JP2012007165A - Polymer thin film device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel polymer compound useful as a material for a thin film for a polymer thin film device such as an organic thin film transistor and an organic solar battery.SOLUTION: The polymer compound contains a repeating unit represented by formula (1) and a repeating unit represented by formula (2), and has a number-average molecular weight in terms of polystyrene of 10to 10. In the formulas, Arand Areach independently denote a trivalent aromatic hydrocarbon or a trivalent heterocyclic group; Xand Xeach independently denote O, S, C(=O), S(=O), SOor the like, and Xand Xare not identical; Y denotes O or S; Rdenotes halogen, alkyl, alkyloxy or the like; and m denotes 0 or 1; n denotes an integer of 1 to 6; o denotes an integer of 1 to 6; and p denotes an integer of 0 to 2.

Description

  The present invention relates to a polymer compound, a polymer thin film containing the polymer compound, and a polymer thin film element using the polymer thin film.

Thin films containing an organic material having an electron transport property or a hole transport property are expected to be applied to thin film elements such as organic thin film transistors and organic solar cells, and various studies have been made.
As a material used for such a thin film, a polyphenylene vinylene derivative, a polyfluorene derivative, a polyphenylene derivative, a polythiophene derivative, a polythienylene vinylene derivative, or the like, which is a high molecular compound having an electron transporting or hole transporting molecular structure in the main chain Is known (Non-Patent Documents 1 to 4).

Appl. Phys. Lett. Vol. 49 (1986) p. 1210 Appl. Phys. Lett. Vol. 63 (1993) p. 1372 Appl. Phys. Lett. Vol. 77 (2000) p. 406 “Semiconductor Polymers”, Eds. G. Hadziioannou and P.M. F. van Hutten (2000) Wiley-VCH.

  An object of the present invention is to provide a novel polymer compound useful as a material for a thin film for a polymer thin film element such as an organic thin film transistor or an organic solar battery.

〔式中、Ａｒ¹およびＡｒ²は、それぞれ独立に、３価の芳香族炭化水素基または３価の複素環基を表し、Ｘ¹およびＸ²は、それぞれ独立に、Ｏ，Ｓ，Ｃ（＝Ｏ），Ｓ（＝Ｏ），ＳＯ₂，Ｃ（Ｒ¹）（Ｒ²），Ｓｉ（Ｒ³）（Ｒ⁴），Ｎ（Ｒ⁵），Ｂ（Ｒ⁶），Ｐ（Ｒ⁷）またはＰ（＝Ｏ）（Ｒ⁸）を表し、Ｒ¹〜Ｒ⁸はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、カルボキシル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アリールアルキルオキシカルボニル基、ヘテロアリールオキシカルボニル基またはシアノ基を表す。Ｃ（Ｒ¹）（Ｒ²）におけるＲ¹とＲ²、Ｓｉ（Ｒ³）（Ｒ⁴）におけるＲ³とＲ⁴は互いに結合して環を形成してもよい。ｍは０または１を表し、ｎは、１から６までの整数を表す。ただし、ｍ＝０の場合、Ｘ¹はＣ（Ｒ¹）（Ｒ²）を表さず、ｍ＝１の場合、Ｘ¹とＸ²は、同一ではない。また、Ｘ¹とＡｒ²は、Ａｒ¹の環を構成する炭素原子のうち隣り合う炭素原子（環の隣接位ということがある）にそれぞれ結合し、ｍ＝１の場合、Ｘ²とＡｒ¹はＡｒ²の環を構成する炭素原子のうち隣り合う炭素原子にそれぞれ結合し、ｍ＝０の場合、Ｘ¹とＡｒ¹はＡｒ²の環を構成する炭素原子のうち隣り合う炭素原子にそれぞれ結合している。〕
Ａｒ¹、Ａｒ²、Ｘ¹およびＸ²がそれぞれ複数個存在する場合、それらは同一であっても異なっていてもよい。

