JP5955660B2 - Composition, polymer compound and light emitting device using them - Google Patents

Description

  The present invention relates to a composition, a polymer compound, an organic thin film, an insolubilized organic thin film, and a light emitting device.

  As a polymer compound used for an organic electroluminescence device (hereinafter referred to as “light-emitting device”), for example, a polymer compound (Patent Document 1) containing the following repeating unit derived from arylamine, and a substituent at a specific position A polymer compound (Patent Document 2) containing the following phenylene group having a repeating unit as a repeating unit is known.

JP 2004-143419 A JP 2010-189630 A

  However, the luminance life of the light emitting device using the above polymer compound is not always sufficient.

  In view of the above, an object of the present invention is to provide a composition and a polymer compound that are useful for producing a light-emitting device having excellent luminance life. Another object of the present invention is to provide an organic thin film, an insolubilized thin film and a light-emitting device containing the composition or polymer compound.

  That is, the present invention provides the following composition, polymer compound, organic thin film, insolubilized organic thin film and light-emitting device containing the composition or polymer compound.

［式中、
Ａｒ¹およびＡｒ³は、それぞれ独立に、置換基を有していてもよいアリーレン基または置換基を有していてもよい２価の複素環基である。
Ａｒ²およびＡｒ⁴は、それぞれ独立に、置換基を有していてもよいアリーレン基、置換基を有していてもよい２価の複素環基、または、置換基を有していてもよいアリーレン基および置換基を有していてもよい２価の複素環基からなる群から選ばれる同一もしくは異なる２以上の基が連結している２価の基である。
Ｒ¹、Ｒ²およびＲ³は、それぞれ独立に、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアリール基または置換基を有していてもよい１価の複素環基である。
Ａｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、Ｒ¹、Ｒ²およびＲ³はそれぞれ、当該基が結合している窒素原子に結合している当該基以外の基と、直接結合していてもよく、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｎ（Ｒ^a1）−または−Ｃ（Ｒ^a1）₂−を介して結合していてもよい。Ｒ^a1は、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基、ハロゲン原子または置換基を有していてもよい１価の複素環基である。Ｒ^a1が複数個存在する場合、各々のＲ^a1は互いに同一であっても異なっていてもよく、互いに結合して各々が結合する炭素原子とともに環構造を形成していてもよい。
ｘおよびｙは、それぞれ独立に、０または１である。］

［式中、
Ａｒ⁵は、Ｒ⁴以外の置換基を有していてもよいアリーレン基またはＲ⁴以外の置換基を有していてもよい２価の複素環基である。
Ｒ⁴は、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアルキルチオ基、置換基を有していてもよいアリール基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアリールチオ基、置換基を有していてもよいアリールアルキル基、置換基を有していてもよいアリールアルコキシ基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアミノ基、置換基を有していてもよいシリル基、ハロゲン原子、置換基を有していてもよいアシル基、置換基を有していてもよいアシルオキシ基、置換基を有していてもよいオキシカルボニル基、置換基を有していてもよい１価の複素環基、置換基を有していてもよい複素環オキシ基、置換基を有していてもよい複素環チオ基、置換基を有していてもよいイミン残基、置換基を有していてもよいアミド化合物残基、置換基を有していてもよい酸イミド残基、置換基を有していてもよいカルボキシル基、ヒドロキシル基、ニトロ基またはシアノ基である。Ｒ⁴が複数個存在する場合、各々のＲ⁴は互いに同一であっても異なっていてもよい。Ｒ⁴は、Ａｒ⁵を構成する炭素原子のうち、他の構成単位と結合を形成する炭素原子の隣の炭素原子に、直接結合している基である。
ａは１以上の整数である。］

［式中、
Ｒ^xは、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアミノ基、置換基を有していてもよいシリル基、ハロゲン原子、置換基を有していてもよいアシル基、置換基を有していてもよい１価の複素環基、置換基を有していてもよいカルボキシル基、ニトロ基またはシアノ基である。各々のＲ^ｘは互いに同一であっても異なっていてもよく、互いに結合して各々が結合する炭素原子とともに環構造を形成していてもよい。］

［式中、
Ｒⁿは、水素原子、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアリール基または置換基を有していてもよい１価の複素環基である。各々のＲⁿは互いに同一であっても異なっていてもよい。
Ａｒ⁶およびＡｒ⁷は、それぞれ独立に、置換基を有していてもよいアリール基または置換基を有していてもよい１価の複素環基である。Ａｒ⁶およびＡｒ⁷はそれぞれ、隣接するＲⁿと直接結合して、それぞれが結合する炭素原子とともに環構造を形成してもよい。］
〔２〕化合物（Ｂ）の含有量（合計含有量）は、高分子化合物（Ａ）に含まれる全構成単位のモル数および化合物（Ｂ）のモル数の合計に対して、０．００１〜５０モル％である、上記〔１〕に記載の組成物。
〔３〕前記式（１）で表される構成単位（１）と、前記式（２）で表される構成単位（２）と、を含む高分子化合物（Ａ）と、
フラーレンまたはフラーレン誘導体を含む構成単位、前記式（３）で表されるアズレンまたはアズレン誘導体を含む構成単位、および、前記式（４）で表されるスチルベンまたはスチルベン誘導体を含む構成単位からなる群から選ばれる１種以上の構成単位である構成単位（ｃ−１）を含む高分子化合物（Ｃ）と、を含む組成物。
〔４〕高分子化合物（Ｃ）に含まれる構成単位（ｃ−１）の含有量（合計含有量）は、高分子化合物（Ａ）および高分子化合物（Ｃ）に含まれる全構成単位に対して、０．００１〜５０モル％である、上記〔３〕に記載の組成物。
〔５〕フラーレンまたはフラーレン誘導体を含む構成単位が、式（５−１）で表される構成単位である、上記〔３〕または〔４〕に記載の組成物。

［式中、
Ａｒ⁸は、１つの置換基を有し、かつ、それ以外の置換基を有していてもよいアリーレン基、または、１つの置換基を有し、かつ、それ以外の置換基を有していてもよい２価の複素環基である。
Ａｒ¹⁴は、置換基を有していてもよいアリーリジン基または置換基を有していてもよい３価の複素環基である。
Ｒ⁷は、単結合、置換基を有していてもよい炭素原子数１〜２０のアルキレン基、置換基を有していてもよい炭素原子数６〜２０のアリーレン基、または、これらを組み合わせた２価の基である。
Ｒ⁵およびＲ⁶は、それぞれ独立に、水素原子、置換基を有していてもよい炭素原子数１〜２０のアルキル基または置換基を有していてもよい炭素原子数１〜２０のアルコキシ基である。
環Ｆはフラーレンである。
ｑは１〜４の整数である。ｐは０又は１である。
Ｒ⁷が複数個存在する場合、各々のＲ⁷は互いに同一であっても異なっていてもよい。Ａｒ¹⁴が複数個存在する場合、各々のＡｒ¹⁴は互いに同一であっても異なっていてもよい。Ｒ⁵が複数個存在する場合、各々のＲ⁵は互いに同一であっても異なっていてもよい。Ｒ⁶が複数個存在する場合、各々のＲ⁶は互いに同一であっても異なっていてもよい。ｐが複数個存在する場合、各々のｐは互いに同一であっても異なっていてもよい。環Ｆが複数個存在する場合、各々の環Ｆは互いに同一であっても異なっていてもよい。ｐが０のとき、Ｒ⁵で置換されている炭素原子とＲ⁶で置換されている炭素原子は直接結合していない。］
〔６〕式（３）で表されるアズレンまたはアズレン誘導体を含む構成単位が、式（１２−１）で表される構成単位である、上記〔３〕〜〔５〕のいずれか一項に記載の組成物。

［式中、Ｒ^xは、前記と同義である。］
〔７〕式（４）で表されるスチルベンまたはスチルベン誘導体を含む構成単位が、式（７ａ）で表される構成単位、式（７ｂ）で表される構成単位および式（７ｃ）で表される構成単位からなる群から選ばれる１種以上の構成単位である、上記〔１〕〜〔６〕のいずれか一項に記載の組成物。

［式中、
ＲⁿおよびＡｒ⁷は、前記と同義である。
Ａｒ⁹は、１つの置換基を有し、かつ、それ以外の置換基を有していてもよいアリーレン基または１つの置換基を有し、かつ、それ以外の置換基を有していてもよい２価の複素環基である。］

［式中、
Ｒⁿは、前記と同義である。
Ａｒ^9’は、置換基を有していてもよいアリーレン基または置換基を有していてもよい２価の複素環基である。各々のＡｒ^9’は、互いに同一であっても異なっていてもよい。Ａｒ^9’はＲⁿと直接結合して、それぞれが結合する炭素原子とともに環構造を形成してもよい。］

［式中、
Ｒⁿ、Ａｒ⁷およびＡｒ^9’は、前記と同義である。
Ｒ^n’は、置換基を有していてもよいアリーレン基または置換基を有していてもよい２価の複素環基である。
Ａｒ^9’はＲ^n’と直接結合して、それぞれが結合する炭素原子とともに環構造を形成してもよい。］
〔８〕式（１）で表される構成単位（１）は、式（１ａ）で表される構成単位である、上記〔１〕〜〔７〕のいずれか一項に記載の組成物。

［式中、
Ｒ^9a、Ｒ^9bおよびＲ^9cは、それぞれ独立に、置換基を有していてもよいアルキル基、置換基を有していてもよいアルコキシ基、置換基を有していてもよいアルキルチオ基、置換基を有していてもよいアリール基、置換基を有していてもよいアリールオキシ基、置換基を有していてもよいアリールチオ基、置換基を有していてもよいアルケニル基、置換基を有していてもよいアルキニル基、置換基を有していてもよいアミノ基、置換基を有していてもよいシリル基、ハロゲン原子、置換基を有していてもよいアシル基、置換基を有していてもよいアシルオキシ基、置換基を有していてもよいオキシカルボニル基、置換基を有していてもよい１価の複素環基、置換基を有していてもよい複素環オキシ基、置換基を有していてもよい複素環チオ基、置換基を有していてもよいイミン残基、置換基を有していてもよいアミド化合物残基、置換基を有していてもよい酸イミド残基、置換基を有していてもよいカルボキシル基、ヒドロキシル基、ニトロ基またはシアノ基である。
Ｒ^9aが複数個存在する場合、各々のＲ^9aは互いに同一であっても異なっていてもよい。Ｒ^9bが複数個存在する場合、各々のＲ^9bは互いに同一であっても異なっていてもよい。Ｒ^9cが複数個存在する場合、各々のＲ^9cは互いに同一であっても異なっていてもよい。
Ａｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、ｘおよびｙは、式（１）のＡｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、ｘおよびｙと、それぞれ同義である。
ｈ、ｉおよびｊは、それぞれ独立に、０〜５の整数である。］
〔９〕Ａｒ¹およびＡｒ³が、置換基を有していてもよいフェニレン基であり、
Ａｒ²またはＡｒ⁴が、置換基を有していてもよいフェニレン基、置換基を有していてもよいビフェニリレン基および置換基を有していてもよいフルオレンジイル基からなる群から選ばれる１種の基である、上記〔１〕〜〔８〕のいずれか一項に記載の組成物。
〔１０〕Ａｒ⁵が、フェニレン基またはフルオレンジイル基である、上記〔１〕〜〔９〕のいずれか一項に記載の組成物。
〔１１〕高分子化合物（Ａ）は、架橋基を有する構成単位をさらに含む、上記〔１〕〜〔１０〕のいずれか一項に記載の組成物。
〔１２〕高分子化合物（Ｃ）は、架橋基を有する構成単位をさらに含む、上記〔３〕〜〔１１〕のいずれか一項に記載の組成物。
〔１３〕架橋基が、式（Ｑ−１）で表される基である、上記〔１１〕または〔１２〕に記載の組成物。

［式中、ベンゾシクロブテンは、置換基を有していてもよい。］
〔１４〕上記式（１）で表される構成単位（１）と、
上記式（２）で表される構成単位（２）と、
フラーレンまたはフラーレン誘導体を含む構成単位、上記式（３）で表されるアズレンまたはアズレン誘導体を含む構成単位、および、上記式（４）で表されるスチルベンまたはスチルベン誘導体を含む構成単位からなる群から選ばれる１種以上の構成単位である構成単位（ｃ−１）と、を含む高分子化合物。
〔１５〕構成単位（ｃ−１）の含有量（合計含有量）は、高分子化合物中に含まれる全構成単位に対して、０．００１〜５０モル％である、上記〔１４〕に記載の高分子化合物。
〔１６〕フラーレンもしくはフラーレン誘導体を含む構成単位が、上記式（５−１）で表される構成単位である、上記〔１４〕または〔１５〕に記載の組成物。
〔１７〕式（３）で表されるアズレンまたはアズレン誘導体を含む構成単位が、上記式（１２−１）で表される構成単位である、上記〔１４〕〜〔１６〕のいずれか一項に記載の高分子化合物。
〔１８〕式（４）で表されるスチルベンまたはスチルベン誘導体を含む構成単位が、上記式（７ａ）で表される構成単位、上記式（７ｂ）で表される構成単位および上記式（７ｃ）で表される構成単位からなる群から選ばれる１種以上の構成単位である、上記〔１４〕〜〔１７〕のいずれか一項に記載の高分子化合物。
〔１９〕式（１）で表される構成単位（１）は、上記式（１ａ）で表される構成単位である、上記〔１４〕〜〔１８〕のいずれか一項に記載の高分子化合物。
〔２０〕Ａｒ¹およびＡｒ³が、置換基を有していてもよいフェニレン基であり、
Ａｒ²またはＡｒ⁴が、置換基を有していてもよいフェニレン基、置換基を有していてもよいビフェニリレン基および置換基を有していてもよいフルオレンジイル基からなる群から選ばれる１種の基である、上記〔１４〕〜〔１９〕のいずれか一項に記載の高分子化合物。
〔２１〕Ａｒ⁵が、フェニレン基またはフルオレンジイル基である、上記〔１４〕〜〔２０〕のいずれか一項に記載の高分子化合物。
〔２２〕高分子化合物は、架橋基を有する構成単位をさらに含む、上記〔１４〕〜〔２１〕のいずれか一項に記載の高分子化合物。
〔２３〕架橋基が、上記式（Ｑ−１）で表される基である、上記〔２２〕に記載の高分子化合物。
〔２４〕上記〔１〕〜〔１３〕のいずれか一項に記載の組成物または上記〔１４〕〜〔２３〕のいずれか一項に記載の高分子化合物と、溶媒と、を含む液状組成物。
〔２５〕上記〔１〕〜〔１３〕のいずれか一項に記載の組成物または上記〔１４〕〜〔２３〕のいずれか一項に記載の高分子化合物を含む、有機薄膜。
〔２６〕上記〔２５〕に記載の有機薄膜を、不溶化させた、不溶化有機薄膜。
〔２７〕上記〔２５〕に記載の有機薄膜または上記〔２６〕に記載の不溶化有機薄膜を備える、発光素子。
〔２８〕上記〔２５〕に記載の有機薄膜または上記〔２６〕に記載の不溶化有機薄膜が、正孔輸送層である、上記〔２７〕に記載の発光素子。 [1] A polymer compound (A) containing the structural unit (1) represented by the formula (1) and the structural unit (2) represented by the formula (2);
A composition comprising a fullerene or a fullerene derivative, an azulene or an azulene derivative represented by formula (3), or a compound (B) that is a stilbene or stilbene derivative represented by formula (4).

[Where:
Ar ¹ and Ar ³ are each independently an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent.
Ar ² and Ar ⁴ may each independently have an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a substituent. A divalent group in which two or more identical or different groups selected from the group consisting of an arylene group and a divalent heterocyclic group which may have a substituent are linked.
R ¹ , R ² and R ³ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is a monovalent heterocyclic group.
Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² and R ³ may each be directly bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded. It may be bonded via —O—, —S—, —C (═O) —, —N (R ^a1 ) — or —C (R ^a1 ) ₂ —. R ^a1 has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a halogen atom or a substituent. And a monovalent heterocyclic group which may be used. When a plurality of R ^a1 are present, each R ^a1 may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atoms to which each is bonded.
x and y are each independently 0 or 1. ]

[Where:
Ar ⁵ is R ⁴ other than a bivalent which may have an optionally substituted arylene group or R ⁴ substituent other than a heterocyclic group.
R ⁴ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and an aryl which may have a substituent. Group, aryloxy group which may have a substituent, arylthio group which may have a substituent, arylalkyl group which may have a substituent, aryl which may have a substituent Alkoxy group, optionally substituted alkenyl group, optionally substituted alkynyl group, optionally substituted amino group, optionally substituted silyl group A halogen atom, an optionally substituted acyl group, an optionally substituted acyloxy group, an optionally substituted oxycarbonyl group, and optionally having a substituent. Even if it has a monovalent heterocyclic group or substituent A heterocyclic oxy group which may have a substituent, a heterocyclic thio group which may have a substituent, an imine residue which may have a substituent, an amide compound residue which may have a substituent, a substituent An acid imide residue which may have, a carboxyl group which may have a substituent, a hydroxyl group, a nitro group or a cyano group. When a plurality of R ⁴ are present, each R ⁴ may be the same as or different from each other. R ⁴ is a group that is directly bonded to a carbon atom adjacent to a carbon atom that forms a bond with another structural unit among the carbon atoms that constitute Ar ⁵ .
a is an integer of 1 or more. ]

[Where:
R ^x has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alkynyl group that may have a substituent, an amino group that may have a substituent, a silyl group that may have a substituent, a halogen atom, and a substituent. An acyl group which may be substituted, a monovalent heterocyclic group which may have a substituent, a carboxyl group which may have a substituent, a nitro group or a cyano group. Each R ^x may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atom to which each is bonded. ]

[Where:
R ⁿ has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is also a monovalent heterocyclic group. Each R ⁿ may be the same as or different from each other.
Ar ⁶ and Ar ⁷ are each independently an aryl group which may have a substituent or a monovalent heterocyclic group which may have a substituent. Ar ⁶ and Ar ⁷ may be directly bonded to adjacent R ⁿ to form a ring structure together with the carbon atom to which each is bonded. ]
[2] The content (total content) of the compound (B) is 0.001 to the total number of moles of all the structural units contained in the polymer compound (A) and the number of moles of the compound (B). The composition according to the above [1], which is 50 mol%.
[3] A polymer compound (A) comprising the structural unit (1) represented by the formula (1) and the structural unit (2) represented by the formula (2);
From the group consisting of a structural unit containing a fullerene or a fullerene derivative, a structural unit containing an azulene or an azulene derivative represented by the formula (3), and a structural unit containing a stilbene or a stilbene derivative represented by the formula (4) And a polymer compound (C) containing the structural unit (c-1) which is one or more selected structural units.
[4] The content (total content) of the structural unit (c-1) contained in the polymer compound (C) is based on the total structural units contained in the polymer compound (A) and the polymer compound (C). The composition according to [3], which is 0.001 to 50 mol%.
[5] The composition according to [3] or [4] above, wherein the structural unit containing fullerene or a fullerene derivative is a structural unit represented by the formula (5-1).

[Where:
Ar ⁸ has one substituent and an arylene group which may have other substituents, or one substituent and other substituents. It may be a divalent heterocyclic group.
Ar ¹⁴ is an arylidine group which may have a substituent or a trivalent heterocyclic group which may have a substituent.
R ⁷ represents a single bond, an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted arylene group having 6 to 20 carbon atoms, or a combination thereof. Divalent group.
R ⁵ and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted alkoxy group having 1 to 20 carbon atoms. It is a group.
Ring F is fullerene.
q is an integer of 1-4. p is 0 or 1.
When a plurality of R ⁷ are present, each R ⁷ may be the same as or different from each other. When a plurality of Ar ¹⁴ are present, each Ar ¹⁴ may be the same as or different from each other. When a plurality of R ⁵ are present, each R ⁵ may be the same as or different from each other. When a plurality of R ⁶ are present, each R ⁶ may be the same as or different from each other. When a plurality of p are present, each p may be the same as or different from each other. When a plurality of rings F are present, each ring F may be the same as or different from each other. When p is 0, the carbon atom substituted with R ⁵ and the carbon atom substituted with R ⁶ are not directly bonded. ]
[6] In any one of the above [3] to [5], the structural unit containing azulene or an azulene derivative represented by the formula (3) is a structural unit represented by the formula (12-1). The composition as described.

[Wherein, R ^x has the same meaning as described above. ]
[7] The structural unit containing the stilbene or stilbene derivative represented by the formula (4) is represented by the structural unit represented by the formula (7a), the structural unit represented by the formula (7b), and the formula (7c). The composition according to any one of [1] to [6], which is one or more structural units selected from the group consisting of:

[Where:
R ⁿ and Ar ⁷ are as defined above.
Ar ⁹ has one substituent and an arylene group which may have other substituents or one substituent and may have other substituents It is a good divalent heterocyclic group. ]

[Where:
R ⁿ has the same meaning as described above.
Ar ^{9 ′} is an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. Each Ar ^{9 ′} may be the same as or different from each other. Ar ^{9 ′} may be directly bonded to R ⁿ to form a ring structure together with the carbon atom to which each is bonded. ]

[Where:
R ⁿ , Ar ⁷ and Ar ^{9 ′} are as defined above.
R ^{n ′} is an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent.
Ar ^{9 ′} may be directly bonded to R ^{n ′} to form a ring structure together with the carbon atom to which each is bonded. ]
[8] The composition according to any one of [1] to [7], wherein the structural unit (1) represented by the formula (1) is a structural unit represented by the formula (1a).

[Where:
R ^9a , R ^9b and R ^9c each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, Aryl group optionally having substituent, aryloxy group optionally having substituent, arylthio group optionally having substituent, alkenyl group optionally having substituent, substituted An alkynyl group which may have a group, an amino group which may have a substituent, a silyl group which may have a substituent, a halogen atom, an acyl group which may have a substituent, An acyloxy group which may have a substituent, an oxycarbonyl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, and a substituent. A heterocyclic oxy group, an optionally substituted heterocyclic thio group, An imine residue optionally having a substituent, an amide compound residue optionally having a substituent, an acid imide residue optionally having a substituent, and optionally having a substituent A carboxyl group, a hydroxyl group, a nitro group or a cyano group.
When a plurality of R ^9a are present, each R ^9a may be the same as or different from each other. When a plurality of R ^9b are present, each R ^9b may be the same as or different from each other. When a plurality of R ^9c are present, each R ^9c may be the same as or different from each other.
^{Ar 1, Ar 2, Ar 3} , Ar 4, x and y, and ^{Ar 1, Ar 2, Ar 3} , Ar 4, x and y of formula (1), which is the same meaning.
h, i, and j are each independently an integer of 0 to 5. ]
[9] Ar ¹ and Ar ³ are an optionally substituted phenylene group,
Ar ² or Ar ⁴ is selected from the group consisting of a phenylene group that may have a substituent, a biphenylylene group that may have a substituent, and a fluorenediyl group that may have a substituent. The composition according to any one of [1] to [8], which is one kind of group.
[10] The composition according to any one of [1] to [9], wherein Ar ⁵ is a phenylene group or a fluorenediyl group.
[11] The composition according to any one of [1] to [10], wherein the polymer compound (A) further includes a structural unit having a crosslinking group.
[12] The composition according to any one of [3] to [11], wherein the polymer compound (C) further includes a structural unit having a crosslinking group.
[13] The composition according to [11] or [12] above, wherein the crosslinking group is a group represented by the formula (Q-1).

[In the formula, benzocyclobutene may have a substituent. ]
[14] The structural unit (1) represented by the above formula (1),
The structural unit (2) represented by the above formula (2);
From the group consisting of a structural unit containing a fullerene or a fullerene derivative, a structural unit containing an azulene or an azulene derivative represented by the above formula (3), and a structural unit containing a stilbene or a stilbene derivative represented by the above formula (4) And a structural unit (c-1) which is one or more selected structural units.
[15] The content (total content) of the structural unit (c-1) is 0.001 to 50 mol% with respect to all structural units contained in the polymer compound, as described in [14] above. High molecular compound.
[16] The composition according to [14] or [15] above, wherein the structural unit containing fullerene or a fullerene derivative is a structural unit represented by the formula (5-1).
[17] Any one of [14] to [16] above, wherein the structural unit containing azulene or an azulene derivative represented by the formula (3) is a structural unit represented by the formula (12-1). The high molecular compound as described in.
[18] The structural unit containing the stilbene or stilbene derivative represented by the formula (4) is a structural unit represented by the above formula (7a), a structural unit represented by the above formula (7b), and the above formula (7c). The polymer compound according to any one of [14] to [17], which is one or more structural units selected from the group consisting of structural units represented by:
[19] The polymer according to any one of [14] to [18], wherein the structural unit (1) represented by the formula (1) is a structural unit represented by the formula (1a). Compound.
[20] Ar ¹ and Ar ³ are an optionally substituted phenylene group,
Ar ² or Ar ⁴ is selected from the group consisting of a phenylene group that may have a substituent, a biphenylylene group that may have a substituent, and a fluorenediyl group that may have a substituent. The polymer compound according to any one of [14] to [19], which is one kind of group.
[21] The polymer compound according to any one of [14] to [20], wherein Ar ⁵ is a phenylene group or a fluorenediyl group.
[22] The polymer compound according to any one of [14] to [21], wherein the polymer compound further includes a structural unit having a crosslinking group.
[23] The polymer compound according to [22], wherein the crosslinking group is a group represented by the formula (Q-1).
[24] A liquid composition comprising the composition according to any one of [1] to [13] or the polymer compound according to any one of [14] to [23], and a solvent. object.
[25] An organic thin film comprising the composition according to any one of [1] to [13] or the polymer compound according to any one of [14] to [23].
[26] An insolubilized organic thin film obtained by insolubilizing the organic thin film according to [25].
[27] A light emitting device comprising the organic thin film according to [25] or the insolubilized organic thin film according to [26].
[28] The light-emitting device according to [27], wherein the organic thin film according to [25] or the insolubilized organic thin film according to [26] is a hole transport layer.

  ADVANTAGE OF THE INVENTION According to this invention, the composition useful for manufacture of the light emitting element which is excellent in a luminance lifetime, and a high molecular compound can be provided. Moreover, according to this invention, the organic thin film, the insolubilized organic thin film, and light emitting element containing the said composition or high molecular compound can be provided.

<Explanation of terms>
Hereinafter, terms commonly used in this specification will be described with examples as necessary.

“Me” represents a methyl group, “Et” represents an ethyl group, “Ph” represents a phenyl group, “t-Bu” and “ ^t Bu” represent tert-butyl groups, “n-Bu” "Represents a normal butyl group," n-Hex "represents a normal hexyl group, and" n-Oct "represents a normal octyl group.

  “Structural unit” means one or more units present in a polymer compound. “Repeating unit” means a unit present in two or more in a polymer compound.

“C _{x to} C _y ” (x and y are positive integers satisfying x <y) means that the number of carbon atoms of the partial structure corresponding to the functional group name described immediately after this term is x Means ~ y. That is, the organic groups described immediately after "C _x -C _y" is more functional groups name combination named organic radicals (e.g., C _x -C _y alkoxyphenyl group), then a plurality of It means that the number of carbon atoms of the partial structure corresponding to the functional group name (for example, alkoxy) described immediately after “C _{x to} C _y ” among the functional group names is _x to _y . For example, “C ₁ -C ₁₂ alkyl group” means an alkyl group having 1 to 12 carbon atoms, and “C ₁ -C ₁₂ alkoxyphenyl group” has “1 to 12 carbon atoms”. It means a phenyl group having an “alkoxy group”.

  In this specification, “may have a substituent” means that part or all of the hydrogen atoms constituting the compound or group described immediately after that may be substituted with a substituent. means. Unless otherwise specified, examples of the substituent include the following substituents. On the other hand, for example, a halogen atom, a hydrocarbyl group having 1 to 30 carbon atoms, a hydrocarbyloxy group having 1 to 30 carbon atoms, and a hydrocarbyl mercapto group having 1 to 30 carbon atoms, among these, a halogen atom A hydrocarbyl group having 1 to 18 carbon atoms, a hydrocarbyloxy group having 1 to 18 carbon atoms, or a hydrocarbyl mercapto group having 1 to 18 carbon atoms, preferably a halogen atom, a hydrocarbyl group having 1 to 12 carbon atoms, Alternatively, a hydrocarbyloxy group having 1 to 12 carbon atoms is more preferable, and a halogen atom or a hydrocarbyl group having 1 to 12 carbon atoms is particularly preferable. The number of substituents is one or more, and when there are a plurality of substituents, each substituent may be the same or different.

  Examples of the substituent in the present specification include an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an alkenyl group, an alkynyl group, an amino group, a silyl group, a halogen atom, an acyl group, and an acyloxy group. Oxycarbonyl group, monovalent heterocyclic group, heterocyclic oxy group, heterocyclic thio group, imine residue, amide compound residue, acid imide residue, carboxyl group, hydroxyl group, nitro group and cyano group . These groups may further have a substituent selected from the above.

  The “alkyl group” may have a substituent, and the alkyl group may be any of a linear alkyl group, a branched alkyl group, and a cyclic alkyl group (cycloalkyl group). Unless otherwise specified, the number of carbon atoms of the linear alkyl group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 12, not including the number of carbon atoms of the substituent. Unless otherwise specified, the number of carbon atoms of the branched alkyl group and the cyclic alkyl group is preferably 3 to 20, more preferably 3 to 15 and even more preferably 3 to 12, not including the number of carbon atoms of the substituent. is there.

  Examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isoamyl group, hexyl group, cyclohexyl group, heptyl group, Examples include octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group and dodecyl group.

  The “alkoxy group” may have a substituent, and may be any of a linear alkoxy group, a branched alkoxy group, and a cyclic alkoxy group (cycloalkoxy group). Unless otherwise specified, the number of carbon atoms of the linear alkoxy group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 12, not including the number of carbon atoms of the substituent. Unless otherwise specified, the number of carbon atoms of the branched alkoxy group and the cyclic alkoxy group is preferably 3 to 20, more preferably 3 to 15 and even more preferably 3 to 12, not including the number of carbon atoms of the substituent. .

  Examples of the alkoxy group include methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyl. Examples thereof include an oxy group, an octyloxy group, a 2-ethylhexyloxy group, a nonyloxy group, a decyloxy group, a 3,7-dimethyloctyloxy group, and a dodecyloxy group.

  The “alkylthio group” may have a substituent, and may be any of a linear alkylthio group, a molecular chain alkylthio group, and a cyclic alkylthio group (cycloalkylthio group). Unless otherwise specified, the number of carbon atoms of the linear alkylthio group is preferably 1 to 20, more preferably 1 to 15, and still more preferably 1 to 12, not including the number of carbon atoms of the substituent. The number of carbon atoms of the branched alkylthio group and the cyclic alkylthio group is preferably 3 to 20, more preferably 3 to 15 and even more preferably 3 to 12, not including the number of carbon atoms of the substituent, unless otherwise specified. .

  Examples of the alkylthio group include methylthio group, ethylthio group, propylthio group, isopropylthio group, butylthio group, isobutylthio group, sec-butylthio group, tert-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, Examples include octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7-dimethyloctylthio group, and dodecylthio group.

  An “aryl group” is an atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring from an aromatic hydrocarbon. The aryl group may have a substituent. The aryl group may be either a group having a benzene ring or a group having a condensed ring. Unless otherwise specified, the number of carbon atoms of the aryl group is preferably 6 to 60, more preferably 6 to 48, and even more preferably 6 to 30 without including the number of carbon atoms of the substituent.

  Examples of the aryl group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthracenyl group, a 2-anthracenyl group, a 9-anthracenyl group, a fluorenyl group (for example, a 2-fluorenyl group), and a naphthylene group. It is done.

