエチルアミン０．１％添加]で２回精製し白色の個体２２．４ｇを得た。この個体にクロロホルム７２ｇ、ヘキサン７２ｇを加え還流下１時間攪拌し室温に冷却後濾過し、ケ−キをヘキサン５０ｍｌで洗浄した。８０℃、３ｍｍＨｇで乾燥し２１．３ｇの結晶を得た。このケ−キを５００ｍｌナス型フラスコに移しトルエン６０ｇを加え８０〜８５℃で１時間攪拌した。室温に冷却後濾過しケ−キを５０ｍｌのトルエンで洗浄した。このケ−キを２００ｍｌナス型フラスコに移し８０〜８５℃、３ｍｍＨｇで乾燥し白色結晶１６．７６ｇを得た。

１Ｈ−ＮＭＲ（２７０ＭＨｚ／ＴＨＦｄ8）：
δ(ｐｐｍ) ＝ ７．２２〔ｍ，２Ｈ〕、７．３７〔ｍ，４Ｈ〕、７．５３〔ｄ，２Ｈ〕、
７．６８〔ｄ，２Ｈ〕、７．８６〔ｍ，４Ｈ〕、８．１２〔ｄ，２Ｈ〕 Synthesis Example 22
<Synthesis of N-biphenylcarbazole>

To a 2-liter three-necked flask, 97.4 g of 4,4′-di-bibiphenyl, 66.3 g of potassium carbonate, 13.4 g of carbazole, 0.36 g of palladium acetate, and 780 g of dehydrated toluene were added. The operation of depressurizing the flask to 40 mmHg and restoring the pressure with argon was repeated three times and replaced with argon. The temperature was raised to 70 to 75 ° C., and 11.6 ml of a 10% toluene solution of tri (t-butyl) phosphine was weighed with a syringe and added to the flask. The temperature was raised to 105 to 107 ° C., and the reaction was conducted for 16 hours under reflux. The reaction mass was cooled to room temperature and filtered, and the cake was washed with 100 ml of toluene. The filter bottle was changed and then washed with 150 ml of ion exchange water three times. The cake was transferred to a 500 ml eggplant-shaped flask and dried at 80 ° C. and 3 mmHg to obtain 52.9 g of a solid. Separately, the filtrate was concentrated in a 500 ml eggplant type flask and dried at 80 ° C. and 3 mmHg to obtain 41.4 g of a solid. To this solid was added 200 g of toluene, dissolved under reflux, and then cooled to room temperature to precipitate crystals. The crystals were filtered, washed with 100 ml of toluene, and then dried at 80 ° C. and 3 mmHg to obtain 24.9 g of crystals. The solid 52.9 g and the crystal 24.9 g were combined and purified twice by silica gel chromatography [developing solvent: chloroform / hexane = 1/5 (V / V), triethylamine 0.1% added] to obtain 22.4 g of a white solid. Obtained. To this solid were added 72 g of chloroform and 72 g of hexane, stirred for 1 hour under reflux, cooled to room temperature, filtered, and the cake was washed with 50 ml of hexane. It was dried at 80 ° C. and 3 mmHg to obtain 21.3 g of crystals. The cake was transferred to a 500 ml eggplant type flask, 60 g of toluene was added, and the mixture was stirred at 80 to 85 ° C. for 1 hour. After cooling to room temperature, it was filtered and the cake was washed with 50 ml of toluene. This cake was transferred to a 200 ml eggplant type flask and dried at 80 to 85 ° C. and 3 mmHg to obtain 16.76 g of white crystals.