〔式中、ｏは、１から１０までの整数を表し、ｐは０から２までの整数を表し、
ＹはＯ，Ｓ，Ｃ（Ｒ¹⁰）（Ｒ¹¹），Ｓｉ（Ｒ¹²）（Ｒ¹³）またはＮ（Ｒ¹⁴）を表し、Ｒ¹⁰、Ｒ¹¹、Ｒ¹²、Ｒ¹³およびＲ¹⁴はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、カルボキシル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アリールアルキルオキシカルボニル基、ヘテロアリールオキシカルボニル基またはシアノ基を表す。Ｒ¹⁰とＲ¹¹、Ｒ¹²とＲ¹³は互いに結合して環を形成してもよい。Ｒ⁹は、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、カルボキシル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アリールアルキルオキシカルボニル基、ヘテロアリールオキシカルボニル基またはシアノ基を表す。Ｒ⁹が複数ある場合、それらは同一でも異なっていてもよく、また、Ｒ⁹同士で互いに結合して環を形成していてもよい。〕 That is, the present invention provides a polymer compound comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the formula (2) and having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ^8. It is.

[Wherein, Ar ¹ and Ar ² each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and X ¹ and X ² each independently represent O, S, C ( = O), S (= O), SO ₂ , C (R ¹ ) (R ² ), Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) Or P (═O) (R ⁸ ), wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, aryl Alkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group Group, monovalent heterocyclic group, hetero An aryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group or cyano group is represented. R ¹ and R ² in C (R ¹ ) (R ² ) and R ³ and R ⁴ in Si (R ³ ) (R ⁴ ) may be bonded to each other to form a ring. m represents 0 or 1, and n represents an integer of 1 to 6. However, when m = 0, X ¹ does not represent C (R ¹ ) (R ² ), and when m = 1, X ¹ and X ² are not the same. X ¹ and Ar ² are bonded to adjacent carbon atoms (sometimes referred to as adjacent positions of the ring) among the carbon atoms constituting the ring of Ar ¹ , and when m = 1, X ² and Ar ¹ Are bonded to adjacent carbon atoms constituting the ring of Ar ² , and when m = 0, X ¹ and Ar ¹ are each bonded to adjacent carbon atoms of the ring constituting Ar ^2. Are connected. ]
When a plurality of Ar ¹ , Ar ² , X ¹ and X ² are present, they may be the same or different.

[Wherein, o represents an integer from 1 to 10, p represents an integer from 0 to 2,
Y represents O, S, C (R ¹⁰ ) (R ¹¹ ), Si (R ¹² ) (R ¹³ ) or N (R ¹⁴ ), and R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are respectively Independently, hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group , Acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, aryl Alkenyl, arylalkynyl, carboxyl, alkyloxycarbonyl, aryloxycarbonyl, arylalkenyl Oxycarbonyl group, a heteroaryloxy group or a cyano group. R ¹⁰ and R ¹¹ , R ¹² and R ¹³ may combine with each other to form a ring. R ⁹ is a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid Imido group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group Represents an arylalkynyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group or a cyano group. If R ⁹ is more, they may be the same or different, and may form a ring together with R ⁹ together. ]

〔式中、Ａｒ³は２価の芳香族炭化水素基、２価の複素環基または−ＣＲ¹⁵＝ＣＲ¹⁶−を表す。Ｒ¹⁵およびＲ¹⁶はそれぞれ独立に、水素原子、ハロゲン原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、アシル基、アシルオキシ基、アミド基、酸イミド基、イミン残基、アミノ基、置換アミノ基、置換シリル基、置換シリルオキシ基、置換シリルチオ基、置換シリルアミノ基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基、アリールアルキニル基、カルボキシル基、アルキルオキシカルボニル基、アリールオキシカルボニル基、アリールアルキルオキシカルボニル基、ヘテロアリールオキシカルボニル基またはシアノ基を表す。ｑは、１から６までの整数を表す。〕 The present invention further includes a repeating unit represented by the above formula (1), a repeating unit represented by the above formula (2), and a repeating unit represented by the following formula (3), and has a number average molecular weight in terms of polystyrene of 10 ^3. The high molecular compound which is -10 < ⁸ > is provided.

