JP5708022B2 - Benzofluoranthene polymer - Google Patents

Description

  The present invention relates to a benzofluoranthene polymer compound, a production method thereof, a polymer composition containing the same, a solution, an organic thin film, an organic semiconductor element, a light emitting element, a planar light source and a display device, and a raw material compound thereof. .

  As a light-emitting material for use in a light-emitting element, for example, a copolymer composed only of a benzo [k] fluoranthene-7,12-diyl group and a fluorene-2,7-diyl group is known (Patent Document 1).

International Publication No. 2009/075203 Pamphlet

  However, the light emitting device using the polymer compound has not had sufficient maximum light emission efficiency.

  Then, an object of this invention is to provide a high molecular compound useful for manufacture of the light emitting element which is excellent in maximum luminous efficiency. Another object of the present invention is to provide a polymer composition, a solution, an organic thin film, an organic semiconductor element, a light emitting element, a planar light source, and a display device containing the polymer compound. Another object of the present invention is to provide a method for producing the polymer compound, a compound useful for producing the polymer compound, and a method for producing the compound.

  The present invention first provides a polymer compound comprising a first structural unit represented by the following general formula (1) and a second structural unit represented by the following general formula (2).

［一般式（１）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹及びＲ¹⁰はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は置換基を有していてもよい。Ｒ^Aは、アルキル基、アリール基、又は、１価の芳香族複素環基を示し、これらの基は置換基を有していてもよい。Ｒ^Aが複数存在する場合、それらは、同一であっても異なっていてもよい。Ａｒ⁵及びＡｒ⁶はそれぞれ独立に、非置換若しくは置換のアリーレン基、又は、非置換若しくは置換の２価の芳香族複素環基を表すか、或いは、アリーレン基及び２価の芳香族複素環基からなる群より選ばれる同一又は異なる基が２以上連結した２価の基を表す。ａａ及びｂｂはそれぞれ独立に、０又は１を表す。］

[In general formula (1), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, or an aryl group. A monovalent aromatic heterocyclic group or a group represented by —O—R ^A is shown, and these groups may have a substituent. R ^A represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. When a plurality of ^RA are present, they may be the same or different. Ar ⁵ and Ar ⁶ each independently represent an unsubstituted or substituted arylene group, or an unsubstituted or substituted divalent aromatic heterocyclic group, or an arylene group and a divalent aromatic heterocyclic group Represents a divalent group in which two or more identical or different groups selected from the group consisting of aa and bb each independently represents 0 or 1; ]

［一般式（２）中、Ａｒ¹、Ａｒ²、Ａｒ³及びＡｒ⁴はそれぞれ独立に、非置換若しくは置換のアリーレン基、又は、非置換若しくは置換の２価の芳香族複素環基を表すか、或いは、アリーレン基及び２価の芳香族複素環基からなる群より選ばれる同一又は異なる基が２以上連結した２価の基を表す。Ａｒ¹とＡｒ²、並びに、Ａｒ²とＡｒ³は、直接結合して（即ち、単結合を介して）、又は、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）−Ｏ−、−Ｎ（Ｒ^A）−、−Ｃ（＝Ｏ）−Ｎ（Ｒ^A）−若しくは−Ｃ（Ｒ^A）₂−で表される基を介して結合して、５〜７員環を形成してもよい。Ｒ¹¹、Ｒ¹²及びＲ¹³はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、アリールアルキル基を表し、これらの基は、置換基を有していてもよい。ａは０〜３の整数を示し、ｂは０又は１を示す。Ｒ^Aは前記と同じ意味を表す。Ｒ^Aが複数存在する場合、それらは、同一であっても異なっていてもよい。］

[In General Formula (2), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an unsubstituted or substituted arylene group or an unsubstituted or substituted divalent aromatic heterocyclic group] Alternatively, it represents a divalent group in which two or more identical or different groups selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group are linked. Ar ¹ and Ar ² , and Ar ² and Ar ³ may be directly bonded (ie, via a single bond), or —O—, —S—, —C (═O) —, —C ( = O) -O -, - N (R a) -, - C (= O) -N (R a) - or -C (R ^a) ₂ - a bond to via the group represented, 5 A ~ 7 membered ring may be formed. R ¹¹ , R ¹² and R ¹³ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an arylalkyl group, and these groups have a substituent. May be. a represents an integer of 0 to 3, and b represents 0 or 1. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. ]

  Second, the present invention provides a method for producing the polymer compound, the method comprising polymerizing a compound represented by the following general formula (3M) and a compound represented by the following general formula (2M) A method for producing a compound is provided.

［一般式（３Ｍ）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹及びＲ¹⁰はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は置換基を有していてもよい。Ｒ^Aは、アルキル基、アリール基、又は、１価の芳香族複素環基を示し、これらの基は置換基を有していてもよい。Ａｒ⁵及びＡｒ⁶はそれぞれ独立に、非置換若しくは置換のアリーレン基、又は、非置換若しくは置換の２価の芳香族複素環基を表すか、或いは、アリーレン基及び２価の芳香族複素環基からなる群より選ばれる同一又は異なる基が２以上連結した２価の基を表す。Ｚ¹及びＺ²はそれぞれ独立に、置換基Ａ群及び置換基Ｂ群からなる群から選ばれるいずれかの基を示す。］
＜置換基Ａ群＞
塩素原子、臭素原子、ヨウ素原子、−Ｏ−Ｓ（＝Ｏ）₂Ｒ¹⁶（Ｒ¹⁶は、アルキル基、又は、アルキル基、アルコキシ基、ニトロ基、フッ素原子若しくはシアノ基で置換されていてもよいアリール基を示す。）で表される基。
＜置換基Ｂ群＞
−Ｂ（ＯＲ¹⁷）₂（Ｒ¹⁷は、水素原子又はアルキル基を示し、２個存在するＲ¹⁷は、同一でも異なっていてもよく、互いに結合して環を形成していてもよい。）で表される基、−ＢＦ₄Ｑ¹（Ｑ¹は、リチウム、ナトリウム、カリウム、ルビジウム又はセシウムの１価の陽イオンを示す。）で表される基、−ＭｇＹ¹（Ｙ¹は、塩素原子、臭素原子又はヨウ素原子を示す。）で表される基、−ＺｎＹ²（Ｙ²は、塩素原子、臭素原子又はヨウ素原子を示す。）で表される基、−Ｓｎ（Ｒ¹⁸）₃（Ｒ¹⁸は、水素原子又はアルキル基を示し、３個存在するＲ¹⁸は、同一でも異なっていてもよく、互いに結合して環を形成していてもよい。）で表される基。

[In the general formula (3M), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, or an aryl group. A monovalent aromatic heterocyclic group or a group represented by —O—R ^A is shown, and these groups may have a substituent. R ^A represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. Ar ⁵ and Ar ⁶ each independently represent an unsubstituted or substituted arylene group, or an unsubstituted or substituted divalent aromatic heterocyclic group, or an arylene group and a divalent aromatic heterocyclic group Represents a divalent group in which two or more identical or different groups selected from the group consisting of Z ¹ and Z ² each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. ]
<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ¹⁶ (R ¹⁶ may be substituted with an alkyl group, an alkyl group, an alkoxy group, a nitro group, a fluorine atom or a cyano group. Represents a good aryl group.)
<Substituent group B>
—B (OR ¹⁷ ) ₂ (R ¹⁷ represents a hydrogen atom or an alkyl group, and two R ^{17 s} may be the same or different and may be bonded to each other to form a ring.) A group represented by the formula: —BF ₄ Q ¹ (Q ¹ is a monovalent cation of lithium, sodium, potassium, rubidium or cesium), —MgY ¹ (Y ¹ is chlorine A group represented by —ZnY ² (Y ² represents a chlorine atom, a bromine atom or an iodine atom), —Sn (R ¹⁸ ) ₃ (R ¹⁸ represents a hydrogen atom or an alkyl group, and three R ^{18 s} may be the same or different, and may be bonded to each other to form a ring).

［一般式（２Ｍ）中、Ａｒ¹、Ａｒ²、Ａｒ³及びＡｒ⁴はそれぞれ独立に、非置換若しくは置換のアリーレン基、又は、非置換若しくは置換の２価の芳香族複素環基を表すか、或いは、アリーレン基及び２価の芳香族複素環基からなる群より選ばれる同一又は異なる基が２以上連結した２価の基を表す。Ｒ¹¹、Ｒ¹²及びＲ¹³はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、アリールアルキル基を表し、これらの基は、置換基を有していてもよい。ａは０〜３の整数を示し、ｂは０又は１を示す。Ｚ³及びＺ⁴はそれぞれ独立に、前記置換基Ａ群及び前記置換基Ｂ群からなる群から選ばれるいずれかの基を示す。］

[In General Formula (2M), each of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ independently represents an unsubstituted or substituted arylene group or an unsubstituted or substituted divalent aromatic heterocyclic group Alternatively, it represents a divalent group in which two or more identical or different groups selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group are linked. R ¹¹ , R ¹² and R ¹³ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an arylalkyl group, and these groups have a substituent. May be. a represents an integer of 0 to 3, and b represents 0 or 1. Z ³ and Z ⁴ each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. ]

  Thirdly, the present invention provides a compound represented by the following general formula (3M-1).

［一般式（３Ｍ−１）中、Ｒ¹、Ｒ²、Ｒ⁵、Ｒ⁶、Ｒ⁷及びＲ¹⁰はそれぞれ独立に、水素原子、アルキル基、アリール基、１価の芳香族複素環基、又は、−Ｏ−Ｒ^Aで表される基を示し、これらの基は、置換基を有していてもよい。Ｒ^Aは前記と同じ意味を表す。Ｒ^Aが複数存在する場合、それらは、同一であっても異なっていてもよい。Ｒ^3a、Ｒ^4a、Ｒ^8a及びＲ^9aは、下記要件（Ａ）又は（Ｂ）を満たす基である。Ａｒ⁵及びＡｒ⁶はそれぞれ独立に、非置換若しくは置換のアリーレン基、又は、非置換若しくは置換の２価の芳香族複素環基を表すか、或いは、アリーレン基及び２価の芳香族複素環基からなる群より選ばれる同一又は異なる基が２以上連結した２価の基を表す。Ｚ¹及びＺ²はそれぞれ独立に、前記置換基Ａ群及び前記置換基Ｂ群からなる群から選ばれるいずれかの基を示す。］
＜要件（Ａ）＞
Ｒ^3a、Ｒ^4a、Ｒ^8a及びＲ^9aのいずれかが、非置換若しくは置換のアリール基、又は、非置換若しくは置換の１価の芳香族複素環基であり、その残りが、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアリール基、非置換若しくは置換の１価の芳香族複素環基、又は、非置換若しくは置換の−Ｏ−Ｒ^Aで表される基である。
＜要件（Ｂ）＞
Ｒ^3a及びＲ^4aの一方と、Ｒ^8a及びＲ^9aの一方とが、非置換若しくは置換のアリール基、又は、非置換若しくは置換の１価の芳香族複素環基であり、Ｒ^3a及びＲ^4aの残りと、Ｒ^8a及びＲ^9aの残りとが、水素原子、非置換若しくは置換のアルキル基、非置換若しくは置換のアリール基、非置換若しくは置換の１価の芳香族複素環基、又は、非置換若しくは置換の−Ｏ−Ｒ^Aで表される基である。

[In General Formula (3M-1), R ¹ , R ² , R ⁵ , R ⁶ , R ⁷ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, or represents a group represented by -O-R ^a, these groups may have a substituent. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. R ^3a , R ^4a , R ^8a and R ^9a are groups satisfying the following requirement (A) or (B). Ar ⁵ and Ar ⁶ each independently represent an unsubstituted or substituted arylene group, or an unsubstituted or substituted divalent aromatic heterocyclic group, or an arylene group and a divalent aromatic heterocyclic group Represents a divalent group in which two or more identical or different groups selected from the group consisting of Z ¹ and Z ² each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. ]
<Requirement (A)>
Any of R ^3a , R ^4a , R ^8a and R ^9a is an unsubstituted or substituted aryl group or an unsubstituted or substituted monovalent aromatic heterocyclic group, and the remainder is a hydrogen atom, non- A substituted or substituted alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted monovalent aromatic heterocyclic group, or a group represented by unsubstituted or substituted —O—R ^A.
<Requirement (B)>
One of R ^3a and R ^4a and one of R ^8a and R ^9a are an unsubstituted or substituted aryl group or an unsubstituted or substituted monovalent aromatic heterocyclic group, and R ^3a and R ^4a And the remainder of R ^8a and R ^9a are a hydrogen atom, an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, an unsubstituted or substituted monovalent aromatic heterocyclic group, or non- It is a group represented by a substituted or substituted —O—R ^A.

  Fourthly, the present invention provides a polymer composition containing the polymer compound and at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material.

  Fifthly, the present invention provides a solution containing the polymer compound and a solvent.

  Sixth, the present invention provides an organic thin film containing the polymer compound or the polymer composition.

  Seventhly, this invention provides a light emitting element provided with the said organic thin film.

  Eighthly, the present invention provides a planar light source and a display device comprising the light emitting element.

  ADVANTAGE OF THE INVENTION According to this invention, the high molecular compound useful for manufacture of the light emitting element which is excellent in maximum luminous efficiency can be provided. In addition, a polymer composition, a solution, an organic thin film, an organic semiconductor element, a light-emitting element, a planar light source, and a display device including the polymer compound can be provided. Furthermore, the manufacturing method of this high molecular compound, the compound useful for manufacture of this high molecular compound, and its manufacturing method can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  In the present specification, the “structural unit” means a unit structure present in one or more polymer compounds. The “structural unit” is preferably contained in the polymer compound as a “repeating unit” (that is, a unit structure existing two or more in the polymer compound). The “n-valent aromatic heterocyclic group” means an atomic group obtained by removing n hydrogen atoms directly bonded to an aromatic ring from an aromatic heterocyclic compound, and has a condensed ring structure Contains groups. “Heterocyclic compound” means not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, a boron atom, a silicon atom, etc. as atoms constituting a ring among organic compounds having a cyclic structure. The compound containing the hetero atom of these is meant. “Aromatic heterocyclic compound” means oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole, etc. A heterocyclic compound containing a heteroatom, wherein the heterocyclic ring itself is aromatic, and a heterocyclic ring containing a heteroatom such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, benzopyran itself is aromatic It means a compound in which an aromatic ring is condensed to the heterocyclic ring even if it does not show a family property. The “n-valent condensed aromatic heterocyclic group” represents a group having a condensed ring in the “n-valent aromatic heterocyclic group”.