1H-NMR (270 MHz / THF d8):
δ (ppm) = 7.22 [m, 2H], 7.37 [m, 4H], 7.53 [d, 2H],
7.68 [d, 2H], 7.86 [m, 4H], 8.12 [d, 2H]

化合物Ｌ
２００ｍｌの３つ口フラスコに合成例２１で合成したヨ−ドビフェニル体８．０２ｇ、炭酸カリウム７．４６ｇ、合成例２０で合成した３，６−ジ-n-ブチルカルバゾ−ル６．５４ｇ、酢酸パラジウム０．０８１ｇ、脱水トルエン１２０ｇを加えた。フラスコを４０ｍｍＨｇまで減圧にしアルゴンで復圧する操作を３回繰り返しアルゴン置換した。７０〜７５℃まで昇温しトリ（ｔ−ブチル）ホスフィンの１０％トルエン溶液２ｍｌをシリンジで量り取りフラスコに加えた。１０５〜１０７℃に昇温し還流下１６時間反応させた。反応マスを室温に冷却後濾過しケ−キをトルエン１００ｍｌで洗浄した。濾洗液を５００ｍｌナス型フラスコで濃縮し最終８０℃、３ｍｍＨｇで乾個し固体１２．５４ｇを得た。シリカゲルクロマトグラフィ−[展開溶媒：クロロホルム/ヘキサン＝１/５(V/V)、トリエチルアミン０．１％添加]で精製し白色の個体９．５１ｇを得た。これを化合物Ｌと呼ぶ。

１Ｈ−ＮＭＲ（２７０ＭＨｚ／ＣＤＣｌ3）：
δ(ｐｐｍ) ＝ ０．９７〔ｔ，６Ｈ〕、１．４４〔ｍ，４Ｈ〕、１．７３〔ｍ，４Ｈ〕、２．８２〔ｔ，４Ｈ〕、７．２９〔ｍ，４Ｈ〕、７．４７〔ｍ，６Ｈ〕、７．８７〔ｄ，４Ｈ〕、７．９２〔ｍ，６Ｈ〕、８．１７〔ｄ，２Ｈ〕
Synthesis Example 23
<Synthesis of Compound L>

Compound L
In a 200 ml three-necked flask, 8.02 g of iodobiphenyl synthesized in Synthesis Example 21, 7.46 g of potassium carbonate, 6.54 g of 3,6-di-n-butylcarbazole synthesized in Synthesis Example 20, acetic acid 0.081 g of palladium and 120 g of dehydrated toluene were added. The operation of depressurizing the flask to 40 mmHg and restoring the pressure with argon was repeated three times and replaced with argon. The temperature was raised to 70 to 75 ° C., and 2 ml of a 10% toluene solution of tri (t-butyl) phosphine was weighed with a syringe and added to the flask. The temperature was raised to 105 to 107 ° C., and the reaction was conducted for 16 hours under reflux. The reaction mass was cooled to room temperature and filtered, and the cake was washed with 100 ml of toluene. The filtrate was concentrated in a 500 ml eggplant type flask and dried at 80 ° C. and 3 mmHg to obtain 12.54 g of a solid. Purification by silica gel chromatography [developing solvent: chloroform / hexane = 1/5 (V / V), 0.1% triethylamine added] gave 9.51 g of a white solid. This is referred to as Compound L.

1H-NMR (270 MHz / CDCl3):
δ (ppm) = 0.97 [t, 6H], 1.44 [m, 4H], 1.73 [m, 4H], 2.82 [t, 4H], 7.29 [m, 4H], 7.47 [m, 6H], 7.87 [d, 4H], 7.92 [m, 6H], 8.17 [d, 2H]

Synthesis Example 24
Synthesis of polyamine polymer compound 4 Under inert atmosphere, N, N′-bis (4-bromophenyl) -N, N′-bis (4-n-butylphenyl) 1,4-phenylenediamine (1.911 g) , N, N′-bis (4-bromophenyl) phenylamine (0.484 g) and 2,2′-bipyridyl (1.687 g) were dissolved in 109 mL of dehydrated tetrahydrofuran previously bubbled with argon. After raising the temperature of this solution to 60 ° C., bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (2.971 g) was added, stirred and allowed to react for 5 hours. The reaction solution was cooled to room temperature, dropped into a mixed solution of 25% aqueous ammonia 14 mL / methanol 109 mL / ion-exchanged water 109 mL, stirred for 1 hour, the deposited precipitate was filtered, dried under reduced pressure, and dissolved in 120 mL of toluene. I let you. After dissolution, 0.48 g of radiolite was added and stirred for 30 minutes, and the insoluble material was filtered. The obtained filtrate was purified through an alumina column. Next, 236 mL of 4% aqueous ammonia was added, and after stirring for 2 hours, the aqueous layer was removed. Further, about 236 mL of ion-exchanged water was added to the organic layer and stirred for 1 hour, and then the aqueous layer was removed. Thereafter, the organic layer was poured into 376 ml of methanol and stirred for 0.5 hour, and the deposited precipitate was filtered and dried under reduced pressure. The yield of the obtained polymer (hereinafter referred to as polymer compound 4) was 1.54 g. Moreover, the number average molecular weight and weight average molecular weight of polystyrene conversion were Mn = 7.4 × 10 ³ and Mw = 7.6 × 10 ⁴ , respectively.