[In the formula, Ar ³ represents a divalent aromatic hydrocarbon group, a divalent heterocyclic group or —CR ¹⁵ ═CR ¹⁶ —. R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl Group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group Represents a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group or a cyano group. q represents an integer of 1 to 6. ]

  The polymer compound of the present invention is useful as a thin film material for a polymer thin film element.

1 is a schematic cross-sectional view of a forward staggered organic thin film transistor according to the present invention. 1 is a schematic cross-sectional view of a forward staggered organic thin film transistor according to the present invention. 1 is a schematic cross-sectional view of an inverted staggered organic thin film transistor according to the present invention. 1 is a schematic cross-sectional view of an inverted staggered oblique organic thin film transistor according to the present invention. 1 is a schematic cross-sectional view of a solar cell according to the present invention. 1 is a schematic cross-sectional view of a multilayer photosensor according to the present invention. 1 is a schematic cross-sectional view of a multilayer photosensor according to the present invention. 1 is a schematic sectional view of a single-layer photosensor according to the present invention. 1 is a schematic sectional view of a single layer type electrophotographic photosensitive member according to the present invention. 1 is a schematic cross-sectional view of a multilayer electrophotographic photoreceptor according to the present invention. 1 is a schematic cross-sectional view of a multilayer electrophotographic photoreceptor according to the present invention. 1 is a schematic cross-sectional view of a spatial light modulation element according to the present invention.

The polymer compound of the present invention includes a repeating unit represented by the above formula (1) and a repeating unit represented by the above formula (2). Furthermore, the polymer compound of the present invention includes a repeating unit represented by the above formula (1), a repeating unit represented by the above formula (2), and a repeating unit represented by the above formula (3).

In the above formula (1), Ar ¹ and Ar ² each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group.

  Here, the trivalent aromatic hydrocarbon group means a remaining atomic group obtained by removing three hydrogen atoms from a benzene ring or condensed ring, and usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms. Examples are groups. Among these, the remaining atomic group obtained by removing three hydrogen atoms from the benzene ring is most preferable. In addition, you may have a substituent on the aromatic hydrocarbon group. The carbon number of the trivalent aromatic hydrocarbon group does not include the carbon number of the substituent.

  Moreover, a trivalent heterocyclic group means the remaining atomic groups remove | excluding three hydrogen atoms from the heterocyclic compound, and carbon number is 4-60 normally, Preferably it is 4-20. Note that the heterocyclic group may have a substituent, and the carbon number of the heterocyclic group does not include the carbon number of the substituent.

  Here, the heterocyclic compound is an organic compound having a cyclic structure, and the elements constituting the ring include not only carbon atoms but also heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and silicon in the ring. Say things. Of the trivalent heterocyclic groups, trivalent aromatic heterocyclic groups are preferred.

  Examples of the trivalent heterocyclic group include the following.

In the above formula, each R ′ is independently a hydrogen atom, halogen atom, alkyl group, alkoxy group, alkylthio group, alkylamino group, aryl group, aryloxy group, arylthio group, arylamino group, arylalkyl group, arylalkoxy group. Represents an arylalkylthio group, an arylalkylamino group, an acyloxy group, an amide group, an arylalkenyl group, an arylalkynyl group, a monovalent heterocyclic group or a cyano group.
R "represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, or a monovalent heterocyclic group, heteroaryloxy group, or heteroarylthio group.

  Examples of the substituent that may be present on the trivalent aromatic hydrocarbon group or the trivalent heterocyclic group include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group. Group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group Substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, hetero Aryloxycarbonyl group or Roh groups. When there are a plurality of substituents, the substituents may form a ring.