The “aryloxy group” is a group represented by —O—Ar ⁵⁰ (Ar ⁵⁰ is an aryl group which may have a substituent), and the number of carbon atoms of the aryloxy group is as specified. Unless otherwise specified, the number is preferably 6 to 60, more preferably 6 to 48, and still more preferably 6 to 30 without including the number of carbon atoms of the substituent.

  Examples of the aryloxy group include a phenoxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, a 1-anthracenyloxy group, a 2-anthracenyloxy group, a 9-anthracenyloxy group, and a 2-fullyl group. An oleenyloxy group is mentioned.

The “arylthio group” is a group represented by —S—Ar ⁶⁰ (Ar ⁶⁰ represents an aryl group which may have a substituent), and the number of carbon atoms of the arylthio group is unless otherwise specified. , Preferably 6 to 60, more preferably 6 to 48, and even more preferably 6 to 30 without including the number of carbon atoms of the substituent.

  Examples of the arylthio group include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 1-anthracenylthio group, a 2-anthracenylthio group, a 9-anthracenylthio group, and a 2-fluorenylthio group.

  The “alkenyl group” may have a substituent, and may be any of a linear alkenyl group, a branched alkenyl group, and a cyclic alkenyl group. Unless otherwise specified, the number of carbon atoms of the linear alkenyl group is preferably 2 to 20, more preferably 2 to 15 and even more preferably 2 to 10 without including the number of carbon atoms of the substituent. Unless otherwise specified, the number of carbon atoms of the branched alkenyl group and the cyclic alkenyl group is preferably 3 to 20, more preferably 3 to 15 and even more preferably 3 to 10 without including the number of carbon atoms of the substituent. .

  Examples of the alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group, 1-butenyl group, 2-butenyl group, 1-pentenyl group, 2-pentenyl group, 1-hexenyl group, 2-hexenyl group and A 1-octenyl group is mentioned.

  The “alkynyl group” may have a substituent, and may be any of a linear alkynyl group, a branched alkynyl group, and a cyclic alkynyl group. Unless otherwise specified, the number of carbon atoms of the linear alkynyl group is preferably 2 to 20, more preferably 2 to 15 and even more preferably 2 to 10 without including the number of carbon atoms of the substituent. Unless otherwise specified, the number of carbon atoms of the branched alkynyl group and cyclic alkynyl group is preferably 3 to 20, more preferably 3 to 15 and even more preferably 3 to 10 without including the number of carbon atoms of the substituent. .

  Examples of the alkynyl group include ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 1-pentynyl group, 2-pentynyl group, 1-hexynyl group, 2-hexynyl group and A 1-octynyl group is mentioned.

  The “amino group” may have a substituent. “Substituted amino group” means an amino group having a substituent, preferably one or two substituents selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. A substituted amino group. The substituent may further have a substituent (hereinafter, the substituent that the organic group further has may be referred to as “secondary substituent”). The number of carbon atoms of the substituted amino group is preferably 1 to 60, more preferably 2 to 48, and still more preferably 2 to 40, not including the number of carbon atoms of the secondary substituent.

Examples of the substituted amino group include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino group, butylamino group, isobutylamino group, sec- Butylamino group, tert-butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3,7-dimethyloctylamino group, dodecylamino group , cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, ditrifluoromethylamino group, phenylamino group, diphenylamino group, C ₁ -C ₁₂ alkoxyphenyl amino group, bis (C ₁ -C ₁₂ alkoxyphenyl) amino groups, C ₁ -C ₁₂ alkylphenyl group, bis (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group, pentafluorophenylamino group , pyridylamino group, pyridazinylamino group, pyrimidinyl group, pyrazinylamino group, triazinylamino group, phenyl _-C 1 -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylamino Group, di (C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkyl) amino group, C ₁ -C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkylphenyl-C) ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl -C ₁ -C ₁₂ alkylamino groups and 2-naphthyl -C ₁ -C ₁₂ alkylamino group ani I can get lost.

  The “silyl group” may have a substituent. “Substituted silyl group” means a silyl group having a substituent, preferably 1 to 3 substituents selected from the group consisting of an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. It is a substituted silyl group. The substituent may have a secondary substituent. The number of carbon atoms of the substituted silyl group is preferably 1 to 60, more preferably 3 to 48, and still more preferably 3 to 40, not including the number of carbon atoms of the secondary substituent.

Examples of the substituted silyl group include trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, tert-butyldimethylsilyl group, pentyldimethylsilyl group, Hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group, phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl _group, C 1 -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ ~C ₁₂ alkyl Lil group, 2-naphthyl -C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, a triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, Examples thereof include a tert-butyldiphenylsilyl group and a dimethylphenylsilyl group.

  A substituted silyloxy group is a group in which an oxygen atom is bonded to a substituted silyl group. Examples of the substituted silyloxy group include trimethylsilyloxy group, triethylsilyloxy group, tripropylsilyloxy group, tri-iso-propylsilyloxy group, tert-butyldimethylsilyloxy group, triphenylsilyloxy group, tri-p- A xylylsilyloxy group, a tribenzylsilyloxy group, a diphenylmethylsilyloxy group, a tert-butyldiphenylsilyloxy group, and a dimethylphenylsilyloxy group may be mentioned.

  The substituted silylthio group is a group in which a sulfur atom is bonded to a substituted silyl group. Examples of the substituted silylthio group include trimethylsilylthio group, triethylsilylthio group, tripropylsilylthio group, tri-iso-propylsilylthio group, tert-butyldimethylsilylthio group, triphenylsilylthio group, tri-p- Examples include xylylsilylthio group, tribenzylsilylthio group, diphenylmethylsilylthio group, tert-butyldiphenylsilylthio group, and dimethylphenylsilylthio group.

  The substituted silylamino group is a group in which one or two hydrogen atoms of the amino group are substituted with a substituted silyl group. Examples of the substituted silylamino group include trimethylsilylamino group, triethylsilylamino group, tripropylsilylamino group, tri-iso-propylsilylamino group, tert-butyldimethylsilylamino group, triphenylsilylamino group, tri-p- Xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, tert-butyldiphenylsilylamino group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group, di (tri Propylsilyl) amino group, di (tri-iso-propylsilyl) amino group, di (tert-butyldimethylsilyl) amino group, di (triphenylsilyl) amino group, di (tri-p-xylylsilyl) amino group, di (Trivenge Silyl) amino group, di (diphenylmethyl silyl) amino, di (tert- butyldiphenylsilyl) amino groups and di (dimethylphenylsilyl) and amino group.

  The “arylalkenyl group” may have a substituent. The number of carbon atoms of the arylalkenyl group is preferably 8-20, more preferably 8-15, not including the number of carbon atoms of the substituent. Examples of the arylalkenyl group include a styryl group.

  The “arylalkynyl group” may have a substituent. The number of carbon atoms of the arylalkynyl group is preferably 8-20, more preferably 8-15, not including the number of carbon atoms of the substituent. Examples of the arylalkynyl group include a phenylacetylenyl group.

  The “carboxyl group” may have a substituent. “Substituted carboxyl group” means a carboxyl group having a substituent, and is preferably a carboxyl group substituted with one substituent selected from the group consisting of an alkyl group and an aryl group. The substituent may have a secondary substituent. The number of carbon atoms of the substituted carboxyl group is preferably 2 to 20 without including the number of carbon atoms of the secondary substituent. Examples of the substituted carboxyl group include a group having a methyl ester structure, a group having an ethyl ester structure, and a group having a butyl ester structure.

  The “halogen atom” is a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, preferably a fluorine atom.

Examples of the “acyl group” include a group represented by —C (═O) —R ⁴⁴ (R ⁴⁴ is an alkyl group, an aryl group, or a monovalent heterocyclic group). Unless otherwise specified, the number of carbon atoms of the acyl group is preferably 2 to 20, more preferably 2 to 18, and still more preferably 2 to 16, not including the number of carbon atoms of the substituent.

  Examples of the acyl group include an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a pivaloyl group, and a benzoyl group. When the acyl group has a substituent, examples of the substituent include a halogen atom. Examples of the acyl group having a substituent include a trifluoroacetyl group and a pentafluorobenzoyl group.

Examples of the “acyloxy group” include a group represented by —O—C (═O) —R ⁴⁵ (R ⁴⁵ is an alkyl group, an aryl group, or a monovalent heterocyclic group). Unless otherwise specified, the number of carbon atoms of the acyloxy group is preferably 2 to 20, more preferably 2 to 18, and still more preferably 2 to 16, not including the number of carbon atoms of the substituent.

  Examples of the acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, an isobutyryloxy group, a pivaloyloxy group, and a benzoyloxy group. When the acyloxy group has a substituent, examples of the substituent include a halogen atom. Examples of the acyloxy group having a substituent include a trifluoroacetyloxy group and a pentafluorobenzoyloxy group.

Examples of the “oxycarbonyl group” include a group represented by —C (═O) —O—R ⁴⁶ (R ⁴⁶ is an alkyl group, an aryl group, or a monovalent heterocyclic group). . Unless otherwise specified, the number of carbon atoms of the oxycarbonyl group is preferably 2 to 20, more preferably 2 to 18, and still more preferably 2 to 16, not including the number of carbon atoms of the substituent.

  The “monovalent heterocyclic group” is the remaining atomic group excluding one hydrogen atom directly bonded to the carbon atom constituting the ring of the heterocyclic compound. The monovalent heterocyclic group may be a monocyclic group or a group having a condensed ring. Unless otherwise specified, the number of carbon atoms of the monovalent heterocyclic group is preferably 2 to 60, more preferably 3 to 30, and still more preferably 4 to 20 without including the number of carbon atoms of the substituent.

  A heterocyclic compound is an organic compound having a cyclic structure, and as an element constituting the ring, 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, A compound containing a heteroatom such as a selenium atom, a tellurium atom or an arsenic atom.

  As the monovalent heterocyclic group, a monovalent aromatic heterocyclic group is preferable. The monovalent aromatic heterocyclic group is the remaining atomic group excluding one hydrogen atom directly bonded to the carbon atom constituting the ring of the aromatic heterocyclic compound. Examples of aromatic heterocyclic compounds include oxadiazole, thiadiazole, thiazole, oxazole, thiophene, pyrrole, phosphole, furan, pyridine, pyrazine, pyrimidine, triazine, pyridazine, quinoline, isoquinoline, carbazole, dibenzophosphole, dibenzofuran. Heterocycles containing heteroatoms such as dibenzothiophene exhibit aromaticity, and heterocycles containing heteroatoms such as phenoxazine, phenothiazine, dibenzoborol, dibenzosilol, and benzopyran themselves are aromatic. Even if not shown, a compound in which an aromatic ring is condensed to the heterocyclic ring can be mentioned.

The “heterocyclic oxy group” means —O—Ar ⁷⁰ (Ar ⁷⁰ is a monovalent heterocyclic group). Unless otherwise specified, the number of carbon atoms of the heterocyclic oxy group is preferably 2 to 60, more preferably 3 to 30, and still more preferably 4 to 20 without including the number of carbon atoms of the substituent.

  Examples of the heterocyclic oxy group include a pyridyloxy group, a pyridazinyloxy group, a pyrimidinyloxy group, a pyrazinyloxy group, and a triazinyloxy group.

The “heterocyclic thio group” means —S—Ar ⁸⁰ (Ar ⁸⁰ is a monovalent heterocyclic group). Unless otherwise specified, the number of carbon atoms of the heterocyclic thio group is preferably 2 to 60, more preferably 3 to 30, and still more preferably 4 to 20 without including the number of carbon atoms of the substituent.

  Examples of the heterocyclic thio group include a pyridylthio group, a pyridazinylthio group, a pyrimidinylthio group, a pyrazinylthio group, and a triazinylthio group.

The “imine residue” refers to an imine compound having a structure represented by the formula: H—N═C (R ⁴⁷ ) ₂ or the formula: H—C (R ⁴⁸ ) ═N—R ⁴⁹ , It means a residue without “H”. In the formula, R ⁴⁷ , R ⁴⁸ and R ⁴⁹ each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a monovalent heterocyclic group. Each R ⁴⁷ may be the same as or different from each other, and may be linked together to form a ring structure together with the carbon atoms to which they are bonded.

  Examples of the imine residue include groups represented by the following structural formulas.

The “amide compound residue” is an amide having a structure represented by the formula: H—N (R ⁵⁰ ) —C (═O) R ⁵¹ or the formula: H—C (═O) —N (R ⁵² ) ₂ It means a residue obtained by removing “H” in the formula from a compound. In the formula, R ⁵⁰ , R ⁵¹ and R ⁵² each independently represents an alkyl group, an aryl group, an alkenyl group, an alkynyl group or a monovalent heterocyclic group. Each R ⁵² may be the same as or different from each other, and may be linked to each other to form a ring structure together with the nitrogen atoms to which they are bonded.

  Examples of amide compound residues include formamide residues, acetamide residues, propioamide residues, butyroamide residues, benzamide residues, trifluoroacetamide residues, pentafluorobenzamide residues, diformamide residues, diacetamide residues. , Dipropioamide residues, dibutyroamide residues, dibenzamide residues, ditrifluoroacetamide residues and dipentafluorobenzamide residues.

  “Acid imide residue” means a residue obtained by removing one hydrogen atom directly bonded to the nitrogen atom from an acid imide. The acid imide group may have a substituent. Unless otherwise specified, the number of carbon atoms of the acid imide residue is preferably 4 to 20, more preferably 4 to 18, and still more preferably 4 to 16, not including the number of carbon atoms of the substituent.

  Examples of the acid imide residue include groups represented by the following formulas.

  The “arylene group” is an atomic group obtained by removing two hydrogen atoms directly bonded to carbon atoms constituting a ring from an aromatic hydrocarbon. The arylene group may be a group having a benzene ring or a group having a condensed ring. Unless otherwise specified, the number of carbon atoms of the arylene group is preferably 6 to 60, more preferably 6 to 48, and still more preferably 6 to 30 without including the number of carbon atoms of the substituent.

  Examples of the arylene group include phenylene groups such as 1,4-phenylene group, 1,3-phenylene group, and 1,2-phenylene group; 1,4-naphthalenediyl group, 1,5-naphthalenediyl group, 2, Naphthalenediyl groups such as 6-naphthalenediyl, 2,7-naphthalenediyl group; 1,4-anthracenediyl group, 1,5-anthracenediyl group, 2,6-anthracenediyl group, 9,10-anthracenediyl group, etc. Anthracenediyl group of 2,7-phenanthenediyl group; dihydrophenanthenediyl group such as 2,7-dihydrophenanthenediyl group; 1,7-naphthacenediyl group, 2,8-naphthacenediyl group, 5,12 -Naphthacenediyl group such as naphthacenediyl group; 2,7-fluorenediyl group, 3,6- Fluorenediyl group such as luorangeyl group; pyrenediyl group such as 1,6-pyrenediyl group, 1,8-pyrenediyl group, 2,7-pyrenediyl group, 4,9-pyrenediyl group; and 3,8-perylenediyl And perylenediyl groups such as 3,9-perylenediyl group and 3,10-perylenediyl group.

  The “divalent heterocyclic group” is an atomic group remaining after removing two hydrogen atoms directly bonded to the carbon atoms constituting the ring of the heterocyclic compound. The divalent heterocyclic group may be a monocyclic group or a condensed ring group. Unless otherwise specified, the number of carbon atoms of the divalent heterocyclic group is preferably 2 to 60, more preferably 3 to 30, and still more preferably 4 to 20 without including the number of carbon atoms of the substituent.

  As the divalent heterocyclic group, a divalent aromatic heterocyclic group is preferable. The divalent aromatic heterocyclic group is a remaining atomic group obtained by removing two hydrogen atoms from an aromatic heterocyclic compound.

  Examples of the divalent heterocyclic group include pyridinediyl groups such as 2,5-pyridinediyl group and 2,6-pyridinediyl group; quinolinediyl groups such as 2,6-quinolinediyl group; 1,4-isoquinolinediyl group , 1,5-isoquinolinediyl group such as 1,5-isoquinolinediyl group; quinoxalinediyl group such as 5,8-quinoxalinediyl group; 2,1,3-benzoyldiadiazole group such as 2,1,3-benzothiadiazole-4,7-diyl group Benzothiadiazole group; benzothiazole diyl group such as 4,7-benzothiazole diyl group; dibenzosilol diyl group such as 2,7-dibenzosilol diyl group; dibenzofuran-4,7-diyl group, dibenzofuran-3,8-diyl A dibenzofurandiyl group such as a group; and dibenzothiophene-4,7-diyl group, dibenzothiophene-3, - it includes dibenzothiophene-diyl group such diyl group.

  Examples of the “optionally substituted alkyl group” include an alkyl group having no substituent and an alkyl group having a substituent. Unless otherwise specified, the alkyl group preferably has a substituent selected from the group consisting of an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a heterocyclic oxy group, and a halogen atom.

  Examples of the “aryl group optionally having a substituent” include an aryl group having no substituent and an aryl group having a substituent. Unless otherwise specified, the aryl group has a substituent selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a heterocyclic oxy group, and a halogen atom. Is preferred.

  Examples of the “monovalent heterocyclic group optionally having a substituent” include a monovalent heterocyclic group having no substituent and a monovalent heterocyclic group having a substituent. Unless otherwise specified, the monovalent heterocyclic group has a substituent selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a heterocyclic oxy group, and a halogen atom. It is preferably a group.

  Examples of the “arylene group optionally having a substituent” include an arylene group having no substituent and an arylene group having a substituent. Unless otherwise specified, the arylene group has a substituent selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a heterocyclic oxy group, and a halogen atom. Is preferred.

  Examples of the “divalent heterocyclic group optionally having a substituent” include a divalent heterocyclic group having no substituent and a divalent heterocyclic group having a substituent. Unless otherwise specified, the divalent heterocyclic group has a substituent selected from the group consisting of an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a heterocyclic oxy group, and a halogen atom. It is preferably a group.

  “A divalent group in which two or more identical or different groups selected from an optionally substituted arylene group and an optionally substituted divalent heterocyclic group are linked” For example, an arylene group which may have a substituent and a divalent heterocyclic ring which may have a substituent such as a biphenylylene group such as a 2,7-biphenylylene group and a 3,6-biphenylylene group And a divalent group in which two groups selected from the group are linked by a single bond. Unless otherwise specified, the arylene group and the substituent that the divalent heterocyclic group may have are an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a monovalent heterocyclic group, a heterocyclic oxy group, and a halogen. It is preferably a substituent selected from the group consisting of atoms.

  Hereinafter, preferred embodiments of the composition, polymer compound, organic thin film, insolubilized organic thin film, and light-emitting element of the present invention will be described in detail.

<First composition>
The first composition of the present invention is a composition comprising a polymer compound (A) and a compound (B).

(Polymer Compound (A))
The polymer compound (A) is a polymer compound containing the structural unit (1) represented by the formula (1) and the structural unit (2) represented by the formula (2).

-Structural unit (1) represented by formula (1)-
The structural unit (1) represented by the formula (1) will be described.

In formula (1),
Ar ¹ and Ar ³ are each independently an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent.
Ar ² and Ar ⁴ may each independently have an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a substituent. A divalent group in which two or more identical or different groups selected from the group consisting of an arylene group and a divalent heterocyclic group which may have a substituent are linked.
R ¹ , R ² and R ³ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is a monovalent heterocyclic group.
Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² and R ³ may each be directly bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded. It may be bonded via —O—, —S—, —C (═O) —, —N (R ^a1 ) — or —C (R ^a1 ) ₂ —. R ^a1 has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a halogen atom or a substituent. And a monovalent heterocyclic group which may be used. When a plurality of R ^a1 are present, each R ^a1 may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atoms to which each is bonded.
x and y are each independently 0 or 1.

In formula (1), R ¹ , R ² and R ³ are preferably each independently an aryl group which may have a substituent. For this reason, the structural unit represented by the formula (1) is preferably the structural unit represented by the formula (1a).

In formula (1a),
R ^9a , R ^9b and R ^9c each independently have an optionally substituted alkyl group, an alkoxy group, an optionally substituted alkylthio group or an optionally substituted group. Aryl group, aryloxy group optionally having substituent, arylthio group optionally having substituent, alkenyl group optionally having substituent, alkynyl optionally having substituent Group, optionally substituted amino group, optionally substituted silyl group, halogen atom, optionally substituted acyl group, optionally substituted. An acyloxy group, an optionally substituted oxycarbonyl group, an optionally substituted monovalent heterocyclic group, an optionally substituted heterocyclic oxy group, and a substituent. May have a heterocyclic thio group, which may have a substituent Imine residue, amide compound residue optionally having substituent, acid imide residue optionally having substituent, carboxyl group optionally having substituent, hydroxyl group, nitro group or It is a cyano group.
When a plurality of R ^9a are present, each R ^9a may be the same as or different from each other. When a plurality of R ^9b are present, each R ^9b may be the same as or different from each other. When a plurality of R ^9c are present, each R ^9c may be the same as or different from each other.
h, i, and j are each independently an integer of 0 to 5.
^{Ar 1, Ar 2, Ar 3} , Ar 4, x and y, and ^{Ar 1, Ar 2, Ar 3} , Ar 4, x and y of formula (1), which is the same meaning.

In the formula (1a), R ^9a , R ^9b and R ^9c are each independently preferably an alkyl group which may have a substituent, an alkoxy group which may have a substituent or a substituent. It is an aryl group which may have, and more preferably an alkyl group which may have a substituent.

  In the formula (1a), h, i and j are each independently preferably an integer of 0 to 3, more preferably an integer of 1 to 3.

In the formula (1), examples of the arylene group as Ar ¹ , Ar ² , Ar ³ and Ar ⁴ include a phenylene group (for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene). Group), naphthalenediyl group (for example, 1,4-naphthalenediyl group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group), anthracenediyl group (for example, 2,6-anthracenediyl group, 9, 10-anthracenediyl group), phenanthrene diyl group (for example, 2,7-phenanthrene diyl group), dihydrophenanthrene diyl group (for example, 2,7-dihydrophenanthrene diyl group), naphthacene diyl group (for example, 5,12-naphthacene diyl group) ), Fluorenediyl group (for example, 2,7-fluorenediyl group, 3,6-fluoreed) A didiyl group) or a perylenediyl group (for example, a 3,8-perylenediyl group).

In the formula (1), examples of the divalent heterocyclic group as Ar ¹ , Ar ² , Ar ³ and Ar ⁴ include 2,5-pyrroldiyl group, 2,1,3-benzothiadiazole-4,7- A diyl group, a dibenzofurandiyl group, a dibenzothiophenediyl group or a dibenzosiloldiyl group can be selected.

In formula (1), the same or different 2 selected from the arylene group which may have a substituent and the divalent heterocyclic group which may have a substituent represented by Ar ² and Ar ⁴ Examples of the divalent group to which the above groups are linked include the following formula (B-1), formula (B-2), formula (B-3), formula (B-4), and formula (B- 5) A group represented by the formula (B-6) or the formula (B-7) can be selected, and a group represented by the formula (B-1) is preferable. In addition, each group represented by Formula (B-1)-(B-7) may have a substituent. The group represented by Formula (B-1), Formula (B-2), and Formula (B-3) may be referred to as a biphenylylene group.

In the formula (1), the arylene group as Ar ¹ , Ar ² , Ar ^3, and Ar ⁴ and the substituent that the divalent heterocyclic group may have are the groups listed in “Explanation of Terms”. And is preferably an alkyl group, an alkoxy group or an aryl group, and more preferably an alkyl group.

In the formula (1), Ar ¹ and Ar ³ are each independently preferably an arylene group which may have a substituent, more preferably a phenylene group which may have a substituent, It is a naphthalenediyl group which may have a substituent, more preferably a phenylene group which may have a substituent, and particularly preferably a group represented by the formula (1b).

In formula (1b),
R ^10a independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituent. Aryl group which may have, aryloxy group which may have substituent, arylthio group which may have substituent, alkenyl group which may have substituent, alkynyl group, substituted An amino group which may have a group, a silyl group which may have a substituent, a halogen atom, an acyl group which may have a substituent, an acyloxy group which may have a substituent, An oxycarbonyl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a heterocyclic oxy group which may have a substituent, and a substituent. May be a heterocyclic thio group or an imine which may have a substituent Residue, amide compound residue optionally having substituent, acid imide residue optionally having substituent, carboxyl group optionally having substituent, hydroxyl group, nitro group or cyano It is a group.
Each R ^10a may be the same as or different from each other.

In the formula (1b), R ^10a is preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl which may have a substituent. Group, more preferably a hydrogen atom or an alkyl group which may have a substituent, and still more preferably a hydrogen atom.

In the formula (1), Ar ² and Ar ⁴ are preferably each independently an arylene group which may have a substituent, or an arylene group and a substituent which may have a substituent. A divalent group in which two or more identical or different groups selected from the group consisting of divalent heterocyclic groups which may be bonded are connected, and more preferably an arylene which may have a substituent Or a divalent group in which two identical or different arylene groups which may have a substituent are linked (the group may have a substituent), and more preferably. Is a phenylene group which may have a substituent, a biphenylylene group which may have a substituent or a fluorenediyl group which may have a substituent, and particularly preferably has a substituent. Full orange And particularly preferably a group represented by the formula (1c).

In formula (1c),
R ^11a independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituent. An aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a halogen atom, an acyl group which may have a substituent, and a substituent. An acyloxy group which may have, an oxycarbonyl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a heterocyclic oxy which may have a substituent Group, optionally substituted heterocyclic thio group, substituent An imine residue which may have a substituent, an amide compound residue which may have a substituent, an acid imide residue which may have a substituent, a carboxyl group which may have a substituent , Hydroxyl group, nitro group or cyano group. Each R ^11a may be the same as or different from each other.
R ^12a has a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, and a substituent. May have an aryl group, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, an alkenyl group which may have a substituent, or a substituent. A good alkynyl group, an amino group which may have a substituent, a silyl group which may have a substituent, a halogen atom, an acyl group which may have a substituent, and a substituent. An acyloxy group which may have a substituent, an oxycarbonyl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a heterocyclic oxy group which may have a substituent, a substituent May have a heterocyclic thio group or a substituent. An imine residue, an amide compound residue optionally having a substituent, an acid imide residue optionally having a substituent, a carboxyl group optionally having a substituent, a hydroxyl group, a nitro group Or it is a cyano group.
Each R ^12a may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atoms to which they are bonded.

In formula (1c), R ^11a is preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl which may have a substituent. More preferably a hydrogen atom or an alkyl group which may have a substituent.

In the formula (1c), R ^12a is preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. More preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, and more preferably, one of two R ^12a is an aryl group which may have a substituent. And the other is an alkyl group which may have a substituent.

  Since the characteristics (for example, luminance lifetime) of a light-emitting element manufactured using the composition containing the polymer compound (A) are more excellent, x and y in formula (1) satisfy x + y = 1. preferable. That is, x = 0 and y = 1, or x = 1 and y = 0 are preferable, and x = 1 and y = 0 are more preferable.

  The structural unit represented by the formula (1) is preferably a structural unit represented by the formula (9a), the formula (9b), the formula (9c), or the formula (9d). The structural unit represented by 9d) is more preferred, and the structural unit represented by formula (9c) is more preferred.

In formula (9a)-formula (9d),
R ⁴¹ and R ^41a are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, Aryl group optionally having substituent, aryloxy group optionally having substituent, arylthio group optionally having substituent, alkenyl group optionally having substituent, substituted An alkynyl group which may have a group, an amino group which may have a substituent, a silyl group which may have a substituent, a halogen atom, an arylalkyl group which may have a substituent An arylalkoxy group which may have a substituent, an amino group which may have a substituent, an acyl group which may have a substituent, an acyloxy group which may have a substituent, Oxyca which may have a substituent Bonyl group, monovalent heterocyclic group which may have a substituent, heterocyclic oxy group which may have a substituent, heterocyclic thio group which may have a substituent, substituent An imine residue which may have, an amide compound residue which may have a substituent, an acid imide residue which may have a substituent, a carboxyl group which may have a substituent, A hydroxyl group, a nitro group or a cyano group; Each R ⁴¹ may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atoms to which they are bonded. Each R ^41a may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atoms to which they are bonded.

In the formulas (9a) to (9d), R ⁴¹ preferably has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. Aryl group which may have a substituent, aryloxy group which may have a substituent, arylalkyl group which may have a substituent, arylalkoxy group which may have a substituent, substituted amino group, substituted An acyl group which may have a group or a cyano group which may have a substituent, more preferably a hydrogen atom, an alkyl group which may have a substituent, or a substituent. An alkoxy group which may be substituted or an aryl group which may have a substituent.

In the formula (9c), R ^41a is preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. More preferably an alkyl group which may have a substituent or an aryl group which may have a substituent, and more preferably, one of two R ^41a is an aryl group which may have a substituent. And the other is an alkyl group which may have a substituent.

  The structural units represented by the formulas (9a) to (9d) are preferably structural units represented by the formula (9-001) to the formula (9-070), and the formulas (9-012) to (9 9-059) is more preferable, and the luminance life of the light-emitting device produced using the first composition containing the polymer compound (A) of the present invention is more excellent. The structural units represented by (9-020) to (9-059) are more preferred, and the structural units represented by (9-036) to (9-059) are particularly preferred.

  The polymer compound (A) may have only one structural unit (1) represented by the formula (1), or may have two or more. When the polymer compound (A) has two or more structural units (1) represented by the formula (1), the structural unit (1) represented by the formula (1) may be one kind or different. Two or more kinds may be used.

  Content (total content) of the structural unit represented by Formula (1) is 0.1 to 50 mol% with respect to all structural units contained in the polymer compound (A) from the viewpoint of luminance life. It is preferable that it is 1 to 49 mol%, more preferably 3 to 45 mol%.

-Structural unit (2) represented by formula (2)-
The structural unit (2) represented by the formula (2) will be described.

In formula (2),
Ar ⁵ is R ⁴ other than a bivalent which may have an optionally substituted arylene group or R ⁴ substituent other than a heterocyclic group.
R ⁴ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and an aryl which may have a substituent. Group, aryloxy group which may have a substituent, arylthio group which may have a substituent, arylalkyl group which may have a substituent, aryl which may have a substituent Alkoxy group, optionally substituted alkenyl group, optionally substituted alkynyl group, optionally substituted amino group, optionally substituted silyl group A halogen atom, an optionally substituted acyl group, an optionally substituted acyloxy group, an optionally substituted oxycarbonyl group, and optionally having a substituent. Even if it has a monovalent heterocyclic group or substituent A heterocyclic oxy group which may have a substituent, a heterocyclic thio group which may have a substituent, an imine residue which may have a substituent, an amide compound residue which may have a substituent, a substituent An acid imide residue which may have, a carboxyl group which may have a substituent, a hydroxyl group, a nitro group or a cyano group. When a plurality of R ⁴ are present, each R ⁴ may be the same as or different from each other. R ⁴ is a group directly bonded to the carbon atom adjacent to the carbon atom that forms a bond with other structural units among the carbon atoms that constitute Ar ⁵ .
a is an integer of 1 or more.

In the formula (2), an arylene group which may have a substituent other than R ⁴ and a divalent heterocyclic group which may have a substituent other than R ⁴ in Ar ⁵ and a divalent group. The heterocyclic group is the same as the examples and preferred examples of the arylene group and divalent heterocyclic group in Ar ¹ , Ar ² , Ar ³ and Ar ⁴ .

In Formula (2), the carbon atom constituting Ar ⁵ to which R ⁴ is bonded is the carbon atom adjacent to the carbon atom that forms a bond with another structural unit other than the structural unit represented by Formula (2). .