Synthesis Example 25
Synthesis of Polymer Compound 5 After charging 22.5 g of compound E and 17.6 g of 2,2′-bipyridyl in a reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this, 1500 g of tetrahydrofuran (dehydrated solvent) deaerated previously by bubbling with argon gas was added. Next, 31 g of bis (1,5-cyclooctadiene) nickel (0) was added to this mixed solution, and the mixture was stirred at room temperature for 10 minutes and then reacted at 60 ° C. for 3 hours. The reaction was performed in a nitrogen gas atmosphere.
After the reaction, this reaction solution was cooled, and then a mixed solution of 25% aqueous ammonia 200 ml / methanol 900 ml / ion exchanged water 900 ml was poured into this solution and stirred for about 1 hour. Next, the produced precipitate was filtered and collected. This precipitate was dried under reduced pressure and then dissolved in toluene. The toluene solution was filtered to remove insoluble matters, and the toluene solution was purified by passing through a column packed with alumina. Next, this toluene solution was washed with a 1N aqueous hydrochloric acid solution, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with about 3% aqueous ammonia, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was washed with ion-exchanged water, allowed to stand and separated, and then the toluene solution was recovered. Next, this toluene solution was poured into methanol and re-precipitated.
Next, the produced precipitate was recovered, washed with methanol, and then dried under reduced pressure to obtain 6.0 g of a polymer. This polymer is referred to as polymer compound 5. The obtained polymer compound 5 had a polystyrene equivalent weight average molecular weight of 8.2 × 10 ⁵ and a number average molecular weight of 1.0 × 10 ⁵ .

Synthesis Example 26
Synthesis of polymer compound 6, 2,7-dibromo-9,9-dioctylfluorene (26 g, 0.047 mol), 2,7-dibromo-9,9-diisopentylfluorene (5.6 g, 0.012 mol) and 2,2′-bipyridyl (22 g, 0.141 mol) was dissolved in 1600 mL of dehydrated tetrahydrofuran, and the system was purged with nitrogen by bubbling with nitrogen. Under a nitrogen atmosphere, bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) ₂ } (40 g, 0.15 mol) was added to this solution, and the temperature was raised to 60 ° C. and allowed to react for 8 hours. It was. After the reaction, this reaction solution was cooled to room temperature (about 25 ° C.), dropped into a mixed solution of 25% ammonia water 200 mL / methanol 1200 mL / ion-exchanged water 1200 mL and stirred for 30 minutes, and then the deposited precipitate was filtered. Air dried. Then, it melt | dissolved in 1100 mL of toluene, it filtered, and the filtrate was dripped at methanol 3300mL, and was stirred for 30 minutes. The deposited precipitate was filtered, washed with 1000 mL of methanol, and dried under reduced pressure for 5 hours. The yield of the obtained polymer was 20 g. This polymer is referred to as polymer compound 6. The average molecular weight in terms of polystyrene of the polymer compound 6 was Mn = 4.6 × 10 ⁴ and Mw = 1.1 × 10 ⁵ .