  In the present specification, in the structural formula, Me represents a methyl group, Et represents an ethyl group, and t-Bu represents a tert-butyl group.

<Polymer compound>
[First structural unit]
The polymer compound according to the present invention includes a structural unit represented by the general formula (1) (hereinafter referred to as “first structural unit”). This 1st structural unit may be contained in the high molecular compound only by 1 type, or may be contained 2 or more types.

In the general formula (1), the alkyl group in R ^{1 to} R ¹⁰ may be linear, branched or cyclic, and usually has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms. The carbon number does not include the carbon number of the substituent. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isoamyl, hexyl, cyclohexyl, heptyl, octyl, and 2-ethylhexyl. Group, nonyl group, decyl group, 3,7-dimethyloctyl group, dodecyl group and the like. The hydrogen atom in the alkyl group is an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , a group represented by —S—R ^A , or —C (═O) —R. ^The group represented by ^A , the group represented by —C (═O) —O—R ^A , a cyano group or a fluorine atom may be substituted. Examples of the alkyl group substituted with a fluorine atom include a trifluoromethyl group, a pentafluoroethyl group, a perfluorobutyl group, a perfluorohexyl group, and a perfluorooctyl group.

The group represented by —S—R ^A may be linear, branched or cyclic, and examples thereof include an alkylthio group having usually 1 to 20 carbon atoms and an arylthio group having usually 6 to 60 carbon atoms, The same applies hereinafter.

The group represented by -C (= O) -R ^A may be linear, branched or cyclic, and is usually an alkylcarbonyl group having 1 to 20 carbon atoms, or an aryl having 6 to 60 carbon atoms. Examples thereof include a carbonyl group, and the same applies hereinafter.

The group represented by —C (═O) —O—R ^A may be linear, branched or cyclic, and is usually an alkyloxycarbonyl group having 1 to 20 carbon atoms, and usually 6 to 6 carbon atoms. 60 aryloxycarbonyl groups are exemplified, and the same applies hereinafter.

The group represented by —N (R ^A ) ₂ is substituted with two groups selected from the group consisting of an alkyl group having 1 to 20 carbon atoms and an aryl group having usually 6 to 60 carbon atoms. The same applies hereinafter.

In the general formula (1), the aryl group in R ^{1 to} R ¹⁰ is an atomic group obtained by removing one hydrogen atom directly bonded to an aromatic ring from an aromatic hydrocarbon, and includes a group having a condensed ring. The aryl group usually has 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms, more preferably 6 to 20 carbon atoms, and still more preferably 6 to 14 carbon atoms. The carbon number does not include the carbon number of the substituent. Examples of the aryl group include phenyl group, 1-naphthyl group, 2-naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group, 1-tetracenyl group, 2-tetracenyl group, 5-tetracenyl group, 1 -Pyrenyl group, 2-pyrenyl group, 4-pyrenyl group, 2-perylenyl group, 3-perylenyl group, 2-fluorenyl group, 3-fluorenyl group, 4-fluorenyl group, 1-biphenylyl group, 2-biphenylyl group, 2 -Phenanthrenyl group, 9-phenanthrenyl group, 6-chrycenyl group, 1-coronenyl group and the like can be mentioned. The hydrogen atom in the aryl group is an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , a group represented by —S—R ^A , or —C (═O ) ^A group represented by -R ^A , a group represented by -C (= O) -O-R ^A , a cyano group or a fluorine atom.

In the general formula (1), the monovalent aromatic heterocyclic group in R ^{1 to} R ¹⁰ usually has 3 to 60 carbon atoms, preferably 3 to 20 carbon atoms. The carbon number does not include the carbon number of the substituent. Examples of the monovalent aromatic heterocyclic group include 1,3,4-oxadiazol-2-yl group, 1,3,4-thiadiazol-2-yl group, 2-thiazolyl group, 2-oxazolyl group, 2-thienyl group, 2-pyrrolyl group, 2-furyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazinyl group, 2-pyrimidinyl group, 2-triazinyl group, 3-pyridazinyl group, 5-quinolyl group, 5-isoquinolyl group, 2-carbazolyl group, 3-carbazolyl group, 2-phenoxazinyl group, 3-phenoxazinyl group, 2-phenothiazinyl group, 3-phenothiazinyl group and the like can be mentioned. The hydrogen atom in the monovalent aromatic heterocyclic group is an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , or a group represented by —S—R ^A. , -C (= O) -R ^A , a group represented by -C (= O) -O-R ^A , a cyano group, or a fluorine atom.

Examples of the alkyl group, aryl group and monovalent aromatic heterocyclic group in R ^A include the same groups as those in R ¹ described above.

In the general formula (1), as the group represented by —O—R ^A in R ^{1 to} R ¹⁰ , when R ^A is an alkyl group, an alkoxy group having a linear, branched or cyclic alkyl group is Can be mentioned. The alkoxy group usually has 1 to 20 carbon atoms. Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, nonyloxy group, decyloxy group, and 3,7-dimethyl. Octyloxy group, dodecyloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyloxy group, perfluorooctyloxy group, methoxymethyloxy group, 2-methoxyethyloxy group, 2-ethoxy An ethyloxy group etc. are mentioned.

In the general formula (1), examples of the group represented by —O—R ^A in R ^{1 to} R ¹⁰ include an aryloxy group having usually 6 to 60 carbon atoms when R ^A is an aryl group. . Examples of the aryl group moiety include the same aryl groups represented by R ¹ described above. The aryloxy group is a phenoxy group, C ₁ -C ₁₂ alkoxy phenoxy group ( "C ₁ -C ₁₂ alkoxy" means that the carbon number of the alkoxy moiety is 1 to 12, and so forth.) , C ₁ -C ₁₂ alkylphenoxy group (“C ₁ -C ₁₂ alkyl” indicates that the alkyl moiety has 1 to 12 carbon atoms, the same shall apply hereinafter), 1-naphthyloxy group, 2- A naphthyloxy group, a pentafluorophenyloxy group, etc. are mentioned.

In the general formula (1), the group represented by —O—R ^A in R ^{1 to} R ¹⁰ has a carbon number of usually 3 to 60 when R ^A is a monovalent aromatic heterocyclic group. Yes, preferably 3-20 groups. Examples of the monovalent aromatic heterocyclic group include the same monovalent aromatic heterocyclic groups as those described above for R ¹ .

In the general formula (1), R ^{1 to} R ¹⁰ are preferably a hydrogen atom, an alkyl group, or an aryl group because the stability of the polymer compound is improved.

In the general formula (1), since the luminous efficiency is improved, any one of R ³ , R ⁴ , R ⁸ and R ⁹ is an unsubstituted or substituted aryl group, or an unsubstituted or substituted monovalent fragrance. A heterocyclic group, or one of R ³ and R ⁴ and one of R ⁸ and R ⁹ is an unsubstituted or substituted aryl group, or an unsubstituted or substituted monovalent aromatic heterocyclic group It is preferably a cyclic group, and one of R ³ and R ⁴ and one of R ⁸ and R ⁹ are more preferably unsubstituted or substituted aryl groups.

  As the structural unit represented by the general formula (1), structural units represented by the following formulas (1-001) to (1-096) are preferable.

  The first structural unit is preferably a structural unit represented by the following general formula (3) because monomer synthesis is facilitated.

［一般式（３）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ａｒ⁵及びＡｒ⁶はそれぞれ独立に、前記と同じ意味を表す。］

[In general formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , Ar ⁵ and Ar ⁶ are each independently Represents the same meaning. ]

In the general formulas (1) and (3), Ar ⁵ and Ar ⁶ are excellent in durability, and are preferably unsubstituted or substituted arylene groups. The following formulas (5′-001) to (5′-) The group represented by formula (5′-002) and the group represented by formula (5′-002) are more preferable in consideration of the balance between durability and ease of monomer synthesis. And a group represented by the formula (5′-010) is more preferable, and considering only ease of monomer synthesis, groups represented by the formulas (5′-001) to (5′-003) (that is, An unsubstituted or substituted phenylene group) is more preferable.

［式（５’−００１）〜（５’−０１１）中、Ｒは、水素原子、アルキル基、アリール基、１価の芳香族複素環基、−Ｏ−Ｒ^Aで表される基、−Ｓ−Ｒ^Aで表される基、−Ｃ（＝Ｏ）−Ｒ^Aで表される基、−Ｃ（＝Ｏ）−Ｏ−Ｒ^Aで表される基、シアノ基又はフッ素原子を示し、Ｒ^aは、アルキル基、アリール基、又は、１価の芳香族複素環基を示す。複数存在するＲは同一でも異なっていてもよい。複数存在するＲ^aは同一でも異なっていてもよい。Ｒ^Aは前記と同じ意味を表す。Ｒ^Aが複数存在する場合、それらは、同一であっても異なっていてもよい。］

[In the formulas (5′-001) to (5′-011), R represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , — ^A group represented by S—R ^A , a group represented by —C (═O) —R ^A , a group represented by —C (═O) —O—R ^A , a cyano group or a fluorine atom; R ^a represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group. A plurality of R may be the same or different. A plurality of R ^a may be the same or different. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. ]

[Second structural unit]
The polymer compound according to the present invention includes a structural unit represented by the general formula (2) (hereinafter referred to as “second structural unit”). This 2nd structural unit may be contained in the high molecular compound only by 1 type, or may be contained 2 or more types.

  In the general formula (2), a = b = 0 is preferable from the viewpoint of durability, and a = 1 is preferable, and b = 0 is preferable from the viewpoint of luminous efficiency.

In the general formula (2), the unsubstituted or substituted arylene groups represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ are represented by the above formulas (5′-001) to (5′-011). Group to be used.

In the general formula (2), as the divalent aromatic heterocyclic group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ , the stability of the polymer compound according to the present invention is improved. A divalent fused aromatic heterocyclic group is preferred. The divalent condensed aromatic heterocyclic group usually has 8 to 60 carbon atoms, preferably 8 to 20 carbon atoms. The carbon number does not include the carbon number of the substituent.

Examples of the divalent condensed aromatic heterocyclic group include quinolinediyl groups such as quinoline-2,6-diyl group (formula (2-101)); isoquinoline-1,4-diyl group (formula (2-102)) Isoquinolinediyl group such as quinoxaline-5,8-diyl group (formula (2-103)), etc .; carbazole-3,6-diyl group (formula (2-104)), carbazole-2,7 A carbazole diyl group such as a diyl group (formula (2-105)); a dibenzofuran-4,7-diyl group (formula (2-106)), a dibenzofuran-3,8-diyl group (formula (2-107)) A dibenzothiophene diyl group such as a dibenzothiophene-4,7-diyl group (formula (2-108)) and a dibenzothiophene-3,8-diyl group (formula (2-109)); Benzosilol-4,7-diyl group (formula (2-110)), dibenzosilol-3,8-diyl group (formula (2-111)) and the like; phenoxazine-3,7-diyl group (Formula (2-112)), phenoxazine-2,8-diyl group (formula (2-113)) and other phenoxazinediyl groups; phenothiazine-3,7-diyl group (formula (2-114)), A phenothiazine diyl group such as a phenothiazine-2,8-diyl group (formula (2-115)); a dihydroacridine diyl group such as a dihydroacridine-2,7-diyl group (formula (2-116)); -117)) and the like. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different.

［式（２−１０１）〜（２−１１７）中、Ｒ及びＲ^aは、前記と同じ意味を表す。］

[In formulas (2-101) to (2-117), R and R ^a represent the same meaning as described above. ]

In the general formula (2), “unsubstituted or substituted arylene group”, “unsubstituted or substituted divalent aromatic heterocyclic group” in Ar ¹ , Ar ² , Ar ³ and Ar ⁴ , and “arylene” The “divalent group in which two or more identical or different groups selected from the group consisting of a group and a divalent aromatic heterocyclic group are linked” usually has 4 to 60 carbon atoms, preferably 12 to 60 carbon atoms. is there. The carbon number does not include the carbon number of the substituent.

  Examples of the divalent group in which two or more identical or different groups selected from the group consisting of the arylene group and the divalent aromatic heterocyclic group are linked include those represented by the following formulas (2-201) to (2-208). And the group represented.

［式（２−２０１）〜（２−２０８）中、Ｒは前記と同じ意味を表す。］

[In formulas (2-201) to (2-208), R represents the same meaning as described above. ]

In the general formula (2), as the group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ , an unsubstituted or substituted arylene group improves the stability of the polymer compound, and A light emitting element using a polymer compound is preferable because it has more excellent luminous efficiency.

In the general formula (2), Ar ² is preferably an unsubstituted or substituted phenylene group in consideration of the balance between luminous efficiency and durability, and in view of durability alone, unsubstituted or substituted biphenyl-4, A 4′-diyl group is preferred.

In the general formula (2), R ¹¹ , R ¹² , and R ^{13 each} represent an alkyl group, an aryl group, or a monovalent aromatic complex because the light emitting element using the polymer compound has better luminous efficiency. A cyclic group is preferred, and an aryl group is more preferred. The alkyl group, aryl group and monovalent aromatic heterocyclic group represented by R ¹¹ , R ¹² and R ¹³ have the same meaning as described above. The arylalkyl group represented by R ¹¹ , R ¹² and R ¹³ is a group in which one of the hydrogen atoms in the alkyl group is substituted with the aryl group.

  As the structural unit represented by the general formula (2), structural units represented by the following formulas (2-001) to (2-005) are preferable.

［式（２−００１）〜（２−００５）中、Ｒ及びＲ^aは、前記と同じ意味を表す。］

[In the formulas (2-001) to (2-005), R and R ^a have the same meaning as described above. ]

R ^a in the general formula (2-004) is preferably an alkyl group or an aryl group because it is excellent in solubility and durability.