In the formula (2), the group represented by Ar ⁵ is preferably an arylene group which may have a substituent group other than R ^4, and more preferably have a substituent group other than R ⁴ Preferred phenylene group or fluorenediyl group optionally having a substituent other than R ⁴ , more preferably fluorenediyl group optionally having a substituent other than R ⁴ .

In the formula (2), R ⁴ is preferably an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, An aryloxy group which may have a group, an arylalkyl group which may have a substituent, an arylalkoxy group which may have a substituent, a substituted amino group, and a substituent which may have a substituent Preferably an acyl group or a cyano group, more preferably an alkyl group which may have a substituent, an alkoxy group which may have a substituent or an aryl group which may have a substituent. More preferably, it is an alkyl group which may have a substituent or an aryl group which may have a substituent.

  In the formula (2), a is preferably 1 or 2, more preferably 2.

  As a structural unit represented by Formula (2), each structural unit represented by Formula (10a)-Formula (10d) is preferable, and is a structural unit represented by Formula (10a) or Formula (10c). Is more preferable, and since the luminance life of the light-emitting device produced using the first composition containing the polymer compound (A) of the present invention is more excellent, it is further a structural unit represented by the formula (10c) preferable.

In formulas (10a) to (10d),
R ¹⁴ and R ¹⁵ are each independently a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, An aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, an arylalkyl group which may have a substituent, An arylalkoxy group which may have a substituent, an alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an amino group which may have a substituent, a substituent A silyl group which may have a group, a halogen atom, an acyl group which may have a substituent, an acyloxy group which may have a substituent, an oxycarbonyl group which may have a substituent , May have a substituent A valent heterocyclic group, a heterocyclic oxy group which may have a substituent, a heterocyclic thio group which may have a substituent, an imine residue which may have a substituent, a substituent It may be an amide compound residue which may have, an acid imide residue which may have a substituent, a carboxyl group which may have a substituent, a hydroxyl group, a nitro group or a cyano group.
Each R ¹⁴ may be the same as or different from each other. When a plurality of R ¹⁵ are present, each R ¹⁵ may be the same as or different from each other. Adjacent R ^14s may be bonded to each other to form a ring structure with the carbon atoms to which they are bonded, and adjacent R ^15s are bonded to each other to form a ring structure with the carbon atoms to which they are bonded. Adjacent R ¹⁴ and R ¹⁵ may be bonded to each other to form a ring structure together with the carbon atoms to which they are bonded.

In formulas (10a) to (10d), R ¹⁴ and R ¹⁵ are preferably each independently a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent. , An aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylalkyl group which may have a substituent, an arylalkoxy which may have a substituent Group, a substituted amino group which may have a substituent, an acyl group which may have a substituent or a cyano group, more preferably a hydrogen atom or an alkyl group which may have a substituent , An alkoxy group which may have a substituent, or an aryl group which may have a substituent.

In each repeating unit represented by formula (10a) to formula (10d), one or more R ¹⁴ is R ⁴ .

In formula (10c) to formula (10d), R ⁸ each independently has a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or a substituent. An optionally substituted alkylthio group, an optionally substituted aryl group, an optionally substituted aryloxy group, an optionally substituted arylthio group, and a substituent. An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an amino group which may have a substituent, a silyl group which may have a substituent, a halogen atom, and a substituent. An acyl group which may have a substituent, an acyloxy group which may have a substituent, an oxycarbonyl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a substituent A heterocyclic oxy group optionally having a group, a substituent Optionally substituted heterocyclic thio group, optionally substituted imine residue, optionally substituted amide compound residue, optionally substituted acid imide residue , An optionally substituted carboxyl group, hydroxyl group, nitro group or cyano group. Each R ⁸ may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atom to which each R ⁸ is bonded.

In the formulas (10c) to (10d), R ⁸ is preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group.

  The structural units represented by the formulas (10a) to (10d) are preferably the respective structural units represented by the formulas (10-1) to (10-117), and the formulas (10-1) to (10) 10-18), more preferably each structural unit represented by formula (10-41) to formula (10-117), using the first composition containing the polymer compound (A) of the present invention. Since the luminance lifetime of the manufactured light emitting element is more excellent, the formula (10-59), the formula (10-68) to the formula (10-74), the formula (10-81), the formula (10-86) to the formula ( 10-89), (10-105) to each structural unit represented by formula (10-117) is more preferable.

  The polymer compound (A) may have only one structural unit (2) represented by the formula (2), or may have two or more kinds. When the polymer compound (A) has two or more structural units (2), the structural unit (2) may be one kind or two or more kinds different from each other. Two or more different structural units may be alternately repeated, may be grouped together, or may be random.

  Content (total content) of the structural unit represented by Formula (2) is 1 to 80 mol% with respect to all structural units contained in the polymer compound (A) from the viewpoint of luminance life. It is preferably 10 to 70 mol%, more preferably 30 to 50 mol%.

  The high molecular compound (A) should just contain the structural unit represented by Formula (1) and the structural unit represented by Formula (2), and may further contain the other structural unit.

-Constituent unit having a crosslinking group-
The polymer compound (A) preferably contains a structural unit having a crosslinking group in addition to the structural unit represented by the formula (1) and the structural unit represented by the formula (2). Thus, a thin film containing a composition containing the polymer compound (A) is used as a hole injection layer or a hole transport layer, and a solution is applied thereon to form a light emitting layer to produce a light emitting device. In some cases, an organic thin film containing a composition containing the polymer compound (A) can be converted into an insolubilized organic thin film. The structural unit having a crosslinking group may contain one or two or more crosslinking groups. When the structural unit having a crosslinking group contains two or more crosslinking groups, they may be a combination of different types of crosslinking groups.

[Crosslinking group]
The crosslinking group is usually a monovalent or divalent crosslinking group. Examples of the crosslinking group include groups represented by formulas (Q-1), (Q-2), and (Q-01) to (Q-19). Among these, since the synthesis | combination of the monomer used as a raw material becomes easy, Formula (Q-1), (Q-2), (Q-01), (Q-03), (Q-04), (Q-06) ) To (Q-19) are preferred, and groups represented by formulas (Q-1), (Q-2) and (Q-09) to (Q-19) are more preferred, Each group represented by formula (Q-1) and (Q-2) is more preferable. Hereinafter, Formula (Q-1), Formula (Q-2), and (Q1-01) to (Q-19) will be described in order.

  In formula (Q-1), benzocyclobutene may have a substituent.

  Examples of the substituent that the benzocyclobutene in the formula (Q-1) may have include a hydrogen atom, an alkyl group that may have a secondary substituent, and a secondary substituent. An alkoxy group which may have a secondary substituent, an arylthio group which may have a secondary substituent, an aryloxy group which may have a secondary substituent, a secondary An arylthio group which may have a substituent, an amino group which may have a secondary substituent, a silyl group which may have a secondary substituent, a halogen atom, and a secondary substituent An acyl group which may have a secondary substituent, an imine residue which may have a secondary substituent, a carbamoyl group which may have a secondary substituent, Even if it has an acid imide group and a secondary substituent which may have a secondary substituent There monovalent heterocyclic group, a secondary substituent a carboxyl group which may have a, a cyano group and a nitro group.

  Examples of formula (Q-1) include formulas (Q-1-1) and (Q-1-2). Since it is easy to synthesize a monomer as a raw material, the formula (Q-1) is preferably the formula (Q-1-1).

In formulas (Q-1-1) and (Q-1-2),
R ^t may be a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, or a substituent. A good aryl group, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, an amino group which may have a substituent, and a substituent which may have A silyl group, a halogen atom, an acyl group which may have a substituent, an acyloxy group which may have a substituent, an imine residue which may have a substituent, and a substituent. A carbamoyl group which may have a substituent, an acid imide group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a carboxyl group which may have a substituent, a cyano group or a nitro group It is a group. Each R ^t may be the same as or different from each other.
“*” Indicates a bond.

In the formulas (Q-1-1) and (Q-1-2), R ^t is easy to synthesize a monomer as a raw material, so that a hydrogen atom, an alkyl group which may have a substituent, a substituent An alkoxy group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent or a monovalent heterocyclic group which may have a substituent It is preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. Further, it is more preferably a hydrogen atom or an alkyl group which may have a substituent.

In formula (Q-2),
nf is 0 or 1.
R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or a substituent. An alkylthio group which may have, an aryl group which may have a substituent, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, and a substituent. A monovalent heterocyclic group which may have, an amino group which may have a substituent, a silyl group which may have a substituent, an acyl group which may have a substituent, a substituent An acyloxy group, a halogen atom, a cyano group or a nitro group which may have
A double bond having a wavy line means that the structural unit enclosed in parentheses with nf may be any of E-form, Z-form, or a mixture of E-form and Z-form.

  In Formula (Q-2), nf is preferably 0 because synthesis of a monomer as a raw material becomes easy.

In the formula (Q-2), R ²¹ , R ²² , R ²³ , R ²⁴ and R ²⁵ may each independently have a hydrogen atom or a substituent from the viewpoint of hole transportability and durability. A good alkyl group, an alkoxy group which may have a substituent, an aryl group which may have a substituent, an aryloxy group which may have a substituent, and a substituent. It is preferably a monovalent heterocyclic group, a halogen atom or a cyano group, more preferably a hydrogen atom, an optionally substituted alkyl group or a fluorine atom, and even more preferably a hydrogen atom. .

In formulas (Q-01) to (Q-19),
R ^s may be a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an alkylthio group that may have a substituent, or a substituent. A good aryl group, an aryloxy group which may have a substituent, an arylthio group which may have a substituent, an amino group which may have a substituent, and a substituent which may have A silyl group, a halogen atom, an acyl group which may have a substituent, an acyloxy group which may have a substituent, an imine residue which may have a substituent, and a substituent. A carbamoyl group which may have a substituent, an acid imide group which may have a substituent, a monovalent heterocyclic group which may have a substituent, a carboxyl group which may have a substituent, a cyano group or a nitro group It is a group. When a plurality of R ^s are present, each R ^s may be the same as or different from each other.
R ^w has a hydrogen atom, an alkyl group which may have a substituent, an acyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is also a monovalent heterocyclic group.
“*” Indicates a bond.

In the formulas (Q-01), (Q-02), and (Q-04) to (Q-19), R ^s has a hydrogen atom and a substituent because synthesis of a monomer as a raw material becomes easy. An alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryl group that may have a substituent, an aryloxy group that may have a substituent, or a substituent. The monovalent heterocyclic group may be preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl group which may have a substituent. More preferred.

In the formulas (Q-01), (Q-02), (Q-05), and (Q-06), R ^w is an alkyl group substituted with an aryl group because synthesis of a monomer as a raw material becomes easy. An acyl group which may have a substituent or a monovalent heterocyclic group which may have a substituent is preferable.

  Examples of the structural unit having a crosslinking group include a structural unit represented by the formula (3A) and a structural unit represented by the formula (4A). Hereinafter, each structural unit will be described in order.

[Structural Unit Represented by Formula (3A)]

In formula (3A),
b is an integer of 1-4.
Ar ¹⁰ is a (2 + b) -valent aromatic hydrocarbon group which may have a substituent or a (2 + b) -valent heterocyclic group which may have a substituent. R ²⁰ is a single bond, an alkylene group which may have a substituent, a phenylene group which may have a substituent, or a divalent group obtained by combining these. When a plurality of R ²⁰ are present, each R ²⁰ may be the same as or different from each other.
Q ¹ is a monovalent crosslinking group. When a plurality of Q ¹ are present, each Q ¹ may be the same as or different from each other.

  In Formula (3A), b is preferably an integer of 1 to 3, and more preferably 2 from the viewpoint of crosslinkability.

In formula (3A), the number of carbon atoms of the (2 + b) -valent aromatic hydrocarbon group which may have a substituent as Ar ¹⁰ is usually 6 including the number of carbon atoms of the substituent. It is -60, Preferably it is 6-48, More preferably, it is 6-20, More preferably, it is 6-14.

In the formula (3A), the (2 + b) -valent aromatic hydrocarbon group as Ar ¹⁰ is preferably a divalent, trivalent, tetravalent or pentavalent aromatic hydrocarbon group, and is trivalent or tetravalent. The aromatic hydrocarbon group is more preferable.

In the formula (3A), “(2 + b) -valent aromatic hydrocarbon group” as Ar ¹⁰ is a group in which (2 + b) hydrogen atoms directly bonded to the carbon atoms constituting the ring are removed from the aromatic hydrocarbon. The remaining atomic group means a group having a benzene ring and a group having a condensed ring. Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, 1-tetracene, pyrene, perylene, fluorene, benzofluorene, phenanthrene, dihydrophenanthrene, chrysene and coronene. Aromatic hydrocarbons are benzene, naphthalene, anthracene, because the stability of the polymer compound (A) is better and the hole transport property of the light-emitting device produced using the polymer compound (A) is better. , Pyrene, fluorene, benzofluorene, phenanthrene or dihydrophenanthrene are preferred, and benzene, naphthalene or fluorene is more preferred.

In the formula (3A), the number of carbon atoms of the (2 + b) -valent heterocyclic group which may have a substituent as Ar ¹⁰ is usually 3 to 60, not including the number of carbon atoms of the substituent. Yes, preferably 3-20.

In the formula (3A), the (2 + b) -valent heterocyclic group as Ar ¹⁰ is preferably a divalent, trivalent, tetravalent or pentavalent heterocyclic group, and is divalent, trivalent or tetravalent. It is more preferable that it is a heterocyclic group.

In the formula (3A), the “(2 + b) -valent heterocyclic group” as Ar ¹⁰ means the rest of the heterocyclic compound excluding (2 + b) hydrogen atoms bonded directly to the carbon atoms constituting the ring. An atomic group means a monocyclic group or a group having a condensed ring. Examples of the heterocyclic compound include pyridine, pyrimidine, triazine, quinoline, isoquinoline, quinoxaline, dibenzofuran, dibenzothiophene, carbazole, phenoxazine, phenothiazine, benzothiadiazole, and dibenzosilole.

In the formula (3A), the substituent that the (2 + b) -valent aromatic hydrocarbon group and the (2 + b) -valent heterocyclic group represented by Ar ¹⁰ may have is preferably an alkyl group, an alkoxy group, Aryl group, aryloxy group, arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group Group or a cyano group, more preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group or a cyano group, and more preferably an alkyl group or an alkoxy group. Group or aryl group.

In the formula (3A), Ar ¹⁰ may have a substituent since the hole transport property and durability of the light-emitting element produced using the composition containing the polymer compound (A) are excellent ( A 2 + b) -valent aromatic hydrocarbon group is preferred.

In formula (3A), the alkylene group for R ²⁰ may be linear, branched or cyclic. A linear alkylene group is preferable because synthesis of the monomer as a raw material is easy. The carbon atom number of a linear alkylene group is 1-20 normally without including the carbon atom number of a substituent, Preferably it is 1-10, More preferably, it is 1-6. The number of carbon atoms of the branched alkylene group and the cyclic alkylene group is usually 3 to 20, preferably 3 to 10, more preferably 3 to 6, not including the number of carbon atoms of the substituent.

In the formula (3A), examples of the alkylene group in R ²⁰ include a methylene group, 1,2-ethylene group, 1,3-propylene group, 1,3-butylene group, 1,3-pentylene group, 1,4 -Pentylene group, 1,5-pentylene group, 1,4-hexylene group, 1,6-hexylene group, 1,7-heptylene group, 1,6-octylene group, 1,8-octylene group and the like.

In the formula (3A), examples of the phenylene group for R ²⁰ include o-phenylene, m-phenylene, and p-phenylene. Examples of the substituent that the phenylene group may have include an alkyl group, an alkoxy group, a halogen atom, and a cyano group.

  As the structural unit represented by the formula (3A), the structural unit represented by the formula (3a) is preferable from the viewpoint of hole transportability and durability.

In formula (3a),
d is 1 or 2.
Definition of R ^20, examples and preferred ranges, the definition of R ²⁰ in the formula (3A), the same as examples and preferred ranges. When a plurality of R ²⁰ are present, each R ²⁰ may be the same as or different from each other.
Q ¹ is the same meaning as Q ¹ in the formula (3A). When a plurality of Q ¹ are present, each Q ¹ may be the same as or different from each other.
R ³⁰ has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. An aryloxy group that may be substituted, a monovalent heterocyclic group that may have a substituent, or a heterocyclic oxy group that may have a substituent.

  In formula (3a), d is a hole-transport property and durability of a light-emitting device manufactured using the composition containing the polymer compound (A), and insolubilizes the organic thin film containing the composition. From the viewpoint of conversion to an organic thin film, it is more preferably 2.

In the formula (3a), R ³⁰ may have a substituent since the hole transport property and durability of the light emitting device produced using the composition containing the polymer compound (A) are more excellent. An aryl group which may have an alkyl group or a substituent is preferable, an aryl group having a substituent is more preferable, and an aryl group substituted with an alkyl group is further preferable.

In the formula (3a), the fluorene ring may have a substituent other than R ²⁰ and R ³⁰ , and the substituent is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group. , Arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group or cyano group, more preferably An alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group or a cyano group, more preferably an alkyl group, an alkoxy group or an aryl group.

  Examples of the structural unit represented by the formula (3A) include structural units represented by the formulas (3-101) to (3-136), and preferably the formulas (3-101) to (3 -111), (3-113) to (3-115), (3-119), and (3-125) to (3-136), and more preferably, 3-101) to (3-104), (3-106) to (3-108), (3-111), (3-114), (3-115), (3-118), (3- 125), (3-127), (3-129), (3-131), and (3-133) to (3-135), and more preferably, the structural unit represented by formula (3) -103), (3-104), (3-111), (3-115), (3-125), (3-131) and Each structural unit represented by 3-133) and the like. In the formula, a double bond having a wavy line means that either E-form or Z-form may be used.

  The polymer compound (A) may have only one type of structural unit represented by the formula (3A) as a structural unit containing a crosslinking group, or the structural unit represented by the above-described formula (3A). Among them, it may have a plurality of different structural units, but from the viewpoint of converting the organic thin film into an insolubilized organic thin film, it contains one or more monovalent crosslinking groups represented by the formula (Q-1), Containing at least one monovalent crosslinking group represented by formula (Q-2), and containing at least one monovalent crosslinking group represented by formula (Q-1) and formula (Q-2), respectively. It is more preferable that it contains at least one monovalent crosslinking group represented by formula (Q-1) and formula (Q-2).

[Structural Unit Represented by Formula (4A)]
Next, Formula (4A) will be described.

In formula (4A),
t is 0 or 1.
Ar ¹¹ and Ar ¹³ are each independently an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent.
Ar ¹² has an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or an arylene group and a substituent which may have a substituent. And a divalent group in which two or more identical or different groups selected from divalent heterocyclic groups which may be bonded are linked.
Q ² is a monovalent crosslinking group.
Q ³ is a monovalent bridging group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent. .

  In the formula (4A), t is easy to synthesize a monomer as a raw material, and is superior to the hole transportability and durability of a light-emitting device manufactured using a composition containing the polymer compound (A). , 0 is preferable.

In the formula (4A), the groups represented by Ar ¹¹ , Ar ¹² and Ar ¹³ are preferably each independently an arylene group which may have a substituent. Thereby, the positive hole transport property and durability of the light emitting element manufactured using the composition containing a high molecular compound (A) can be improved more.

In the formula (4A), as the arylene group as Ar ¹¹ , Ar ¹² and Ar ¹³ , for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthalenediyl Group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group, 2,6-anthracenediyl group, 9,10-anthracenediyl group, 2,7-phenanthenediyl group, 5,12-naphthacenediyl group, 2 , 7-fluorenediyl group, 3,6-fluorenediyl group, 1,6-pyrenediyl group, 2,7-pyrenediyl group or 3,8-perylenediyl group can be selected, and 1,4-phenylene group 2,7-fluorenediyl group, 2,6-anthracenediyl group, 9,10-anthracenediyl group, 2,7-phenanthrenediyl group or 1,6 A -pyrene diyl group is preferable, and a 1,4-phenylene group is more preferable.

In the formula (4A), examples of the divalent heterocyclic group as Ar ¹¹ , Ar ^12, and Ar ¹³ include 2,5-pyrroldiyl group, dibenzofurandiyl group, dibenzothiophenediyl group, and 2,1,3-benzoic group. A thiadiazole-4,7-diyl group can be selected.

In Formula (4A), two or more identical or different groups selected from an arylene group which may have a substituent in Ar ¹² and a divalent heterocyclic group which may have a substituent are linked to each other. Examples of the divalent group include formulas (B-1), (B-2), (B-3), (B-4), (B-5), (B-6) or (B-7). Is preferably a group represented by the formula (B-1). The groups represented by the formulas (B-1), (B-2), (B-3), (B-4), (B-5), (B-6) and (B-7) are It may have a substituent.

In the formula (4A), examples of the substituent that the arylene group and divalent heterocyclic group in Ar ¹¹ , Ar ^12, and Ar ¹³ may have include an alkyl group, an alkoxy group, an aryl group, and an aryloxy group. , Arylalkyl group, arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group and cyano group Preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group or a cyano group, more preferably an alkyl group, an alkoxy group or an aryl group. It is.

In the formula (4A), examples of the monovalent bridging group represented by Q ² include the formulas (Q-1), (Q-2), and (Q-01) to (Q-19). Group, and the light-emitting device manufactured using the composition containing the polymer compound (A) has more excellent hole transportability and durability, and therefore the formulas (Q-1), (Q-2), ( Q-01), (Q-03), (Q-04) and a group represented by the formula selected from the group consisting of (Q-06) to (Q-18) are preferred, and the formula (Q-1), A group represented by the formula selected from the group consisting of (Q-2) and (Q-07) to (Q-18) is more preferred, and a group represented by formula (Q-1) is more preferred.

In the formula (4A), examples of the monovalent crosslinking group represented by Q ³ include those represented by the formulas (Q-1), (Q-2), and (Q-01) to (Q-19). Group, and the light-emitting device manufactured using the composition containing the polymer compound (A) has more excellent hole transportability and durability, and therefore the formulas (Q-1), (Q-2), ( Q-01), (Q-03), (Q-04) and a group represented by the formula selected from the group consisting of (Q-06) to (Q-18) are preferred, and the formula (Q-1), A group represented by the formula selected from the group consisting of (Q-2) and (Q-07) to (Q-18) is more preferred, and a group represented by formula (Q-1) is more preferred.

In formula (4A), the definition and examples of the alkyl group as Q ^{3 are the same} as the definitions and examples of the “alkyl group” in “Explanation of terms”, but are preferably C _{1 to} C ₂₀ alkyl groups. .

In formula (4A), the definition and example of the aryl group as Q ^{3 are the same} as the definition and example of “aryl group” in “Explanation of Terms”, but preferably a phenyl group, 1-naphthyl group, 2 -It is a naphthyl group, 1-anthracenyl group, 2-anthracenyl group, 9-anthracenyl group or 2-fluorenyl group.

In formula (4A), the definition and examples of the monovalent heterocyclic group as Q ^{3 are the same} as the definitions and examples of “monovalent heterocyclic group” in “Explanation of Terms”, but preferably pyridyl Group, pyrimidyl group, triazyl group or quinolyl group.

In Formula (4A), Q ³ is preferably a monovalent cross-linking group like Q ¹ because synthesis of a monomer as a raw material becomes easy.

In the formula (4A), the substituent that the alkyl group, arylene group or divalent heterocyclic group of Q ³ may have is preferably an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group. , Arylalkoxy group, arylalkenyl group, arylalkynyl group, amino group, substituted amino group, halogen atom, acyl group, acyloxy group, monovalent heterocyclic group, carboxyl group, nitro group or cyano group, more preferably An alkyl group, an alkoxy group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkoxy group, a substituted amino group, an acyl group or a cyano group, more preferably an alkyl group, an alkoxy group or an aryl group.

  Examples of the structural unit represented by the formula (4A) include structural units represented by the formulas (4-101) to (4-105), and the formulas (4-101), (4-102), The structural unit represented by (4-104) or (4-105) is preferable, the structural unit represented by formula (4-101) or (4-102) is more preferable, and the structural unit represented by formula (4-101) More preferred is a structural unit.

  When the polymer compound (A) contains a structural unit having a crosslinkable group, the content of the structural unit (total content) depends on the crosslinkability when a light emitting device is produced using the first composition. Since it is excellent, it is preferable that it is 0.1-30 mol% with respect to all the structural units contained in a high molecular compound (A), It is more preferable that it is 1-25 mol%, 3-20 mol% More preferably.

-Structure and properties of polymer compound (A)-
In the polymer compound (A), the existence form of each structural unit is not particularly limited. The same type of structural units may be bonded continuously, or different types of structural units may be bonded.

  Since the characteristic (for example, luminous efficiency) of the light emitting element manufactured using the 1st composition containing the high molecular compound (A) of this invention is more excellent, a high molecular compound (A) is represented by Formula (1). It is preferable that the structural units (1) are not substantially adjacent to each other. The polymer compound (A) is a structural unit other than the structural unit (1) represented by the formula (1) and the structural unit (2) represented by the formula (2) (hereinafter referred to as X (formula 1)). When the structural unit other than the structural unit (1) and the structural unit (2) represented by the formula (2) is sometimes referred to as the structural unit X), it is represented by the formula (1). It is preferable that the structural units (1), the structural units X, and the structural unit (1) represented by the formula (1) and the structural unit X are not substantially adjacent to each other. That is, the structural unit (1) and the structural unit X represented by the formula (1) are preferably adjacent to the structural unit (2) represented by the formula (2).

  Here, the term “substantially not adjacent to each other” means that the total number of bonds in which the structural units (1) represented by the formula (1) are adjacent to each other is less than 0.05. Yes, the total number of bonds adjacent to each other in the structural units X with respect to the number of bonds between all the structural units is less than 0.05, and is expressed by the formula (1) for the number of bonds between all the structural units. It means that the total number of bonds adjacent to the structural unit (1) and the structural unit X is less than 0.05.

  If the polymerizable group remains as it is in the terminal group of the polymer compound (A), there is a possibility that the light emission characteristics or the lifetime of the light emitting device manufactured using the composition containing the polymer compound (A) may be deteriorated. Therefore, the terminal group of the polymer compound (A) is preferably a stable group. Examples of the stable group include an aryl group and a monovalent heterocyclic group (preferably a monovalent aromatic heterocyclic group).

The number average molecular weight in terms of polystyrene by gel permeation chromatography (hereinafter referred to as “GPC”) of the polymer compound (A) is preferably 1 × 10 ³ to 1 × 10 ⁷ , more preferably 1 × 10 ^4. ~ 5x10 ⁶ . Moreover, the polystyrene equivalent weight average molecular weight of the polymer compound (A) is preferably 1 × 10 ^{4 to} 5 × 10 ⁷ , more preferably 5 × 10 ⁴ to 1 × 10 ⁷ .

  Since the durability to various processes for producing a light emitting device is excellent and the heat resistance of the produced light emitting device is good, the glass transition temperature of the polymer compound (A) is preferably 70 ° C. or higher. .

-Synthesis method of polymer compound (A)-
Below, the preferable manufacturing method of a high molecular compound (A) is demonstrated. The polymer compound (A) can be produced, for example, by condensation polymerization.

  As a method of condensation polymerization, a method of polymerizing by a Suzuki reaction (Chem. Rev., Vol. 95, p. 2457 (1995)), a method of polymerizing by a Grignard reaction (Kyoritsu Shuppan, Polymer Functional Materials Series) Volume 2, Polymer Synthesis and Reaction (2), pages 432-433), and a method of polymerizing with Ni (0) (Prog. Polym. Sci.), Volume 17, 1153-1205. Page, 1992).

  When the polymer compound (A) is polymerized so that the structural unit (1) represented by the formula (1) and the structural unit X are adjacent to the structural unit represented by the formula (2), the sequence can be controlled. A polymerization method using a Suzuki reaction is preferred, but a reaction other than the Suzuki reaction may be employed as long as the polymerization method can control the sequence.

  Hereinafter, the method of polymerizing by the Suzuki reaction will be described. The polymer compound (A) is represented by, for example, a compound represented by the formula (1M) and a compound represented by the formula (2M), or a compound represented by the formula (3M) and the formula (4M). Can be produced by condensation polymerization with a compound. In the polymer compound (A), structural units other than the structural units represented by the formulas (1) and (2) may be introduced by condensation polymerization.

In formula (1M),
Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , R ³ , x and y are as defined above.
A is a group selected from the substituent group A.

In formula (2M),
Ar ⁵ , R ⁴ and a are as defined above.
B is a group selected from the substituent group B.

In the formula (3M), Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² , R ³ , x, y, and B are as defined above.

（４Ｍ）

(4M)

In the formula (4M), Ar ⁵ , R ⁴ , a and A are as defined above.

-Substituent group A chlorine atom;
Bromine atom;
An iodine atom; and —O—S (═O) ₂ R ³¹ (R ³¹ has an alkyl group or a substituent selected from the group consisting of an alkyl group, an alkoxy group, a nitro group, a fluorine atom, and a cyano group) An aryl group that may be present).

-Substituent group B -B (OR ³² ) ₂ (R ³² is a hydrogen atom or an alkyl group, and each R ³² may be the same as or different from each other, and is bonded to each other. A ring structure together with an oxygen atom.)
A group represented by -BF ₄ Q ¹⁰ (Q ¹⁰ is a monovalent cation selected from the group consisting of Li ⁺ , Na ⁺ , K ⁺ , Rb ⁺ and Cs ⁺ );
A group represented by -MgY ¹ (Y ¹ is a chlorine atom, a bromine atom or an iodine atom);
-ZnY ² (. Y ² is a chlorine atom, a bromine atom or an iodine atom) group represented by; and -Sn (R ³³⁾ ₃ (R ³³ is a hydrogen atom or an alkyl group, each of R ³³ May be the same as or different from each other, and may be bonded to each other to form a ring structure together with the tin atoms to which they are bonded.

  As the compound represented by the formula (1M), (2M), (3M) or (4M), a compound synthesized and isolated in advance may be used, or a compound synthesized in a reaction system may be used as it is. Good. When the composition containing the obtained polymer compound (A) is used for the production of a light-emitting device, its purity affects the performance of the light-emitting device. Therefore, these monomers are preferably purified by a method such as distillation, chromatography, sublimation purification, recrystallization, or a combination thereof.

  When the monomer is polymerized in the method of polymerizing by the Suzuki reaction, it is preferable to use a catalyst and / or a base.

  Examples of the catalyst include transition metal complexes such as palladium complexes such as palladium [tetrakis (triphenylphosphine)], [tris (dibenzylideneacetone)] dipalladium, palladium acetate, dichlorobistriphenylphosphine palladium, and transitions thereof. A complex in which a ligand such as triphenylphosphine, tri-tert-butylphosphine, or tricyclohexylphosphine is coordinated with a metal complex can be given.

  The catalyst can be synthesized and used in advance, or can be prepared in a reaction system and used as it is. These catalysts may be used individually by 1 type, and may be used in combination of 2 or more type.

  When a catalyst is used, the amount of metal atoms in the catalyst with respect to the total number of moles of the compound represented by the formula (1M), (2M), (3M) or (4M) is 0.00001 to 3 molar equivalents. Preferably, it is 0.00005 to 0.5 molar equivalent, more preferably 0.0001 to 0.2 molar equivalent, and 0.0001 to 0.01 molar equivalent. Particularly preferred.

  Examples of the base include inorganic bases such as sodium carbonate, potassium carbonate, cesium carbonate, potassium fluoride, cesium fluoride, or tripotassium phosphate, and tetrabutylammonium fluoride, tetrabutylammonium chloride, and tetrabutylammonium bromide. And organic bases such as tetrabutylammonium hydroxide. These bases may be used alone or in combination of two or more.

  When a base is used, the amount used is 0.5 to 20 molar equivalents relative to the total number of moles of the compound represented by the formula (1M), (2M), (3M) or (4M). It is preferable that it is 1 to 10 molar equivalents.