<Preparation of polymer light emitter solution composition>
As shown in Table 1, polymer compound 2 or polymer compound 3 and polymer compound 1 and 50:50 (weight ratio) mixture of polymer compound 1 in toluene are 1 wt% in toluene, and additives are the types shown in Table 1. Were mixed and dissolved in the added amount. For Example 6, which was not completely dissolved, chloroform was added as a solvent. Thereafter, the solution was filtered through a 0.2 micron diameter Teflon (registered trademark) filter to prepare a coating solution.

１ 高分子発光体の合計重量１００重量部に対する添加物の添加量
２ ＤＣＢＰ：下式4,4’-ビス（9-カルバゾイル）-ビフェニル （（株）同仁化学研究所製）

1 Amount of additive added to 100 parts by weight of the total weight of the polymer light emitter 2 DCBP: Formula 4,4′-bis (9-carbazoyl) -biphenyl (made by Dojindo Laboratories)

<Creation and evaluation of device>
A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is formed to a thickness of 70 nm by spin coating using a solution of poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Bayer, Baytron). Dried on plate for 10 minutes at 200 ° C. Next, a film having a thickness of about 70 nm was formed by spin coating at a rotational speed of 1400 rpm using the prepared polymer light emitter coating solution. Further, this was dried at 90 ° C. under reduced pressure for 1 hour, and then, as a cathode buffer layer, lithium fluoride was deposited at 4 nm, cathode was deposited as calcium at 5 nm, and then aluminum was deposited at 100 nm to produce a polymer LED. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻⁵ Torr. By applying voltage stepwise to the obtained element having a light emitting part of 2 mm × 2 mm (area 4 mm ² ), the luminance of EL light emission from the polymer light emitter was measured, and the current efficiency value was obtained therefrom. . Table 1 shows the maximum value of current efficiency of the obtained element. A device using a 50/50 mixture of polymer compound 1 and polymer compound 2 as a polymer light emitter emits EL light of λmax = 470 nm, and a device using a 50/50 mixture of polymer compound 1 and polymer compound 3. Was EL emission at λmax = 460 nm. Compared with the polymer light emitting device of the comparative example which does not contain the compounds F to K, L and DCBP, the polymer light emitting device prepared using the coating solutions of Examples 1 to 13 containing the compounds F to K, L and DCBP A significant improvement in efficiency was seen.

Preparation of polyamine hole transport layer 1 A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering is used with a solution of PEDOT: poly (ethylenedioxythiophene) / polystyrene sulfonic acid (Stark Vitec, Baytron). A film was formed by spin coating, and dried at 200 ° C. for 10 minutes on a hot plate to form a PEDOT layer as a hole injection layer with a thickness of 50 nm. Next, a 1 wt% toluene solution of polyamine polymer compound 4 was applied at a rotational speed of 500 rpm. Thereafter, the substrate was baked at 200 ° C. for 10 minutes in a nitrogen atmosphere to form a polyamine hole transport layer 1.

Preparation of polyamine hole transport layer 2 A glass substrate with an ITO film having a thickness of 150 nm formed by sputtering, and then dipentaerythritol hexaacrylate (KAYARAD DPHA made by Nippon Kayaku Co., Ltd.) in a 1 wt% toluene solution of polyamine polymer compound 4. ) As a crosslinking agent was mixed and dissolved in a polymer compound at 25% by weight and applied at a rotation speed of 500 rpm. Thereafter, the substrate was baked at 300 ° C. for 20 minutes in a nitrogen atmosphere to form a polyamine hole transport layer 2 having a thickness of 50 nm.

<Preparation of polymer light emitter solution composition>
As shown in Table 2, the polymer compound of the polymer luminescent material, and further the additive and the dye were mixed in the types and addition amounts shown in Table 2 and dissolved in toluene. Thereafter, the solution was filtered through a 0.2 micron diameter Teflon (registered trademark) filter to prepare a coating solution.