  As the structural unit represented by the general formula (2), the stability of the polymer compound according to the present invention is improved, and the light emission efficiency of the light emitting device using the polymer compound is further improved. A structural unit in which R in (2-001) to (2-005) is a hydrogen atom, an alkyl group, an aryl group or a monovalent aromatic heterocyclic group is preferred, and a structural unit which is a hydrogen atom or an alkyl group is more preferred. preferable.

[3rd structural unit], [4th structural unit]
Since the polymer compound according to the present invention can reduce the driving voltage, the following general formula (4):

［一般式（４）中、Ｒ¹⁴及びＲ¹⁵はそれぞれ独立に、非置換若しくは置換のアルキル基、非置換若しくは置換のアリール基、又は、非置換若しくは置換の１価の芳香族複素環基を示す。］
で表される構成単位（以下、「第３構成単位」と言う。）、及び／又は、下記一般式（５）：

[In General Formula (4), each of R ¹⁴ and R ¹⁵ independently represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted monovalent aromatic heterocyclic group. Show. ]
(Hereinafter referred to as “third structural unit”) and / or the following general formula (5):

［一般式（５）中、Ａｒ⁷は、非置換若しくは置換のアリーレン基、又は、非置換若しくは置換の２価の芳香族複素環基を表すか、或いは、アリーレン基及び２価の芳香族複素環基からなる群より選ばれる同一又は異なる基が２以上連結した２価の基を表す。］
で表される構成単位（以下、「第４構成単位」と言う。なお、第４構成単位は、第１構成単位及び第３構成単位とは異なる。）を含むことが好ましく、第３構成単位を含むことがより好ましい。これらの第３構成単位、第４構成単位は、各々、高分子化合物中に、一種のみ含まれていても二種以上含まれていてもよい。

[In the general formula (5), Ar ⁷ represents an unsubstituted or substituted arylene group, an unsubstituted or substituted divalent aromatic heterocyclic group, or an arylene group and a divalent aromatic heterocyclic group. It represents a divalent group in which two or more identical or different groups selected from the group consisting of cyclic groups are linked. ]
(Hereinafter referred to as “fourth structural unit”. Note that the fourth structural unit is different from the first structural unit and the third structural unit). It is more preferable to contain. Each of these third structural unit and fourth structural unit may be contained in the polymer compound alone or in a combination of two or more.

In the general formula (4), the unsubstituted alkyl group represented by R ¹⁴ and R ¹⁵ includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, and a pentyl group. 2-methylbutyl group, isoamyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, dodecyl group and the like.

In the general formula (4), examples of the unsubstituted aryl group represented by R ¹⁴ and R ¹⁵ include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group.

In the general formula (4), the monovalent aromatic heterocyclic group represented by R ¹⁴ and R ¹⁵ is the same as described and exemplified as the monovalent aromatic heterocyclic group in R ¹ .

In the general formula (4), as R ¹⁴ and R ¹⁵ , since the heat resistance and solubility of the polymer compound according to the present invention are improved, a substituted or unsubstituted aryl group, or substituted or unsubstituted An alkyl group is preferred, more preferably an unsubstituted aryl group; an aryl group substituted with an alkyl group, an alkoxy group, an aryl group or a substituted amino group; an unsubstituted alkyl group, or an alkyl group, an alkoxy group, an aryl group Or an alkyl group substituted with a substituted amino group, and more preferably a 4-tolyl group, 4-butylphenyl group, 4-tert-butylphenyl group, 4-hexylphenyl group, 4-octylphenyl group, 4- (2-ethylhexyl) phenyl group, 4- (3,7-dimethyloctyl) phenyl group, 3-tolyl group, 3-butylphenyl group, 3-te t-butylphenyl group, 3-hexylphenyl group, 3-octylphenyl group, 3- (2-ethylhexyl) phenyl group, 3- (3,7-dimethyloctyl) phenyl group, 3,5-dimethylphenyl group, 3 , 5-Di- (tert-butyl) phenyl group, 3,5-dihexylphenyl group, 3,5-dioctylphenyl group, 3,4-dihexylphenyl group, 3,4-dioctylphenyl group, 4-hexyloxyphenyl Group, 4-octyloxyphenyl group, 4- (2-ethoxy) ethoxyphenyl group, 4- (4′-tert-butylbiphenylyl) group, 9,9-dihexylfluoren-2-yl group, 9,9- Dioctylfluoren-2-yl group, pentyl group, hexyl group, 2-ethylhexyl group, octyl group, or 3,7-dimethyloctyl group That.

In the general formula (5), Ar ⁷ is an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , a group represented by —S—R ^A , From a group represented by C (═O) —R ^A , a group represented by —C (═O) —O—R ^A , a group represented by —N (R ^A ) ₂ , a cyano group and a fluorine atom. One or more substituents selected from the group consisting of: R ^A represents the same meaning as described above. When a plurality of R ^A are present, they may be the same or different.

In the general formula (5), the arylene group represented by Ar ⁷ generally has 6 to 60 carbon atoms, preferably 6 to 48 carbon atoms, more preferably 6 to 30 carbon atoms, still more preferably. 6-14. The carbon number does not include the carbon number of the substituent. Examples of the arylene group include 1,4-phenylene group (formula (5-001)), 1,3-phenylene group (formula (5-002)), and 1,2-phenylene group (formula (5-003)). Naphthylene-1,4-diyl group (formula (5-004)), naphthalene-1,5-diyl group (formula (5-005)), naphthalene-2,6-diyl group (formula ( 5-006)), naphthalenediyl groups such as naphthalene-2,7-diyl group (formula (5-007)); 4,5-dihydrophenanthrene-2,7-diyl group (formula (5-008)) and the like Dihydrophenanthrenediyl group of fluorene-3,6-diyl group (formula (5-009)); benzofluorenediyl group represented by formulas (5-010) to (5-012); anthracene-2,6 A diyl group (formula (5-013)), a Like anthracene-diyl groups such as anthracene-9,10-diyl group (formula (5-014)) and the like. The hydrogen atom in these arylene groups is an alkyl group, an aryl group, a monovalent aromatic heterocyclic group, a group represented by —O—R ^A , a group represented by —S—R ^A , —C (= O) a group represented by -R ^A , a group represented by -C (= O) -O-R ^A , a group represented by -N (R ^A ) ₂ , a cyano group or a fluorine atom. May be.

［式（５−００１）〜（５−０１４）中、Ｒ及びＲ^aは、前記と同じ意味を表す。］

[In the formulas (5-001) to (5-014), R and R ^a have the same meaning as described above. ]

In the general formula (5), the divalent aromatic heterocyclic group represented by Ar ⁷ is a divalent aromatic heterocyclic group represented by the above-mentioned Ar ¹ , Ar ² , Ar ³ and Ar ^4. This is the same as described and exemplified as.

In the general formula (5), “unsubstituted or substituted arylene group”, “unsubstituted or substituted divalent aromatic heterocyclic group” represented by Ar ⁷ , and “arylene group and divalent aromatic” “A divalent group in which two or more identical or different groups selected from the group consisting of group heterocyclic groups are linked” has been explained and exemplified as the group represented by Ar ¹ , Ar ² , Ar ³ and Ar ⁴ described above. It is the same as that.

In the general formula (5), as Ar ⁷ , the stability of the polymer compound according to the present invention is improved, and the luminous efficiency of the light emitting device using the polymer compound is further improved. (5-001), (5-002), (5-008), (5-009), (5-010), (5-011), (5-012), (5-013), or Group represented by (5-014); carbazole-3,6-diyl group, carbazole-2,7-diyl group, dibenzofuran-4,7-diyl group, dibenzofuran-3,8-diyl group, dibenzothiophene- 4,7-diyl group, dibenzothiophene-3,8-diyl group, dibenzosilol-4,7-diyl group, dibenzosilol-3,8-diyl group, phenoxazine-3,7-diyl group, phenothiazine-3 , 7-diyl group, Hydro acridine-2,7-diyl group.

In the general formula (5), as Ar ⁷ , the stability of the polymer compound according to the present invention is improved, and the luminous efficiency of the light emitting device using the polymer compound is further improved. (5-001), (5-002), (5-008), (5-009), (5-010), (5-011), (5-012), (5-013), or A group in which R in the group represented by (5-014) is a hydrogen atom, an alkyl group, an aryl group or a monovalent aromatic heterocyclic group is preferred, and a group which is a hydrogen atom or an alkyl group is more preferred.

In the general formula (5), Ar ⁷ is excellent in heat resistance, so the above formulas (5-001), (5-002), (5-008), (5-009), (5-010) , (5-011), (5-012), (5-013), or a group represented by (5-014), R ^a is preferably an alkyl group or an aryl group.

  Since the polymer compound according to the present invention has excellent heat resistance and the light emitting device obtained using the polymer compound has excellent luminous efficiency, the driving voltage of the light emitting device can be lowered. It is preferable that

[Relationship between each structural unit]
When the polymer compound according to the present invention contains the first constitutional unit, the second constitutional unit, and the third constitutional unit because the light emission efficiency of a light-emitting device obtained using the polymer compound is improved. The content of the first structural unit is 0.1 to 20 mol% with respect to the total content of the first structural unit, the second structural unit, and the third structural unit, and The content of the second structural unit is preferably 0.1 to 30 mol% with respect to the total content of the first structural unit, the second structural unit, and the third structural unit.

  In the polymer compound according to the present invention, the luminous efficiency of the light-emitting element obtained using the polymer compound is further improved, so that the first structural unit, the second structural unit, the third structural unit, and the first When four structural units are contained, the content of the first structural unit is based on the total content of the first structural unit, the second structural unit, the third structural unit, and the fourth structural unit. 0.01 to 90 mol% is preferable, 0.1 to 50 mol% is more preferable, 0.1 to 20 mol% is further preferable, and 0.5 to 10 mol% is preferable. Particularly preferably, the content of the second structural unit is 0.01 to the total content of the first structural unit, the second structural unit, the third structural unit, and the fourth structural unit. It is preferably 90 mol%, and is 0.1 to 50 mol% Preparative more preferably, more preferably from 0.1 to 30 mol%, particularly preferably 1 to 10 mol%.

  In the polymer compound according to the present invention, the total content of the first constituent unit, the second constituent unit, the third constituent unit, and the fourth constituent unit is 80% by weight or more based on the total amount of the polymer compound. It is preferable that it is 90% by weight or more.

  Examples of the polymer compound according to the present invention include polymer compounds P1 to P19 obtained by combining the first structural unit, the second structural unit, the third structural unit, and the fourth structural unit. The total content of the first structural unit, the second structural unit, the third structural unit, and the fourth structural unit is 100% by weight based on the total amount of the polymer compound. In Tables 1 to 3, it is meant that the structural unit with “-” is not present in the polymer compound.

  In the polymer compound according to the present invention, if a group that is active in the polymerization reaction remains at the end of the molecular chain, the light emitting characteristics and life of a light-emitting device produced using the polymer compound may be reduced. Therefore, the molecular chain terminal is preferably a stable group such as an aryl group or a monovalent aromatic heterocyclic group.

  The polymer compound of the present invention may be any copolymer, and may be any of a block copolymer, a random copolymer, an alternating copolymer, a graft copolymer, and the like.

  The polymer compound according to the present invention is useful as a light-emitting material, a charge transport material, and the like. When used, the polymer compound may be used alone or in combination with other compounds and used as a polymer composition described later. May be.

The number average molecular weight (Mn) in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”) of the polymer compound according to the present invention is usually 1 × 10 ³ to 1 × 10 ⁸ , preferably Is 1 × 10 ⁴ to 1 × 10 ⁶ . Moreover, the weight average molecular weight (Mw) in terms of polystyrene of the polymer compound according to the present invention is usually 1 × 10 ³ to 1 × 10 ⁸ , the film formability is improved, and the polymer compound is obtained from the polymer compound. Since the luminous efficiency of the obtained light emitting device becomes better, it is preferably 1 × 10 ^{4 to} 5 × 10 ⁶ , more preferably 3 × 10 ⁴ to 1 × 10 ⁶ , still more preferably 5 × 10 ⁴ to 5 × 10 ⁵ .

  Since the durability against various processes for producing a light emitting element or the like, the stability due to heat generation during driving of the light emitting element, and the heat resistance are improved, the glass transition temperature of the polymer compound according to the present invention is 70. It is preferable that the temperature is higher than 100 ° C., more preferably higher than 100 ° C.

  The polymer compound according to the present invention usually emits fluorescence in a solid state and is useful as a material for a light emitting device. A light-emitting element using this polymer compound is a high-performance light-emitting element that can be driven with high luminous efficiency. Therefore, the light emitting element is useful for a display device such as a backlight of a liquid crystal display, a curved or flat light source for illumination, a segment type display element, a dot matrix flat panel display. Furthermore, the polymer compound according to the present invention includes a laser dye, an organic solar cell material, an organic semiconductor for an organic transistor, a conductive thin film, a conductive thin film material such as an organic semiconductor thin film, and a light emitting property that emits fluorescence or phosphorescence. It can also be used as a thin film material.

<Method for producing polymer compound>
The polymer compound according to the present invention may be produced by any production method. Hereinafter, a representative method for producing a polymer compound will be described.

  When the polymer compound according to the present invention is a polymer compound containing a first structural unit (particularly the structural unit represented by the general formula (3)) and a second structural unit, It can be produced by a method comprising a step of polymerizing a compound represented by the formula (1M) (particularly a compound represented by the general formula (3M)) and a compound represented by the general formula (2M).

［一般式（１Ｍ）中、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰、Ａｒ⁵、Ａｒ⁶、ａａ及びｂｂは、前記と同じ意味を表す。Ｚ¹⁰及びＺ¹¹はそれぞれ独立に、置換基Ａ群及び置換基Ｂ群からなる群から選ばれるいずれかの基を示す。］

[In the general formula (1M), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , Ar ⁵ , Ar ⁶ , aa and bb are Means the same. Z ¹⁰ and Z ¹¹ each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. ]

Z ¹⁰ and Z ¹¹ in the general formula (1M), Z ¹ and Z ² in the general formula (3M), and Z ³ and Z ⁴ in the general formula (2M) are each independently a substituent A. Represents any group selected from the group consisting of the group and the substituent B group, but since the synthesis of the monomer and the polymer compound is easy, Z ¹⁰ and Z ¹¹ are the same selected from the group consisting of the substituent A group Or the same group selected from the group consisting of the substituent group B.