  The condensation polymerization is usually performed in the presence of a solvent such as an organic solvent.

  The organic solvent can be appropriately selected depending on the type and / or reaction of the compound represented by the formula (1M), (2M), (3M) or (4M). For example, toluene, xylene, mesitylene, tetrahydrofuran, 1,4 -Dioxane, dimethoxyethane, N, N-dimethylacetamide and N, N-dimethylformamide. In order to suppress side reactions, it is desirable to deoxidize the solvent. A solvent may be used individually by 1 type and may be used in combination of 2 or more type.

  The total amount of the compounds represented by the formula (1M), (2M), (3M) or (4M) is usually 0.1 to 90% by mass, preferably 1 to 50% by mass, More preferably, the amount is 2 to 30% by mass.

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

  The reaction time depends on conditions such as the reaction temperature, but is usually 1 hour or longer, preferably 2 to 500 hours.

  In the polymerization reaction, a compound represented by the formula (1T) may be used as a chain terminator in order to avoid leaving a polymerizable group at the terminal of the polymer compound (A). As a result, a polymer compound whose terminal is an aryl group or a monovalent heterocyclic group (preferably a monovalent aromatic heterocyclic group) can be obtained.

Z ^T -Ar ^T (1T)

In formula (1T),
Ar ^T is an aryl group which may have a substituent, or a monovalent heterocyclic group which may have a substituent.
Z ^T is a group selected from the group consisting of the substituent group A and the substituent group B.

Examples of the aryl group and monovalent heterocyclic group in Ar ^T are the same as the examples of the aryl group and monovalent heterocyclic group in R ⁴ , respectively.

  The post-treatment of the polymerization reaction can be performed by a known method. For example, a method of removing water-soluble impurities by liquid separation, a reaction solution after the polymerization reaction is added to a lower alcohol such as methanol, and the precipitated precipitate is removed. Methods such as filtration and drying can be performed alone or in combination.

  When the purity of the polymer compound (A) is low, the polymer compound (A) may be purified by usual methods such as recrystallization, reprecipitation, continuous extraction with a Soxhlet extractor, column chromatography, etc. In the case where a compound containing the compound is used for the production of a light emitting device, the purity affects the performance of the light emitting device such as the light emitting properties. Therefore, it is preferable to perform a purification treatment such as reprecipitation purification and fractionation by chromatography after condensation polymerization.

(Compound (B))
The compound (B) is fullerene or a fullerene derivative, an azulene or azulene derivative represented by the formula (3), or a stilbene or stilbene derivative represented by the formula (4). Among these, fullerene or fullerene derivatives are preferable.

-Fullerene or fullerene derivative-
The fullerene includes, for example, fullerene C60, fullerene C70, fullerene C76, fullerene C78 and fullerene C84, preferably fullerene C60, fullerene C70 or fullerene C84, more preferably fullerene C60 or fullerene C70. More preferred is fullerene C60.

  A fullerene derivative refers to two monovalent groups or one two bonds each formed by breaking one bond constituting a carbon-carbon double bond of a skeleton constituting a fullerene. A compound substituted with a valent group. The number of carbon-carbon double bonds to be cut may be one or two or more.

  Examples of fullerene derivatives include molecules represented by Formulas A-1 to A-23.

In formulas A-1 to A-23,
Ring A is a fullerene ring selected from the group consisting of fullerene C60, fullerene C70, fullerene C76, fullerene C78, and fullerene C84.
R is a hydrogen atom, a halogen atom or a monovalent organic group. When a plurality of R are present, each R may be the same as or different from each other.
nn is an integer of 0-10.

  In the formulas A-1 to A-23, the ring A is preferably fullerene C60, fullerene C70 or fullerene C84, and more preferably fullerene C60 or fullerene C70.

  In the formulas A-3, A-5, A-6, A-8, A-9, A-11 to A-16, A-22 and A-23, as the monovalent organic group as R, for example, , An alkyl group which may have a substituent, an alkyloxy group which may have a substituent, an alkylthio group which may have a substituent, an aryl group which may have a substituent, Aryloxy group which may have a substituent, arylthio group which may have a substituent, arylalkyl group which may have a substituent, arylalkyloxy which may have a substituent Group, arylalkylthio group which may have a substituent, acyl group which may have a substituent, acyloxy group which may have a substituent, amide compound which may have a substituent A residue, an acid imide residue optionally having a substituent, An imine residue which may have a substituent, an amino group which may have a substituent, a substituted amino group, a substituted silyl group, a substituted silyloxy group, a substituted silylthio group, a substituted silylamino group, and a substituent An optionally substituted monovalent heterocyclic group, an optionally substituted heterocyclic oxy group, an optionally substituted heterocyclic thio group, and an optionally substituted arylalkenyl Group, an arylalkynyl group which may have a substituent, a carboxyl group which may have a substituent, and a cyano group.

  The fullerene or fullerene derivative is preferably fullerene, more preferably fullerene C60, fullerene C70 or fullerene C84, still more preferably fullerene C60 or fullerene C70, particularly preferably fullerene C60.

-Azulene or azulene derivative represented by formula (3)-
The azulene or azulene derivative represented by the formula (3) will be described.

In formula (3),
R ^x has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alkynyl group that may have a substituent, an amino group that may have a substituent, a silyl group that may have a substituent, a halogen atom, and a substituent. An acyl group which may be substituted, a monovalent heterocyclic group which may have a substituent, a carboxyl group which may have a substituent, a nitro group or a cyano group. Each R ^x may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atoms to which they are bonded.

In the formula (3), an alkyl group, alkoxy group, aryl group, alkenyl group, alkynyl group, amino group, silyl group, halogen atom, acyl group, monovalent heterocyclic group, carboxyl group, nitro group as R ^x and The definitions and examples of the cyano group are the same as the definitions and examples of each group in “Explanation of Terms”.

In the formula (3), R ^x is preferably a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryl which may have a substituent. The group is preferable, more preferably a hydrogen atom, an alkyl group which may have a substituent, or an aryl group which may have a substituent, and more preferably a hydrogen atom. Each R ^x may be the same as or different from each other.

  Examples of the azulene or azulene derivative represented by the formula (3) include each compound represented by the following formula.

-Stilbene or stilbene derivative represented by formula (4)-
The stilbene or stilbene derivative represented by the formula (4) will be described.

In formula (4),
R ⁿ has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, and a substituent. It is also a monovalent heterocyclic group. Each R ⁿ may be the same as or different from each other.
Ar ⁶ and Ar ⁷ are each independently an aryl group which may have a substituent or a monovalent heterocyclic group which may have a substituent. Ar ⁶ and Ar ⁷ may be directly bonded to adjacent R ⁿ to form a ring structure together with the carbon atom to which each is bonded.

In formula (4), the definitions and examples of the alkyl group, alkoxy group, aryl group and monovalent heterocyclic group as R ^{n are the same} as the definitions and examples of each group in “Explanation of terms”.

In the formula (4), R ⁿ is preferably a hydrogen atom, an alkyl group which may have a substituent or an aryl group which may have a substituent, more preferably a hydrogen atom or a substituent. An aryl group optionally having a hydrogen atom, and more preferably a hydrogen atom or a phenyl group optionally having a substituent.

In formula (4), the definitions and examples of the aryl group and monovalent heterocyclic group as Ar ⁶ and Ar ^{7 are the same} as the definitions and examples of each group in “Explanation of terms”.

In the formula (4), Ar ⁶ and Ar ⁷ are each independently preferably an aryl group which may have a substituent, more preferably a phenyl group which may have a substituent, An anthracenyl group which may have a substituent, a naphthylene group which may have a substituent, or a fluorenyl group which may have a substituent, more preferably a substituent. It is a phenyl group.

  The stilbene or stilbene derivative represented by the formula (4) is preferably a stilbene or each stilbene derivative represented by the formula (11-1) to the formula (11-16) from the viewpoint of luminance life, 1) and the stilbene or each stilbene derivative represented by the formula (11-7) to the formula (11-10) are more preferable.

In formula (11-1)-formula (11-16),
R ^y has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is also a monovalent heterocyclic group. Each R ^y may be the same as or different from each other.
R ⁸ has the same meaning as R ⁸ in formula (10c) ~ formula (10d).

In formulas (11-1) to (11-16), definitions and examples of the alkyl group, alkoxy group, aryl group and monovalent heterocyclic group as R ^y are the definitions of each group in “Explanation of Terms”. And similar to the example.

In the formulas (11-1) to (11-16), R ^y preferably has a hydrogen atom, an alkyl group which may have a substituent, or a substituent from the viewpoint of luminance life. More preferably an aryl group which may have a hydrogen atom or a substituent, and still more preferably a phenyl group which may have a hydrogen atom or a substituent.

  As the stilbene or stilbene derivative represented by the formula (4), the formula (11-01) which is a preferred form of the formula (11-1) and the formula (11-07) which is a preferred form of the formula (11-7). Formula (11-08), which is a preferred form of Formula (11-8), Formula (11-09) which is a preferred form of Formula (11-9), or a preferred form of Formula (11-10) Each compound represented by Formula (11-010) is preferable.

-Composition of the first composition-
In the first composition, the content (total content) of the compound (B) is superior in the luminance life of the light-emitting device produced using the first composition of the present invention. ) Is preferably 0.001 to 50 mol%, more preferably 0.1 to 30 mol%, based on the total number of moles of all structural units and the total number of moles of compound (B). More preferably, it is 1-10 mol%.

<Second composition>
The 2nd composition of this invention is a composition containing a high molecular compound (A) and a high molecular compound (C).

  In the second composition, the polymer compound (A) is the same as the definition, examples and preferred examples of the polymer compound (A) in the first composition.

  Hereinafter, the polymer compound (C) will be described.

(Polymer compound (C))
The polymer compound (C) is a polymer compound containing the structural unit (c-1). The structural unit (c-1) includes a structural unit containing fullerene or a derivative thereof, a structural unit containing azulene or an azulene derivative represented by the formula (3), and a stilbene or stilbene derivative represented by the formula (4). One or more structural units selected from the group consisting of structural units. Among these, the structural unit (c-1) is preferably a structural unit containing fullerene or a fullerene derivative.

-Structural unit containing fullerene or fullerene derivative-
The structural unit containing fullerene or a fullerene derivative is a structural unit containing a group containing an atomic group in which one bond constituting a carbon-carbon double bond of a skeleton constituting fullerene is cut from fullerene or a fullerene derivative. (The number of carbon-carbon double bonds to be cleaved may be one or two or more, but preferably one.) Although not particularly limited, Formula (5-1) Or a structural unit represented by the formula (5-2), more preferably a structural unit represented by the formula (5-1). Hereinafter, Formula (5-1) and Formula (5-2) will be described in order.

In formula (5-1),
Ar ⁸ has one substituent and an arylene group which may have other substituents, or one substituent and other substituents. Or a divalent heterocyclic group.
Ar ¹⁴ is an arylidine group which may have a substituent or a trivalent heterocyclic group which may have a substituent.
R ⁷ represents a single bond, an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted arylene group having 6 to 20 carbon atoms, or a combination thereof. Divalent group.
R ⁵ and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted alkoxy group having 1 to 20 carbon atoms. It is a group.
Ring F is fullerene.
q is an integer of 1-4. p is 0 or 1.
When a plurality of R ⁷ are present, each R ⁷ may be the same as or different from each other. When a plurality of Ar ¹⁴ are present, each Ar ¹⁴ may be the same as or different from each other. When a plurality of R ⁵ are present, each R ⁵ may be the same as or different from each other. When a plurality of R ⁶ are present, each R ⁶ may be the same as or different from each other. When a plurality of p are present, each p may be the same as or different from each other. When a plurality of rings F are present, each ring F may be the same as or different from each other. When p is 0, the carbon atom substituted with R ⁵ and the carbon atom substituted with R ⁶ are not directly bonded.

In the formula (5-1), examples of the arylene group as Ar ⁸ include a phenylene group (for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group), naphthalenediyl group ( For example, 1,4-naphthalenediyl group, 2,6-naphthalenediyl group, 2,7-naphthalenediyl group), anthracenediyl group (for example, 2,6-anthracenediyl group, 9,10-anthracenediyl group), Phenanthrene diyl group (for example, 2,7-phenanthrene diyl group), dihydrophenanthrene diyl group (for example, 2,7-dihydrophenanthrene diyl group), naphthacene diyl group (for example, 5,12-naphthacene diyl group), fluorenediyl group ( For example, 2,7-fluorenediyl group, 3,6-fluorenediyl group) and peri Njiiru group (e.g., 3,8-perylenediyl group).

In the formula (5-1), examples of the divalent heterocyclic group as Ar ⁸ include the following groups: pyrroldiyl groups such as N-methyl-2,5-pyrroldiyl group; 2,5-furandiyl Flangedyl groups such as groups; pyridinediyl groups such as 2,5-pyridinediyl groups and 2,6-pyridinediyl groups; quinolinediyl groups such as 2,4-quinolinediyl groups and 2,6-quinolinediyl groups; Isoquinolinediyl groups such as isoquinolinediyl group and 1,5-isoquinolinediyl group; carbazolediyl groups such as 3,6-carbazolediyl group, 2,5-pyrrolediyl group, 2,1,3-benzothiadiazole-4,7- Diyl group, dibenzofurandiyl group, dibenzothiophene diyl group and dibenzosilol diyl group. In addition, these groups may have a substituent.

In the formula (5-1), Ar ⁸ is preferably an arylene group which has one substituent and may have other substituents, and has one substituent. More preferred is a fluorenediyl group which may have a substituent other than.

In the formula (5-1), the number of carbon atoms of the arylidine group (also referred to as “trivalent aromatic hydrocarbon group”) which may have a substituent represented by Ar ¹⁴ is It is 6-30 normally without including the carbon atom number of group, Preferably it is 6-16.
The carbon atom number of the trivalent heterocyclic group which may have a substituent represented by Ar ¹⁴ is usually 6-30, preferably 6-16, not including the carbon atom number of the substituent. It is. The heteroarylidine group may contain a nitrogen atom, an oxygen atom, a sulfur atom, etc. in addition to a carbon atom as an atom forming an aromatic ring.

In the formula (5-1), as the arylidine group as Ar ¹⁴ , for example, a phenyridine group, a naphthalenetriyl group, an anthracentriyl group, a phenanthrenetriyl group, a naphthacentriyl group, a fluorenetriyl group, a perylenetriyl group Groups and chrysantyl groups.

In the formula (5-1), examples of the trivalent heterocyclic group as Ar ¹⁴ include a pyrrole triyl group, a furan triyl group, a pyridine triyl group, a quinoline triyl group, and an isoquinoline triyl group.

In Formula (5-1), R ⁷ is preferably an alkylene group having 1 to 20 carbon atoms that does not have a single bond or substituent, and more preferably 1 to 1 carbon atoms that does not have a single bond or substituent. 6 alkylene group.

In formula (5-1), R ⁵ and R ⁶ are each independently preferably a hydrogen atom.

  Examples of fullerene as ring F in formula (5-1) include fullerene C60, fullerene C70, fullerene C76, fullerene C78, and fullerene C84, preferably fullerene C60, fullerene C70, or fullerene C84. Fullerene C60 is preferable. Here, the fullerene may have an alkyl group or a cyano group on its surface.

  In the formula (5-1), q is preferably an integer of 1 to 3, and more preferably 1 or 2.

  In the formula (5-1), p is preferably 0.

式（５−２）中、
Ａｒ⁸は、置換基を有していてもよいアリーレン基、置換基を有していてもよいヘテロアリーレン基または置換基を有していてもよい２価の複素環基である。
Ｒ⁷は、単結合、置換基を有していてもよい炭素原子数１〜２０のアルキレン基、置換基を有していてもよい炭素原子数６〜２０のアリーレン基、または、これらを組み合わせた２価の基を示す。
Ｒ^aは、水素原子、置換基を有していてもよい炭素原子数１〜２０のアルキル基、置換基を有していてもよい炭素原子数１〜２０ののアルコキシ基、または、Ｒ⁷との直接結合である。各々のＲ^aは互いに同一であっても異なっていてもよい。
環Ｆはフラーレンである。
ｑは１〜４の整数を示す。
Ｒ⁷が複数個存在する場合、各々のＲ⁷は互いに同一であっても異なっていてもよい。環Ｆが複数個存在する場合、各々の環Ｆは互いに同一であっても異なっていてもよい。

In formula (5-2),
Ar ⁸ is an arylene group which may have a substituent, a heteroarylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent.
R ⁷ represents a single bond, an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted arylene group having 6 to 20 carbon atoms, or a combination thereof. Divalent group.
R ^a is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkoxy group having 1 to 20 carbon atoms, or R ^7. Is a direct bond. Each R ^a may be the same as or different from each other.
Ring F is fullerene.
q shows the integer of 1-4.
When a plurality of R ⁷ are present, each R ⁷ may be the same as or different from each other. When a plurality of rings F are present, each ring F may be the same as or different from each other.

In the formula (5-2), Ar ^8, R ^7, ring F and q, Ar ^8, R ⁷ in the formula (5-1), each have the same meanings as defined ring F and q.

In the formula (5-2), R ^a is preferably a hydrogen atom.

  The structural unit represented by the formula (5-1) is preferably a structural unit represented by the formula (6).

In formula (6),
R ⁷ represents a single bond, an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted arylene group having 6 to 20 carbon atoms, or a combination thereof. Divalent group. If R ⁷ is more, each of R ⁷ may being the same or different.
R ^b has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. It may be a monovalent heterocyclic group.
s is 1 or 2.
Fullerene is fullerene C60.
R ⁷ has the same meaning as R ⁷ in the formula (5-1) and (5-2).

In the formula (6), R ⁷ is preferably a C 1-20 alkylene group having no single bond or substituent, and more preferably a C 1-6 carbon atom having no single bond or substituent. An alkylene group;

In formula (6), the definition and examples of the alkyl group, alkoxy group, aryl group and monovalent heterocyclic group represented by R ^b are the same as the definitions and examples of each group in “Explanation of terms”.

In Formula (6), R ^b is preferably an alkyl group which may have a substituent, or an aryl group which may have a substituent, more preferably an alkyl group having no substituent or An aryl group having a substituent.

  Examples of the structural unit represented by the formula (6) include structural units represented by the formulas (6A-1) to (6A-11).

-Structural unit containing azulene or azulene derivative represented by formula (3)-
Examples of the structural unit containing azulene or an azulene derivative represented by the formula (3) include a structural unit including a group consisting of an atomic group obtained by removing one R ^X in the formula (3), and an R ^{X in the} formula (3). Is a structural unit obtained by removing two R ^X in formula (3).

As the structural unit obtained by removing two R ^X in formula (3), structural units represented by formulas (12-1) to (12-6) are preferable. More preferred are structural units represented by formula (12-1), formula (12-2), formula (12-4), formula (12-5) or formula (12-6), and particularly preferred is formula It is a structural unit represented by (12-1).

In formula (12-1) to (12-6), the definition of R ^x, examples and preferred ranges, the definition of R ^x in formula (3), is similar to the example and preferred ranges.

  Examples of structural units represented by formulas (12-1) to (12-6) include structural units represented by formulas (12-01) to (12-013). Preferably, formula (12 -01) to (12-06), more preferably structural units represented by formulas (12-01) to (12-03), and still more preferably formula (12-01). ).

-Constituent Unit Containing Stilbene or Stilbene Derivative Represented by Formula (4)-
The structural unit containing a stilbene or stilbene derivative represented by the formula (4) is one or more selected from the group consisting of R ⁿ , Ar ⁶ and Ar ⁷ from the stilbene or stilbene derivative represented by the formula (4) A structural unit comprising a group consisting of an atomic group obtained by removing one hydrogen atom directly bonded to a carbon atom constituting a ring in the group, and a stilbene or stilbene derivative represented by formula (4) from R ⁿ , Ar ⁶ and Examples of the structural unit include a group consisting of an atomic group obtained by removing two hydrogen atoms directly bonded to the carbon atoms constituting the ring in one or more groups selected from the group consisting of Ar ^7. in R ⁿ stilbene or a stilbene derivative represented ^directly to a carbon atom constituting the ring in one or more groups selected from the group consisting of Ar ⁶ and Ar ⁷ The case for hydrogen atom a structural unit comprising two exception was made of atomic groups.

Two hydrogen atoms directly bonded to the carbon atoms constituting the ring in one or more groups selected from the group consisting of R ⁿ , Ar ⁶ and Ar ⁷ were removed from the stilbene or stilbene derivative represented by the formula (4). The structural unit containing a group consisting of an atomic group is selected from the group consisting of a structural unit represented by the formula (7a), a structural unit represented by the formula (7b), and a structural unit represented by the formula (7c). It is preferable that it is 1 or more types of structural units, and among these, it is more preferable that it is a structural unit represented by Formula (7a). Hereinafter, formulas (7a), (7b), and (7c) will be described in order.

In formula (7a),
R ⁿ and Ar ⁷ are as defined above.
Ar ⁹ has one substituent and an arylene group which may have other substituents or one substituent and may have other substituents It is a good divalent heterocyclic group.

In formula (7b),
R ⁿ has the same meaning as described above.
Ar ^{9 ′} is an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. Each Ar ^{9 ′} may be the same as or different from each other. Ar ⁹ may be directly bonded to R ⁿ to form a ring structure together with the carbon atom to which each is bonded.

In formula (7c),
R ⁿ , Ar ⁷ and Ar ^{9 ′} are as defined above.
R ^{n ′} is an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent.
Ar ^{9 ′} may be directly bonded to R ^{n ′} to form a ring structure together with the carbon atom to which each is bonded.

Equation (7a), in (7b) and (7c), the definition of R ^n, examples and preferred ranges, the definition of R ⁿ in the formula (4), is similar to the example and preferred ranges.

In the formula (7a) and (7c), the definition of Ar ^7, examples and preferred ranges, the definition of Ar ⁷ in the formula (4), is similar to the example and preferred ranges.

In formula (7a), the definition and examples of the arylene group represented by Ar ⁹ and the divalent heterocyclic group are the same as the definitions and examples of each group in “Explanation of terms”.

In the formula (7a), Ar ⁹ is preferably an arylene group having one substituent and optionally having other substituents, and more preferably having one substituent. And a phenylene group which may have other substituents, a naphthalenediyl group which has one substituent and which may have other substituents, and one substituent. And an anthracenediyl group optionally having other substituents and a fluorenediyl group having one substituent and optionally having other substituents, More preferably, it is a phenylene group which has one substituent and may have other substituents. “Has one substituent and may have other substituents” means that when there are one or more substituents and a plurality of substituents, each substituent It means that the groups may be the same or different from each other.

In formulas (7b) and (7c), the definitions and examples of the arylene group represented by Ar ^{9 ′} and the divalent heterocyclic group are the same as the definitions and examples of each group in “Explanation of terms”.

In the formulas (7b) and (7c), Ar ^{9 ′} is preferably an arylene group which may have a substituent, more preferably a phenylene group or a substituent which may have a substituent. A naphthalenediyl group optionally having a substituent, an anthracenediyl group optionally having a substituent, and a fluorenediyl group, and more preferably a phenylene group optionally having a substituent.

In formula (7c), the definitions and examples of the arylene group represented by R ^{n ′} and the divalent heterocyclic group are the same as the definitions and examples in “Explanation of Terms” above.

In the formula (7c), R ^{n ′} is preferably an arylene group which may have a substituent, more preferably a phenylene group which may have a substituent, or a substituent. A naphthalenediyl group which may be substituted, an anthracenediyl group which may have a substituent, and a fluorenediyl group, and a phenylene group which may have a substituent.

  As the structural unit represented by the formula (7a), from the viewpoint of the luminance life, each structural unit represented by the formula (7a-1) to the formula (7a-11) is preferable, and the formula (7a-1) and the formula Each structural unit represented by (7a-7) to formula (7a-10) is more preferable.

In formula (7a-1)-formula (7a-11),
R ^y has the same meaning as R ^y in formula (11-1) to (11-16).
R ⁸ has the same meaning as R ⁸ in formula (10c) ~ formula (10d).
c is an integer of 0-3.
Each R ^y may be the same as or different from each other. Each R ⁸ may be the same as or different from each other.

  In formula (7a-1) to formula (7a-11), c is preferably 0 or 1, more preferably 0.

  The structural unit represented by the formula (7a) is represented by the formula (7a-20) which is a preferred form of the formula (7a-10) and the formula (7a-30) which is a preferred form of the formula (7a-1). The structural unit is preferred.

  The structural unit represented by the formula (7b) is preferably a structural unit represented by the formula (7b-1) to the formula (7b-9) from the viewpoint of luminance life, and is represented by the formula (7b-1). The structural unit is more preferable.

In formula (7b-1) to formula (7b-9),
R ^y has the same meaning as R ^y in formula (11-1) to (11-16).
R ⁸ has the same meaning as R ⁸ in formula (10c) ~ formula (10d).
Each R ^y may be the same as or different from each other. Each R ⁸ may be the same as or different from each other.

  As the structural unit represented by the formula (7b), a structural unit represented by the formula (7b-20) which is a preferred form of the formula (7b-1) is preferable.

  As a structural unit represented by Formula (7c), each structural unit represented by Formula (7c-1)-Formula (7c-3) is preferable from a viewpoint of a brightness | luminance lifetime.

In formula (7c-1)-formula (7c-3),
R ^y has the same meaning as R ^y in formula (11-1) to (11-16).

  The structural unit containing a stilbene or stilbene derivative represented by the formula (4) is a formula (7c-20) which is a preferred form of the formula (7c-1) or a formula which is a preferred form of the formula (7c-2). The structural unit represented by (7c-30) is preferred.

  The polymer compound (C) may have only one structural unit (c-1), or may have two or more. When the polymer compound (A) has two or more structural units (c-1), the structural unit (1) may be one type or two or more different types.

  In the second composition, the content (total content) of the structural unit (c-1) contained in the polymer compound (C) is such that the luminance lifetime of the light-emitting device produced using the second composition is high. Since it is more excellent, it is preferable that it is 0.001-50 mol% with respect to all the structural units contained in a high molecular compound (A) and a high molecular compound (C), and it is 0.001-30 mol%. Is more preferable, and it is still more preferable that it is 0.01-10 mol%.

-Structure and properties of polymer compound (C)-
The high molecular compound (C) should just contain the structural unit (c-1), and may contain structural units other than the structural unit (c-1). For example, it is preferable that the structural unit represented by Formula (1) and / or the structural unit represented by Formula (2) is included. Thereby, the charge transport property of the light emitting element manufactured using a high molecular compound (C), luminous efficiency, and a brightness | luminance lifetime can be improved more. Furthermore, it is more preferable that the structural unit which has a crosslinking group is included. Accordingly, when a thin film containing the second composition is used as a hole injecting or hole transporting layer and a solution is applied thereon to form a light emitting layer, a light emitting device is manufactured. The organic thin film containing the composition can be converted into an insolubilized organic thin film.

  The structural unit having a crosslinking group may contain one or two or more crosslinking groups. When the structural unit having a crosslinking group contains two or more crosslinking groups, they may be a combination of different types of crosslinking groups. Examples and preferred examples of the crosslinking group are the same as the examples and preferred examples given in the column of the polymer compound (A).

  Examples of the structural unit having a crosslinking group include a structural unit represented by the formula (3A) and a structural unit represented by the formula (4A). Examples and preferred examples of the structural unit represented by the formula (3A) and the structural unit represented by the formula (4A) are the same as the examples and preferred examples given in the column of the polymer compound (A).

  When the polymer compound (C) contains a structural unit having a crosslinkable group, the content (total content) of the structural unit depends on the crosslinkability when a light emitting device is produced using the first composition. Since it is excellent, it is preferable that it is 0.1-30 mol% with respect to all the structural units contained in a high molecular compound (C), It is more preferable that it is 1-25 mol%, 3-20 mol% More preferably.

  If the polymerizable group remains as it is in the terminal group of the polymer compound (C), there is a possibility that the light emission characteristics or the lifetime of the light emitting device produced using the composition containing the polymer compound (C) may be deteriorated. For this reason, the terminal group of the polymer compound (C) is preferably a stable group. Examples of the stable group include an aryl group and a monovalent heterocyclic group (preferably a monovalent aromatic heterocyclic group).

The number average molecular weight in terms of polystyrene by GPC of the polymer compound (C) is preferably 1 × 10 ³ to 1 × 10 ⁷ , more preferably 1 × 10 ^{4 to} 5 × 10 ⁶ . Moreover, the polystyrene equivalent weight average molecular weight of the polymer compound (C) is preferably 1 × 10 ^{4 to} 5 × 10 ⁷ , more preferably 5 × 10 ⁴ to 1 × 10 ⁷ .

  Since the durability to various processes for producing a light emitting device is excellent and the heat resistance of the produced light emitting device becomes good, the glass transition temperature of the polymer compound (C) is preferably 70 ° C. or higher. .

-Method for producing polymer compound (C)-
Below, the preferable manufacturing method of a high molecular compound (C) is demonstrated. The polymer compound (C) can be obtained by condensation polymerization of a compound (monomer) corresponding to a group contained in the polymer compound. As the monomer, a compound synthesized and isolated in advance may be used, or it may be synthesized in a reaction system and used as it is. When the composition containing the obtained polymer compound (C) is used for the production of a light emitting device, the purity of the monomer affects the performance of the light emitting device. Therefore, these monomers are preferably purified by a method such as distillation, sublimation purification, recrystallization, or a combination thereof.

  Examples of the condensation polymerization method include the same methods as those described in the above-mentioned “Method for producing polymer compound (A)”.

  When the polymer compound (C) contains one or more structural units selected from the group consisting of the structural unit represented by the formula (5-1) and the structural unit represented by the formula (5-2) It can also be obtained by reacting a precursor polymer compound previously synthesized by condensation polymerization with fullerene. Examples of the precursor polymer compound include compounds having each structural unit represented by the formula (2a), (2b), or (2c).

In formulas (2a) to (2c),
Ar ^8, R ^5, R ⁶ and R ⁷ are the same meaning as Ar ^8, R ^5, R ⁶ and R ⁷ of formula (5-1).

  An example of the reaction between the precursor polymer compound and fullerene is shown below.

Wherein, Ar ^8, R ^5, R ⁶ and R ⁷ are the same meaning as Ar ^8, R ^5, R ⁶ and R ⁷ of formula (5-1).

Wherein, Ar ⁸ and R ⁷ are each synonymous with Ar ⁸ and R ⁷ in the formula (5-1).

Wherein, Ar ⁸ and R ⁷ are each synonymous with Ar ⁸ and R ⁷ in the formula (5-1).

  The reaction between the precursor polymer compound and fullerene is usually performed in the presence or absence of a solvent such as an organic solvent, and preferably in the presence of a solvent such as an organic solvent.

  The organic solvent is, for example, toluene, xylene, chlorobenzene, dichlorobenzene or trichlorobenzene, preferably chlorobenzene, dichlorobenzene or trichlorobenzene, more preferably dichlorobenzene or trichlorobenzene.

  The amount of the organic solvent used is such that the total concentration of the precursor polymer compound in the organic solvent is usually 0.1 to 90% by mass, preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass. This is the amount.

  The reaction temperature of the precursor polymer compound and fullerene is preferably 60 to 250 ° C, more preferably 100 to 220 ° C, and further preferably 180 to 220 ° C.

  The reaction time depends on the reaction temperature and other conditions, but is usually 1 hour or longer, preferably 10 to 500 hours.

  The amount of fullerene used in the reaction is preferably 0.5 to 5 equivalents, more preferably 1.0 to 4 equivalents, and more preferably 1.5 to 5 moles with respect to the number of moles of all crosslinking groups contained in the precursor polymer compound. 3 equivalents are more preferred.