In the above formula (1), X ¹ and X ² are each independently O, S, C (═O), S (═O), SO ₂ , C (R ¹ ) (R ² ), Si (R ³ ) represents (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (═O) (R ⁸ ). However, X ¹ and X ² are not the same.

In formula (1), R ^{1 to} R ⁸ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group , Arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic ring Represents a group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group or cyano group.

R ¹ and R ² in C (R ¹ ) (R ² ) and R ³ and R ⁴ in Si (R ³ ) (R ⁴ ) may be bonded to each other to form a ring. In this case, specific examples of the ring structure moiety are as follows.

When m = 0, X ¹ does not represent C (R ¹ ) (R ² ).
In the above formula (1), n represents an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably an integer of 1 to 2.
In the above formula (1), m represents 0 or 1, and the organic thin film transistor material and the like are preferably m = 1, and particularly preferably n = 1 and m = 1.

Among them, X ² in the formula (1) is C (R ¹ ) (R ² ), Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (O) (R ⁸ ) is preferred, and C (R ¹ ) (R ² ) is more preferred.
(Wherein R ^{1 to} R ⁸ each independently represent the same meaning as described above.)

X ¹ in the formula (1) is O, S, C (═O), S (O), SO ₂ , Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ). , P (R ⁷ ) or P (═O) (R ⁸ ), more preferably O, S, C (═O), S (O) or SO ₂ , It is particularly preferred.

When m = 1, examples of —X ¹ —X ² — include groups represented by the following (4), (5), and (6).

（４）

(4)

（５）

(5)

（６）

(6)

Of these, groups of the formulas (5) and (6) are preferable from the viewpoint of the stability of the compound, and a group of the formula (6) is more preferable.

The polymer compound of the present invention includes a repeating unit of the formula (2) in addition to the repeating unit of the above formula (1).

In the formula (2), o represents an integer of 1 to 10, more preferably an integer of 1 to 6, and still more preferably an integer of 1 to 5.

In the above formula (2), p represents an integer from 0 to 2.
When o is 2 or less, p = 0 or 1 is preferable, and p = 0 is more preferable. When o is 3 or more, it is preferable that one or more of the plurality of 5-membered rings is p = 1 or 2 from the viewpoint of solubility.

In the above formula (2), Y represents O, S, C (R ¹⁰ ) (R ¹¹ ), Si (R ¹² ) (R ¹³ ), N (R ¹⁴ ), and O and S are preferable, more preferably S.
R ^{10 to} R ¹⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group , Acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryl An oxy group, a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group, or a cyano group is represented.

In the above formula (2), R ⁹ is a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, Acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, hetero An arylthio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group or a cyano group, preferably a halogen atom or an alkyl group , Archi Oxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, arylalkyloxy group, an arylalkylthio group, more preferably an alkyl group, an alkyloxy group, if R ⁹ is more These may be the same or different, and R ⁹ may be bonded to each other to form a ring.

When R ⁹ is bonded to each other to form a ring, specific examples of the ring structure portion include the following.

The polymer compound of the present invention may contain a repeating unit of the formula (3) in addition to the repeating unit of the above formula (1) and the repeating unit of the above formula (2).

In the formula (3), Ar ³ represents a divalent aromatic hydrocarbon group, a divalent heterocyclic group or —CR ¹⁵ ═CR ¹⁶ —, preferably a divalent heterocyclic group, —CR ¹⁵ ═CR ¹⁶ -, more preferably -CR ¹⁵ = CR ¹⁶ - it is.

Here, the divalent aromatic hydrocarbon group means a remaining atomic group obtained by removing two hydrogen atoms from a benzene ring or condensed ring, and usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms. Examples are groups in which one hydrogen atom is added to any of the three trivalent aromatic hydrocarbon groups except for three hydrogen atoms. Among these, the remaining atomic group obtained by removing two hydrogen atoms from the benzene ring is most preferable. In addition, you may have a substituent on the aromatic hydrocarbon group. The carbon number of the divalent aromatic hydrocarbon group does not include the carbon number of the substituent.