<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ¹⁶ (R ¹⁶ may be substituted with an alkyl group, an alkyl group, an alkoxy group, a nitro group, a fluorine atom or a cyano group. Represents a good aryl group.)

<Substituent group B>
—B (OR ¹⁷ ) ₂ (R ¹⁷ represents a hydrogen atom or an alkyl group, and two R ^{17 s} may be the same or different and may be bonded to each other to form a ring.) A group represented by the formula: —BF ₄ Q ¹ (Q ¹ is a monovalent cation of lithium, sodium, potassium, rubidium or cesium), —MgY ¹ (Y ¹ is chlorine A group represented by —ZnY ² (Y ² represents a chlorine atom, a bromine atom or an iodine atom), —Sn (R ¹⁸ ) ₃ (R ¹⁸ represents a hydrogen atom or an alkyl group, and three R ^{18 s} may be the same or different, and may be bonded to each other to form a ring).

Examples of the alkyl group represented by R ¹⁶ , R ¹⁷ and R ¹⁸ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a pentyl group, a 2-methylbutyl group, and an isoamyl group. Hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, dodecyl group and the like, and these groups may have a substituent. Carbon number of these alkyl groups is 1-20 normally, Preferably it is 1-15, More preferably, it is 1-10.

The aryl group represented by R ¹⁶ is the same as that explained and exemplified as the aryl group represented by R ¹ in the general formula (1), but the synthesis of the polymer compound is facilitated, and Since the reactivity at the time of polymerization becomes high, phenyl group, 4-tolyl group, 4-methoxyphenyl group, 4-nitrophenyl group, 3-nitrophenyl group, 2-nitrophenyl group and 4-trifluoromethylphenyl group preferable.

As the group represented by the formula: —O—S (═O) ₂ R ¹⁶ , methanesulfonyloxy group, trifluoromethanesulfonyloxy group, phenylsulfonyloxy group, 4-methylphenylsulfonyloxy group, 4-trifluoromethyl A phenylsulfonyloxy group etc. are mentioned.

Examples of the group represented by the formula: -B (OR ¹⁷ ) ₂ include groups represented by the following formula.

Formula: The group represented by -BF ₄ Q ^1, -BF ₄ ^- include groups represented by K ^+.

Examples of the group represented by the formula: —Sn (R ¹⁸ ) ₃ include a trimethylstannyl group, a triethylstannyl group, and a tributylstannyl group.

  As the compound represented by the general formula (3M), a compound represented by the general formula (3M-1) is preferable because of excellent luminous efficiency.

  The polymer compound according to the present invention includes the first structural unit (particularly, the structural unit represented by the general formula (3)), the second structural unit, the third structural unit, and / or the fourth structural unit. In the case of a polymer compound containing a structural unit, the polymer compound is a compound represented by the general formula (1M) (particularly a compound represented by the general formula (3M)), A compound represented by the general formula (2M), a compound represented by the following general formula (4M), and / or a compound represented by the following general formula (5M) are dissolved in an organic solvent as necessary. Then, it can be synthesized by a method including a step of copolymerization by a polymerization method such as a known aryl-aryl coupling using an alkali, an appropriate catalyst, or a ligand.

［一般式（４Ｍ）中、Ｒ¹⁴及びＲ¹⁵は、前記と同じ意味を表す。Ｚ⁵及びＺ⁶はそれぞれ独立に、置換基Ａ群及び置換基Ｂ群からなる群から選ばれるいずれかの基を示す。）

[In General Formula (4M), R ¹⁴ and R ¹⁵ represent the same meaning as described above. Z ⁵ and Z ⁶ each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. )

［一般式（５Ｍ）中、Ａｒ⁷は、前記と同じ意味を表す。Ｚ⁷及びＺ⁸はそれぞれ独立に、置換基Ａ群及び置換基Ｂ群からなる群から選ばれるいずれかの基を示す。］

[In the general formula (5M), Ar ⁷ represents the same meaning as described above. Z ⁷ and Z ⁸ each independently represent any group selected from the group consisting of Substituent Group A and Substituent Group B. ]

  The compound represented by the general formula (1M), the compound represented by the general formula (2M), the compound represented by the general formula (4M), and the compound represented by the general formula (5M) are: In addition, those synthesized and isolated in advance may be used, or those synthesized in the reaction system may be used as they are. When the polymer compound according to the present invention is used for a light-emitting device, the purity thereof affects the performance of the light-emitting device. Therefore, the compounds represented by the general formulas (1M) to (5M) are distilled, sublimated and purified. It is preferably purified by a method such as crystallization.

  As a polymerization method, polymerization is performed by Suzuki coupling reaction (Chem. Rev., 95, 2457-2483 (1995)), polymerization by Grignard reaction (Bull. Chem. Soc. Jpn., 51, 2091 (1978)), a method of polymerizing with Ni (0) catalyst (Progress in Polymer Science, 17, 1153-1205, 1992), Still. Examples include a method using a coupling reaction (European Polymer Journal, Vol. 41, pages 2923-2933 (2005)). Among these, from the viewpoint of easy synthesis of raw materials and easy operation of the polymerization reaction, a method of polymerizing by Suzuki coupling reaction and a method of polymerizing by Ni (0) catalyst are preferable, and the structure of the polymer compound From the viewpoint of ease of control, a method of polymerizing by an aryl-aryl cross-coupling reaction such as a Suzuki coupling reaction, a Grignard reaction, or a Stille coupling reaction is preferred, and a reaction of polymerizing by a Suzuki coupling reaction is more preferred.

As the group selected from the group consisting of the substituent group A and the substituent group B, an appropriate group may be selected according to the kind of the polymerization reaction. However, when a method of polymerization by the Suzuki coupling reaction is selected, synthesis is performed. The group selected from the substituent group A is preferably a chlorine atom, bromine atom, or iodine atom, more preferably a bromine atom, and the group selected from the substituent group B is- A group represented by B (OR ¹⁷ ) ₂ is preferred.

  When the Suzuki coupling reaction is selected as the polymerization method, in order to control the molecular weight, the total number of moles of groups selected from the substituent group A possessed by the compounds represented by the general formulas (1M) to (5M) Is preferably 0.95 to 1.05, more preferably 0.98 to 1.02, and preferably 0.99 to 1.09. More preferably, it is 1.01.

  As the catalyst in the polymerization, when polymerizing by Suzuki coupling reaction, palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, palladium acetate such as dichlorobistriphenylphosphine palladium, etc. Transition metal complexes, and complexes in which ligands such as triphenylphosphine, tri-tert-butylphosphine, and tricyclohexylphosphine are coordinated to these transition metal complexes.

  When polymerizing with a Ni (0) catalyst, nickel [tetrakis (triphenylphosphine)], [1,3-bis (diphenylphosphino) propane] dichloronickel, [bis (1,4-cyclooctadiene)] nickel, etc. Transition metal complexes such as nickel complexes, and complexes in which ligands such as triphenylphosphine, tri-tert-butylphosphine, tricyclohexylphosphine, diphenylphosphinopropane, and bipyridyl are coordinated to these transition metal complexes. Can be mentioned.

  As these catalysts, those synthesized in advance may be used, or those prepared in the reaction system may be used as they are. Moreover, these catalysts may be used individually by 1 type, or may use 2 or more types together.

  The amount of the catalyst used may be an effective amount as a catalyst. For example, the amount of the transition metal is generally 0.1% in terms of the number of moles of the transition metal with respect to 100 mol% in total of all compounds serving as monomers in the polymerization reaction. It is 0001-300 mol%, Preferably it is 0.001-50 mol%, More preferably, it is 0.01-20 mol%.

  Moreover, it is preferable to use a base in the polymerization by the Suzuki coupling reaction. This base includes inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, tripotassium phosphate, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, hydroxide Examples include organic bases such as tetraethylammonium and tetrabutylammonium hydroxide.

  The usage-amount of the said base is 50-2000 mol% normally with respect to a total of 100 mol% of all the compounds used as the monomer in a polymerization reaction, Preferably it is 100-1000 mol%.

  The polymerization reaction may be performed in the absence of a solvent or in the presence of a solvent, but is usually performed in the presence of an organic solvent. Here, examples of the organic solvent include toluene, xylene, mesitylene, tetrahydrofuran, 1,4-dioxane, dimethoxyethane, N, N-dimethylacetamide, N, N-dimethylformamide, etc., in order to suppress side reactions. Further, it is desirable to use a solvent that has been subjected to deoxygenation treatment. An organic solvent may be used individually by 1 type, or may use 2 or more types together.

  The amount of the organic solvent used is preferably such an amount that the total concentration of all compounds as monomers in the polymerization reaction is 0.1 to 90% by weight, and 1 to 50% by weight. More preferably, the amount is 2 to 30% by weight.

  The reaction temperature of the polymerization reaction is preferably −100 to 200 ° C., more preferably −80 to 150 ° C., and still more preferably 0 to 120 ° C.

  The reaction time of the polymerization reaction is usually 1 hour or longer, preferably 2 to 500 hours.

In the method for producing a polymer compound according to the present invention, when Z ¹ , Z ² , Z ³ , Z ⁴ , Z ⁵ , Z ⁶ , Z ¹⁰ or Z ¹¹ is a group represented by —MgY ¹ , a polymerization reaction Is preferably carried out under dehydrating conditions.

  In the method for producing a polymer compound according to the present invention, when the polymerization reaction is a Suzuki coupling reaction, the base to be used may be used as an aqueous solution, or water may be used in addition to the organic solvent. Good.

  In the method for producing a polymer compound according to the present invention, a compound represented by the following formula (6) is used as a chain terminator in order to avoid a group active in the polymerization reaction remaining at the terminal of the polymer compound. It is preferable to use it.

［式（６）中、Ａｒ⁸は、アリール基又は１価の芳香族複素環基を示す。Ｚ⁹は、置換基Ａ群及び置換基Ｂ群からなる群から選ばれるいずれかの基を示す。］

[In the formula (6), Ar ⁸ represents an aryl group or a monovalent aromatic heterocyclic group. Z ⁹ represents any group selected from the group consisting of the substituent group A and the substituent group B. ]

In the formula (6), the aryl group represented by Ar ⁸ and the monovalent aromatic heterocyclic group are respectively described as the aryl group represented by R ¹ and the monovalent aromatic heterocyclic group. It is the same as that illustrated.

  The post-treatment of the polymerization reaction can be performed by a known method. For example, the reaction solution after the polymerization reaction is added to a lower alcohol such as methanol, and the precipitated precipitate is filtered and dried.

  When the purity of the polymer compound according to the present invention is low, the polymer compound according to the present invention may be purified by a usual method such as recrystallization, reprecipitation, continuous extraction with a Soxhlet extractor, column chromatography, etc. When a compound is used for a light-emitting device, the purity affects the performance of the device such as light-emitting properties. Therefore, it is preferable to perform a purification treatment such as reprecipitation purification and fractionation by chromatography after condensation polymerization.

<Polymer composition>
The polymer composition according to the present invention contains the polymer compound and at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light emitting material.

  Examples of the hole transport material include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amines in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, polyaniline and derivatives thereof, polythiophene And derivatives thereof, polypyrrole and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, and the like. In addition, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, JP-A-3- Examples thereof include hole transport materials described in JP-A-379992 and JP-A-3-152184.

  In the polymer composition according to the present invention, the content of the hole transport material can lower the driving voltage, and therefore preferably 1 to 500 parts by weight, more preferably 5 to 5 parts by weight with respect to 100 parts by weight of the polymer compound. 200 parts by weight.

  Examples of the electron transport material include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone derivatives, diphenyldicyano Examples include ethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, polyfluorene and its derivatives, and the like. In addition, JP-A-63-70257, JP-A-63-175860, JP-A-2-135359, JP-A-2-135361, JP-A-2-209998, JP-A-3- Examples thereof include electron transport materials described in JP-A-379992 and JP-A-3-152184.

  In the polymer composition according to the present invention, the content of the electron transporting material can lower the driving voltage, so that it is preferably 1 to 500 parts by weight, more preferably 5 to 200 parts per 100 parts by weight of the polymer compound. Parts by weight.

Examples of the light emitting material include a low molecular fluorescent light emitting material and a phosphorescent light emitting material.
Examples of the low molecular fluorescent light-emitting material include naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, dyes such as polymethine dyes, xanthene dyes, coumarin dyes, and cyanine dyes, and 8-hydroxyquinoline as a ligand. Metal complexes having 8-hydroxyquinoline derivatives as ligands, other fluorescent metal complexes, aromatic amines, tetraphenylcyclopentadiene and derivatives thereof, tetraphenylbutadiene and derivatives thereof, stilbene-based, silicon-containing compounds Examples thereof include fluorescent materials of low molecular weight compounds such as aromatic, oxazole, furoxan, thiazole, tetraarylmethane, thiadiazole, pyrazole, metacyclophane, and acetylene.
Examples of the phosphorescent material include triplet light-emitting complexes such as metal complexes such as iridium complexes and platinum complexes.
Other examples include porphyrin compounds described in JP-A-57-51781, JP-A-59-194393, and the like.

  In the polymer composition according to the present invention, the content of the light emitting material is preferably 1 to 500 parts by weight, more preferably 5 to 200 parts by weight with respect to 100 parts by weight of the polymer compound.

<Solution>
The polymer compound according to the present invention can be dissolved or dispersed in a solvent to form a solution. This solution is sometimes called ink, liquid composition, or the like. The solution may contain at least one material selected from the group consisting of a hole transport material, an electron transport material, and a light emitting material.