  The purity of fullerene used in the reaction is preferably 98% or more, and more preferably 99% or more, because the characteristics of the light-emitting element are excellent.

  The post-reaction treatment can be performed by a known method such as a method of adding a reaction solution obtained by the above reaction to a lower alcohol such as methanol and filtering and drying the deposited precipitate.

  After the reaction, the fullerene not supported on the polymer compound is preferably removed. The fullerene not supported on the polymer compound is an unreacted fullerene that does not react with the (precursor) polymer compound but is liberated in the polymer compound.

The fullerene (fixed fullerene) supported on the polymer compound and the fullerene not supported (free fullerene) can be quantified by, for example, GPC-UV. That is, it can be quantified by separating fixed fullerene and free fullerene using the difference in elution time with GPC and measuring UV absorption (335 nm) of fullerene. Quantification of free fullerene in the case of fullerene C60 can be performed, for example, according to the following procedures (1) to (4).
(1) A plurality of toluene solutions of fullerene C60 are prepared at different concentrations, and GPC-UV (detected at 335 nm) measurement is performed.
(2) A calibration curve (fullerene elution peak area value with respect to fullerene concentration) is prepared using the chromatogram obtained by the measurement in (1).
(3) GPC-UV measurement is performed on the actual sample.
(4) The amount of free fullerene in the actual sample is calculated using the fullerene elution peak area value of the chromatogram obtained by the measurement in (3) and the calibration curve in (2).

The fixed fullerene in the case of fullerene C60 can be quantified, for example, according to the following procedures (1) to (5).
(1) A plurality of standard samples in which fullerene C60 is mixed with the precursor polymer compound at different concentrations are prepared, and each UV absorption spectrum is measured.
(2) The relative intensity of absorption at 335 nm is determined from the UV absorption spectrum obtained in (1), and a calibration curve (the amount of mixed fullerene with respect to the relative intensity of absorption at 335 nm) is prepared.
(3) The polymer compound elution fraction (including fixed fullerene) in the actual sample is collected by GPC to obtain the polymer compound elution fraction.
(4) The UV absorption spectrum of the polymer compound elution fraction obtained in (3) is measured.
(5) The relative intensity of absorption at 335 nm is determined from the UV absorption spectrum obtained in (4), and the amount of fixed fullerene in the actual sample is calculated using the calibration curve in (2).

  Examples of the purification method for removing fullerene not supported on the polymer compound include ordinary methods such as recrystallization, continuous extraction with a Soxhlet extractor, column chromatography and the like.

  When the purification method is purification by column chromatography, it is preferable to use silica gel, alumina and activated carbon, more preferably silica gel and activated carbon, and particularly preferable to use them in combination.

  The precursor polymer compound can be produced by the same production method as described in “Production method of polymer compound (A)”.

-Composition of the second composition-
In the second composition, since the content (total content) of the polymer compound (A) is more excellent in the luminance life of the light-emitting device produced using the second composition, the polymer compound (A) Is preferably from 0.1 to 99.9 mol%, more preferably from 1 to 99 mol%, based on the total of all structural units contained in and all the structural units contained in the polymer compound (C). Preferably, it is 10-90 mol%, and it is still more preferable.

  In the second composition, the content (total content) of the structural unit (c-1) contained in the polymer compound (C) is light emission produced using the second composition according to this embodiment. Since the luminance life of the device is more excellent, it should be 0.001 to 50 mol% with respect to the total of all the structural units contained in the polymer compound (A) and all the structural units contained in the polymer compound (C). Is preferable, 0.1 to 30 mol% is more preferable, and 1 to 10 mol% is further preferable.

(Polymer compound)
The polymer compound of the present invention includes a structural unit (1) represented by the formula (1), a structural unit (2) represented by the formula (2), and a structural unit (c-1). It is a molecular compound. The structural unit (c-1) includes a structural unit containing fullerene or a fullerene derivative, a structural unit containing an azulene or an azulene derivative represented by the formula (3), and a stilbene or stilbene derivative represented by the formula (4). And at least one structural unit selected from the group consisting of structural units.

  In the polymer compound of the present invention, the structural unit (1) represented by the formula (1) is defined by the definition, examples and preferred ranges of the structural unit (1) represented by the formula (1) in the first composition. It is the same.

  In the polymer compound of the present invention, the definition, examples and preferred range of the structural unit (2) represented by the formula (2) are the same as those of the structural unit (2) represented by the formula (2) in the first composition. Definitions, examples and preferred ranges are the same. Also in the polymer compound of the present invention, it is preferable that the structural units (1) represented by the formula (1) are not substantially adjacent to each other. Further, when the polymer compound of the present invention includes the structural unit X, the structural units (1) represented by the formula (1), the structural units X, and the structural unit (1) represented by the formula (1) And the structural unit X are preferably not substantially adjacent to each other. That is, it is preferable that the structural unit (1) and the structural unit X represented by the formula (1) are adjacent to the structural unit (2) represented by the formula (2).

  Here, the term “substantially not adjacent to each other” means that the total number of bonds in which the structural units (1) represented by the formula (1) are adjacent to each other is less than 0.05. Yes, the total number of bonds adjacent to each other in the structural units X with respect to the number of bonds between all the structural units is less than 0.05, and is expressed by the formula (1) for the number of bonds between all the structural units. It means that the total number of bonds adjacent to the structural unit (1) and the structural unit X is less than 0.05.

  In the polymer compound of the present invention, the definition, examples and preferred ranges of the structural unit (c-1) are the same as the definitions, examples and preferred ranges of the structural unit (c-1) in the second composition.

  In the polymer compound of the present invention, the structural unit (1) represented by the formula (1) is preferably bonded to the structural unit (2) represented by the formula (2).

  The content (total content) of the structural unit (1) represented by the formula (1) is superior in the luminance life of a light emitting device produced using the polymer compound of the present invention. It is preferable that it is 0.1-50 mol% with respect to all the structural units contained in a compound, It is more preferable that it is 1-49 mol%, It is further more preferable that it is 5-45 mol%.

  The content (total content) of the structural unit (2) represented by the formula (2) is superior in the luminance life of the light emitting device produced using the polymer compound of the present invention, and therefore the polymer of the present invention. It is preferable that it is 50-99.9 mol% with respect to all the structural units contained in a compound, It is more preferable that it is 50-99 mol%, It is further more preferable that it is 50-95 mol%.

  The content (total content) of the structural unit (c-1) is more excellent in the luminance life of the light-emitting element produced using the polymer compound of the present invention, and therefore is included in the polymer compound of the present invention. It is preferable that it is 0.001-50 mol% with respect to a structural unit, It is more preferable that it is 0.001-30 mol%, It is further more preferable that it is 0.01-10 mol%.

  The high molecular compound of this invention should just contain the structural unit (1), the structural unit (2), and the structural unit (c-1), and may further contain the other structural unit.

  The polymer compound of the present invention preferably contains a structural unit having a crosslinking machine in addition to the structural unit (1), the structural unit (2) and the structural unit (c-1). Thus, a thin film containing the composition containing the polymer compound of the present invention is used as a hole injection layer or a hole transport layer, and a light emitting layer is formed thereon by applying a solution to produce a light emitting device. In some cases, the organic thin film containing the polymer compound of the present invention can be converted into an insolubilized organic thin film.

  Examples of the structural unit having a crosslinking group include a structural unit represented by the formula (3A) and a structural unit represented by the formula (4A). Examples and preferred examples of the structural unit represented by the formula (3A) and the structural unit represented by the formula (4A) are the same as the examples and preferred examples given in the column of the polymer compound (A).

  The content (total content) of the structural unit having a crosslinkable group is included in the polymer compound of the present invention because it is more excellent in thermal crosslinkability when a light emitting device is produced using the polymer compound of the present invention. It is preferable that it is 0.1-30 mol% with respect to all the structural units, It is more preferable that it is 1-25 mol%, It is further more preferable that it is 3-20 mol%.

The number average molecular weight in terms of polystyrene of the polymer compound of the present invention by GPC is preferably 1 × 10 ³ to 1 × 10 ⁷ , more preferably 1 × 10 ^{4 to} 5 × 10 ⁶ . Moreover, the polystyrene equivalent weight average molecular weight of the polymer compound of the present invention is preferably 1 × 10 ^{4 to} 5 × 10 ⁷ , more preferably 5 × 10 ⁴ to 1 × 10 ⁷ .

  Since the durability to various processes for producing a light emitting device is excellent and the heat resistance of the produced light emitting device is good, the glass transition temperature of the polymer compound of the present invention is preferably 70 ° C. or higher. .

-Method for synthesizing polymer compound of the present invention-
The polymer compound of the present invention is preferably synthesized by condensation polymerization. In the polymer compound of the present invention, when the structural unit (1) represented by the formula (1) and the structural unit X are polymerized so as to be adjacent to the structural unit (2) represented by the formula (2), A polymerization method by which a sequence can be controlled and a polymerization by a Suzuki reaction is preferred, but a reaction other than the Suzuki reaction may be adopted as long as the polymerization method can control a sequence. The method of polymerizing by the Suzuki reaction is the same as the above-mentioned “Method for producing polymer compound (A)”.

  The first composition and the second composition of the present invention may further contain one or more materials selected from the group consisting of a hole transport material, an electron transport material, and a light emitting material. Further, the polymer compound of the present invention may constitute a composition together with one or more materials selected from the group consisting of a hole transport material, an electron transport material and a light emitting material. Hereinafter, these compositions will be described. The hole transport material and the electron transport material mainly play a role of adjusting the charge (hole and electron) balance.

  Examples of hole transport materials include polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, polysiloxane derivatives having aromatic amine residues in the side chain or main chain, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine Derivatives, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, poly (p-phenylene vinylene) and its derivatives, and poly (2,5-thienylene vinylene) and its derivatives. In addition, for example, JP-A 63-70257, JP-A 63-175860, JP 2-135359, JP 2-135361, JP 2-20988, JP Examples thereof also include each hole transport material described in JP-A-3-37992 and JP-A-3-152184.

  In the case of low molecular hole transport materials (for example, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, and triphenyldiamine derivatives), it is preferable to use them dispersed in a polymer binder. The polymer binder preferably does not extremely impede charge transport, and preferably has no strong absorption against visible light. Polymer binders include 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, and polysiloxane.

  Polyvinylcarbazole and derivatives thereof are obtained, for example, from a vinyl monomer by cation polymerization or radical polymerization.

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

  Since the siloxane skeleton structure has almost no hole transporting property, it is preferable that the polysiloxane and the derivative thereof as the hole transporting material have the structure of the low molecular weight hole transporting material in the side chain or the main chain. It is more preferable to have a hole-transporting aromatic amine in the side chain or main chain.

  When the first composition and the second composition of the present invention contain a hole transport material, the content ratio of the hole transport material is 100 parts by mass of the first composition or the second composition of the present invention. On the other hand, it is preferably 3 to 30 parts by mass, more preferably 3 to 20 parts by mass, and further preferably 3 to 10 parts by mass. Thereby, the charge balance is improved.

  When the polymer compound of the present invention and a hole transport material are combined to form a composition, the content ratio of the hole transport material is preferably 3 to 30 parts by mass with respect to 100 parts by mass of the polymer compound of the present invention, More preferably, it is 3-20 mass parts, More preferably, 3-10 mass parts is added. Thereby, the charge balance is improved.

  Examples of electron transport materials 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, diphenyl Examples include dicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, polyquinoline and derivatives thereof, polyquinoxaline and derivatives thereof, and polyfluorene and derivatives thereof. In addition, for example, JP-A 63-70257, JP-A 63-175860, JP 2-135359, JP 2-135361, JP 2-20988, JP Examples thereof also include each electron transport material described in JP-A-3-37992 and JP-A-3-152184.

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

  The content ratio of the electron transport material when the first composition and the second composition of the present invention include an electron transport material is based on 100 parts by mass of the first composition or the second composition of the present invention. Preferably, it is 5-50 mass parts, More preferably, it is 5-30 mass parts, More preferably, it is 5-20 mass parts. Thereby, the charge balance is improved.

  When the composition of the polymer compound of the present invention is combined with a light-emitting material, the content ratio of the electron transport material is preferably 5 to 50 parts by mass, more preferably 100 parts by mass of the polymer compound of the present invention. 5-30 mass parts, More preferably, 5-20 mass parts is added. Thereby, the charge balance is improved.

  Examples of the light emitting material include low molecular weight compounds, high molecular weight compounds, and triplet light emitting complexes known as light emitting materials.

  Examples of the low molecular weight compound include naphthalene derivatives, anthracene and derivatives thereof, perylene and derivatives thereof, polymethine-based, xanthene-based, coumarin-based and cyanine-based pigments, 8-hydroxyquinoline and metal complexes of its derivatives, aromatic Group amine, tetraphenylcyclopentadiene and derivatives thereof, and tetraphenylbutadiene and derivatives thereof. In addition, for example, compounds described in JP-A-57-51781 and JP-A-59-194393 are exemplified.

  Examples of the high molecular weight compound include International Publication No. WO 99/13692, International Publication No. 99/48160, German Patent Application Publication No. 2340304, International Publication No. 00/53656, International Publication No. 01/19834. No., International Publication No. 00/55927, German Patent Application No. 2348316, International Publication No. 00/46321, International Publication No. 00/06665, International Publication No. 99/54943, International Publication No. 99 / No. 54385, US Pat. No. 5,777,070, WO 98/06773 pamphlet, WO 97/05184, WO 00/35987, WO 00/53655, WO 01/34722. No., International Publication No. 99/24526, International Publication No. 00/22027, International Publication No. 00/220 No. 6, WO 98/27136, US Pat. No. 5,736,636, WO 98/21262, US Pat. No. 5,741,921, WO 97/09394, WO 96/29356 International Publication No. 96/10617, European Patent Application No. 0707020, International Publication No. 95/07955, Japanese Patent Application Laid-Open No. 2001-181618, Japanese Patent Application Laid-Open No. 2001-123156, Japanese Patent Application Laid-Open No. 2001-3045. JP, 2000-351967, JP 2000-303066, JP 2000-299189, JP 2000-252065, JP 2000-136379, JP 2000-104057, JP 2000-80167, JP 10-324870, JP 10-114891, JP-A-9-111233, JP-A-9-45478, and the like (for example, polyfluorene, copolymers of polyfluorene derivatives, polyarylene, polyarylene derivatives) And a copolymer of polyarylene vinylene, a polyarylene derivative, an aromatic amine, and an aromatic amine derivative (co) polymer).

Examples of triplet light-emitting complexes include Ir (ppy) ₃ , Btp ₂ Ir (acac), FIrpic, COM-1, COM-2, COM-3, COM-4, COM-5, COM-, which have iridium as a central metal. 6, COM-7, COM-8, iridium complexes such as ADS066GE commercially available from American Dye Source, platinum complexes such as PtOEP with platinum as the central metal, or Eu (TTA) ₃ with europium as the central metal Europium complexes such as phen are preferred. The structural formulas of these triplet light-emitting complexes are shown below.

  When the first composition and the second composition of the present invention contain a light emitting material, the content ratio of the light emitting material is preferably relative to 100 parts by weight of the first composition or the second composition of the present invention. 5 to 50 parts by mass, more preferably 5 to 70 parts by mass, and still more preferably 5 to 80 parts by mass.

  When the composition of the polymer compound of the present invention is combined with a light-emitting material, the content of the light-emitting material is preferably 5 to 50 parts by mass, more preferably 5 to 100 parts by mass of the polymer compound of the present invention. -70 mass parts, More preferably, 5-80 mass parts is added.

(Liquid composition)
The first composition or the second composition of the present invention or the polymer compound of the present invention is a composition dissolved or dispersed in a solvent, preferably an organic solvent (hereinafter referred to as “liquid composition”). The liquid composition may be in the form of a solution or a dispersion. Such a liquid composition is also called ink or varnish. When this liquid composition is used to form an organic thin film used for a light emitting device, the liquid composition is preferably a solution.

  The liquid composition may contain at least one selected from the group consisting of the above-described hole transport material, electron transport material, and light emitting material. In addition, other substances may be added to the liquid composition as long as the effects of the present invention are not hindered. Examples of other substances include an antioxidant, a viscosity modifier, and a surfactant.

  Here, the organic solvent is not particularly limited as long as the first composition or the second composition of the present invention or the polymer compound of the present invention dissolves or disperses. Is mentioned.

  Aromatic hydrocarbon solvents: for example, toluene, xylene (each isomer or a mixture thereof), 1,2,3-trimethylbenzene, 1,2,4-trimethylbenzene, mesitylene (1,3,5-trimethylbenzene) ), Ethylbenzene, propylbenzene, isopropylbenzene, butylbenzene, isobutylbenzene, 2-phenylbutane, tert-butylbenzene, pentylbenzene, neopentylbenzene, isoamylbenzene, hexylbenzene, cyclohexylbenzene, heptylbenzene, octylbenzene, 3- Propyltoluene, 4-propyltoluene, 1-methyl-4-propylbenzene, 1,4-diethylbenzene, 1,4-dipropylbenzene, 1,4-di-tert-butylbenzene, indane, tetralin (1,2 3,4 tetrahydronaphthalene), and the like.

  Aliphatic hydrocarbon solvent: For example, n-pentane, n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, decalin and the like.

  Aromatic ether solvents: for example, anisole, ethoxybenzene, propoxybenzene, butoxyoxybenzene, pentyloxybenzene, cyclopentyloxybenzene, hexyloxybenzene, cyclohexyloxybenzene, heptyloxybenzene, octyloxybenzene, 2-methylanisole, 3 -Methylanisole, 4-methylanisole, 4-ethylanisole, 4-propylanisole, 4-butylanisole, 4-pentylanisole, 4-hexylanisole, diphenylether, 4-methylphenoxybenzene, 4-ethylphenoxybenzene, 4- Propylphenoxybenzene, 4-butylphenoxybenzene, 4-pentylphenoxybenzene, 4-hexylphenoxybenzene, 4-phenoxytoluene 3-phenoxy toluene, 1,3-dimethoxybenzene, 2,6-dimethyl anisole, 2,5-dimethyl anisole, 2,3-dimethyl anisole, 3,5- dimethyl anisole, and the like.

  Aliphatic ether solvents: for example, tetrahydrofuran, dioxane, dioxolane and the like.

  Ketone solvents: for example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, and the like.

  Ester solvent: For example, ethyl acetate, butyl acetate, methyl benzoate, ethyl cellosolve acetate and the like.

  Chlorinated solvent: For example, methylene chloride, chloroform, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene, o-dichlorobenzene and the like.

  Alcohol solvents: For example, methanol, ethanol, propanol, isopropanol, cyclohexanol, phenol and the like.

  Polyhydric alcohol and derivatives thereof: for example, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane, propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, 1, 2 -Hexanediol and the like.

  Aprotic polar solvent: for example, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.

These organic solvents may be used alone or in combination of two or more.
When using a mixed solvent, it is preferable to combine two or more of the above solvent groups. However, even if a plurality of solvents from the same system illustrated above are combined, one or more from a group of solvents of different systems may be combined. May be. The composition ratio can be determined in consideration of the physical properties of each solvent and the solubility of a polymer compound or the like.

  Preferable examples in the case of selecting and combining a plurality of types from the same solvent group include a plurality of types from an aromatic hydrocarbon solvent, a plurality of types from an aromatic ether solvent, and the like. Preferable examples in the case of combining one or more kinds selected from different solvent groups include the following combinations: a combination of an aromatic hydrocarbon solvent and an aliphatic hydrocarbon solvent; an aromatic hydrocarbon solvent A combination of an aromatic hydrocarbon solvent and an aliphatic ether solvent; a combination of an aromatic hydrocarbon solvent and an aprotic polar solvent; an aromatic ether solvent and an aprotic polar solvent Combination of etc. Water may be added to the single solvent or the mixed solvent.

  Among these organic solvents, a single solvent or a mixed solvent containing one or more organic solvents having a structure containing a benzene ring, a melting point of 0 ° C. or less, and a boiling point of 100 ° C. or more has viscosity, film-forming properties. From the viewpoint of the above, a single solvent or a mixed solvent containing at least one aromatic hydrocarbon solvent or aromatic ether solvent is preferable.

  The organic solvent may be used singly or in combination of two or more types as a mixed solvent, but it is preferable to use a mixed solvent from the viewpoint of controlling the film formability. Moreover, you may use an organic solvent, after refine | purifying with methods, such as washing | cleaning, distillation, and an adsorbent, as needed.

According to the liquid composition, an organic thin film containing the first composition or the second composition of the present invention or the polymer compound of the present invention can be easily produced. Specifically, by applying the liquid composition onto a substrate and distilling off the organic solvent by heating, blowing, decompressing, etc., the first composition or the second composition of the present invention, or An organic thin film containing the polymer compound of the present invention can be produced. The evaporation of the organic solvent can be changed depending on the organic solvent used. For example, the step of heating at a temperature of 50 ° C. or higher and 250 ° C. or lower, or a reduced pressure atmosphere of about 10 ⁻³ Pa is maintained. And the like.

  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 ink jet printing method, or a nozzle coating method can be used.

  Although the suitable viscosity of the said liquid composition changes with printing methods, at 25 degreeC, Preferably it is 0.5-1000 mPa * s, More preferably, it is 0.5-500 mPa * s. Further, when the liquid composition passes through a discharge device as in the ink jet printing method, the viscosity at 25 ° C. is preferably 0.5 to 50 mPa · s in order to prevent clogging and flight bending at the time of discharge. More preferably, it is 0.5 to 20 mPa · s. Although the density | concentration of the high molecular compound of this embodiment in a liquid composition is not specifically limited, It is preferable that it is 0.01-10 weight%, and it is more preferable that it is 0.1-5 weight%.

(Organic thin film)
The organic thin film of the present invention contains the first composition, the second composition or the polymer compound of the present invention. The organic thin film of the present invention can be easily produced from the liquid composition of the present invention.

  The insolubilized organic thin film of the present invention is an insolubilized organic thin film obtained by insolubilizing the organic thin film of the present invention. Insolubilization can usually be performed by external stimulation such as heating or light irradiation and subsequent curing. By insolubilization, the first composition, the second composition and the polymer compound of the present invention can be crosslinked. Since the insolubilized organic thin film of the present invention is hardly soluble in a solvent, it is advantageous when a light emitting device is laminated.

  The temperature when insolubilization is performed by heating is not particularly limited, but is generally in the range of room temperature to 300 ° C, and the upper limit is preferably 250 ° C from the viewpoint of luminous efficiency, and 200 ° C. More preferably, it is 180 degreeC. Further, the lower limit is preferably 50 ° C., more preferably 70 ° C., and further preferably 100 ° C. from the viewpoint of easy formation of the insolubilized organic thin film.

  The light that can be used when insolubilization is performed by light irradiation is not particularly limited, but in general, ultraviolet light, near ultraviolet light, or visible light is used, and it is preferable to use ultraviolet light or near ultraviolet light. .

  The organic thin film and insolubilized organic thin film of this invention can be used conveniently as a positive hole injection layer or a positive hole transport layer in the light emitting element mentioned later. Moreover, it can use suitably also for organic semiconductor elements, such as an organic transistor and an organic solar cell. Since the organic thin film of the present invention contains the first composition, the second composition or the polymer compound, when used as a hole injection layer or a hole transport layer of the light emitting device, the luminance life of the light emitting device. Can be further improved.

(Light emitting element)
The light emitting device of the present invention includes the organic thin film or the insolubilized organic thin film of the present invention.

  The light-emitting element of the present invention usually has an anode, a cathode, and a layer made of the organic thin film or insolubilized organic thin film of the present invention between the anode and the cathode. The layer comprising the organic thin film or insolubilized organic thin film of the present invention preferably functions as a hole injection layer or a hole transport layer. In addition, when the layer which consists of an organic thin film or insolubilized organic thin film of this invention functions as a hole injection layer or a hole transport layer, it is preferable that the said layer is a layer which consists of said insolubilized organic thin film.

  Examples of the light emitting device of the present invention include a light emitting device in which an electron transport layer is provided between a cathode and a light emitting layer, a light emitting device in which a hole transport layer is provided between an anode and a light emitting layer, and a cathode and light emitting. And a light-emitting element in which an electron transport layer is provided between the layers and a hole transport layer is provided between the anode and the light-emitting layer.

As a light emitting element of this invention, each laminated structure of a) -d) is illustrated, for example.
a) Anode / light emitting layer / cathode b) Anode / hole transport layer / light emitting layer / cathode c) Anode / light emitting layer / electron transport layer / cathode d) Anode / hole transport layer / light emitting layer / electron transport layer / cathode (Here, “/” indicates that each layer is laminated adjacently. The same shall apply hereinafter.)

  When the light-emitting element of the present invention has a hole transport layer, the first composition, the second composition, or the polymer compound of the present invention can be used for the hole transport layer. In addition, hole transport materials other than these can also be used for the hole transport layer. Examples of the hole transport material other than the first composition, the second composition, or the polymer compound of the present invention are examples of the hole transport material that the first composition of the present invention may contain. It is the same.

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

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing the hole transport material is preferable. Solvents include chloro solvents such as chloroform, methylene chloride, 1,2-dichloroethane, 1,1,2-trichloroethane, chlorobenzene and o-dichlorobenzene, ether solvents such as tetrahydrofuran and dioxane, and aromatics such as toluene and xylene. Aliphatic hydrocarbon solvents, cyclohexane, methylcyclohexane, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane and other aliphatic hydrocarbon solvents, acetone, methyl ethyl ketone, cyclohexanone, etc. Ketone solvents, ester solvents such as ethyl acetate, butyl acetate, ethyl cellosolve acetate, ethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, ethylene glycol monomethyl ether, dimethoxyethane , Propylene glycol, diethoxymethane, triethylene glycol monoethyl ether, glycerin, polyhydric alcohols such as 1,2-hexanediol and derivatives thereof, alcohol solvents such as methanol, ethanol, propanol, isopropanol, cyclohexanol, dimethyl sulfoxide And amide solvents such as N-methyl-2-pyrrolidone and N, N-dimethylformamide. These organic solvents may be used alone or in combination of two or more.

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

  The thickness of the hole transport layer varies depending on the material used, so it may be selected so that the drive voltage and the light emission efficiency are appropriate. However, the hole transport layer may have a thickness that does not cause pinholes. preferable. On the other hand, if the thickness is too thick, the drive voltage of the element may increase, which is not preferable. Therefore, the thickness of the hole transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  When the light-emitting element of the present invention has an electron transport layer, an electron transport material can be used for the electron transport layer. Examples of this electron transport material are the same as those of the electron transport material that may be contained in the first composition of the present invention.

  There are no particular restrictions on the method for forming the electron transport layer, but examples of low-molecular electron transport materials include vacuum deposition from powder and film deposition from a solution or a molten state. Examples of the material include a method by film formation from a solution or a molten state. When forming a film from a solution or a molten state, the polymer binder described for the low-molecular hole transport material may be used in combination.

  As a solvent used for film formation from a solution, a solvent capable of dissolving or uniformly dispersing the electron transport material and / or the polymer binder is preferable. Examples of the solvent are the same as the examples of the solvent used for film formation from the solution of the hole transport layer in the section of the hole transport layer. A solvent may be used individually by 1 type, or may use 2 or more types together.

  An example of the film formation method from a solution or a molten state is the same as the example of the film formation method from a solution of the hole transport layer.

  The thickness of the electron transport layer varies depending on the material used, and may be selected so that the drive voltage and the light emission efficiency are appropriate. However, the thickness is preferably such that no pinholes are generated. On the other hand, if it is too thick, the drive voltage of the element may increase, which is not preferable. Therefore, the thickness of the electron transport layer is usually 1 nm to 1 μm, preferably 2 nm to 500 nm, and more preferably 5 nm to 200 nm.

  Of the hole transport layer provided adjacent to the electrode, the layer that has the function of improving the charge injection efficiency from the electrode and has the effect of lowering the driving voltage of the device may be generally called a hole injection layer. . Of the electron transport layers provided adjacent to the electrodes, a layer having a function of improving charge injection efficiency from the electrodes and having an effect of lowering the driving voltage of the element may be generally called an electron injection layer. Hereinafter, the generic name of the hole injection layer and the electron injection layer may be referred to as “charge injection layer”.

  In order to improve adhesion with the electrode and / or improve charge injection from the electrode, a charge injection layer or an insulating layer may be provided adjacent to the electrode. In addition, a thin buffer layer may be inserted at the interface between the charge transport layer and / or the light-emitting layer in order to improve interface adhesion, prevent mixing, and the like.

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

When the light emitting device of the present invention is a light emitting device having a charge injection layer, examples of the light emitting device include a light emitting device having a charge injection layer adjacent to the cathode and a light emitting device having a charge injection layer adjacent to the anode. An element is mentioned. Examples of the laminated structure of the light emitting element include the laminated structures e) to p).
e) Anode / hole injection layer / light emitting layer / cathode f) Anode / light emitting layer / electron injection layer / cathode g) Anode / hole injection layer / light emitting layer / electron injection layer / cathode h) Anode / hole injection layer / Hole transport layer / light emitting layer / cathode i) anode / hole transport layer / light emitting layer / electron injection layer / cathode j) anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode k ) Anode / hole injection layer / light emitting layer / electron transport layer / cathode l) Anode / light emitting layer / electron transport layer / electron injection layer / cathode m) Anode / hole injection layer / light emitting layer / electron transport layer / electron injection Layer / cathode n) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode o) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode p) anode / Hole injection layer / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

  As described above, the light emitting device of the present invention includes a light emitting device in which the first composition, the second composition or the polymer compound of the present invention is contained in the hole transport layer and / or the electron transport layer. . The light emitting device of the present invention also includes a light emitting device in which the first composition, the second composition or the polymer compound of the present invention is contained in a hole injection layer and / or an electron injection layer.

  When the first composition, the second composition or the polymer compound of the present invention is used for the hole injection layer, it is preferably used simultaneously with the electron accepting compound. When the first composition, the second composition, or the polymer compound of this embodiment is used for the electron injection layer, it is preferably used simultaneously with the electron donating compound. Here, examples of methods for using a plurality of materials “simultaneously” include methods such as mixing, copolymerization, introduction as a side chain, and the like.

  As the charge injection layer, for example, a layer containing a conductive polymer, provided between the anode and the hole transport layer, ionization of an intermediate value between the anode material and the hole transport material contained in the hole transport layer A layer including a material having a potential, and a layer including a material provided between the cathode and the electron transport layer and having a material having an electron affinity intermediate between the cathode material and the electron transport material included in the electron transport layer. It is done.

When the charge injection layer is a layer containing a conductive polymer, the electrical conductivity of the conductive polymer is preferably 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less. To reduce the leak current between light emitting pixels, more preferably at most 10 ^-5 S / cm or more and 10 ² S / cm, more preferably not more than 10 ^-5 S / cm or more and 10 ¹ S / cm. In order to make the electric conductivity of the conductive polymer 10 ⁻⁵ S / cm or more and 10 ³ S / cm or less, the conductive polymer is usually doped with an appropriate amount of ions.

  The type of ions to be doped is an anion for the hole injection layer and a cation for the electron injection layer. Examples of anions include polystyrene sulfonate ions, alkylbenzene sulfonate ions, and camphor sulfonate ions. Examples of the cation include lithium ion, sodium ion, potassium ion and tetrabutylammonium ion.

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

  The material used for the charge injection layer may be appropriately selected depending on the material of the electrode and / or the adjacent layer. For example, polyaniline and its derivatives, polythiophene and its derivatives, polypyrrole and its derivatives, polyphenylene vinylene and its derivatives, polythienylene Examples include vinylene and its derivatives, polyquinoline and its derivatives, polyquinoxaline and its derivatives, conductive polymers such as polymers containing an aromatic amine structure in the main chain or side chain, metal phthalocyanines (such as copper phthalocyanine), and carbon Is done.