  Moreover, a bivalent heterocyclic group means the remaining atomic groups remove | excluding two hydrogen atoms from the heterocyclic compound, and carbon number is 4-60 normally, Preferably it is 4-20. Examples of the divalent heterocyclic group include groups in which one hydrogen atom is added to any of the trivalent heterocyclic groups exemplified above except for three hydrogen atoms. Note that the heterocyclic group may have a substituent, and the carbon number of the heterocyclic group does not include the carbon number of the substituent.

In the above formula (3), R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy Group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent complex Represents a cyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group or cyano group. .

In Formula (3), q represents an integer of 1 to 6, more preferably an integer of 1 to 3, and still more preferably an integer of 1 to 2.

Among the polymer compounds of the present invention, those having a structure (7) in which the formula (1) and the formula (2) are combined are preferable from the viewpoint of enhancing the electron transport property or the hole transport property.

ここで、Ｙ'、Ｒ^9'、ｏ'、ｐ'は上記Ｙ、Ｒ⁹、ｏ、ｐと同じ意味を表し、Ｙ、Ｒ⁹、ｏ、ｐと同一でも異なっていてもよい。 When the polymer compound of the present invention contains a repeating unit of the above formula (3) in addition to the repeating unit of the above formula (1) and the repeating unit of the above formula (2), the repeating of the formula (2) A plurality of units may be included. When a plurality of repeating units of the formula (2) are included, they may be the same or different. From the viewpoint of enhancing electron transportability or hole transportability, those having a structure (8) in which the formula (1), the formula (2) and the formula (3) are combined are preferable.

^{Here, Y ', R 9',} o ', p' are the Y, R ^9, o, represents the same meaning as ^{p, Y, R 9, o} , may be the same or different and p.

  Examples of the structure represented by the above formula (7) include, for example, the structures represented by the following formulas (9) to (14), where n = 1; o = 2, 3 or 5; Examples of the structure further include a substituent on the aromatic hydrocarbon or heterocyclic group in these structures. Further, as an example of the structure represented by the above formula (8), for example, if n = 1; o = 1; o ′ = 1; q = 1; Y = S; Y ′ = S, the following formula ( Examples are the structures represented by 15) to (17) and the structure further having a substituent on the aromatic hydrocarbon group or heterocyclic group in these structures.

（９）

(9)

（１０）

(10)

（１１）

(11)

（1２）

(12)

（1３）

(13)

（1４）

(14)

（１５）

(15)

（１６）

(16)

（1７）

(17)

(Wherein, R ¹ ~R ^9, R ¹⁵ and R ¹⁶ are the same meanings as .R ^{1 '~R 4'} are as defined above R ¹ ~R ^4.)

  Of these, groups represented by formula (9), formula (14), formula (15), and formula (17), and groups further having substituents on these aromatic hydrocarbon groups or heterocyclic rings are preferred, A group represented by the formula (9) or the formula (15) and a group further having a substituent on the aromatic hydrocarbon group or the heterocyclic ring are more preferable. Examples of the substituent include a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, Acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl Group, arylalkynyl, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group or cyano group, and the substituents may be bonded to each other to form a ring. Good.

  In the above formula (1), formula (2) or formula (3), examples of the halogen atom include fluorine, chlorine, bromine and iodine.

  The alkyl group may be linear, branched or cyclic, and may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, and a propyl group. I-propyl group, butyl group, i-butyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyl Examples include octyl group, lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, perfluorooctyl group and the like.