<Creation and evaluation of device>
Next, a film having a thickness of about 70 nm was formed by spin coating using the prepared polymer light emitter coating solution. Further, this was dried at 90 ° C. under reduced pressure for 1 hour, and then, as a cathode buffer layer, lithium fluoride was deposited at 4 nm, cathode was deposited as calcium at 5 nm, and then aluminum was deposited at 100 nm to produce a polymer LED. The degree of vacuum at the time of vapor deposition was 1 to 9 × 10 ⁻⁵ Torr. By applying voltage stepwise to the obtained element having a light emitting part of 2 mm × 2 mm (area 4 mm ² ), the luminance of EL light emission from the polymer light emitter was measured, and the current efficiency value was obtained therefrom. . Table 2 shows the maximum value of current efficiency of the obtained element.

３ 高分子発光体の合計重量１００重量部に対する添加物の添加量
４ 高分子発光体と添加物の合計重量１００重量部に対する色素の添加量
ADS078GE：下式で示されるアメリカンダイソース社製のイリジウム錯体色素

3 Amount of additive added to 100 parts by weight of the total weight of the polymer light emitter 4 Amount of dye added to 100 parts by weight of the total weight of the polymer light emitter and additive
ADS078GE: Iridium complex dye made by American Daissource, Inc.

The element not containing the dye in the polymer light emitting coating solution emitted blue EL light having λmax = 460 nm, and the element containing the dye emitted white EL light having two peaks of λmax = 460 nm and λmax = 555 nm. Compared with the polymer light emitting device of the comparative example which does not contain the compounds J, L and DCBP, the polymer light emitting device prepared using the coating solutions of Examples 14 to 21 containing the compounds J, L and DCBP are significantly more efficient. An improvement was seen.

Claims (8)

A polymer light emitter and a compound selected from the following formulas (1a) and (1b):
(I) a mixture comprising a conjugated polymer, and a compound selected from the following formulas (1a) and (1b) including a triplet emitters in conjugated form, and,
And (ii) co-auditors polymer, a compound selected from the following formulas (1a) and (1b), except a mixture containing the triplet emitters] that light emitting polymer composition characterized.

(X represents an atom or an atomic group for forming a 5-membered ring or a 6-membered ring together with 4 carbon atoms on two benzene rings in the formula, and R ^{1 to} R ⁴⁶ are respectively Independently hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group , Arylalkynyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, substituted amino group, amide group, acid imide group, acyloxy group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, cyano group Or represents a nitro group.) The polymer light-emitting composition according to claim 1, wherein R ^{1 to} R ⁴⁶ are each independently a hydrogen atom or an alkyl group. The polymer light emitter composition according to claim 1 or 2, wherein the polymer light emitter comprises a repeating unit represented by the following formula (2).

(In the formula, A represents an atom or an atomic group for forming a 5-membered ring or a 6-membered ring together with 4 carbon atoms on the two benzene rings in the formula, R ^4a , R ^4b , R ^4c , R ^5a , R ^5b and R ^5c are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, aryl Alkyloxy group, arylalkylthio group, alkenyl group, alkynyl group, arylalkenyl group, arylalkynyl group, acyl group, acyloxy group, amide group, acid imide group, imine residue, substituted amino group, substituted silyl group, substituted silyloxy group Substituted silylthio group, substituted silylamino group, cyano group, nitro group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthiol O group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group or a carboxyl group, R ^4b and R ^4C , and R ^5b and R ^5c are each taken together to form a ring May be formed.)   The content of the compound selected from the formulas (1a) and (1b) is 0.1 to 10,000 parts by weight when the polymer light emitter is 100 parts by weight. A polymer light emitter composition according to claim 1.   The polymer light emitter composition according to claim 1, further comprising a solvent.   A polymer light-emitting device comprising a light-emitting layer between electrodes composed of an anode and a cathode, wherein the light-emitting layer contains the polymer light-emitting composition according to claim 1.   A polymer light emitting device comprising a light emitting layer between electrodes comprising an anode and a cathode, wherein the light emitting layer is formed using the polymer light emitter solution composition according to claim 5.   The electrode according to claim 6 or 7, further comprising a hole transport layer between the anode and the cathode, wherein the hole transport layer contains a polyamine having a repeating unit derived from an aromatic amine. The polymer light-emitting device described.