  Here, examples of the solvent include chlorine solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, and o-dichlorobenzene; ether solvents such as tetrahydrofuran and dioxane; toluene, xylene , Aromatic hydrocarbon solvents such as trimethylbenzene and mesitylene; aliphatic hydrocarbon solvents such as cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane and n-decane Solvents; Ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc .; Ester solvents such as ethyl acetate, butyl acetate, methyl benzoate, ethyl cellosolve acetate; ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether Ter, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1,2-hexanediol and other polyhydric alcohols and derivatives thereof; methanol, ethanol, propanol, isopropanol, cyclo Examples include alcohol solvents such as hexanol; sulfoxide solvents such as dimethyl sulfoxide; amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These solvents may be used alone or in combination of two or more. Considering the viscosity and film-forming property of the polymer compound, the solvent may contain a solvent having a structure containing a benzene ring, a melting point of 0 ° C. or lower, and a boiling point of 100 ° C. or higher. preferable.

According to the said solution, the organic thin film containing the high molecular compound which concerns on this invention can be manufactured easily. Specifically, the organic thin film containing the polymer compound according to the present invention is obtained by applying the solution onto a substrate and distilling off the solvent by heating, decompression, or the like. The solvent can be distilled off by changing the conditions depending on the organic solvent to be used. For example, the solvent can be distilled by heating at about 50 to 150 ° C. and reducing the pressure at about 10 ⁻³ Pa.

  For coating, spin coating method, casting method, micro gravure method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method, spray coating method, screen printing A coating method such as a printing method, a flexographic printing method, an offset printing method, an inkjet printing method, or a nozzle coating method can be used.

  Although the suitable viscosity of the said solution changes also with printing methods, Preferably it is 0.5-500 mPa * s in 25 degreeC. Further, when the solution passes through a discharge device as in the ink jet printing method, the viscosity at 25 ° C. is preferably 0.5 to 20 mPa · s in order to prevent clogging and flight bending at the time of discharge.

<Organic thin film>
The organic thin film according to the present invention contains the polymer compound according to the present invention or the polymer composition according to the present invention. The organic thin film which concerns on this invention can be easily manufactured from the said solution as mentioned above.

  The organic thin film which concerns on this invention can be used conveniently as a light emitting layer in the light emitting element mentioned later. Moreover, it can be used suitably also for an organic semiconductor element. Since the organic thin film according to the present invention contains the polymer compound, when used as a light emitting layer of a light emitting element, the light emitting efficiency of the light emitting element is very excellent.

<Organic semiconductor element>
The organic semiconductor element according to the present invention includes the organic thin film. Examples of the organic semiconductor element include an organic thin film solar cell and a field effect organic transistor. For the production of this organic semiconductor element, the organic thin film according to the present invention is suitably used. Specifically, the organic thin film is formed on a Si substrate on which an insulating film such as SiO ₂ and a gate electrode are formed, and a source electrode and a drain electrode are formed using Au or the like, thereby forming a field effect organic transistor. be able to.

<Light emitting element>
The light-emitting device according to the present invention includes the organic thin film, and usually includes an anode, a cathode, and a layer containing the polymer compound present between the anode and the cathode. Here, the layer containing the polymer compound is preferably a layer composed of the organic thin film, and the layer preferably functions as a light emitting layer. Hereinafter, a case where the layer containing the polymer compound functions as a light emitting layer will be exemplified as a preferred embodiment.

Examples of the structure of the light emitting device according to the present invention include the following structures (a) to (d). Note that “/” indicates that the layers before and after the adjacent layers are laminated. For example, “anode / light-emitting layer” indicates that the anode and the light-emitting layer are stacked adjacent to each other.
(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

  Note that 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. is there. The hole transport layer and the electron transport layer may be collectively referred to as a charge transport layer. The hole transport layer adjacent to the light emitting layer may be referred to as an interlayer layer.

  Lamination and film formation of each layer can be performed using a solution containing the constituent components of each layer. For lamination and film formation from solution, spin coating method, casting method, micro gravure coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, slit coating method, capillary coating method Application methods such as spray coating, screen printing, flexographic printing, offset printing, inkjet printing, and nozzle coating can be used.

  The thickness of the light emitting layer may be selected so that the driving voltage and the light emission efficiency are moderate values, but is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, more preferably 5 nm to 200 nm. .

  The hole transport layer preferably contains the hole transport material. The hole transport layer may be formed by any method, but when the hole transport material is a polymer compound, it is preferably formed from a solution containing the hole transport material. When the transport material is a low molecular compound, it is preferable to form a film from a mixed solution containing a polymer binder and a hole transport material. As a film forming method, a method similar to the above-described coating method can be used.

  The polymer binder is preferably one that does not extremely inhibit charge transport and does not strongly absorb visible light. Examples of the polymer binder include polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, and the like.

  The thickness of the hole transport layer may be selected so that the driving voltage and the light emission efficiency are appropriate values, and a thickness that does not cause pinholes is necessary, but is usually 1 nm to 1 μm, Preferably it is 2 nm-500 nm, More preferably, it is 5 nm-200 nm.

The electron transport layer preferably contains the electron transport material. The electron transport layer may be formed by any method. When the electron transport material is a polymer compound, a method of forming a film from a solution containing the electron transport material, A film forming method or the like is preferable. In addition, when the electron transport material is a low-molecular compound, a method of forming a film by vacuum deposition using a powder of the electron transport material, a method of forming a film from a solution containing the electron transport material, and melting the electron transport material Thus, a film forming method is preferable. Examples of a method for forming a film from a solution containing an electron transport material include the same methods as those described above. It may also contain a polymeric binder in solution.

  The polymer binder is preferably one that does not extremely inhibit charge transport and does not strongly absorb visible light. As the polymer binder, poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylene vinylene) and derivatives thereof, poly (2,5-thienylene vinylene) and derivatives thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  The thickness of the electron transport layer may be selected so that the driving voltage and the light emission efficiency become appropriate values, and a thickness that does not cause pinholes is necessary, but is usually 1 nm to 1 μm, preferably Is 2 nm to 500 nm, more preferably 5 nm to 200 nm.

  Among the charge transport layers provided adjacent to the electrode, those having the function of improving the charge injection efficiency from the electrode and having the effect of lowering the driving voltage of the element are particularly charge injection layers (hole injection layers, Sometimes called an electron injection layer. In order to improve the adhesion with the electrode and the charge injection from the electrode, the charge injection layer or the insulating layer may be provided adjacent to the electrode. A thin buffer layer may be inserted at the interface between the charge transport layer and the light emitting layer. Note that the order and number of layers to be stacked, and the thickness of each layer may be selected in consideration of light emission efficiency and element lifetime.

Examples of the light emitting element provided with the charge injection layer include those having the following structures (e) to (p).
(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 / charge 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 / charge 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

  As the charge injection layer, (I) a layer containing a conductive polymer, (II) an anode material in the anode and a hole transport material in the hole transport layer provided between the anode and the hole transport layer; A layer containing a material having an ionization potential of an intermediate value of (III), provided between the cathode and the electron transport layer, and having an intermediate value between the cathode material in the cathode and the electron transport material in the electron transport layer Examples thereof include a layer containing a material having an electron affinity.

When the charge injection layer is (I) a layer containing a conductive polymer, the electric conductivity of the conductive polymer is preferably 10 ⁻⁵ to 10 ³ S / cm, and the leakage current between the light emitting pixels is reduced. For this purpose, 10 ⁻⁵ to 10 ² S / cm is more preferable, and 10 ⁻⁵ to 10 ¹ S / cm is particularly preferable. In order to satisfy this range, the conductive polymer may be 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 the anion include polystyrene sulfonate ion, alkylbenzene sulfonate ion, camphor sulfonate ion and the like.
Examples of the cation include lithium ion, sodium ion, potassium ion, and tetrabutylammonium ion.

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

  The conductive polymer may be selected in relation to the electrode and the material of the adjacent layer. Polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene vinylene and its Examples thereof include conductive polymers such as derivatives, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polymers containing an aromatic amine structure in the main chain or side chain.

  Examples of the charge injection layer include a layer containing metal phthalocyanine (such as copper phthalocyanine) and carbon.

  The insulating layer is a layer having a function of facilitating charge injection. The thickness of this insulating layer is usually 0.1 to 20 nm, preferably 0.5 to 10 nm, more preferably 1 to 5 nm. Examples of the material used for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.

Examples of the light emitting element provided with an insulating layer include those having the following structures (q) to (ab).
(Q) Anode / insulating layer / light emitting layer / cathode (r) anode / light emitting layer / insulating layer / cathode (s) anode / insulating layer / light emitting layer / insulating layer / cathode (t) anode / insulating layer / hole transport Layer / light emitting layer / cathode (u) anode / hole transport layer / light emitting layer / insulating layer / cathode (v) anode / insulating layer / hole transporting layer / light emitting layer / insulating layer / cathode (w) anode / insulating layer / Light emitting layer / electron transport layer / cathode (x) anode / light emitting layer / electron transport layer / insulating layer / cathode (y) anode / insulating layer / light emitting layer / electron transport layer / insulating layer / cathode (z) anode / insulating Layer / hole transport layer / light emitting layer / electron transport layer / cathode (aa) anode / hole transport layer / light emitting layer / electron transport layer / insulating layer / cathode (ab) anode / insulating layer / hole transport layer / light emitting Layer / electron transport layer / insulating layer / cathode

  The light emitting device according to the present invention preferably includes a substrate adjacent to the anode or the cathode. The substrate is preferably a substrate whose shape and properties do not change when forming the electrode and each layer, and examples thereof include substrates such as glass, plastic, polymer film, and silicon. In the case of an opaque substrate, the electrode on the side opposite to the electrode with which the substrate is in contact is preferably transparent or translucent.

  In the light-emitting device according to the present invention, it is usually preferable that at least one of the electrode including the anode and the cathode is transparent or translucent, and the anode is transparent or translucent.

  As the material of the anode, a conductive metal oxide film, a translucent metal thin film, etc. are used. Specifically, a composite oxide composed of indium oxide, zinc oxide, tin oxide, indium tin oxide (ITO). , Films made using conductive inorganic compounds such as composite oxides composed of indium, zinc, and oxide, NESA, gold, platinum, silver, copper, etc. are used, as well as polyaniline and its derivatives, polythiophene and its derivatives An organic transparent conductive film such as is used. In order to facilitate charge injection, a layer made of a phthalocyanine derivative, a conductive polymer, carbon, or the like, or a layer made of a metal oxide, a metal fluoride, an organic insulating material, or the like may be provided on the anode. Good.

  Examples of a method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method.

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

  As a material for the cathode, a material having a small work function is preferable, lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, Europium, terbium, ytterbium and other metals, alloys containing two or more of the metals, one or more of the metals, gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin An alloy containing at least one kind, graphite, or a compound in which these metals are sandwiched between layers of graphite are used.

  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.

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

  Between the cathode and the light emitting layer or between the cathode and the electron transport layer, a layer made of a conductive polymer, or a layer made of a metal oxide, a metal fluoride, an organic insulating material or the like may be provided. A protective layer for protecting the light emitting element may be attached. In order to use the light emitting element stably for a long period of time, it is preferable to attach a protective layer and / or a protective cover in order to protect the element from the outside.

  As the protective layer, resins, metal oxides, metal fluorides, metal borides and the like can be used. Further, as the protective cover, a glass plate, a plastic plate having a surface subjected to low water permeability treatment, or the like can be used, and a method of sealing the protective cover by bonding it to the element substrate with a thermosetting resin or a photocurable resin is used. Preferably used. If the space is maintained by using the spacer, the element can be easily prevented from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, oxidation of the cathode can be prevented, and further, moisture adsorbed in the manufacturing process can be obtained by installing a desiccant such as barium oxide in the space. It becomes easy to suppress giving an image to an element.

  The light emitting device according to the present invention includes a planar light source (illumination, etc.) such as a curved light source and a planar light source; a segment display device, a dot matrix display device (dot matrix flat display, etc.), a liquid crystal display device (back of a liquid crystal display). This is useful for display devices such as lights. The polymer compound according to the present invention is not only suitable as a material used for the production thereof, but also a dye for laser, an organic solar cell material, an organic semiconductor for an organic transistor, a conductive thin film, and an organic semiconductor thin film. It is also useful as a material for conductive thin films such as a light emitting thin film material that emits fluorescence, and a material for polymer field effect transistors.

  In order to obtain planar light emission using the light emitting element according to 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 in which a mask having a pattern-like window is provided on the surface of the planar light-emitting element, either the anode or the cathode, or both electrodes in a pattern form There is a method of forming. A segment display device capable of displaying numbers, letters, simple symbols, etc. can be obtained by forming a pattern by any of these methods and arranging several electrodes so that they can be turned ON / OFF independently. Furthermore, in order to obtain a dot matrix display device, both the anode and the cathode may be formed in stripes 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 compounds having different emission colors or a method using a color filter or a fluorescence conversion filter. The dot matrix display device can be driven passively or may be driven actively in combination with a TFT or the like. These display devices can be used in computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these.

  The polystyrene-equivalent number average molecular weight and weight average molecular weight of the polymer compound were determined under the following measurement conditions using gel permeation chromatography (GPC) (manufactured by Shimadzu Corporation, trade name: LC-10Avp).

[Measurement condition]
The polymer compound to be measured was dissolved in tetrahydrofuran to a concentration of about 0.05% by weight, and 10 μL was injected into gel permeation chromatography (GPC). Tetrahydrofuran was used as the mobile phase of SEC and was allowed to flow at a flow rate of 2.0 mL / min. As a column, PLgel MIXED-B (manufactured by Polymer Laboratories) was used. A UV-VIS detector (manufactured by Shimadzu Corporation, trade name: SPD-10Avp) was used as the detector.

<Example 1>
{Synthesis of Compound A}
According to the synthesis method described in International Publication WO02 / 066552 pamphlet, the following formula:

で表される化合物Ａを合成した。具体的には、窒素雰囲気下、トリブロモベンゼンと、２．２当量の４−ｔｅｒｔ−ブチルフェニルホウ酸とのＳｕｚｕｋｉカップリング（触媒：テトラキス（トリフェニルホスフィン）パラジウム（０）、塩基：２Ｍ炭酸ナトリウム水溶液、溶媒：エタノール、トルエン）により、化合物Ａを得た。

The compound A represented by these was synthesize | combined. Specifically, Suzuki coupling of tribromobenzene and 2.2 equivalents of 4-tert-butylphenylboric acid under a nitrogen atmosphere (catalyst: tetrakis (triphenylphosphine) palladium (0), base: 2M carbonic acid Aqueous sodium solution, solvent: ethanol, toluene) gave compound A.