  The insulating layer is a layer having a function of facilitating charge injection. The thickness of the insulating layer is usually 0.5 to 7.0 nm. Examples of the material for the insulating layer include metal fluorides, metal oxides, and organic insulating materials.

Examples of the light emitting element provided with the insulating layer include a light emitting element provided with an insulating layer adjacent to the cathode and a light emitting element provided with an insulating layer adjacent to the anode. Examples of the laminated structure of the light emitting element provided with the insulating layer include the laminated 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 transport 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 of the present invention has, for example, the laminated structure exemplified in a) to ab) and is selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. Examples include a light emitting device in which the layer contains the polymer compound or the first composition of the present invention. Preferably, the hole injection layer and / or the hole transport layer contains the first composition, the second composition or the polymer compound of the present invention.

  The light emitting device of the present invention is usually formed on a substrate. Any substrate that does not change when the electrode is formed and the organic layer is formed may be used. Examples of the material for the substrate include glass, plastic, polymer film, and silicon substrate. In the case of using an opaque substrate, the opposite electrode (that is, the electrode far from the substrate) is preferably transparent or translucent. Usually, one or both of the anode and the cathode of the light emitting device of the present invention is transparent or translucent. The anode side is preferably transparent or translucent.

  As the material for the anode, a conductive metal oxide film and a translucent metal thin film are usually used. As the material of the anode, for example, conductive glass made of a metal oxide such as indium oxide, zinc oxide, tin oxide, or a composite thereof (for example, indium / tin / oxide (ITO), indium / zinc / oxide) is used. A film such as NESA, gold, platinum, silver, or copper is used, and ITO, indium / zinc / oxide, or tin oxide is preferable. Examples of the method for producing the anode include a vacuum deposition method, a sputtering method, an ion plating method, and a plating method. Moreover, you may use organic transparent conductive films, such as polyaniline and its derivative (s), polythiophene, and its derivative (s) as an anode.

  The thickness of the anode can be appropriately adjusted in consideration of light transmittance and electrical conductivity, but is usually 10 nm to 10 μm, preferably 20 nm to 1 μm, more preferably 40 nm to 500 nm. .

  A layer for facilitating charge injection may be provided on the anode. Examples of the layer for facilitating charge injection include a layer containing a material selected from the group consisting of a phthalocyanine derivative, a conductive polymer, carbon, a metal oxide, a metal fluoride, and an organic insulating material.

  As a material for the cathode, a material having a small work function is preferable. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like An alloy of two or more metals selected from the group consisting of one or more metals selected from these metals and one selected from the group consisting of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten and tin Alloys with two or more metals, graphite or graphite intercalation compounds are used. Examples of alloys include magnesium-silver alloys, magnesium-indium alloys, magnesium-aluminum alloys, indium-silver alloys, lithium-aluminum alloys, lithium-magnesium alloys, lithium-indium alloys, and calcium-aluminum alloys. The cathode may have a laminated structure of two or more layers.

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

  As a method for producing the cathode, for example, a vacuum deposition method, a sputtering method, or a laminating method in which a metal thin film is thermocompression bonded is used. A layer made of a conductive polymer or a layer made of a material such as a metal oxide, a metal fluoride, or an organic insulating material may be provided between the cathode and the organic layer. The light emitting element may be provided with a protective layer and / or a protective cover. This is preferable because the light emitting element can be protected from the outside and the light emitting element can be used stably for a long period of time. The protective layer and / or protective cover is usually provided after the cathode is formed.

  As a material for the protective layer, for example, a polymer compound, a metal oxide, a metal fluoride, a metal boride, a metal nitride, an organic-inorganic hybrid material, or the like can be used. As the protective cover, for example, a glass plate or a plastic plate having a surface subjected to low water permeability treatment can be used. As a method for installing the protective cover, a method in which the protective cover is bonded to the element substrate with a thermosetting resin or a photocurable resin and sealed is preferably used. If a space is maintained using a spacer between the protective cover and the light emitting element, it is easy to prevent the element from being damaged. If an inert gas such as nitrogen or argon is sealed in the space, the oxidation of the cathode can be prevented. By installing a desiccant such as barium oxide in the space, it becomes easy to suppress moisture adsorbed in the manufacturing process from giving the element a target. When providing the protective cover, it is preferable to take one or more measures selected from the group consisting of maintaining a space using a spacer, sealing an inert gas in the space, and installing a desiccant in the space. .

  The light emitting device of the present invention includes, for example, a planar light source such as a curved light source and a planar light source (for example, illumination); a segment display device (for example, a segment type display device); a dot matrix display device (for example, a dot light source). It can be used for display devices such as a matrix flat display) and a liquid crystal display device (for example, a liquid crystal display device, a backlight of a liquid crystal display, etc.).

  In order to obtain planar light emission using the light emitting element of the present invention, the planar anode and cathode may be arranged so as to overlap each other. As a method for obtaining pattern-like light emission, for example, a method in which a mask having a pattern-like window is provided on the surface of a planar light-emitting element, an organic layer of a non-light-emitting portion is formed extremely thick and substantially non-light-emitting And a method of forming either the anode or the cathode or both electrodes in a pattern. A segment type display element capable of displaying numbers, characters, simple symbols, etc. is obtained by forming a pattern by any of these methods and arranging several electrodes so that they can be turned ON / OFF independently. In order to obtain a dot matrix element, 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 multi-color display can be achieved by applying a method of separately coating a plurality of types of polymeric fluorescent substances having different emission colors, or a method using a color filter or a fluorescence conversion filter. The dot matrix element can be driven passively, or may be actively driven in combination with a TFT or the like. These display elements can be used as display devices for computers, televisions, mobile terminals, mobile phones, car navigation systems, video camera viewfinders, and the like.

  The planar light emitting element is thin and self-luminous, and can be suitably used as a planar light source for a backlight of a liquid crystal display device or a planar illumination light source. If a flexible substrate is used, it can also be used as a curved light source or display device.

  EXAMPLES Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.

(Number average molecular weight and weight average molecular weight)
The number average molecular weight (Mn) and the weight average molecular weight (Mw) were analyzed by gel permeation chromatography (GPC), and the polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) were calculated from the analysis results. .

<Analysis conditions>
Measuring device: HLC-8320GPC (manufactured by Tosoh Corporation)
Column: PLgel MIXED-B (manufactured by Polymer Laboratories)
Column temperature: 40 ° C
Moving layer: Tetrahydrofuran (hereinafter sometimes referred to as “THF”)
Flow rate: 2.0 mL / min
Detection wavelength: 228 nm

(NMR measurement)
Unless otherwise specified, NMR measurement is performed by dissolving 5 to 20 mg of a measurement sample in about 0.5 mL of an organic solvent and using NMR (trade name: MERCURY 300, manufactured by Varian, Inc.). went.

(Measurement of LC-MS)
The measurement of LC-MS was performed by the following method. The measurement sample was dissolved in chloroform or tetrahydrofuran to a concentration of about 2 mg / mL, and 1 μL was injected into LC-MS (manufactured by Agilent Technologies, trade name: 1100LCMSD). For the mobile phase of LC-MS, ion-exchanged water, acetonitrile, tetrahydrofuran and a mixed solution thereof were used, and acetic acid was added as necessary. As the column, L-column 2 ODS (3 μm) (manufactured by Chemicals Evaluation and Research Institute, inner diameter: 2.1 mm, length: 100 mm, particle size: 3 μm) was used.

<Synthesis Example 1: Synthesis of Monomer CM1 and Monomers CM1 to CM14>
CM1 was synthesized according to the synthesis method described in JP2010-189630A.
CM2 was synthesized according to the synthesis method described in JP2010-189630A.
CM3 was synthesized by the following method.
CM4 was synthesized by the following method.
CM5 was synthesized according to the synthesis method described in WO2009 / 131255.
CM6 was synthesized according to the synthesis method described in WO2002 / 045184.
CM7 was synthesized according to the synthesis method described in WO2009 / 131255.
CM8 was synthesized according to the synthesis method described in JP-A-2008-106241.
CM9 was synthesized according to the synthesis method described in JP 2010-215886 A.
CM10 was synthesized according to the synthesis method described in WO2011 / 049241.
CM11 was synthesized by the following method.
CM12 was synthesized according to WO2011 / 161417A1 synthesis method.
CM13 was synthesized according to the synthesis method described in WO2005 / 049546.
CM14 was synthesized by the following method.
CM15 was synthesized according to the synthesis method described in JP-A No. 2006-169265.
CM16 was synthesized according to the synthesis method described in JP2010-189630A.

<Synthesis Example 2: Synthesis of Monomer CM3>
Monomer CM3 was synthesized according to the following first to seventh steps.

(First step)
In a reaction vessel equipped with a reflux cooling apparatus under an argon gas atmosphere, 3-bromo-4-chlorotoluene (the above compound CM3a, 30.82 g, 150 mmol), 2,5-dimethylphenylboronic acid (the above compound CM3b, 24. 75 g, 165 mmol), anhydrous potassium carbonate (124.39 g, 900 mmol), palladium (II) acetate (0.67 g, 6 mmol), tricyclohexylphosphine (1.68 g, 12 mmol), dimethylacetamide (commercially dehydrated product, 600 ml), A mixture of pivalic acid (15.32 g, 150 mmol) was stirred with heating in an oil bath set at 150 ° C. for 10 hours. After dilution with toluene (500 ml), washing and separation were performed 3 times using ion exchange water. Subsequently, activated clay (Wako Pure Chemical Industries, Ltd., 60 g) was added to the obtained oil layer, and the mixture was stirred for 2 hours, and then the insoluble matter was removed by passing through Celite and a silica gel pad, and the operation was repeated twice. After removing the solvent from the obtained solution by concentration under reduced pressure, recrystallization purification (mixed solvent of chloroform and ethanol) was performed, and the precipitated crystals were collected by filtration and dried under reduced pressure to obtain the target compound CM3c (35. 5 g) was obtained as a light yellow to white solid. The yield was 51%. The HPLC area percentage value of the obtained compound CM3c was 99.3% (UV254 nm).

(Second step)
Under an argon gas atmosphere, trifluoroacetic acid (11.15 mL, 150 mmol) and chloroform (commercial dehydrated product, 400 mL) were added to the above compound CM3c (14.58 g, 75 mmol), and the homogeneous mixture was added using an ice bath. Cooled below 5 ° C. Thereto, bromine (8.46 mL, 165 mmol) was added slowly, taking care that the temperature of the mixture did not exceed 5 ° C., then the ice bath was removed, and the reaction solution was stirred at room temperature for 4 hours. Obtained. A saturated aqueous solution of sodium dithionite was added to the resulting reaction solution to decompose excess bromine, and then the solvent was removed by concentration under reduced pressure to obtain a solid. By adding tetrahydrofuran (1 L) to the obtained solid and stirring at 70 ° C. for 1 hour, cooling to room temperature, adding water, dissolving the precipitated inorganic salt, and then concentrating again under reduced pressure. Tetrahydrofuran was removed to obtain a solid-liquid mixture. The precipitated solid was collected by filtration, dissolved by adding toluene, passed through a silica gel short column, and the obtained toluene solution was concentrated to obtain a solid. By repeating the operation of recrystallizing and purifying the obtained solid using a mixed solvent of toluene and isopropanol, the target compound CM3d (22.3 g) was obtained. The yield was 84%. The resulting compound CM3d showed> 99.9% in terms of HPLC area percentage (UV254 nm).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.67 (s, 2H), 7.58 (s, 2H), 3.79 (s, 2H), 2.48 (s, 6H) ).

(Third process)
After adding pyridine (34.70 mL) to the above compound CM3d (12.22 g, 34.70 mmol), benzyltrimethylammonium hydroxide (40% pyridine solution) (prepared according to the following, 0.87 mL) was added at room temperature. The reaction vessel was heated in an oil bath at 40 ° C. while the atmosphere was vented and stirred for 16 hours. Thereafter, benzyltrimethylammonium hydroxide (40% pyridine solution) (prepared according to the following, 0.87 mL) was added again, heated in an oil bath at 60 ° C., and stirred for 8 hours to obtain a reaction solution. Ion exchange water and acetic acid were added to the resulting reaction solution to adjust to acidic conditions, and the mixture was stirred at room temperature for 1 hour. The precipitated yellow solid was collected by filtration and washed well with water. The obtained solid was dried and then dispersed in a mixed solvent of tetrahydrofuran and methanol (tetrahydrofuran / methanol = 4/30 (v / v)) and stirred for 1.5 hours while heating in an oil bath at 80 ° C. The solid precipitated after cooling to room temperature was collected by filtration and dried under reduced pressure to obtain the target compound CM3e (11.87 g) as a yellow solid. The yield was 93.5%. The obtained compound CM3e showed 96.7% by HPLC area percentage value (UV254 nm).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.77 (s, 2H), 7.36 (s, 2H), 2.47 (s, 6H).
LC / MS (APPI (posi)): 364 [M] ⁺

(Preparation of benzyltrimethylammonium hydroxide (40% pyridine solution))
After adding pyridine (50 mL) to benzyltrimethylammonium hydroxide (40% methanol solution) (sometimes called “TRITON B”, manufactured by Kanto Chemical Co., Inc., 50 mL), it is concentrated to 25 mL or less with an evaporator. It was prepared by adding pyridine again and diluting to 50 mL. The solution obtained by this operation is called benzyltrimethylammonium hydroxide (40% pyridine solution).

(Fourth process)
While stirring a solution of 3,5-di-n-hexyl-1-bromobenzene (compound CM3f, 13.82 g, 42.5 mmol) dissolved in tetrahydrofuran (commercially dehydrated product, 324 mL) under an argon gas atmosphere The mixture was cooled using a -78 ° C dry ice-methanol bath. Thereafter, a hexane solution of n-butyllithium (1.63 mol / L, 25.7 mL) was slowly added dropwise so that the temperature of the solution was kept at −75 ° C. or lower, and the mixture was further stirred for 1 hour. Next, the compound CM3e (11.87 g, 32.4 mmol) was added little by little so that the temperature of the solution was kept at −75 ° C. or lower, and after further stirring for 2 hours, methanol (about 20 mL) was slowly added. Then, the dry ice-methanol bath was removed and the temperature was slowly raised to room temperature. After the solvent was distilled off by concentration under reduced pressure, the resulting reaction solution was added with hexane and washed with ion-exchanged water to obtain an oil layer. The obtained oil layer was dried over anhydrous sodium sulfate, the insoluble matter was filtered off, the solvent was distilled off by concentration under reduced pressure, and further recrystallization purification (hexane) was performed, followed by filtration and drying under reduced pressure. Compound 3g (9.12 g) as a white solid was obtained. The yield was 45%. 3 g of the obtained compound CM showed 97.9% in terms of HPLC area percentage (UV254 nm).

LC / MS (ESI (posi)): 610 [M] ⁺

(Fifth process)
In an argon gas atmosphere, 3 g (9.12 g, 14.89 mmol) of the above compound CM, triethylsilane (4.53 mL, 59.6 mmol), hexane (39 mL) were mixed, and heating was started in a 70 ° C. oil bath. Trifluoroacetic acid (4.5 mL, 59.6 mmol) was added dropwise, and the mixture was further stirred with heating for 3 hours to obtain a reaction solution. After cooling the resulting reaction solution to room temperature, a 10 wt% aqueous potassium phosphate solution was added, and the organic layer was further washed with saturated brine, dried over anhydrous sodium sulfate, and insolubles were filtered off. The solvent was distilled off by concentration under reduced pressure and drying under reduced pressure to obtain an oily substance (8.9 g) containing Compound CM3h. The obtained oil was used in the next step without further purification.

LC / MS (ESI (posi)): 594 [M] ⁺

(Sixth process)
Under an argon gas atmosphere, N, N-dimethylformamide (74 mL) was added to an oily substance (8.9 g) containing the compound CM3h to obtain a uniform solution. After performing argon gas bubbling for 15 minutes and then cooling to 5 ° C. or lower using an ice bath, potassium hydroxide (2.76 g, 49.1 mmol) was dissolved in ion-exchanged water (2.4 mL), and then argon was added. Aqueous potassium hydroxide solution substituted with an argon gas atmosphere by bubbling gas was added. Subsequently, methyl iodide (6.34 g, 44.7 mmol) was added dropwise, and the mixture was stirred at 0 to 5 ° C. for 4 hours. The ice bath was removed, ion-exchanged water was added, and extraction with hexane was performed to obtain an oil layer. The obtained oil layer was dried using anhydrous sodium sulfate, insolubles were filtered off, the solvent was distilled off, and the residue was purified by medium pressure silica gel column chromatography (hexane). Fractions containing the target compound CM3i were integrated and concentrated, and then recrystallized and purified (hexane-isopropanol). The obtained crystals were collected by filtration and dried under reduced pressure to obtain the target compound CM3i (7 .10 g) as a white solid. The yield was 77%. The resulting compound CM3i showed> 99.9% in terms of HPLC area percentage (UV254 nm).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.57 (s, 2H), 7.35 (s, 2H), 6.83 (s, 1H), 6.71 (s, 2H) ), 2.50-2.44 (m, 10H), 1.79 (s, 3H), 1.54-1.45 (m, 4H), 1.34-1.17 (m, 12H), 0.84 (t, 6H).
LC / MS (ESI (posi)): 608 [M] ⁺

(Seventh step)
Under an argon gas atmosphere, bispinacol diboron (9.10 g, 35.9 mmol),
Dichloromethane complex (1: 1) of potassium acetate (7.04 g, 71.7 mmol), 1,4-dioxane (36 mL), [1,1′-bis (diphenylphosphino) ferrocene] dichloropalladium (II) (Pd (Dppf) Cl ₂ .CH ₂ Cl ₂ , CAS No. 95464-05-4, Sigma-Aldrich Co. LLC, 0.293 g, 0.36 mmol) A solution prepared by dissolving the above compound CM3i (7.13 g, 11.9 mmol) dissolved in 1,4-dioxane (36 mL) was added dropwise over 2 hours, and then added at the same temperature for about 18 hours. The reaction solution was obtained by stirring. The resulting reaction solution was cooled to room temperature, diluted with toluene, and then passed through Celite and a silica gel pad to remove insolubles and polar components. The obtained solution was dried over anhydrous sodium sulfate, insoluble matters were filtered off, the solvent was distilled off by concentration under reduced pressure, and toluene was added to obtain a uniform solution. Activated carbon is added to the resulting solution, stirred for 30 minutes while heating in an oil bath at 70 ° C., cooled to room temperature, then insolubles are removed by celite filtration, and the resulting solution is concentrated and recrystallized. Purification (toluene-acetonitrile) was performed. The obtained crystals were collected by filtration and dried under reduced pressure to obtain the target monomer CM3 (6.94 g) as a white solid. The yield was 82%. The resulting monomer CM3 showed> 99.9% by HPLC area percentage value (UV254 nm).

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 7.64 (s, 2H), 7.55 (s, 2H), 6.81 (s, 2H), 6.77 (s, 1H ), 2.62 (s, 6H), 2.48-2.42 (m, 4H), 1.85 (s, 3H), 1.55-1.45 (m, 4H), 1.31 ( s, 24H), 1.31-1.17 (m, 12H), 0.83 (t, 6H).
LC / MS (ESI (posi)): 704 [M] ⁺

<Synthesis Example 3: Synthesis of Monomer CM4>
Compound CM4 was synthesized according to the following first to seventh steps.

(First step)
In a reaction vessel, acetamide (59.1, 1.00 mol), tris (dibenzylideneacetone) dipalladium (0) (3.66 g, 4 mmol), 4,5-bis (diphenylphosphino) -9,9-dimethyl Xanthene (sometimes referred to as “Xantphos”. 6.94 g, 12 mmol), cesium carbonate (391 g, 1.20 mol), 1,4-dioxane (800 ml) and ion-exchanged water (7.2 ml) are added, followed by argon. The inside of the reaction vessel was replaced with an argon gas atmosphere by bubbling gas. After heating to 100 ° C., a solution of 9,9-dihexyl-2,7-dibromofluorene (compound CM4a, 98.5 g, 200 mmol) dissolved in 1,4-dioxane (300 ml) was added over about 0.5 hour. The mixture was slowly added and stirred at the same temperature for 4 hours. The obtained reaction mixture was passed through a silica gel pad, and the obtained filtrate was concentrated and then slowly added to ion-exchanged water. The solid precipitated by stirring was collected by filtration, washed with ion-exchanged water, By drying under reduced pressure, 94.5 g of solid was obtained. The resulting solid was recrystallized using ethanol-ion exchange water, then recrystallized twice with chloroform-hexane, further added with activated carbon in a state dissolved in ethanol, heated to reflux, and then filtered through Celite. The activated carbon was filtered off. Thereafter, the filtrate was concentrated and purified by adding hexane to precipitate a solid. The resulting solid was collected by filtration and dried under reduced pressure to obtain the target compound CM4b (52.8 g) as a skin-colored solid. The yield was 58.9%. The HPLC area percentage value of the obtained compound CM4b was 97.6%.

¹ H-NMR (300 MHz, THF-d ₈ ) δ (ppm) = 9.05 (s, 2H), 7.69 (s, 2H), 7.51 (t, 4H), 2.06 (s, 6H), 1.95 (m, 4H), 1.10 (m, 12H), 0.78 (t, 6H), 0.66 (m, 4H)
¹³ C-NMR (75 MHz, THF-d ₈ ) δ (ppm) = 169.1, 152.9, 140.8, 138.3, 120.9, 119.6, 115.3, 56.9, 42 .7, 33.7, 31.9, 25.8, 25.3, 24.6, 15.5

(Second step)
The above compound CM4b (43.1 g, 96 mmol), calcium carbonate (11.5 g, 115 mmol), chloroform (384 ml), methanol (384 ml) were mixed, and nitrogen gas was bubbled to bring the gas in the reaction vessel into a nitrogen gas atmosphere. It was. Benzyltrimethylammonium tribromide (89.84 g, 230 mmol) was slowly added over 1 hour while stirring the above mixture under light shielding. Thereafter, the mixture was stirred at room temperature for 17 hours, then stirred for 2 hours while being heated to 50 ° C., again stirred at room temperature for 23 hours, and stirred at 50 ° C. for 9 hours. After cooling to room temperature, insoluble materials were removed by filtration, 10 wt% aqueous sodium sulfite solution (384 ml) was added, and the mixture was stirred for 1 hour. The aqueous layer was removed by liquid separation, and the resulting oil layer was mixed with 5 wt% carbonic acid carbonate. A sodium hydrogen aqueous solution (384 ml), ion-exchanged water (384 ml), and 15% by weight brine (384 ml) were washed successively and concentrated under reduced pressure to obtain about 80 g of a solid. After the obtained solid was dissolved in ethyl acetate (400 ml) at room temperature, silica gel (40 g) was added and stirred for 30 minutes, and then the silica gel was removed by filtration, and the obtained filtrate was concentrated. The mixture was dissolved in ethyl acetate (80 ml) with heating, hexane (320 ml) was added dropwise, the mixture was cooled to room temperature, and the precipitated solid was collected by filtration. The obtained solid was dissolved again in ethyl acetate (68 ml) by heating, hexane (280 ml) was added dropwise, and the mixture was cooled to room temperature, and the precipitated solid was collected by filtration. The obtained solid was dried under reduced pressure to obtain the target compound CM4c (39.0 g) as a pale yellow solid. Yield 67.0%. The HPLC area percentage value of the obtained compound was 98.5%. The recrystallized filtrates were combined and concentrated, and then recrystallized and purified under the same conditions. The obtained crystals were collected by filtration and dried under reduced pressure to recover Compound CM4c (7.56 g). The yield was 13.0%. The HPLC area percentage value of the obtained compound CM4c was 96.6%. As a result, the total yield was 80.0%.

¹ H-NMR (300 MHz, THF-d ₈ ) δ (ppm) = 8.36 (s, 2H), 8.26 (s, 2H), 7.96 (s, 2H), 2.16 (s, 6H), 1.98 (m, 4H), 1.11 (m, 12H), 0.79 (t, 6H), 0.68 (m, 4H)
¹³ C-NMR (75 MHz, THF-d ₈ ) δ (ppm) = 169.5, 152.8, 139.1, 137.8, 125.5, 120.0, 114.8, 57.3, 41 .9, 33.5, 31.7, 25.8, 25.2, 24.6, 15.5

(Third process)
Compound CM4c (42.5 g, 70 mmol), butyl boronic acid (28.5 g, 280 mmol), palladium acetate (157 mg, 0.70 mmol), tri-tert-butylphosphine tetrafluoroborate salt (204 mg, 0.70 mmol), anhydrous Potassium carbonate (58.1 g, 420 mmol) and commercially available dehydrated toluene (700 ml) were mixed, and argon gas was bubbled to make the gas in the reaction vessel an argon gas atmosphere. The mixture was heated in an oil bath and stirred for 19 hours under reflux. After confirming the reaction progress by HPLC, diluted with toluene (350 ml) and ethyl acetate (350 ml), cooled to room temperature, filtered through Celite and passed through a silica gel pad to remove insolubles and highly polar impurities. Removed. The obtained solution was concentrated and then recrystallized and purified using ethyl acetate. The obtained crystals were collected by filtration and dried under reduced pressure to obtain the target compound CM4d (19.3 g) as a white solid. . The HPLC area percentage value of the obtained compound was 99.2% (UV254 nm). The yield was 49.1%. The target component was extracted with chloroform from the celite and silica gel residues used above, and purified by the same operation as above to recover the compound CM4d (8.7 g) as a white solid. The HPLC area percentage value of the obtained compound CM4d was 99.3% (UV254 nm). The yield was 22.1%. As a result, the total yield was 28.0 g, and the yield was 71.2%.

¹ H-NMR (300 MHz, THF-d ₈ ) δ (ppm) = 8.30 (s, 2H), 7.66 (s, 2H), 7.49 (s, 2H), 2.66 (t, 4H), 2.07 (s, 6H), 1.93 (m, 4H), 1.67 (m, 4H), 1.44 (m, 4H), 1.15 (m, 12H),. 99 (t, 6H), 0.79 (t, 6H), 0.73 (m, 4H)
¹³ C-NMR (75 MHz, THF-d ₈ ) δ (ppm) = 169.1, 150.7, 139.9, 137.3, 135.6, 121.5, 121.3, 56.5, 42 .3, 34.3, 33.6, 33.2, 31.9, 26.7, 25.9, 24.8, 24.6, 15.6, 15.5

(Fourth process)
The above compound CM4d (28.0 g, 50 mmol) was dissolved in 2-propanol (500 ml) at room temperature, 48 wt% HBr aqueous solution (569 ml) and ion-exchanged water (50 ml) were added, and the mixture was heated under reflux. Stir for 33 hours. At this time, the inside of the flask was a white slurry. After completion of the reaction, the reaction mixture was cooled to room temperature, and the precipitated solid was collected by filtration and washed twice with ion-exchanged water (250 ml). Thereafter, the resultant was dried under reduced pressure at room temperature for 5 hours and then dried under reduced pressure at 50 ° C. overnight to obtain the target compound CM4e (26.3 g) as a white solid. The yield was 82.2%. The HPLC area percentage value of the obtained compound CM4e was 92.7%.

¹ H-NMR (300 MHz, Methanol-d ₄ ) δ (ppm) = 7.93 (s, 2H), 7.44 (s, 2H), 4.91 (s, 6H), 2.85 (t, 4H), 2.09 (m, 4H), 1.80 (m, 4H), 1.56 (m, 4H), 1.07 (m, 18H), 0.77 (t, 6H), 0. 59 (m, 4H)
¹³ C-NMR (75 MHz, Methanol-d ₄ ) δ (ppm) = 152.4, 143.0, 137.8, 130.6, 124.1, 119.9, 57.3, 42.0, 34 2, 33.5, 32.2, 31.4, 24.7, 24.3, 15.2, 15.1

(Fifth process)
The above-mentioned compound CM4e (12.8 g, 20 mmol), commercially available dehydrated tetrahydrofuran (1000 ml), commercially available dehydrated ethanol (200 ml) and a 48 wt% aqueous HBr solution (60 ml) were sequentially added. At this time, the solution was light yellow and transparent. After cooling the internal temperature to 1 ° C. with an ice bath, it is sometimes called tert-butyl nitrite (“tert-BuONO”. Content: 90%, 4.82 g, 42 mmol) is added to commercially available dehydrated tetrahydrofuran (252 ml). The diluted solution was added dropwise over 30 minutes. The mixture was further stirred for 30 minutes in an ice bath, and then 50% by weight diphosphorous acid aqueous solution (H ₃ PO ₂ , 200 ml) was added dropwise over 1 hour. After completion of dropping, the mixture was stirred for 5 hours in an ice bath and then allowed to stand overnight at room temperature. Ion exchanged water was added to the resulting reaction solution, extracted three times with ethyl acetate, and the resulting organic layers were combined, and then 5% by weight aqueous sodium bicarbonate, ion exchanged water, and 15% by weight brine. The extract was washed and dried over anhydrous magnesium sulfate, insoluble matters were filtered off, and the filtrate was concentrated to obtain 10.8 g of black candy-like product.
In the same manner as described above, after uniting with 7.98 g of black candy-like material obtained from compound CM4e (9.58 g), it was purified by medium pressure silica gel chromatography (φ6 × 30 cm, hexane) to contain the desired product. Fractions were combined, activated clay (31 g) was added, and the mixture was stirred for 1 hour at room temperature. The solid was filtered off and the filtrate was concentrated to give the target compound CM4f (10.72 g) as yellow. Obtained as an oil. The yield was 68.6%. The HPLC area percentage value of the obtained compound CM4f was 95.1%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm) = 7.49 (s, 2H), 7.20 (d, 2H), 7.08 (d, 2H), 2.68 (t, 4H) , 1.89 (m, 4H), 1.67 (m, 4H), 1.40 (m, 4H), 1.04 (m, 14H), 0.95 (t, 6H), 0.76 ( t, 6H), 0.66 (m, 4H)
¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm) = 148.8, 141.56, 141.52, 127.4, 122.9, 119.7, 54.6, 40.7, 36.2 34.3, 31.9, 30.2, 24.2, 23.0, 22.9, 14.40, 14.36.