{Synthesis of Compound B}
After dissolving Compound A in dehydrated THF under a nitrogen atmosphere, the resulting solution was cooled to −78 ° C., and a small excess of tert-butyllithium was added dropwise. Under cooling, B (OC ₄ H ₉ ) ₃ was further added dropwise and reacted at room temperature. The reaction solution was post-treated with 3M hydrochloric acid to obtain the following formula:

で表される化合物Ｂを得た。

The compound B represented by these was obtained.

{Synthesis of Compound C}
Further, in the above {Synthesis of Compound B}, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane was used in place of B (OC ₄ H ₉ ) ₃ . Except for the following formula:

で表される化合物Ｃを得た。

The compound C represented by these was obtained.

{Synthesis of Compound D}
4-Bromophthalic anhydride (25 g, 0.11 mol) and ethanol (250 mL) were charged into a 500 mL four-necked flask and heated to reflux for 15 hours while dehydrating with anhydrous magnesium sulfate. After cooling to room temperature, the reaction solvent was concentrated. Thereto was added ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate after washing three times with a saturated aqueous sodium hydrogen carbonate solution and once with water. The solvent of the organic layer thus obtained is concentrated and purified by silica gel column chromatography using hexane: ethyl acetate = 4: 1 (volume ratio) as a developing solvent, whereby the following formula:

で表される化合物Ｄを定量的に得た。
HNMR 300MHz δ（CDCl₃）：1.34-1.40 (m, 6H), 4.32-4.41 (m, 4H), 7.60-7.68 (m, 2H), 7.83 (s, 1H)ppm

The compound D represented by these was obtained quantitatively.
HNMR 300 MHz δ (CDCl ₃ ): 1.34-1.40 (m, 6H), 4.32-4.41 (m, 4H), 7.60-7.68 (m, 2H), 7.83 (s, 1H) ppm

{Synthesis of Compound E}
A 100 mL one-necked eggplant flask was charged with compound D (0.5 g, 1.66 mmol), compound C (0.78 g, 1.66 mmol), Pd (PPh ₃ ) ₄ (96 mg, 0.083 mmol), and toluene ( 17 mL) was added and stirred. A 2M aqueous potassium hydroxide solution (2 mL) was charged, tetrabutylammonium bromide (30 mg, 0.083 mmol) was added, and the mixture was heated to reflux for 6 hours. After cooling to room temperature, the aqueous layer was removed and washed 3 times with water. The obtained solution was concentrated through a glass filter covered with silica gel, and purified with a silica gel column using hexane: ethyl acetate = 4: 1 (volume ratio) as a developing solvent. Thus, the following formula:

で表される化合物Ｅを０．６８ｇ（純度９５％）、収率６９．１％で得た。
m/z： 563.32 for [[C₃₈H₄₂O₄]＋H]+@TLC-MS
HNMR 300MHz δ（CDCl₃）：1.30-1.48 (m, 24H), 4.33-4.47 (m, 4H), 7.52 (d, 9Hz, 4H), 7.63 (d, 9H, 4H), 7.75 (d, 0.6Hz, 1H), 7.79-7.90 (m, 3H), 7.96-7.99 (s, 1H)ppm

Was obtained in a yield of 69.1% (0.68 g, purity 95%).
m / z: 563.32 for [[C ₃₈ H ₄₂ O ₄ ] + H] + @ TLC-MS
HNMR 300 MHz δ (CDCl ₃ ): 1.30-1.48 (m, 24H), 4.33-4.47 (m, 4H), 7.52 (d, 9Hz, 4H), 7.63 (d, 9H, 4H), 7.75 (d, 0.6Hz , 1H), 7.79-7.90 (m, 3H), 7.96-7.99 (s, 1H) ppm

{Synthesis of Compound F}
To a 500 mL one-necked eggplant flask, compound E (12 g, 21.3 mmol) and ethanol (96 mL) were added, 27 wt% aqueous sodium hydroxide solution (192 mL) was added, and the mixture was heated to reflux for 4 hours. After completion of the reaction, the reaction solution cooled to room temperature was poured into 2M hydrochloric acid (500 mL) and stirred at room temperature for 1 hour. The resulting precipitate was collected by filtration, thoroughly washed with water, and then left to dry for 2 hours while sucking on a suction filter. The obtained wet cake was transferred to a 500 mL eggplant flask and heated to reflux at 160 ° C. for 6 hours while adding and dehydrating xylene and activated carbon. After cooling to such an extent that the reflux was settled, acetic anhydride was charged and the mixture was again heated to reflux for 3 hours. After completion of the reaction, the reaction solution was cooled to room temperature, and a filter was made by spreading Celite on the Kiriyama funnel, and the reaction solution was filtered using it. After washing with toluene, the resulting solution was concentrated. Toluene was added to the resulting residue and dissolved completely with heating, and then hexane was added to the resulting solution while stirring with a stirrer. After stirring at room temperature for 30 minutes, further hexane is added, and the resulting precipitate is collected by filtration to give the following formula:

で表される化合物Ｆ（６．７ｇ，１３．７ｍｍｏｌ）を収率８０．４％で得た。
HNMR 300MHz δ（CDCl₃）：1.40 (s, 18H), 7.53 (d, 6Hz, 4H), 7.63 (d, 6Hz, 4H), 7.78 (s, 2H), 7.91 (d, 0.3Hz, 1H), 8.10 (dd, 3, 0.3Hz, 1H), 8.20 (dd, 3, 0.3Hz, 1H), 8.30 (s, 1H)ppm

The compound F (6.7g, 13.7mmol) represented by this was obtained with the yield of 80.4%.
HNMR 300 MHz δ (CDCl ₃ ): 1.40 (s, 18H), 7.53 (d, 6Hz, 4H), 7.63 (d, 6Hz, 4H), 7.78 (s, 2H), 7.91 (d, 0.3Hz, 1H), 8.10 (dd, 3, 0.3Hz, 1H), 8.20 (dd, 3, 0.3Hz, 1H), 8.30 (s, 1H) ppm

{Synthesis of Compound G}
A 100 mL three-necked round bottom flask was charged with Compound F (2 g, 4.09 mmol) and anhydrous THF (60 mL) under an argon gas atmosphere, and cooled to −20 ° C. with stirring in a dry ice-acetone bath. LiAl (Ot-Bu) ₃ H (4.09 mL, 4.09 mmol, 1M THF solution) was added dropwise, and the mixture was stirred at that temperature for 1 hour. The dry ice-acetone bath was removed and the mixture was gradually warmed to 0 ° C., and 2M hydrochloric acid was added to stop the reaction. The reaction solution was transferred to a separatory funnel and extracted with 2M hydrochloric acid and ethyl acetate. The obtained organic layer was dehydrated with anhydrous sodium sulfate and concentrated. Anhydrous methanol was added to the resulting residue, heated to reflux for 3 hours, and the following formula:

で表される化合物Ｇと化合物Ｇ’との混合物を得た。シリカゲルカラムクロマトグラフィーにより、ヘキサン：酢酸エチル＝４：１（体積比）を展開溶媒として用いて単離精製を行ったところ、化合物ＧとＧ’との混合物（目的とする還元体）（１．２５ｇ，２．５ｍｍｏｌ）を収率５６．３％で得た。
HNMR 300MHz δ（CDCl₃）：1.39 (s, 18H), 3.67-3.68 (3H), 6.36-6.37 (1H), 7.52 (d, 9Hz, 4H), 7.58-7.70 (m, 5H), 7.76 (m, 2H), 7.81-7.88 (m, 2H), 7.88-8.00 (1H), 8.00-8.22 (1H)ppm

The mixture of the compound G represented by these and compound G 'was obtained. When isolation and purification were performed by silica gel column chromatography using hexane: ethyl acetate = 4: 1 (volume ratio) as a developing solvent, a mixture (target reduced form) of compound G and G ′ (1. 25 g, 2.5 mmol) was obtained with a yield of 56.3%.
HNMR 300 MHz δ (CDCl ₃ ): 1.39 (s, 18H), 3.67-3.68 (3H), 6.36-6.37 (1H), 7.52 (d, 9Hz, 4H), 7.58-7.70 (m, 5H), 7.76 (m , 2H), 7.81-7.88 (m, 2H), 7.88-8.00 (1H), 8.00-8.22 (1H) ppm

{Synthesis of Compound H}
Under an argon gas atmosphere, 4-bromoiodobenzene (0.6 g, 2.06 mmol) and THF (18 mL) were charged into a 100 mL two-necked eggplant flask and cooled to −20 ° C. with stirring to prepare solution A.
In a separate 10 mL two-necked eggplant flask, a mixture of Compound G and Compound G ′ (0.55 g, 0.98 mmol) and THF (28 mL) were charged to prepare Liquid B.
Isopropylmagnesium chloride solution (1.1 mL, 2.16 mmol, 2M THF solution) was added dropwise to solution A and stirred, and solution B was added to solution A. After stirring at 0 ° C. for 1 hour, 2M hydrochloric acid was added to stop the reaction, and the mixture was extracted with toluene. The obtained solution was dehydrated with anhydrous sodium sulfate, filtered through a glass filter covered with silica gel, and concentrated. By drying the obtained residue in a vacuum dryer, the following formula:

で表される化合物Ｈを得た。化合物Ｈは、そのまま次の反応に用いた。
m/z： 785.12 for [[C₄₆H₄₀Br_2O]＋H₂O+H]+@TLC-MS （Br体のパターン確認）

The compound H represented by these was obtained. Compound H was used in the next reaction as it was.
m / z: 785.12 for [[ C 46 H 40 Br 2O] + H 2 O + H] + @ ( pattern confirmation Br body) TLC-MS

{Synthesis of Compound J}
In an argon atmosphere, in a 1 L three-necked flask, the following formula:

で表される５-ブロモアセナフチレン（化合物Ｉ、１０ｇ、３６．８ｇ、３６．８ｍｍｏｌ）、化合物Ｃ（１７．２ｇ，３６．８ｍｍｏｌ）、ＰｄＣｌ₂（ＰＰｈ₃）₂（２．１ｇ，１．８ｍｍｏｌ）、及び、トルエン（５５０ｍＬ）を加え撹拌し、１０分間アルゴンでバブリングを行った。そこに、２Ｍ 水酸化カリウム水溶液１４０ｍＬ、テトラブチルアンモニウムブロマイド（０．６ｍｇ，１．８ｍｍｏｌ）を加え、１００℃で９０分加熱し攪拌した。反応の追跡は、液体クロマトグラフィー（ＬＣ）を用いて行った。反応溶液を室温に戻し、反応を停止した。反応溶液から水層を除去した後、蒸留水で３回洗浄し、飽和食塩水で洗浄した。得られた溶液を、硫酸ナトリウムで乾燥させた後、残渣を濾別し、減圧濃縮することで、茶色液体（２３ｇ）を得た。ヘキサン：クロロホルム＝４：１（体積比）を展開溶媒とするシリカゲルカラムクロマトグラフィーで精製することにより、以下の式：

5-bromoacenaphthylene (Compound I, 10 g, 36.8 g, 36.8 mmol), Compound C (17.2 g, 36.8 mmol), PdCl ₂ (PPh ₃ ) ₂ (2.1 g, 1 .8 mmol) and toluene (550 mL) were added and stirred, and bubbled with argon for 10 minutes. Thereto were added 2M aqueous potassium hydroxide solution (140 mL) and tetrabutylammonium bromide (0.6 mg, 1.8 mmol), and the mixture was heated at 100 ° C. for 90 minutes and stirred. The reaction was monitored using liquid chromatography (LC). The reaction solution was returned to room temperature to stop the reaction. After removing the aqueous layer from the reaction solution, it was washed 3 times with distilled water and then with saturated brine. The obtained solution was dried over sodium sulfate, and then the residue was filtered off and concentrated under reduced pressure to obtain a brown liquid (23 g). By purifying by silica gel column chromatography using hexane: chloroform = 4: 1 (volume ratio) as a developing solvent, the following formula:

で表される橙色粉末の化合物Ｊ（１３．５ｇ，２５．４ｍｍｏｌ)を収率７５％で得た。
HNMR 300MHz δ（CDCl₃）：1.38 (s, 18H), 7.12 (s, 2H), 7.46-7.58 (m, 5H), 7.60-7.73 (m, 6H), 7.73-7.80 (m, 3H), 7.86-7.90 (m, 1H), 7.98 (d, 8.4Hz, 1H)ppm

The compound J (13.5 g, 25.4 mmol) of the orange powder represented by this was obtained with a yield of 75%.
HNMR 300 MHz δ (CDCl ₃ ): 1.38 (s, 18H), 7.12 (s, 2H), 7.46-7.58 (m, 5H), 7.60-7.73 (m, 6H), 7.73-7.80 (m, 3H), 7.86 -7.90 (m, 1H), 7.98 (d, 8.4Hz, 1H) ppm

{Synthesis of Compound K}
Under an argon gas atmosphere, Compound H (6.9 g, 5.35 mmol), Compound J (3.10 g, 5.35 mmol) and xylene (62 mL) were charged into a 100 mL eggplant flask and heated to 100 ° C. with stirring. P-Toluenesulfonic acid (0.29 g, 1.60 mmol) was added thereto, and then heated to 160 ° C. in an oil bath and heated to reflux for 6 hours. The reaction solution was cooled to room temperature, diluted with toluene, washed twice with water, filtered through a glass filter covered with silica gel, and the resulting solution was concentrated under reduced pressure. The obtained residue was isolated and purified by silica gel column chromatography using hexane as a developing solvent. Thus, the following formula:

で表される淡黄色固体の化合物Ｋ（１．４０ｇ，１．０９ｍｍｏｌ）を収率２０．４％で得た。
LC-MS: m/z calcd for [C₈₄H₇₄Br₂], 1240.42; found, 1240.
HNMR 300MHz δ（CDCl₃）：1.35-1.42 (m, 36H), 6.72-6.86 (m, 2H), 7.36-7.44 (m, 3H), 7.44-7.57 (m, 18H), 7.57-7.65 (m, 11H), 7.65-7.76 (m, 8H), 7.76-7.79 (m, 2H), 7.81-7.90 (m, 7H), 7.92-7.99 (m, 2H)ppm

The compound K (1.40 g, 1.09 mmol) of the pale yellow solid represented by this was obtained with a yield of 20.4%.
LC-MS: m / z calcd for [C ₈₄ H ₇₄ Br ₂ ], 1240.42; found, 1240.
HNMR 300 MHz δ (CDCl ₃ ): 1.35-1.42 (m, 36H), 6.72-6.86 (m, 2H), 7.36-7.44 (m, 3H), 7.44-7.57 (m, 18H), 7.57-7.65 (m, 11H), 7.65-7.76 (m, 8H), 7.76-7.79 (m, 2H), 7.81-7.90 (m, 7H), 7.92-7.99 (m, 2H) ppm

<Example 2>
The following compound L was synthesized according to the method described in the pamphlet of International Publication No. 2009/075203. In an inert atmosphere, the following formula:

で表される化合物Ｌ（０．１３８ｇ、０．２０ｍｍｏｌ）と、下記式：

Compound L (0.138 g, 0.20 mmol) represented by the following formula:

で表される化合物Ｍ（０．１６３ｇ、０．２０ｍｍｏｌ）と、下記式：

Compound M (0.163 g, 0.20 mmol) represented by the following formula:

で表される化合物Ｎ（０．３６０ｇ、０．５６ｍｍｏｌ）と、下記式：

Compound N (0.360 g, 0.56 mmol) represented by the following formula:

で表される化合物Ｏ（１．１０４ｇ、１．４４ｍｍｏｌ）と、下記式：

And compound O (1.104 g, 1.44 mmol) represented by the following formula:

で表される化合物Ｐ（１．０３１ｇ、１．６０ｍｍｏｌ）と、ジクロロビス（トリフェニルホスフィン）パラジウム（１．４ｍｇ）と、トルエン（５０ｍＬ）とを混合し、１０５℃に加熱した。反応溶液に２０重量％水酸化テトラエチルアンモニウム水溶液（６．６ｍＬ）を滴下し、２時間４０分還流させた。反応後、そこに、フェニルホウ酸（２４．４ｍｇ）、トルエン（５ｍＬ）を加え、更に１８．５時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。冷却後、有機層を、水で２回、３重量％酢酸水溶液で２回、水で２回洗浄し、得られた溶液をメタノールに滴下したところ、沈殿物が生じたので、それをろ取した。この沈殿物をトルエンに溶解させ、アルミナカラム、シリカゲルカラムを順番に通し、得られた溶液をメタノールに滴下し、撹拌したところ、沈殿物が生じた。この沈殿物をろ取し、乾燥させることにより、下記式（Ｋ−１）で表される構成単位と、下記式（Ｋ−２）で表される構成単位と、下記式（Ｋ−３）で表される構成単位と、下記式（Ｋ−４）で表される構成単位と、下記式（Ｋ−５）で表される構成単位とを、５：５：１４：３６：４０のモル比で有する重合体（以下、「高分子化合物Ａ」と言う。）を１．５ｇ得た。
高分子化合物Ａのポリスチレン換算数平均分子量は１．６×１０⁵であり、ポリスチレン換算重量平均分子量は４．１×１０⁵であった。

Embedded image Compound P (1.031 g, 1.60 mmol), dichlorobis (triphenylphosphine) palladium (1.4 mg), and toluene (50 mL) were mixed and heated to 105 ° C. A 20 wt% tetraethylammonium hydroxide aqueous solution (6.6 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 2 hours and 40 minutes. After the reaction, phenylboric acid (24.4 mg) and toluene (5 mL) were added thereto, and the mixture was further refluxed for 18.5 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the organic layer was washed twice with water, twice with a 3% by weight acetic acid aqueous solution and twice with water, and when the resulting solution was added dropwise to methanol, a precipitate was formed. did. This precipitate was dissolved in toluene, passed through an alumina column and a silica gel column in this order, and the resulting solution was added dropwise to methanol and stirred to produce a precipitate. The precipitate is collected by filtration and dried, whereby the structural unit represented by the following formula (K-1), the structural unit represented by the following formula (K-2), and the following formula (K-3) The structural unit represented by the following formula (K-4) and the structural unit represented by the following formula (K-5) are in a molar ratio of 5: 5: 14: 36: 40. 1.5 g of a polymer having a ratio (hereinafter referred to as “polymer compound A”) was obtained.
The polymer compound A had a polystyrene equivalent number average molecular weight of 1.6 × 10 ⁵ and a polystyrene equivalent weight average molecular weight of 4.1 × 10 ⁵ .

<Example 3>
Under an inert atmosphere, the compound L (0.138 g, 0.20 mmol), the compound M (0.163 g, 0.20 mmol), the following formula: the compound N (0.360 g, 0.56 mmol), Following formula:

で表される化合物Ｑ（１．０６４ｇ、１．４４ｍｍｏｌ）と、下記式：

Compound Q (1.064 g, 1.44 mmol) represented by the following formula:

で表される化合物Ｒ（１．０３１ｇ、１．６０ｍｍｏｌ）と、ジクロロビス（トリフェニルホスフィン）パラジウム（１．４ｍｇ）と、トルエン（５０ｍＬ）とを混合し、１０５℃に加熱した。反応溶液に２０重量％水酸化テトラエチルアンモニウム水溶液（６．６ｍＬ）を滴下し、２時間４０分還流させた。反応後、そこに、フェニルホウ酸（２４．４ｍｇ）、トルエン（５ｍＬ）を加え、更に１８．５時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。冷却後、有機層を、水で２回、３重量％酢酸水溶液で２回、水で２回洗浄し、得られた溶液をメタノールに滴下したところ、沈殿物が生じたので、それをろ取した。この沈殿物をトルエンに溶解させ、アルミナカラム、シリカゲルカラムを順番に通し、得られた溶液をメタノールに滴下し、撹拌したところ、沈殿物が生じた。この沈殿物をろ取し、乾燥させることにより、前記式（Ｋ−１）で表される構成単位と、前記式（Ｋ−２）で表される構成単位と、前記式（Ｋ−３）で表される構成単位と、下記式（Ｋ−６）で表される構成単位とを、５：５：１４：７６のモル比で有する重合体（以下、「高分子化合物Ｂ」と言う。）を１．６ｇ得た。
高分子化合物Ｂのポリスチレン換算数平均分子量は１．０×１０⁵であり、ポリスチレン換算重量平均分子量は３．０×１０⁵であった。

Embedded image R (1.031 g, 1.60 mmol), dichlorobis (triphenylphosphine) palladium (1.4 mg), and toluene (50 mL) were mixed and heated to 105 ° C. A 20 wt% tetraethylammonium hydroxide aqueous solution (6.6 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 2 hours and 40 minutes. After the reaction, phenylboric acid (24.4 mg) and toluene (5 mL) were added thereto, and the mixture was further refluxed for 18.5 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the organic layer was washed twice with water, twice with a 3% by weight acetic acid aqueous solution and twice with water, and when the resulting solution was added dropwise to methanol, a precipitate was formed. did. This precipitate was dissolved in toluene, passed through an alumina column and a silica gel column in this order, and the resulting solution was added dropwise to methanol and stirred to produce a precipitate. By filtering this precipitate and drying, the structural unit represented by the formula (K-1), the structural unit represented by the formula (K-2), and the formula (K-3) A polymer having a structural unit represented by formula (K-6) and a structural unit represented by the following formula (K-6) in a molar ratio of 5: 5: 14: 76 (hereinafter referred to as “polymer compound B”). ) Was obtained.
The polymer compound B had a polystyrene equivalent number average molecular weight of 1.0 × 10 ⁵ and a polystyrene equivalent weight average molecular weight of 3.0 × 10 ⁵ .

<Example 4>
Under an inert atmosphere, the compound K (0.257 g, 0.20 mmol), the compound M (0.163 g, 0.20 mmol), the compound N (0.360 g, 0.56 mmol), and the compound Q (1.064 g, 1.44 mmol), the compound R (1.031 g, 1.60 mmol), dichlorobis (triphenylphosphine) palladium (1.4 mg), and toluene (50 mL) are mixed, Heated. A 20 wt% tetraethylammonium hydroxide aqueous solution (6.6 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 2 hours and 40 minutes. After the reaction, phenylboric acid (24.4 mg) and toluene (5 mL) were added thereto, and the mixture was further refluxed for 18.5 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the organic layer was washed twice with water, twice with a 3% by weight acetic acid aqueous solution and twice with water, and when the resulting solution was added dropwise to methanol, a precipitate was formed. did. This precipitate was dissolved in toluene, passed through an alumina column and a silica gel column in this order, and the resulting solution was added dropwise to methanol and stirred to produce a precipitate. The precipitate is collected by filtration and dried, whereby the structural unit represented by the following formula (K-7), the structural unit represented by the formula (K-2), and the formula (K-3) A polymer having a structural unit represented by formula (K-6) and a structural unit represented by the following formula (K-6) in a molar ratio of 5: 5: 14: 76 (hereinafter referred to as “polymer compound C”). ) Was obtained.
The polymer compound C had a polystyrene-equivalent number average molecular weight of 4.6 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.2 × 10 ⁵ .

<Synthesis Example 1>
In an inert atmosphere, the following formula:

で表される化合物Ｓ（３．８６３ｇ、７．２８３ｍｍｏｌ）と、下記式：

Compound S (3.863 g, 7.283 mmol) represented by the following formula:

で表される化合物Ｔ（３．１７７ｇ、６．９１９ｍｍｏｌ）と、下記式：

Compound T (3.177 g, 6.919 mmol) represented by the following formula:

で表される化合物Ｕ（１５６．３ｍｇ、０．３６４ｍｍｏｌ）と、ジクロロビス（トリフェニルホスフィン）パラジウム（４．９ｍｇ）と、トリオクチルメチルアンモニウムクロリドの０．７４Ｍトルエン溶液（シグマアルドリッチ社製、商品名：Ａｌｉｑｕａｔ（登録商標）３３６、３．１ｍＬ）と、トルエン（５０ｍＬ）とを混合し、１０５℃に加熱した。反応溶液に炭酸ナトリウム水溶液（２．０Ｍ、１４ｍＬ）を滴下し、１６．５時間還流させた。反応後、そこに、フェニルホウ酸（０．５ｇ）と、トルエン（１４０ｍＬ）とを加え、更に１８．５時間還流させた。次いで、そこに、ジエチルジチオカルバミン酸ナトリウム（０．７５ｇ）及び水（５０ｍＬ）を添加した。反応溶液を油浴（８５℃）中、１６時間撹拌した。反応溶液から、水層を除去し、有機層を水で３回洗浄し、次いでシリカゲル及び塩基性アルミナのカラムに通した。こうして得られた溶液をメタノールに沈殿させ、得られた固体を、再度、トルエンに溶解させた後にメタノールに沈殿させ、得られた高分子化合物を６０℃で真空乾燥させることにより、下記式（Ｋ−８）で表される構成単位と、下記式（Ｋ−９）で表される構成単位と、前記式（Ｋ−３）で表される構成単位とを、４７．５：２．５：５０のモル比で有する重合体（以下、「高分子化合物Ｅ」と言う。）を４．２ｇ得た。
高分子化合物Ｅのポリスチレン換算数平均分子量は４．４×１０^４であり、ポリスチレン換算重量平均分子量は１．２４×１０⁵であった。

Compound U (156.3 mg, 0.364 mmol), dichlorobis (triphenylphosphine) palladium (4.9 mg), and a 0.74M toluene solution of trioctylmethylammonium chloride (manufactured by Sigma-Aldrich, trade name) : Aliquat® 336, 3.1 mL) and toluene (50 mL) were mixed and heated to 105 ° C. A sodium carbonate aqueous solution (2.0 M, 14 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 16.5 hours. After the reaction, phenylboric acid (0.5 g) and toluene (140 mL) were added thereto, and the mixture was further refluxed for 18.5 hours. Then, sodium diethyldithiocarbamate (0.75 g) and water (50 mL) were added thereto. The reaction solution was stirred in an oil bath (85 ° C.) for 16 hours. The aqueous layer was removed from the reaction solution, and the organic layer was washed three times with water and then passed through a column of silica gel and basic alumina. The solution thus obtained is precipitated in methanol, and the obtained solid is again dissolved in toluene and then precipitated in methanol. The resulting polymer compound is vacuum-dried at 60 ° C. to obtain the following formula (K The structural unit represented by -8), the structural unit represented by the following formula (K-9), and the structural unit represented by the formula (K-3) are 47.5: 2.5: 4.2 g of a polymer having a molar ratio of 50 (hereinafter referred to as “polymer compound E”) was obtained.
The polymer compound E had a polystyrene equivalent number average molecular weight of 4.4 × 10 ⁴ and a polystyrene equivalent weight average molecular weight of 1.24 × 10 ⁵ .

<Example 5>
{Production and evaluation of organic EL element A}
Using a glass substrate with an ITO film having a thickness of 45 nm formed by sputtering, an ethylene glycol monobutyl ether: water = 3: 2 (volume ratio) solution of polythiophenesulfonic acid (Sigma Aldrich, trade name: Plexcore OC 1200). The film 1 was formed by spin coating to a thickness of 50 nm and dried on a hot plate at 170 ° C. for 15 minutes.
Next, the polymer compound E was spin-coated in a 0.7% by weight xylene solution to form a film having a thickness of about 20 nm. Then, it heated at 180 degreeC for 60 minutes on the hotplate.
Thereafter, the polymer compound A was dissolved in a xylene solvent at a concentration of 1.1% by weight, and was further formed on the film 1 by spin coating at a rotational speed of 1700 rpm, whereby a film 2 was obtained. The thickness of the film 2 was about 60 nm. This was dried at 130 ° C. for 10 minutes in a nitrogen gas atmosphere, and then sodium fluoride was vacuum-deposited as a cathode at about 3 nm, and then aluminum was vacuum-deposited at about 80 nm to produce an organic EL device A. In vacuum deposition, metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.
When voltage was applied to the obtained organic EL device A, EL light emission having a peak at 480 nm derived from the polymer compound A was obtained from this device. The organic EL device A started to emit light at 2.8 V, showed light emission of 1000 cd / m ^{2 at} 5.0 V, and the maximum light emission efficiency was 8.0 cd / A.