(Sixth process)
The above compound CM4f (10.1 g, 23 mmol) and chloroform (345 ml) were added, and after bubbling argon gas, N-bromosuccinimide (12.31 g, 69 mmol) was added at room temperature under light shielding. Stir for 10 minutes. After cooling to 0 ° C. in an ice bath, trifluoroacetic acid (85 ml) was added dropwise over 30 minutes. After completion of dropping, the ice bath was removed and the mixture was stirred at room temperature for 1.5 hours. After moving to another container, methanol (1700 ml) was added and stirred at room temperature for 1 hour. The precipitated solid was collected by filtration, washed with methanol, and dried under reduced pressure to obtain 11.1 g of a white solid. Purify by medium pressure silica gel chromatography (φ5 × 30cm, hexane), combine fractions containing the target compound, concentrate, dissolve in hexane (232 ml), add activated clay (23 g), stir for 1 hour at room temperature. did. Thereafter, the solid was filtered off, the filtrate was concentrated, and then recrystallized from ethyl acetate, filtered and dried under reduced pressure to obtain 4 g (10.85 g) of the target compound CM as light yellow crystals. The yield was 74.8%. The HPLC area percentage value of 4 g of the obtained compound CM was 99.52%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm) = 7.49 (s, 2H), 7.43 (s, 2H), 2.79 (t, 4H), 1.86 (m, 4H) , 1.67 (m, 4H), 1.45 (m, 4H), 1.05 (m, 12H), 0.99 (t, 6H), 0.78 (t, 6H), 0.63 ( m, 4H)
¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm) = 149.1, 148.2, 130.5, 120.9, 83.5, 54.8, 40.3, 36.3, 36.2 31.8, 31.0, 25.3, 24.0, 23.3, 22.9, 14.5, 14.4.
TLC / MS: [M] ⁺ = 604

(Seventh step)
Bispinacolatodiboron (13.3 g, 52.5 mmol) and commercially available dehydrated 1,4-dioxane (140 ml) were added to 4 g (10.6 g, 17.5 mmol) of the above compound CM, and heated to 45 ° C. to dissolve. Later, argon gas was bubbled for 30 minutes. After adding potassium acetate (10.3 g, 105 mmol) and bubbling with argon gas again, [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct (PdCl ₂ (dppf) · CH _{2 Cl 2, 400mg, 0.49mmol)} , 1,1'- bis (diphenylphosphino) ferrocene (dppf, 290 mg, 0.53 mmol) was added, while heating with an oil bath and stirred for 20 hours under reflux. Dilute with toluene (100 ml) and cool to room temperature. Thereafter, the solution was passed through a filter on which celite was spread to remove insoluble matters. The celite was further washed with toluene (twice with 100 ml), and the filtrates were combined and concentrated. Next, hexane (280 ml) and activated carbon (21 g) were added, and the mixture was stirred for 1 hour under heating and refluxing, then cooled to room temperature, and passed through a filter covered with celite to remove insoluble matters. Further, celite was washed with toluene (twice with 100 ml), and the filtrates were combined and concentrated. The operation of concentration was repeated twice, ethanol (250 ml) was added, and the mixture was stirred with heating under reflux for 1 hour. Thereafter, the mixture was cooled to room temperature, and the solid was collected by filtration, washed with ethanol (twice with 30 ml), and dried under reduced pressure to obtain 11.3 g of a white solid. The operation of complete dissolution in hexane (45 ml), ethanol (270 g) was added dropwise, and after cooling to room temperature, the precipitated solid was collected by filtration, washed with a small amount of methanol, and dried under reduced pressure twice. As a result, the target product monomer CM4 (9.88 g) was obtained as white crystals. The yield was 69.8%. The obtained HPLC area percentage value of the monomer CM4 was 99.96%.

¹ H-NMR (300 MHz, CDCl ₃ ) δ (ppm) = 7.66 (s, 2H), 7.49 (s, 2H), 2.95 (t, 4H), 1.93 (m, 4H) , 1.59 (m, 4H), 1.41 (m, 28H), 1.08 (m, 12H), 0.95 (t, 6H), 0.76 (t, 6H), 0.64 ( m, 4H)
¹³ C-NMR (75 MHz, CDCl ₃ ) δ (ppm) = 149.1, 148.2, 130.5, 120.9, 83.5, 54.8, 40.3, 36.3, 36.2 31.8, 31.0, 25.3, 24.0, 23.3, 22.9, 14.5, 14.4.
TLC / MS: [M] ⁺ = 698

<Synthesis Example 4: Synthesis of Monomer CM11>
Monomer CM11 is disclosed in Eur. J. et al. Org. Chem. 2005, pp. Synthesized according to the method described in 2207.

  Under a nitrogen atmosphere, azulene (3.0 parts by mass) was charged into a three-necked eggplant flask, and hexane was added and stirred. The mixture was cooled to 0 ° C. using an ice bath, and NBS (N-bromosuccinimide) (10.4 parts by mass) was added little by little while maintaining the reaction temperature. After completion of the reaction, the resulting mixture was stirred at room temperature for 2 hours, after which the solvent was removed. The obtained solid was purified by recrystallization from silica gel column chromatography and hexane. The target compound 1A is 3.75 parts by mass (HPLC purity: 100%) as a recovery from recrystallization, and 2.83 parts by mass (HPLC purity: 99.6%) as a recovery from a filtrate. It was. The overall yield was 99.1%. The structure of monomer CM11 was confirmed by NMR.

¹ H-NMR (300 MHz, CDCl ₃ ): δ (ppm) = 8.32 (d, 12 Hz, 2H), 7.81 (s, 1H), 7.68 (t, 12 Hz, 1H), 7.27 (M, 2H).
¹³ C-NMR (75 MHz, CDCl ₃ ): δ (ppm) = 140.36, 138.50, 137.01, 136.007, 124.33, 102.99.

<Synthesis Example 5: Synthesis of monomer CM14>
Monomer CM14 was synthesized according to the following first to sixth steps.

<First Step: Synthesis of Compound CM14c>
Under a nitrogen gas atmosphere, a solution consisting of 1-bromo-3,5-di-n-hexylbenzene (compound CM14a, 650 g) and tetrahydrofuran (6.5 L) was added to n-butyllithium (-75 to -70 ° C). 1.6M hexane solution, 1237 mL) was added dropwise over 1 hour, and the mixture was further stirred at the same temperature for 4 hours. Then, 2,7-dibromofluorenone (Compound CM14b, 613 g) was added at −75 to −70 ° C. over 1 hour, and the temperature of the reaction mixture was raised to room temperature while stirring. 2M hydrochloric acid (982 mL) was then added to adjust the pH of the reaction mixture to 7. Tetrahydrofuran was removed under reduced pressure, n-hexane was added to the remaining mixture and stirred, and the oil layer obtained by liquid separation was washed with water. Anhydrous sodium sulfate was added to the oil layer and the mixture was stirred and filtered, and then the filtrate was concentrated under reduced pressure to remove the solvent to obtain an oily substance. The oily product was recrystallized from n-hexane to obtain the target compound CM14c (674 g).

<Second Step: Synthesis of Compound CM14d>
Under nitrogen gas atmosphere, n-hexane (1215 mL) was added to compound CM14c (674 g), trifluoroacetic acid (877 mL) was added with stirring at 10 ° C., and then triethylsilane (147 g) and n-hexane (300 mL) were added. The solution consisting of was added dropwise at 10-15 ° C. The reaction mixture was then stirred overnight at room temperature. Next, water (1200 mL) was slowly added to the obtained reaction mixture at 10 ° C., and the solvent was removed by concentration under reduced pressure. N-Hexane was added to the resulting mixture and stirred, and the aqueous layer separated after standing was separated from the oil layer. A 10% aqueous potassium phosphate solution (5 L) was added to the obtained oil layer, and the mixture was stirred for 2 hours. After standing, the separated aqueous layer was separated from the oil layer. The oil layer was washed with water, anhydrous sodium sulfate was added and stirred, and the filtrate was concentrated under reduced pressure to remove the solvent and obtain an oil. A solution prepared by dissolving the oil in dichloromethane (610 mL) is added to stirred methanol (8.5 L) over 1 hour, and the mixture is further stirred for 3 hours. The precipitated crystals are filtered and dried under reduced pressure. As a result, 538 g of the target compound CM14d was obtained.

<Third Step: Synthesis of Compound CM14e>
Under a nitrogen gas atmosphere, 26.7 wt% hydroxylation was carried out at 85 ° C. with stirring to a mixture consisting of compound CM14d (25 g), 1-bromooctane (12.9 g), tetraethylammonium chloride (manufactured by Aldrich: trademark Aliquat 336). A potassium aqueous solution was slowly added, and the mixture was stirred at the same temperature for 20 hours. To the obtained reaction mixture, water (120 mL) and dichloromethane (250 mL) were added at room temperature, and the mixture was stirred and allowed to stand. After separation, the aqueous layer was removed from the oil layer. Anhydrous sodium sulfate was added to the oil layer and stirred, and the filtrate obtained by filtration was concentrated under reduced pressure, and the solvent was removed to obtain an oil. Dichloromethane and methanol were added to the oil and recrystallized to obtain a white solid. The solid was recrystallized from isopropyl alcohol to obtain 22 g of the intended compound CM14e.

<Fourth Step: Synthesis of Compound CM14f>
Under nitrogen gas atmosphere, compound CM14e (125 g), 2,4,6-trimethylaniline (54.63 g), toluene (1.7 L), [tris (dibenzylideneacetone)] dipalladium (0.84 g), tri- Tert-butylphosphine tetrafluoroborate (t-Bu ₃ .BF ₄ H, 0.400 g) and sodium tert-butoxide (53 g) were stirred under reflux for 16 hours. Subsequently, water (400 mL) was added and stirred at room temperature, and the aqueous layer separated after standing was removed from the oil layer. The oil layer was concentrated under reduced pressure to remove the solvent to obtain an oil. The oil was dissolved in toluene (500 mL) to prepare a solution, and the solution was passed through a filter packed with celite and a filter packed with silica gel. The obtained filtrate was concentrated under reduced pressure to remove the solvent to obtain an oily substance. Isopropyl alcohol and dichloromethane were added to the oil and allowed to stand, and the precipitated crystals were filtered to obtain a yellow solid. The solid was recrystallized from isopropyl alcohol and toluene to obtain 94 g of the target compound CM14f.

<Fifth Step: Synthesis of Compound CM14g>
Under nitrogen gas atmosphere, compound CM14f (94.2 g), bromobenzene (32 mLg), toluene (1.4 L), [tris (dibenzylideneacetone)] dipalladium (1.09 g), tri-tert-butylphosphine tetra Fluoroborate (t-Bu ₃ .BF ₄ H, 0.69 g) and sodium-tert-butoxide (34.4 g) were stirred overnight under reflux. Subsequently, water (300 mL) was added and stirred at room temperature, and the aqueous layer separated after standing was removed from the oil layer. The oil layer was concentrated under reduced pressure to remove the solvent to obtain an oil. The oil was dissolved in toluene (200 mL) to prepare a solution, and the solution was passed through a filter packed with celite and a filter packed with silica gel. The obtained filtrate was concentrated under reduced pressure to remove the solvent to obtain an oily substance. Isopropyl alcohol and methanol were added to the oily substance, and the mixture was stirred and allowed to stand to remove the separated supernatant. The resulting oily substance was removed under reduced pressure to obtain 14 g of the target compound CM14g.

<Sixth Step: Synthesis of Monomer CM14>
A solution consisting of 14 g (55.8 g) of compound CM and chloroform (550 mL) was added to a solution consisting of N-bromosuccinimide (NBS, 21.2 g) and N, N-dimethylformamide (550 mL) at −15 ° C. with stirring. The solution was added dropwise and stirred at the same temperature for 3 hours. Subsequently, methanol (400 mL) was added and stirred at room temperature, water (400 mL) was added and stirred, and the solvent was removed by concentration under reduced pressure. After the resulting mixture was allowed to stand, the supernatant was removed to obtain a brown solid. Dichloromethane (500 mL) was added to the solid to dissolve it, water was added and stirred, and after standing, the separated aqueous layer was removed from the oil layer. Next, 10% aqueous sodium carbonate solution was added and stirred, and the aqueous layer separated after standing was removed from the oil layer. Subsequently, water was added and stirred, and the aqueous layer separated after standing was removed from the oil layer. The solvent was removed from the obtained oil layer under reduced pressure to obtain a brown oily substance. The brown oil was subjected to column chromatography using celite and silica gel, and the solvent was removed to obtain a transparent oil. Isopropyl alcohol and toluene were added to the transparent oily substance, stirred and allowed to stand, and then the supernatant was removed to obtain a highly viscous solid. Next, methanol was added to the solid and stirred vigorously, and the resulting solid was filtered. Then, 40.6 g of the target monomer CM14 was obtained by recrystallization using methanol and n-butyl acetate.

<Synthesis Example 3: Synthesis of phosphorescent material 1>
The phosphorescent material 1 was synthesized according to the synthesis method described in International Publication No. 2002/066652.

<Polymerization Example 1: Synthesis of polymer compound 1>
After making the inside of the reaction vessel a nitrogen gas atmosphere, monomer CM1 (4.9717 g, 9.90 mmol), monomer CM13 (7.7427 g, 8.50 mmol), monomer CM8 (0.7924 g, 1.90 mmol). 50 mmol) and toluene (243 mL) were added and heated to 105 ° C. To this was added 20% by weight aqueous tetraethylammonium hydroxide solution (35 g) and dichlorobis (tris-o-methoxyphenylphosphine) (8.9 mg), and the reaction solution was refluxed for 7.5 hours. After the reaction, phenylboronic acid (122 mg), 20 wt% tetraethylammonium hydroxide aqueous solution (35 g) and dichlorobis [tri (o-methoxyphenyl) phosphine] palladium (8.8 mg) were added thereto and refluxed for 12.2 hours. I let you. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the resulting reaction solution 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, precipitation occurred. The precipitate was collected by filtration to obtain a precipitate. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 6.55 g of polymer compound 1. The number average molecular weight in terms of polystyrene of the polymer compound 1 was 3.3 × 10 ⁴ , and the weight average molecular weight in terms of polystyrene was 13.7 × 10 ⁴ .

  Polymer compound 1 has the following structural units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which structural units of (PA) and structural units selected from (PB) are alternately polymerized Is done.

<Polymerization Example 2: Synthesis of Polymer Compound 2>
After making the inside of the reaction vessel a nitrogen gas atmosphere, monomer CM1 (0.9947 g, 2.00 mmol), monomer CM13 (1.4575 g, 1.60 mmol), monomer CM8 (0.1057 g, 0.005 g). 20 mmol), monomer CM9 (0.0920 g, 0.20 mmol), dichlorobis (tris-o-methoxyphenylphosphine) (1.8 mg) and toluene (47 mL) were mixed and heated to 105 ° C. A 20 wt% tetraethylammonium hydroxide aqueous solution (7 mL) was added dropwise to the resulting reaction solution, and the mixture was refluxed for 23 hours. After the reaction, phenylboronic acid (24.4 mg) and dichlorobis (orthomethoxyphenylphosphine) palladium (1.8 mg) were added thereto and refluxed for 9 hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the resulting reaction solution 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, precipitation occurred. The precipitate was collected by filtration to obtain a precipitate. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.46 g of polymer compound 2. The polymer compound 2 had a polystyrene-equivalent number average molecular weight of 1.6 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 1.0 × 10 ⁵ .

  Polymer compound 2 has the following structural units and molar ratios based on the monomer charge ratio, and is presumed to be a polymer compound in which structural units of (PA) and structural units selected from (PB) are alternately polymerized Is done.

<Polymerization Example 3: Synthesis of Polymer Compound 3>
After the reaction vessel was filled with a nitrogen gas atmosphere, monomer CM1 (1.0465 g), monomer CM2 (0.4817 g), monomer CM13 (2.7367 g), monomer CM10 (0.2253 g) And a mixture of toluene (83 ml) was heated to about 80 ° C., bistriphenylphosphine palladium dichloride (2.43 mg) and a 20 wt% tetraethylammonium hydroxide aqueous solution (12.1 g) were added, and the mixture was stirred at reflux for about 30 hours. did. Next, phenylboronic acid (42.5 mg), bistriphenylphosphine palladium dichloride (2.45 mg) and 20 wt% tetraethylammonium hydroxide aqueous solution (12.1 g) were added, and the mixture was further stirred for about 17.5 hours under reflux. . Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.94 g) in ion-exchanged water (39 ml) was added, and the mixture was stirred for 3 hours while heating to 85 ° C. Thereafter, the obtained organic layer was washed sequentially with ion-exchanged water twice, 3% by weight acetic acid twice and ion-exchanged water twice. The obtained organic layer was dropped into methanol to cause precipitation, and the solid was obtained by filtration and drying. This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance. The obtained solution was added dropwise to methanol to cause precipitation, and the polymer compound 3 (2.62 g) was obtained by filtration and drying. The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene of the polymer compound 3 were Mn = 1.3 × 10 ⁴ and Mw = 5.2 × 10 ⁴ .

  Polymer compound 3 has the following structural units and molar ratios based on the monomer charge ratio, and is presumed to be a polymer compound in which structural units of (PA) and structural units selected from (PB) are alternately polymerized: Is done.

<Polymerization Example 4: Synthesis of Polymer Compound 4>
After the reaction vessel was filled with nitrogen gas atmosphere, monomer CM1 (0.9967 g), monomer CM14 (1.7588 g), monomer CM8 (0.1057 g), monomer CM9 (0.0920 g) And a mixture of toluene (55 ml) was heated to about 80 ° C., then dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.77 mg) and 20 wt% aqueous tetraethylammonium hydroxide (7.5 g) were added, Stir for about 6 hours under reflux.

  Next, phenylboronic acid (26.1 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.76 mg) and a 20 wt% tetraethylammonium hydroxide aqueous solution (7.5 g) were added, and further under reflux. Stir for about 15 hours.

  Next, a solution of sodium N, N-diethyldithiocarbamate trihydrate (1.11 g) in ion-exchanged water (26 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C.

The obtained organic layer was washed successively with ion-exchanged water twice, with 3.0% by weight acetic acid aqueous solution twice and with ion-exchanged water twice. The obtained organic layer was dropped into methanol to cause precipitation, and the solid was obtained by filtration and drying. This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance. The obtained solution was added dropwise to methanol to cause precipitation, which was collected by filtration and dried to obtain polymer compound 4 (1.57 g). The polystyrene equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer compound 4 were Mn = 3.5 × 10 ⁴ and Mw = 2.8 × 10 ⁵ .

  The polymer compound 4 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.

<Polymerization Example 5: Synthesis of Polymer Compound 5>
After the reaction vessel was filled with a nitrogen gas atmosphere, monomer CM3 (1.4093 g), monomer CM13 (1.4574 g), monomer CM8 (0.1057 g), monomer CM9 (0.0920 g) And a mixture of toluene (58 ml) was heated to about 80 ° C., then dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (3.53 mg) and 20 wt% aqueous tetraethylammonium hydroxide (6.29 g) were added, The mixture was stirred for about 4.5 hours under reflux.

  Next, phenylboronic acid (24.4 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.76 mg) and 20 wt% tetraethylammonium hydroxide aqueous solution (6.29 g) were added, and further under reflux. Stir for about 18 hours.

  Next, a solution prepared by dissolving sodium N, N-diethyldithiocarbamate trihydrate (1.11 g) in ion-exchanged water (27 ml) was added, and the mixture was stirred for 2 hours while being heated to 85 ° C.

The obtained organic layer was washed successively with ion-exchanged water twice, with 3.0% by weight acetic acid aqueous solution twice and with ion-exchanged water twice. The obtained organic layer was dropped into methanol to cause precipitation, and the solid was obtained by filtration and drying. This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance. The obtained solution was added dropwise to methanol to cause precipitation, and the polymer compound 5 (1.77 g) was obtained by filtration and drying. The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene of the polymer compound 5 were Mn = 4.7 × 10 ⁴ and Mw = 2.8 × 10 ⁵ .

  Polymer compound 5 has the following structural units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which structural units of (PA) and structural units selected from (PB) are alternately polymerized: Is done.

<Polymerization Example 6: Synthesis of Polymer Compound 6>
After the reaction vessel was filled with a nitrogen gas atmosphere, monomer CM3 (1.4093 g), monomer CM14 (1.7588 g), monomer CM8 (0.1057 g), monomer CM9 (0.0920 g) And a mixture of toluene (45 ml) was heated to about 80 ° C., then dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.81 mg) and 20 wt% aqueous tetraethylammonium hydroxide (7.3 g) were added, Stir for about 9 hours under reflux.

  Next, phenylboronic acid (24.6 mg), dichlorobis (tris (2-methoxyphenyl) phosphine) palladium (1.74 mg) and 20 wt% tetraethylammonium hydroxide aqueous solution (7.4 g) were added, and further under reflux. Stir for about 13.5 hours.

  Next, a solution prepared by dissolving sodium N, N-diethyldithiocarbamate trihydrate (1.11 g) in ion-exchanged water (31 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C.

The obtained organic layer was washed successively with ion-exchanged water twice, with 3.0% by weight acetic acid aqueous solution twice and with ion-exchanged water twice. The obtained organic layer was dropped into methanol to cause precipitation, and the solid was obtained by filtration and drying. This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance. The obtained solution was added dropwise to methanol to cause precipitation, and the polymer compound 6 (1.92 g) was obtained by filtering and drying. The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene of the polymer compound 6 were Mn = 6.4 × 10 ⁴ and Mw = 2.9 × 10 ⁵ .

  Polymer compound 6 has the following structural units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which the structural units of (PA) and the structural units selected from (PB) are alternately polymerized: Is done.

<Polymerization Example 7: Synthesis of polymer compound 7>
After the reaction vessel was filled with a nitrogen gas atmosphere, a mixture of monomer CM4 (1.4924 g), monomer CM13 (1.6539 g), monomer CM10 (0.1375 g) and toluene (57 ml) was added to about 80 After heating to 0 ° C., palladium acetate (0.80 mg), tris (2-methoxyphenyl) phosphine (4.57 mg) and 20 wt% tetraethylammonium hydroxide aqueous solution (7.7 g) were added, and the mixture was refluxed for about 6 hours. Stir.

  Next, phenylboronic acid (26.3 mg), palladium acetate (0.82 mg), tris (2-methoxyphenyl) phosphine (4.58 mg) and 20 wt% tetraethylammonium hydroxide aqueous solution (7.7 g) were added. Further, the mixture was stirred for about 14.5 hours under reflux.

  Next, a solution obtained by dissolving sodium N, N-diethyldithiocarbamate trihydrate (1.21 g) in ion-exchanged water (24 ml) was added, and the mixture was stirred for 2 hours while being heated to 85 ° C.

The obtained organic layer was washed successively with ion-exchanged water twice, 3% by weight acetic acid twice, and ion-exchanged water three times. The obtained organic layer was dropped into methanol to cause precipitation, and the solid was obtained by filtration and drying. This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance. The obtained solution was added dropwise to methanol to cause precipitation, which was collected by filtration and dried to obtain polymer compound 7 (2.148 g). The polystyrene equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) of the polymer compound 7 were Mn = 4.2 × 10 ⁴ and Mw = 2.9 × 10 ⁵ .

  Polymer compound 7 has the following structural units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which structural units of (PA) and structural units selected from (PB) are alternately polymerized Is done.

<Example 1: Synthesis of polymer compound 8>
After making the inside of the reaction vessel a nitrogen gas atmosphere, monomer CM1 (1.0043 g, 2.02 mmol), monomer CM13 (1.4028 g, 1.54 mmol), monomer CM11 (0.0172 g, 0. 06 mmol), monomer CM8 (0.1057 g, 0.20 mmol), monomer CM9 (0.0921 g, 0.20 mmol) and toluene (46 mL) were added and heated to 105 ° C. 20% by weight tetraethylammonium hydroxide aqueous solution (6.9 g) and dichlorobis [tri (o-methoxyphenyl) phosphine] palladium (1.8 mg) were added thereto, and the resulting reaction solution was refluxed for 6.0 hours. . After the reaction, phenylboronic acid (24.6 mg), 20 wt% tetraethylammonium hydroxide aqueous solution (6.9 g) and dichlorobis (tris-o-methoxyphenylphosphine) (1.8 mg) were added thereto, and 14.0 Reflux for hours. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the resulting reaction solution 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, precipitation occurred. The precipitate was collected by filtration to obtain a precipitate. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.52 g of polymer compound 8. The polymer compound 8 had a polystyrene-equivalent number average molecular weight of 3.42 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 66.8 × 10 ⁴ .

  The polymer compound 8 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.

<Example 2: Synthesis of polymer compound 9>
After making the inside of the reaction vessel a nitrogen gas atmosphere, monomer CM1 (1.0033 g, 2.01 mmol), monomer CM13 (1.4028 g, 1.54 mmol), monomer CM12 (0.0248 g, 0.001 g). 06 mmol), monomer CM8 (0.1056 g, 0.20 mmol), monomer CM9 (0.0921 g, 0.20 mmol) and toluene (47 mL) were added and heated to 105 ° C. 20% by weight tetraethylammonium hydroxide aqueous solution (6.9 g) and dichlorobis (tris-o-methoxyphenylphosphine) (1.8 mg) were added thereto, and the resulting reaction solution was refluxed for 7.5 hours. After the reaction, phenylboronic acid (24.4 mg), 20 wt% tetraethylammonium hydroxide aqueous solution (6.9 g) and dichlorobis [tri (o-methoxyphenyl) phosphine] palladium (1.8 mg) were added thereto. Refluxed for 0 hour. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the resulting reaction solution 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, precipitation occurred. The precipitate was collected by filtration to obtain a precipitate. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 1.52 g of polymer compound 9. The polymer compound 9 had a polystyrene-equivalent number average molecular weight of 12.4 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 59.5 × 10 ⁴ .

  The polymer compound 9 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which constitutional units of (PA) and constitutional units selected from (PB) are alternately polymerized Is done.

<Example 3: Synthesis of polymer compound 10>
After making the gas in the reaction vessel a nitrogen gas atmosphere, polymer compound 1 (3.25 g, 6.93 mmol), fullerene (manufactured by Sigma-Aldrich) (1.49 g, 2.08 mmol) and orthodichlorobenzene (349 ml) Were mixed. The resulting solution was bubbled with nitrogen gas for 30 minutes, then heated to 190 ° C. and stirred for 24 hours. Then, the obtained reaction solution was reprecipitated in methanol (1500 ml), filtered and dried under reduced pressure.

  After drying, THF (183 ml) was added to the obtained crude polymer and dissolved. Thereafter, the Kiriyama funnel was charged with activated carbon (6.85 g), a mixture of activated carbon (6.93 g) and silica gel (32.97 g), and celite (6.71 g). The uppermost layer was laminated so as to be Celite, and the polymer solution was passed therethrough.

  Activated charcoal (6.90 g) was added to the solution after passing through, and this suspension was passed through activated charcoal (13.9 g). After concentration under reduced pressure to distill off THF, toluene (100 mL) was added. In addition, it was dissolved.

The toluene solution of the polymer obtained above was dropped into methanol (1000 ml) and stirred, and then the obtained precipitate was collected by filtration and dried to obtain 1.85 g of polymer compound 10. The polymer compound 10 had a polystyrene-equivalent number average molecular weight of 9.5 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 20.7 × 10 ⁴ .

  The amount of fullerene supported on the entire polymer of the obtained polymer compound 10 was 6.9 mol%, and the amount of fullerene not supported was 0 mol%. In addition, it is estimated that the structural unit containing fullerene in the high molecular compound 10 is a structural unit represented by the said Formula (6A-1).

<Polymerization Example 8: Synthesis of polymer compound 11>
After the inside of the reaction vessel was filled with nitrogen gas, monomer CM3 (5.1791 g, 7.35 mmol), monomer CM13 (5.8070 g, 6.38 mmol), monomer CM8 (0.5943 g, 1. 13 mmol) and toluene (222 mL) were added and heated to 105 ° C. 20% by weight tetraethylammonium hydroxide aqueous solution (26 g) and dichlorobis [tri (o-methoxyphenyl) phosphine] palladium (6.6 mg) were added thereto, and the resulting reaction solution was refluxed for 6.0 hours. After the reaction, phenylboronic acid (92 mg), 20 wt% tetraethylammonium hydroxide aqueous solution (26 g) and dichlorobis [tri (o-methoxyphenyl) phosphine] palladium (6.6 mg) were added thereto, and refluxed for 13.2 hours. I let you. Next, an aqueous sodium diethyldithiacarbamate solution was added thereto, and the mixture was stirred at 80 ° C. for 2 hours. After cooling, the resulting reaction solution 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, precipitation occurred. The precipitate was collected by filtration to obtain a precipitate. This precipitate was dissolved in toluene and purified by passing through an alumina column and a silica gel column in this order. The obtained solution was added dropwise to methanol and stirred, and then the resulting precipitate was collected by filtration and dried to obtain 7.61 g of polymer compound 11. The polymer compound 11 had a polystyrene-equivalent number average molecular weight of 3.3 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 12.3 × 10 ⁴ .

  The polymer compound 11 has the following constitutional units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which (PA) constitutional units and (PB) constitutional units are alternately polymerized. The

<Polymerization Example 9: Synthesis of polymer compound 12>
After making the gas in the reaction vessel a nitrogen gas atmosphere, polymer compound 11 (3.26 g, 5.70 mmol), fullerene (manufactured by Sigma-Aldrich) (1.23 g, 1.70 mmol) and orthodichlorobenzene (285 ml) Were mixed. After bubbling with nitrogen gas for 30 minutes, it was heated to 190 ° C. and stirred for 24 hours. Then, the obtained reaction solution was reprecipitated with methanol (1500 ml), filtered and dried under reduced pressure.

  After drying, THF (184 ml) was added to the obtained crude polymer and dissolved. A Kiriyama funnel was charged with activated carbon (6.84 g), a mixture of activated carbon (6.86 g) and silica gel (33.55 g), and celite (6.49 g), and the bottom layer was activated carbon, the middle layer was a mixture of activated carbon and silica gel, The uppermost layer was laminated so as to be celite, and a polymer solution was passed therethrough.

  Activated charcoal (6.90 g) was added to the solution after passing through, and this suspension was passed through activated charcoal (13.8 g). After concentration under reduced pressure to distill off THF, toluene (100 mL) was added. In addition, it was dissolved.

The toluene solution of the polymer obtained above was dropped into methanol (1000 ml) and stirred, and then the obtained precipitate was collected by filtration and dried to obtain 1.56 g of polymer compound 12. The polymer compound 12 had a polystyrene-equivalent number average molecular weight of 9.4 × 10 ⁴ and a polystyrene-equivalent weight average molecular weight of 20.9 × 10 ⁴ .

  The amount of fullerene supported on the whole polymer of the obtained polymer compound 12 was 6.7 mol%, and the amount of fullerene not supported was 0 mol%. In addition, it is estimated that the structural unit containing fullerene in the high molecular compound 10 is a structural unit represented by the said Formula (6A-1).

<Polymerization Example 10: Synthesis of Polymer Compound L1>
After making the gas in the reaction vessel a nitrogen gas atmosphere, monomer CM6 (9.0 g, 16.4 mmol), monomer CM15 (1.3 g, 1.8 mmol), monomer CM5 (13.4 g, 18.0 mmol), tetraethylammonium hydroxide (43.0 g, 58.3 mmol), palladium acetate (8 mg, 0.04 mmol), tri (2-methoxyphenyl) phosphine (0.05 g, 0.1 mmol) and toluene (200 mL) ) And stirred with heating at 90 ° C. for 8 hours. Phenylboronic acid (0.22 g, 1.8 mmol) was then added and the resulting mixture was stirred for 14 hours. After allowing to cool, the aqueous layer was removed, an aqueous sodium diethyldithiocarbamate solution was added and stirred, the aqueous layer was removed, and the resulting organic layer was washed with water and 3% aqueous acetic acid. The obtained organic layer was poured into methanol to precipitate a polymer compound, and then the polymer compound collected by filtration was dissolved again in toluene and passed through silica gel and alumina columns. The eluted toluene solution containing the polymer compound was recovered, and the recovered eluted toluene solution was poured into methanol to precipitate the polymer compound. The precipitated polymer compound was vacuum dried at 50 ° C. to obtain polymer compound L1 (12.5 g). The polymer compound L1 had a polystyrene equivalent weight average molecular weight of 3.1 × 10 ⁵ and a molecular weight distribution index (Mw / Mn) of 2.9.

  The polymer compound L1 has the following structural units and molar ratios from the monomer charge ratio, and is presumed to be a polymer compound in which the structural unit of (PA) and the structural unit selected from (PB) are alternately polymerized Is done.