<Example 6>
{Production and evaluation of organic EL element B}
In Example 5, instead of dissolving the polymer compound A in a xylene solvent at a concentration of 1.1% by weight, the polymer compound B was dissolved in a xylene solvent at a concentration of 1.3% by weight, and spin An organic EL element B was produced in the same manner as in Example 5 except that the rotation speed of the coat was changed from 1700 rpm to 3000 rpm. When voltage was applied to the organic EL element B, EL light emission having a peak at 475 nm derived from the polymer compound B was obtained. The organic EL element B started to emit light at 3.0 V, showed light emission of 1000 cd / m ^{2 at} 5.8 V, and the maximum light emission efficiency was 7.2 cd / A.

<Example 7>
{Production and evaluation of organic EL element C}
In Example 5, instead of dissolving the polymer compound A in a xylene solvent at a concentration of 1.1% by weight, the polymer compound C was dissolved in a xylene solvent at a concentration of 1.3% by weight, and spin An organic EL element C was produced in the same manner as in Example 5 except that the rotation speed of the coat was changed from 1700 rpm to 1030 rpm. When voltage was applied to the organic EL element C, EL light emission having a peak at 455 nm derived from the polymer compound C was obtained. The organic EL device C started to emit light at 2.8 V, and emitted light of 1000 cd / m ² at 4.9 V, and the maximum light emission efficiency was 6.9 cd / A.

<Comparative Example 1>
{Synthesis of polymer compound D}
Under an inert atmosphere, the compound L (0.275 g, 0.40 mmol), the compound N (1.289 g, 2.00 mmol), and the following formula:

で表される化合物（０．８７８ｇ、１．６０ｍｍｏｌ）と、ジクロロビス（トリフェニルホスフィン）パラジウム（４．２７ｍｇ）と、トルエン（１４５ｍＬ）とを混合し、１０５℃に加熱した。反応溶液に２０重量％水酸化テトラエチルアンモニウム水溶液（２０ｍＬ）を滴下し、２時間４０分還流させた。反応後、そこに、フェニルホウ酸（７３ｍｇ）と、トルエン（１４０ｍＬ）とを加え、更に１８．５時間還流させた。次いで、そこに、ジエチルジチアカルバミン酸ナトリウム水溶液を加え、８０℃で２時間撹拌した。冷却後、有機層を、水で２回、３重量％酢酸水溶液で２回、水で２回洗浄し、得られた溶液をメタノールに滴下したところ、沈殿物が生じたので、それをろ取した。この沈殿物をトルエンに溶解させ、アルミナカラム、シリカゲルカラムを順番に通し、得られた溶液をメタノールに滴下し、撹拌したところ、沈殿物が生じた。この沈殿物をろ取し、乾燥させることにより、前記式（Ｋ−１）で表される構成単位と、前記式（Ｋ−３）で表される構成単位とを、１０：９０のモル比で有する重合体（以下、「高分子化合物Ｄ」と言う。）を１．１ｇ得た。
高分子化合物Ｄのポリスチレン換算数平均分子量は１．８×１０⁵であり、ポリスチレン換算重量平均分子量は４．８×１０⁵であった。

Embedded image (0.878 g, 1.60 mmol), dichlorobis (triphenylphosphine) palladium (4.27 mg), and toluene (145 mL) were mixed and heated to 105 ° C. A 20 wt% tetraethylammonium hydroxide aqueous solution (20 mL) was added dropwise to the reaction solution, and the mixture was refluxed for 2 hours and 40 minutes. After the reaction, phenylboric acid (73 mg) and toluene (140 mL) were added thereto, and the mixture was further refluxed for 18.5 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the organic layer was washed twice with water, twice with a 3% by weight acetic acid aqueous solution and twice with water, and when the resulting solution was added dropwise to methanol, a precipitate was formed. did. This precipitate was dissolved in toluene, passed through an alumina column and a silica gel column in this order, and the resulting solution was added dropwise to methanol and stirred to produce a precipitate. The precipitate is filtered and dried, so that the structural unit represented by the formula (K-1) and the structural unit represented by the formula (K-3) are in a molar ratio of 10:90. 1.1 g of a polymer (hereinafter referred to as “polymer compound D”) obtained in (1) was obtained.
The polymer compound D had a polystyrene equivalent number average molecular weight of 1.8 × 10 ⁵ and a polystyrene equivalent weight average molecular weight of 4.8 × 10 ⁵ .

{Production and evaluation of organic EL element D}
In Example 5, instead of dissolving the polymer compound A in the xylene solvent at a concentration of 1.1% by weight, the polymer compound D was dissolved in the xylene solvent at a concentration of 1.3% by weight, and spin An organic EL element D was produced in the same manner as in Example 5 except that the rotation speed of the coat was changed from 1700 rpm to 2150 rpm. When voltage was applied to the organic EL element D, EL light emission having a peak at 480 nm derived from the polymer compound D was obtained. The organic EL element D started to emit light at 3.2 V, showed light emission of 1000 cd / m ^{2 at} 5.6 V, and the maximum light emission efficiency was 6.3 cd / A.

Claims (18)

The high molecular compound containing the 1st structural unit represented by the following general formula ( 3 ), and the 2nd structural unit represented by the following general formula (2).

[In general formula ( 3 ),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic ring. Group or a group represented by —O—R ^A is shown, and these groups optionally have a substituent. R ^A represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. When a plurality of ^RA are present, they may be the same or different. However, one of R ³ and R ⁴ and one of R ⁸ and R ⁹ are unsubstituted or substituted aryl groups.
Ar ⁵ and Ar ⁶ each independently represent an unsubstituted or substituted arylene group, or an unsubstituted or substituted divalent aromatic heterocyclic group, or an arylene group and a divalent aromatic heterocyclic group identical or different radicals selected from the group consisting of the divalent group linked two or more. ]

[In General Formula (2), Ar ¹ , Ar ² , Ar ³ and Ar ⁴ each independently represent an unsubstituted or substituted arylene group or an unsubstituted or substituted divalent aromatic heterocyclic group] Alternatively, it represents a divalent group in which two or more identical or different groups selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group are linked. Ar ¹ and Ar ² , and Ar ² and Ar ³ are directly bonded to each other, or —O—, —S—, —C (═O) —, —C (═O) —O—, —N Even if bonded via a group represented by (R ^A )-, -C (= O) -N (R ^A )-or -C (R ^A ) _2- , a 5- to 7-membered ring is formed. Good. R ¹¹ , R ¹² and R ¹³ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an arylalkyl group, and these groups have a substituent. May be. a represents an integer of 0 to 3, and b represents 0 or 1. R ^A represents the same meaning as described above. When a plurality of ^RA are present, they may be the same or different. ] In the general formula (3), the R ^Three And R ^Four On the other hand, the aforementioned R ⁸ And R ⁹ The other, R ¹ , R ² , R ^Five , R ⁶ , R ⁷ And R ^Ten The polymer compound according to claim 1, wherein is a hydrogen atom.   The polymer compound according to claim 1, wherein in the general formula (2), a = b = 0.   The polymer compound according to claim 1 or 2, wherein in the general formula (2), a = 1 and b = 0. The high molecular compound according to any one of claims 1 to 4, wherein Ar ² in the general formula (2) is an unsubstituted or substituted phenylene group. In the general formula (2), Ar ² is an unsubstituted or substituted biphenyl-4,4'-diyl group, a polymer compound according to any one of claims 1-4. In Formula (3), Ar ⁵ and Ar ⁶ is an unsubstituted or substituted phenylene group, a polymer compound according to any one of claims 1 to 6. The first structural unit, the second structural unit, the third structural unit represented by the following general formula (4) and / or the fourth structural unit represented by the following general formula (5) (however, the first structural unit : configuration is different from the unit and a third structural unit.) a polymer compound according to any one of claims 1-7.

[In General Formula (4), each of R ¹⁴ and R ¹⁵ independently represents an unsubstituted or substituted alkyl group, an unsubstituted or substituted aryl group, or an unsubstituted or substituted monovalent aromatic heterocyclic group. Show. ]

[In the general formula (5), Ar ⁷ represents an unsubstituted or substituted arylene group, an unsubstituted or substituted divalent aromatic heterocyclic group, or an arylene group and a divalent aromatic heterocyclic group. It represents a divalent group in which two or more identical or different groups selected from the group consisting of cyclic groups are linked. ] The polymer compound according to any one of claims 1 to 8 , which is a conjugated polymer compound. The content of the first structural unit is 0.1 to 20 mol% with respect to the total content of the first structural unit, the second structural unit, and the third structural unit, and the second the content of structural units, wherein the first structural unit, the total content of the second structural unit, and the third structural unit, 0.1 to 30 mol%, of claim 8 or 9 High molecular compound. It is a manufacturing method of the high molecular compound as described in any one of Claims 1-10 , Comprising : The process of superposing | polymerizing the compound shown by the following general formula (3M), and the compound shown by the following general formula (2M). A method for producing a polymer compound, comprising:

[In the general formula (3M),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic ring. Group or a group represented by —O—R ^A is shown, and these groups optionally have a substituent. R ^A represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. When a plurality of ^RA are present, they may be the same or different. However, one of R ³ and R ⁴ and one of R ⁸ and R ⁹ are unsubstituted or substituted aryl groups.
Ar ⁵ and Ar ⁶ each independently represent an unsubstituted or substituted arylene group, or an unsubstituted or substituted divalent aromatic heterocyclic group, or an arylene group and a divalent aromatic heterocyclic group Represents a divalent group in which two or more identical or different groups selected from the group consisting of
Z ¹ and Z ² each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. ]
<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ¹⁶ (R ¹⁶ may be substituted with an alkyl group, an alkyl group, an alkoxy group, a nitro group, a fluorine atom or a cyano group. Represents a good aryl group.)
<Substituent group B>
—B (OR ¹⁷ ) ₂ (R ¹⁷ represents a hydrogen atom or an alkyl group, and two R ^{17 s} may be the same or different and may be bonded to each other to form a ring.) A group represented by the formula: —BF ₄ Q ¹ (Q ¹ is a monovalent cation of lithium, sodium, potassium, rubidium or cesium), —MgY ¹ (Y ¹ is chlorine A group represented by —ZnY ² (Y ² represents a chlorine atom, a bromine atom or an iodine atom), —Sn (R ¹⁸ ) ₃ (R ¹⁸ represents a hydrogen atom or an alkyl group, and three R ^{18 s} may be the same or different, and may be bonded to each other to form a ring).

[In General Formula (2M), each of Ar ¹ , Ar ² , Ar ³ and Ar ⁴ independently represents an unsubstituted or substituted arylene group or an unsubstituted or substituted divalent aromatic heterocyclic group Alternatively, it represents a divalent group in which two or more identical or different groups selected from the group consisting of an arylene group and a divalent aromatic heterocyclic group are linked. R ¹¹ , R ¹² and R ¹³ each independently represents a hydrogen atom, an alkyl group, an aryl group, a monovalent aromatic heterocyclic group or an arylalkyl group, and these groups have a substituent. May be. a represents an integer of 0 to 3, and b represents 0 or 1. Z ³ and Z ⁴ each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. ] The compound represented by the following general formula ( 3M) .

[In the general formula (3M),
R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom, an alkyl group, an aryl group, or a monovalent aromatic heterocyclic ring. Group or a group represented by —O—R ^A is shown, and these groups optionally have a substituent. R ^A represents an alkyl group, an aryl group, or a monovalent aromatic heterocyclic group, and these groups optionally have a substituent. When a plurality of ^RA are present, they may be the same or different. However, one of R ³ and R ⁴ and one of R ⁸ and R ⁹ are unsubstituted or substituted aryl groups.
Are each A r ⁵ and Ar ⁶ independently an unsubstituted or substituted arylene group, or, or an unsubstituted or substituted divalent aromatic heterocyclic group, or an arylene group and a divalent aromatic heterocyclic It represents a divalent group in which two or more identical or different groups selected from the group consisting of groups are linked.
Z ¹ and Z ² each independently represent any group selected from the group consisting of the substituent group A and the substituent group B. ]
<Substituent group A>
Chlorine atom, bromine atom, iodine atom, —O—S (═O) ₂ R ¹⁶ (R ¹⁶ may be substituted with an alkyl group, an alkyl group, an alkoxy group, a nitro group, a fluorine atom or a cyano group. Represents a good aryl group.)
<Substituent group B>
—B (OR ¹⁷ ) ₂ (R ¹⁷ represents a hydrogen atom or an alkyl group, and two R ^{17 s} may be the same or different and may be bonded to each other to form a ring.) A group represented by the formula: —BF ₄ Q ¹ (Q ¹ is a monovalent cation of lithium, sodium, potassium, rubidium or cesium), —MgY ¹ (Y ¹ is chlorine A group represented by —ZnY ² (Y ² represents a chlorine atom, a bromine atom or an iodine atom), —Sn (R ¹⁸ ) ₃ (R ¹⁸ represents a hydrogen atom or an alkyl group, and three R ^{18 s} may be the same or different, and may be bonded to each other to form a ring). A polymer composition comprising the polymer compound according to any one of claims 1 to 10 and at least one material selected from the group consisting of a hole transport material, an electron transport material and a light emitting material. The solution containing the high molecular compound and solvent as described in any one of Claims 1-10 . An organic thin film containing the polymer compound according to any one of claims 1 to 10 , or the polymer composition according to claim 13 . A light emitting element provided with the organic thin film of Claim 15 . A planar light source comprising the light emitting device according to claim 16 . A display device comprising the light emitting device according to claim 16 .