<Polymerization Example 11: Synthesis of Polymer Compound L2>
After making the gas in the reaction vessel a nitrogen gas atmosphere, a mixture of monomer CM1 (0.8222 g), monomer CM7 (0.8507 g), monomer CM16 (0.2097 g) and toluene (37 ml) was added. After heating to about 80 ° C., palladium acetate (0.41 mg), tris (2-methoxyphenyl) phosphine (2.30 mg) and a 20 wt% tetraethylammonium hydroxide aqueous solution (5.8 g) were added, and the mixture was heated under reflux. Stir for 4 hours. Next, phenylboronic acid (40.6 mg) was added, and the mixture was further stirred under reflux for about 2 hours. Thereafter, a solution of sodium N, N-diethyldithiocarbamate trihydrate (0.46 g) in ion-exchanged water (9 ml) was added, and the mixture was stirred for 2 hours while heating to 85 ° C. Thereafter, the obtained organic layer was washed successively with 3.6 wt% hydrochloric acid twice, 2.5 wt% aqueous ammonia solution twice, and ion-exchanged water five times. The obtained organic layer was dropped into methanol to cause precipitation, and the solid was obtained by filtration and drying. This solid was dissolved in toluene and passed through a silica gel column and an alumina column through which toluene was passed in advance. The obtained solution was added dropwise to methanol to cause precipitation, which was collected by filtration and dried to obtain polymer compound L2 (1.110 g). The number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene of the polymer compound L2 were Mn = 8.7 × 10 ⁴ and Mw = 2.3 × 10 ⁵ .

  Polymer compound L2 has the following structural units and molar ratios based on the monomer charge ratio, and is presumed to be a polymer compound in which the structural unit of (PA) and the structural unit selected from (PB) are alternately polymerized Is done.

<Example D1: Production and evaluation of light-emitting element D1>
A glass substrate having an ITO film with a thickness of 45 nm formed by sputtering is spin-coated using AQ-1200 (manufactured by Plextronics), which is a polythiophene / sulfonic acid-based hole injecting agent, as a hole injecting material. Then, a film was formed and dried in an air atmosphere at 170 ° C. for 15 minutes on a hot plate.

  Next, the high molecular compound 1 and the high molecular compound 10 were respectively melt | dissolved in xylene, and 0.7 mass% xylene solution was prepared.

  Next, the xylene solution of the polymer compound 1 and the xylene solution of the polymer compound 10 were mixed so that the mass ratio of the solid content of the polymer compound 1 and the polymer compound 10 was 80:20. An organic thin film having a thickness of 20 nm was formed by spin coating using this xylene solution. This was heated on a hot plate at 180 ° C. for 60 minutes in a nitrogen gas atmosphere.

Next, the polymer compound L1 was dissolved in xylene to prepare a 1.3% by mass xylene solution. An organic thin film having a thickness of 60 nm was formed by spin coating using this xylene solution, dried by heating at 150 ° C. for 10 minutes in a nitrogen gas atmosphere, and then about 7 nm of sodium fluoride as the cathode and then about aluminum. 120 nm was vapor-deposited and the light emitting element D1 was produced. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.

When voltage was applied to the resulting light emitting device D1, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , the device was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 72.5 hours. The results are shown in Table 1.

<Example D2: Production and Evaluation of Light-Emitting Element D2>
A light emitting device D2 was produced in the same manner as in Example D1, except that the polymer compound 2 was used instead of the polymer compound 1 in Example D1.

When voltage was applied to the obtained light emitting device D2, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , the device was driven with a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 85.0 hours. The results are shown in Table 1.

<Example D3: Production and evaluation of light-emitting element D3>
A light emitting device D3 was produced in the same manner as in Example D1, except that the polymer compound 3 was used instead of the polymer compound 1 in Example D1.

When voltage was applied to the resulting light emitting device D3, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , the device was driven with a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 46.4 hours. The results are shown in Table 1.

<Example D4: Production and evaluation of light-emitting element D4>
A light emitting device D4 was produced in the same manner as in Example D1, except that the polymer compound 4 was used instead of the polymer compound 1 in Example D1.

When voltage was applied to the obtained light emitting device D4, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , the device was driven with a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 96.0 hours. The results are shown in Table 1.

<Example D5: Production and evaluation of light-emitting element D5>
A light emitting device D5 was produced in the same manner as in Example D1, except that polymer compound 5 and polymer compound 12 were used instead of polymer compound 1 and polymer compound 10 in Example D1.

When voltage was applied to the resulting light emitting device D5, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 109.0 hours. The results are shown in Table 1.

<Example D6: Production and evaluation of light-emitting element D6>
A light emitting device D6 was produced in the same manner as in Example D1, except that the polymer compound 6 and the polymer compound 12 were used in place of the polymer compound 1 and the polymer compound 10 in Example D1.

When voltage was applied to the resulting light emitting device D6, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 137.6 hours. The results are shown in Table 1.

<Example D7: Production and evaluation of light-emitting element D7>
A light emitting device D7 was produced in the same manner as in Example D1, except that the polymer compound 7 and the polymer compound 12 were used instead of the polymer compound 1 and the polymer compound 10 in Example D1.

When voltage was applied to the resulting light emitting device D7, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 56.4 hours. The results are shown in Table 1.

<Example D8: Production and evaluation of light-emitting element D8>
Instead of the xylene solution in which the polymer compound 1 and the polymer compound 10 in Example D1 were mixed, the xylene solution adjusted so that the mass ratio of the solid content of the polymer compound 1 and the polymer compound 8 was 20:80. A light emitting device D8 was produced in the same manner as in Example D1 except that was used.

When voltage was applied to the obtained light emitting device D8, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 46.9 hours. The results are shown in Table 1.

<Example D9: Production and evaluation of light-emitting element D9>
Instead of the xylene solution in which the polymer compound 1 and the polymer compound 10 in Example D1 were mixed, the xylene solution adjusted so that the mass ratio of the solids of the polymer compound 1 and the polymer compound 9 was 20:80. A light emitting device D9 was produced in the same manner as in Example D1 except that was used.

When voltage was applied to the resulting light emitting device D9, EL light emission having a peak at 465 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 39.4 hours. The results are shown in Table 1.

<Example D10: Production and evaluation of light-emitting element D10>
Instead of the xylene solution in which the polymer compound 1 and the polymer compound 10 in Example D1 were mixed, a xylene solution adjusted so that the mass ratio of the solid content of the polymer compound 1 and fullerene C60 was 97: 3 was used. A light emitting device D10 was produced in the same manner as in Example D1 except that.

When voltage was applied to the resulting light emitting device D10, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , the device was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 197.7 hours. The results are shown in Table 1.

<Example D11: Production and evaluation of light-emitting element D11>
In the same manner as in Example D1, except that a xylene solution containing only the polymer compound 10 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D1, a light emitting device D11 was produced.

When voltage was applied to the obtained light emitting device D11, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven with a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 289 hours. The results are shown in Table 1.

<Comparative Example CD1: Production and Evaluation of Light-Emitting Element CD1>
In the same manner as in Example D1, except that a xylene solution containing only the polymer compound 1 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D1, the light emitting device CD1 was produced.

When voltage was applied to the obtained light emitting device CD1, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 26.4 hours. The results are shown in Table 1.

<Comparative Example CD2: Production and Evaluation of Light-Emitting Element CD2>
In the same manner as in Example D1, except that a xylene solution containing only the polymer compound 2 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D1, the light emitting device CD2 was produced.

When voltage was applied to the resulting light emitting device CD2, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 49.9 hours. The results are shown in Table 1.

<Comparative Example CD3: Production and Evaluation of Light-Emitting Element CD3>
In the same manner as in Example D1, except that a xylene solution containing only the polymer compound 3 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D1, the light emitting device CD3 was produced.

When voltage was applied to the resulting light emitting device CD3, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 13.7 hours. The results are shown in Table 1.

<Comparative Example CD4: Production and Evaluation of Light-Emitting Element CD4>
In the same manner as in Example D1, except that a xylene solution containing only the polymer compound 4 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D1, the light emitting device CD4 was produced.

When voltage was applied to the obtained light emitting device CD4, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 63.9 hours. The results are shown in Table 1.

<Comparative Example CD5: Production and Evaluation of Light-Emitting Element CD5>
In the same manner as in Example D1, except that a xylene solution containing only the polymer compound 5 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D1, the light emitting device CD5 was produced.

When voltage was applied to the resulting light emitting device CD5, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 46.4 hours. The results are shown in Table 1.

<Comparative Example CD6: Production and Evaluation of Light-Emitting Element CD6>
In the same manner as in Example D1, except that a xylene solution containing only the polymer compound 6 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D1, the light emitting device CD6 was produced.

When voltage was applied to the resulting light emitting device CD6, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven with a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 75.0 hours. The results are shown in Table 1.

<Comparative Example CD7: Production and Evaluation of Light-Emitting Element CD7>
In the same manner as in Example D1, except that a xylene solution containing only the polymer compound 7 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D1, the light emitting device CD7 was produced.

When voltage was applied to the resulting light emitting device CD7, EL light emission having a peak at 455 nm was obtained from this device, and after setting the current value so that the initial luminance was 2500 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 18.9 hours. The results are shown in Table 1.

  From a comparison between Example D10 and Comparative Example CD1, it can be seen that the first composition containing the polymer compound (A) and the compound (B) of the present invention is useful for production of a light-emitting device having excellent luminance life. .

  Also, a comparison between Example D1 and Comparative Example CD1, a comparison between Example D2 and Comparative Example CD2, a comparison between Example D3 and Comparative Example CD3, a comparison between Example D4 and Comparative Example CD4, and Example D5 Comparison with Comparative Example CD5, Comparison between Example D6 and Comparative Example CD6, Comparison between Example D7 and Comparative Example CD7, Comparison between Example D8 and Comparative Example CD1, Comparison between Example D9 and Comparative Example CD1 Thus, it can be seen that the second composition containing the polymer compound (A) and the polymer compound (C) of the present invention is useful for the production of a light-emitting device having excellent luminance life.

  Furthermore, from the comparison between Example D11 and Comparative Example CD1, it can be seen that the polymer compound of the present invention is useful for the production of a light-emitting device having excellent luminance life.

<Example D12: Production and evaluation of light-emitting element D12>
A glass substrate with an ITO film having a thickness of 45 nm formed by sputtering is spin-coated using AQ-1200 (manufactured by Plextronics), which is a polythiophene-sulfonic acid-based hole injecting agent, as a hole injecting material. Then, a film was formed and dried in an air atmosphere at 170 ° C. for 15 minutes on a hot plate.

  Next, the high molecular compound 1 and the high molecular compound 10 were respectively melt | dissolved in xylene, and 0.7 mass% xylene solution was prepared. Next, the xylene solution of the polymer compound 1 and the xylene solution of the polymer compound 10 were mixed so that the mass ratio of the solid content of the polymer compound 1 and the polymer compound 10 was 80:20. An organic thin film having a thickness of 20 nm was formed by spin coating using this xylene solution. This was heated on a hot plate at 180 ° C. for 60 minutes in a nitrogen gas atmosphere.

Next, the polymer compound L2 and the phosphorescent material 1 were each dissolved in xylene to prepare a 2.0 mass% xylene solution. Next, the xylene solution of the polymer compound L2 and the xylene solution of the phosphorescent material 1 were mixed so that the mass ratio of the solid content of the polymer compound L2 and the phosphorescent material 1 was 70:30. An organic thin film having a thickness of 80 nm is formed by spin coating using this xylene solution. After drying in a nitrogen gas atmosphere at 150 ° C. for 10 minutes, sodium fluoride is about 7 nm as a cathode, and then aluminum is about 120 nm was vapor-deposited and the light emitting element D12 was produced. The metal deposition was started after the degree of vacuum reached 1 × 10 ⁻⁴ Pa or less.

When voltage was applied to the obtained light emitting device D12, EL light emission having a peak at 520 nm was obtained from this device, and after setting the current value so that the initial luminance was 24000 cd / m ² , the device was driven with a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 119.1 hours. The results are shown in Table 2.

<Example D13: Production and evaluation of light-emitting element D13>
A light emitting device D13 was produced in the same manner as in Example D12 except that the polymer compound 3 was used instead of the polymer compound 1 in Example D12.

When voltage was applied to the obtained light emitting device D13, EL light emission having a peak at 520 nm was obtained from this device, and after setting the current value so that the initial luminance was 24000 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 86.5 hours. The results are shown in Table 2.

<Example D14: Production and evaluation of light-emitting element D14>
Instead of the xylene solution in which the polymer compound 1 and the polymer compound 10 were mixed in Example D12, a xylene solution adjusted so that the mass ratio of the solid content of the polymer compound 1 and the polymer compound 8 was 20:80. A light emitting device D14 was produced in the same manner as in Example D12 except that was used.

When voltage was applied to the obtained light emitting device D14, EL light emission having a peak at 520 nm was obtained from this device, and after setting the current value so that the initial luminance was 24000 cd / m ² , it was driven with a constant current, The change in luminance with time was measured. As a result, the time until the luminance reached 60% of the initial luminance (LT60) was 93.0 hours. The results are shown in Table 2.

<Example D15: Production and evaluation of light-emitting element D15>
Instead of the xylene solution in which the polymer compound 1 and the polymer compound 10 were mixed in Example D12, the xylene solution adjusted so that the mass ratio of the solid content of the polymer compound 1 and the polymer compound 9 was 20:80. A light emitting device D15 was produced in the same manner as in Example D12 except that was used.

When voltage was applied to the obtained light emitting device D15, EL light emission having a peak at 520 nm was obtained from this device, and after setting the current value so that the initial luminance was 24000 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance reached 60% of the initial luminance (LT60) was 93.0 hours. The results are shown in Table 2.

<Example D16: Production and evaluation of light-emitting element D16>
Instead of the xylene solution in which the polymer compound 1 and the polymer compound 10 were mixed in Example D12, a xylene solution adjusted so that the mass ratio of the solid content of the polymer compound 1 and fullerene C60 was 97: 3 was used. A light emitting device D16 was produced in the same manner as in Example D12, except for that.

When voltage was applied to the resulting light emitting device D16, EL light emission having a peak at 520 nm was obtained from this device, and after setting the current value so that the initial luminance was 24000 cd / m ² , the device was driven with a constant current, The change in luminance with time was measured. As a result, the time required for the luminance to reach 60% of the initial luminance (LT60) was 123.1 hours. The results are shown in Table 2.

<Example D17: Production and evaluation of light-emitting element D17>
In the same manner as in Example D12 except that a xylene solution containing only the polymer compound 8 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D12, a light emitting device D17 was produced.

When voltage was applied to the obtained light emitting device D17, EL light emission having a peak at 520 nm was obtained from this device, and after setting the current value so that the initial luminance was 24000 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time required for the luminance to reach 60% of the initial luminance (LT60) was 104.6 hours. The results are shown in Table 2.

<Example D18: Production and evaluation of light-emitting element D18>
In the same manner as in Example D12 except that a xylene solution containing only the polymer compound 9 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D12, a light emitting device D18 was produced.

When voltage was applied to the obtained light emitting device D18, EL light emission having a peak at 520 nm was obtained from this device, and after setting the current value so that the initial luminance was 24000 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance reached 60% of the initial luminance (LT60) was 92.5 hours. The results are shown in Table 2.

<Comparative Example CD8: Production and Evaluation of Light-Emitting Element CD8>
In the same manner as in Example D12 except that a xylene solution containing only the polymer compound 1 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D12, a light emitting device CD8 was produced.

When voltage was applied to the resulting light emitting device CD8, EL light emission having a peak at 520 nm was obtained from this device, and after setting the current value so that the initial luminance was 24000 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance reached 60% of the initial luminance (LT60) was 58.9 hours. The results are shown in Table 2.

<Comparative Example CD9: Production and Evaluation of Light-Emitting Element CD9>
In the same manner as in Example D12 except that a xylene solution containing only the polymer compound 2 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D12, a light emitting device CD9 was produced.

When voltage was applied to the resultant light emitting device CD9, EL light emission having a peak at 520 nm was obtained from this device, and after setting the current value so that the initial luminance was 24000 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time required for the luminance to reach 60% of the initial luminance (LT60) was 65.5 hours. The results are shown in Table 2.

<Comparative Example CD10: Production and Evaluation of Light-Emitting Element CD10>
In the same manner as in Example D12 except that a xylene solution containing only the polymer compound 3 was used instead of the xylene solution obtained by mixing the polymer compound 1 and the polymer compound 10 in Example D12, a light emitting device CD10 was produced.

When voltage was applied to the resulting light emitting device CD10, EL light emission having a peak at 520 nm was obtained from this device, and after setting the current value so that the initial luminance was 24000 cd / m ² , it was driven at a constant current, The change in luminance with time was measured. As a result, the time until the luminance became 60% of the initial luminance (LT60) was 23.0 hours. The results are shown in Table 2.

  From a comparison between Example D16 and Comparative Example CD8, it can be seen that the first composition containing the polymer compound (A) and the compound (B) of the present invention is useful for the production of a light emitting device having excellent luminance life. .

  Further, from the comparison between Example D12 and Comparative Example CD8, the comparison between Example D13 and Comparative Example CD10, the comparison between Example D14 and Comparative Example CD8, and the comparison between Example D15 and Comparative Example CD8, It turns out that the 2nd composition containing a high molecular compound (A) and a high molecular compound (C) is useful for manufacture of the light emitting element which is excellent in a luminance lifetime.

Furthermore, the comparison between Example D17 and Comparative Example CD9 and the comparison between Example D18 and Comparative Example CD9 show that the polymer compound of the present invention is useful for the production of a light-emitting device having excellent luminance life.

Claims (21)

A polymer compound (A) comprising a structural unit (1) represented by formula (1) and a structural unit (2) represented by formula (2);
Structural unit containing a fullerene or a fullerene derivative, and, including the formula (4) represented by stilbene or structural unit is at least one structure unit selected from the group consisting of structural units containing a stilbene derivative (c-1) See
The structural unit containing fullerene or a fullerene derivative is a structural unit represented by the formula (5-1),
The structural unit containing the stilbene or stilbene derivative represented by the formula (4) includes a structural unit represented by the formula (7a), a structural unit represented by the formula (7b), and a structural unit represented by the formula (7c). One or more structural units selected from the group consisting of units;
A polymer compound (C);
A composition comprising

[Where:
Ar ¹ and Ar ³ are each independently an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent.
Ar ² and Ar ⁴ may each independently have an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a substituent. A divalent group in which two or more identical or different groups selected from the group consisting of an arylene group and a divalent heterocyclic group which may have a substituent are linked.
R ¹ , R ² and R ³ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is a monovalent heterocyclic group.
Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² and R ³ may each be directly bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded. It may be bonded via —O—, —S—, —C (═O) —, —N (R ^a1 ) — or —C (R ^a1 ) ₂ —. R ^a1 has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a halogen atom or a substituent. And a monovalent heterocyclic group which may be used. When a plurality of R ^a1 are present, each R ^a1 may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atoms to which each is bonded.
x and y are each independently 0 or 1. ]

[Where:
Ar ⁵ is R ⁴ other than a bivalent which may have an optionally substituted arylene group or R ⁴ substituent other than a heterocyclic group.
R ⁴ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and an aryl which may have a substituent. Group, aryloxy group which may have a substituent, arylthio group which may have a substituent, arylalkyl group which may have a substituent, aryl which may have a substituent Alkoxy group, optionally substituted alkenyl group, optionally substituted alkynyl group, optionally substituted amino group, optionally substituted silyl group A halogen atom, an optionally substituted acyl group, an optionally substituted acyloxy group, an optionally substituted oxycarbonyl group, and optionally having a substituent. Even if it has a monovalent heterocyclic group or substituent A heterocyclic oxy group which may have a substituent, a heterocyclic thio group which may have a substituent, an imine residue which may have a substituent, an amide compound residue which may have a substituent, a substituent An acid imide residue which may have, a carboxyl group which may have a substituent, a hydroxyl group, a nitro group or a cyano group. When a plurality of R ⁴ are present, each R ⁴ may be the same as or different from each other. R ⁴ is a group that is directly bonded to a carbon atom adjacent to a carbon atom that forms a bond with another structural unit among the carbon atoms that constitute Ar ⁵ .
a is an integer of 1 or more. ]

[Where:
R ⁿ has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is also a monovalent heterocyclic group. Each R ⁿ may be the same as or different from each other.
Ar ⁶ and Ar ⁷ are each independently an aryl group which may have a substituent or a monovalent heterocyclic group which may have a substituent. Ar ⁶ and Ar ⁷ may be directly bonded to adjacent R ⁿ to form a ring structure together with the carbon atom to which each is bonded. ]

[Where:
Ar ⁸ has one substituent and an arylene group which may have other substituents, or one substituent and other substituents. It may be a divalent heterocyclic group.
Ar ¹⁴ is an arylidine group which may have a substituent or a trivalent heterocyclic group which may have a substituent.
R ⁷ represents a single bond, an optionally substituted alkylene group having 1 to 20 carbon atoms, an optionally substituted arylene group having 6 to 20 carbon atoms, or a combination thereof. Divalent group.
R ⁵ and R ⁶ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, or an optionally substituted alkoxy group having 1 to 20 carbon atoms. It is a group.
Ring F is fullerene.
q is an integer of 1-4. p is 0 or 1;
When a plurality of R ⁷ are present, each R ⁷ may be the same as or different from each other. When a plurality of Ar ¹⁴ are present, each Ar ¹⁴ may be the same as or different from each other. When a plurality of R ⁵ are present, each R ⁵ may be the same as or different from each other. When a plurality of R ⁶ are present, each R ⁶ may be the same as or different from each other. When a plurality of p are present, each p may be the same as or different from each other. When a plurality of rings F are present, each ring F may be the same as or different from each other. When p is 0, the carbon atom substituted with R ⁵ and the carbon atom substituted with R ⁶ are not directly bonded. ]

[Where:
R ⁿ and Ar ⁷ are as defined above.
Ar ⁹ has one substituent and an arylene group which may have other substituents or one substituent and may have other substituents It is a good divalent heterocyclic group. ]

[Where:
R ⁿ has the same meaning as described above.
Ar ^{9 ′} is an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. Each Ar ^{9 ′} may be the same as or different from each other. Ar ^{9 ′} may be directly bonded to R ⁿ to form a ring structure together with the carbon atom to which each is bonded. ]

[Where:
R ⁿ , Ar ⁷ and Ar ^{9 ′} are as defined above.
R ^{n ′} is an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent.
Ar ^{9 ′} may be directly bonded to R ^{n ′} to form a ring structure together with the carbon atom to which each is bonded. ] The content (total content) of the structural unit (c-1) contained in the polymer compound (C) is 0 with respect to all the structural units contained in the polymer compound (A) and the polymer compound (C). .001～50 a mole percent composition of claim 1. The composition unit according to claim 1 or 2 , wherein the structural unit (1) represented by the formula (1) is a structural unit represented by the formula (1a).

[Where:
R ^9a , R ^9b and R ^9c each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, Aryl group optionally having substituent, aryloxy group optionally having substituent, arylthio group optionally having substituent, alkenyl group optionally having substituent, substituted An alkynyl group which may have a group, an amino group which may have a substituent, a silyl group which may have a substituent, a halogen atom, an acyl group which may have a substituent, An acyloxy group which may have a substituent, an oxycarbonyl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, and a substituent. A heterocyclic oxy group, an optionally substituted heterocyclic thio group, An imine residue optionally having a substituent, an amide compound residue optionally having a substituent, an acid imide residue optionally having a substituent, and optionally having a substituent A carboxyl group, a hydroxyl group, a nitro group or a cyano group.
When a plurality of R ^9a are present, each R ^9a may be the same as or different from each other. When a plurality of R ^9b are present, each R ^9b may be the same as or different from each other. When a plurality of R ^9c are present, each R ^9c may be the same as or different from each other.
^{Ar 1, Ar 2, Ar 3} , Ar 4, x and y, and ^{Ar 1, Ar 2, Ar 3} , Ar 4, x and y of formula (1), which is the same meaning.
h, i, and j are each independently an integer of 0 to 5. ] Ar ¹ and Ar ³ are an optionally substituted phenylene group,
Ar ² or Ar ⁴ is selected from the group consisting of a phenylene group that may have a substituent, a biphenylylene group that may have a substituent, and a fluorenediyl group that may have a substituent. The composition according to any one of claims 1 to 3 , which is one kind of group. The composition according to any one of claims 1 to 4 , wherein Ar ⁵ is a phenylene group or a fluorenediyl group. The polymer compound (A) is a composition according to any one of claims 1 to 5 , further comprising a structural unit having a crosslinking group. The polymer compound (C) is a composition according to any one of claims 1 to 6 , further comprising a structural unit having a crosslinking group. The composition according to claim 6 or 7 , wherein the crosslinking group is a group represented by the formula (Q-1).

[In the formula, benzocyclobutene may have a substituent. ] A structural unit (1) represented by the formula (1);
A structural unit (2) represented by the formula (2);
A structural unit that is one or more structural units selected from the group consisting of a structural unit containing azulene or an azulene derivative represented by formula (3) and a structural unit containing a stilbene or stilbene derivative represented by formula (4) ( c-1) and a polymer compound comprising a structural unit having a crosslinking group .

[Where:
Ar ¹ and Ar ³ are each independently an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent.
Ar ² and Ar ⁴ may each independently have an arylene group which may have a substituent, a divalent heterocyclic group which may have a substituent, or a substituent. A divalent group in which two or more identical or different groups selected from the group consisting of an arylene group and a divalent heterocyclic group which may have a substituent are linked.
R ¹ , R ² and R ³ may each independently have a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is a monovalent heterocyclic group.
Ar ¹ , Ar ² , Ar ³ , Ar ⁴ , R ¹ , R ² and R ³ may each be directly bonded to a group other than the group bonded to the nitrogen atom to which the group is bonded. It may be bonded via —O—, —S—, —C (═O) —, —N (R ^a1 ) — or —C (R ^a1 ) ₂ —. R ^a1 has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, a halogen atom or a substituent. And a monovalent heterocyclic group which may be used. When a plurality of R ^a1 are present, each R ^a1 may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atoms to which each is bonded.
x and y are each independently 0 or 1. ]

[Where:
Ar ⁵ is R ⁴ other than a bivalent which may have an optionally substituted arylene group or R ⁴ substituent other than a heterocyclic group.
R ⁴ represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, and an aryl which may have a substituent. Group, aryloxy group which may have a substituent, arylthio group which may have a substituent, arylalkyl group which may have a substituent, aryl which may have a substituent Alkoxy group, optionally substituted alkenyl group, optionally substituted alkynyl group, optionally substituted amino group, optionally substituted silyl group A halogen atom, an optionally substituted acyl group, an optionally substituted acyloxy group, an optionally substituted oxycarbonyl group, and optionally having a substituent. Even if it has a monovalent heterocyclic group or substituent A heterocyclic oxy group which may have a substituent, a heterocyclic thio group which may have a substituent, an imine residue which may have a substituent, an amide compound residue which may have a substituent, a substituent An acid imide residue which may have, a carboxyl group which may have a substituent, a hydroxyl group, a nitro group or a cyano group. When a plurality of R ⁴ are present, each R ⁴ may be the same as or different from each other. R ⁴ is a group that is directly bonded to a carbon atom adjacent to a carbon atom that forms a bond with another structural unit among the carbon atoms that constitute Ar ⁵ .
a is an integer of 1 or more. ]

[Where:
R ^x has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alkynyl group that may have a substituent, an amino group that may have a substituent, a silyl group that may have a substituent, a halogen atom, and a substituent. An acyl group which may be substituted, a monovalent heterocyclic group which may have a substituent, a carboxyl group which may have a substituent, a nitro group or a cyano group. Each R ^x may be the same as or different from each other, and may be bonded to each other to form a ring structure together with the carbon atoms to which they are bonded. ]

[Where:
R ⁿ has a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent. It is also a monovalent heterocyclic group. Each R ⁿ may be the same as or different from each other.
Ar ⁶ and Ar ⁷ are each independently an aryl group which may have a substituent or a monovalent heterocyclic group which may have a substituent. Ar ⁶ and Ar ⁷ may be directly bonded to adjacent R ⁿ to form a ring structure together with the carbon atom to which each is bonded. ] The polymer compound according to claim 9 , wherein the content (total content) of the structural unit (c-1) is 0.001 to 50 mol% with respect to all structural units contained in the polymer compound. . The polymer compound according to claim 9 or 10 , wherein the structural unit containing azulene or an azulene derivative represented by formula (3) is a structural unit represented by formula (12-1).

[Wherein, R ^x has the same meaning as described above. ] The structural unit containing a stilbene or stilbene derivative represented by the formula (4) is a structural unit represented by the formula (7a), a structural unit represented by the formula (7b), and a structural unit represented by the formula (7c). The polymer compound according to any one of claims 9 to 11 , which is one or more structural units selected from the group consisting of:

[Where:
R ⁿ and Ar ⁷ are as defined above.
Ar ⁹ has one substituent and an arylene group which may have other substituents, or one substituent and other substituents. It may be a divalent heterocyclic group. ]

[Where:
R ⁿ has the same meaning as described above.
Ar ^{9 ′} is an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent. Each Ar ^{9 ′} may be the same as or different from each other. Ar ^{9 ′} may be directly bonded to R ⁿ to form a ring structure together with the carbon atom to which each is bonded. ]

[Where:
R ⁿ , Ar ⁷ and Ar ^{9 ′} are as defined above.
R ^{n ′} is an arylene group which may have a substituent or a divalent heterocyclic group which may have a substituent.
Ar ^{9 ′} may be directly bonded to R ^{n ′} to form a ring structure together with the carbon atom to which each is bonded. ] The high molecular compound according to any one of claims 9 to 12 , wherein the structural unit (1) represented by the formula (1) is a structural unit represented by the formula (1a).

[Where:
R ^9a , R ^9b and R ^9c each independently represents an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an alkylthio group which may have a substituent, Aryl group optionally having substituent, aryloxy group optionally having substituent, arylthio group optionally having substituent, alkenyl group optionally having substituent, substituted An alkynyl group which may have a group, an amino group which may have a substituent, a silyl group which may have a substituent, a halogen atom, an acyl group which may have a substituent, An acyloxy group which may have a substituent, an oxycarbonyl group which may have a substituent, a monovalent heterocyclic group which may have a substituent, and a substituent. A heterocyclic oxy group, an optionally substituted heterocyclic thio group, An imine residue optionally having a substituent, an amide compound residue optionally having a substituent, an acid imide residue optionally having a substituent, and optionally having a substituent A carboxyl group, a hydroxyl group, a nitro group or a cyano group.
When a plurality of R ^9a are present, each R ^9a may be the same as or different from each other. When a plurality of R ^9b are present, each R ^9b may be the same as or different from each other. When a plurality of R ^9c are present, each R ^9c may be the same as or different from each other.
^{Ar 1, Ar 2, Ar 3} , Ar 4, x and y, and ^{Ar 1, Ar 2, Ar 3} , Ar 4, x and y of formula (1), which is the same meaning.
h, i, and j are each independently an integer of 0 to 5. ] Ar ¹ and Ar ³ are an optionally substituted phenylene group,
Ar ² or Ar ⁴ is selected from the group consisting of a phenylene group that may have a substituent, a biphenylylene group that may have a substituent, and a fluorenediyl group that may have a substituent. The polymer compound according to any one of claims 9 to 13 , which is one kind of group. Ar ⁵ is a phenylene group or a fluorenediyl group, the polymer compound according to any one of claims 9-14. The polymer compound according to any one of claims 9 to 15 , wherein the crosslinking group is a group represented by the formula (Q-1).

[In the formula, benzocyclobutene may have a substituent. ] The liquid composition containing the composition as described in any one of Claims 1-8 , and a solvent. To any one of claims 1-8 comprising the composition described organic thin film. The insolubilized organic thin film containing the crosslinked body of the composition as described in any one of Claims 1-8, or the crosslinked body of the high molecular compound as described in any one of Claims 9-16 . A light emitting device comprising the organic thin film according to claim 18 or the insolubilized organic thin film according to claim 19 . The light emitting device according to claim 20 , wherein the organic thin film according to claim 18 or the insolubilized organic thin film according to claim 19 is a hole transport layer.