  The alkyloxy group may be linear, branched or cyclic, and may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methoxy group, an ethoxy group, and a propyl group. Oxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, pentyloxy group, hexyloxy group, cyclohexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, nonyloxy group Decyloxy group, 3,7-dimethyloctyloxy group, lauryloxy group, trifluoromethoxy group, pentafluoroethoxy group, perfluorobutoxy group, perfluorohexyl group, perfluorooctyl group, methoxymethyloxy group, 2-methoxy Examples include an ethyloxy group.

  The alkylthio group may be linear, branched or cyclic, and may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, and a propylthio group. I-propylthio group, butylthio group, i-butylthio group, t-butylthio group, pentylthio group, hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, nonylthio group, decylthio group, 3,7 -A dimethyloctylthio group, a laurylthio group, a trifluoromethylthio group, etc. are illustrated.

The aryl group may have a substituent and usually has about 3 to 60 carbon atoms. Specific examples thereof include a phenyl group, a C _{1 to} C ₁₂ alkoxyphenyl group (C _{1 to} C ₁₂ are C ₁ -C ₁₂ alkylphenyl group, 1-naphthyl group, 2-naphthyl group, pentafluorophenyl group, pyridyl group, pyridazinyl group, pyrimidyl. Group, pyrazyl group, triazyl group and the like are exemplified.

The aryloxy group may have a substituent on the aromatic ring and usually has about 3 to 60 carbon atoms. Specific examples thereof include a phenoxy group, a C _{1 to} C ₁₂ alkoxyphenoxy group, and a C _1. -C ₁₂ alkylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, pentafluorophenyloxy group, pyridyloxy group, pyridazinyloxy group, pyrimidyloxy group, pyrazyloxy group, triazyl group is exemplified The

Arylthio group may have a substituent on the aromatic ring, and the carbon number is usually about 3 to 60, and specific examples thereof include a phenylthio group, C ₁ -C ₁₂ alkoxyphenyl-thio group, C ₁ -C ₁₂ alkyl phenylthio group, 1-naphthylthio group, 2-naphthylthio group, pentafluorophenylthio group, pyridylthio group, pyridazinylthio group, pyrimidylthio group, pyrazylthio group, etc. Toriajiruchio groups.

The arylalkyl group may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkyl group, a C ₁ -C ₁₂ alkoxyphenyl- C ₁ -C ₁₂ alkyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl group, 1-naphthyl -C ₁ -C ₁₂ alkyl group, 2-naphthyl -C ₁ -C ₁₂ alkyl group exemplified Is done.

The arylalkyloxy group may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkoxy group and a C ₁ -C ₁₂ alkoxyphenyl. -C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxy groups, 1-naphthyl -C ₁ -C ₁₂ alkoxy groups, 2-naphthyl -C ₁ -C ₁₂ alkoxy group Illustrated.

The arylalkylthio group may have a substituent and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl-C ₁ -C ₁₂ alkylthio group, a C ₁ -C ₁₂ alkoxyphenyl- C ₁ -C ₁₂ alkylthio group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylthio group, 1-naphthyl -C ₁ -C ₁₂ alkylthio group, 2-naphthyl -C ₁ -C ₁₂ alkylthio group are exemplified Is done.

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

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

  The amide group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples thereof include formamide group, acetamide group, propioamide group, butyroamide group, benzamide group, trifluoroacetamide group, penta Examples include a fluorobenzamide group, a diformamide group, a diacetamide group, a dipropioamide group, a dibutyroamide group, a dibenzamide group, a ditrifluoroacetamide group, a dipentafluorobenzamide group, and the like.

The acid imide group includes a residue obtained by removing a hydrogen atom bonded to the nitrogen atom from an acid imide, and usually has about 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms. Specific examples include the following groups.

As the imine residue, an imine compound (refers to an organic compound having —N═C— in the molecule. For example, aldimine, ketimine, and hydrogen atoms on these N are substituted with alkyl groups or the like. And a residue obtained by removing one hydrogen atom from the compound, usually having about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include groups represented by the following structural formulas.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl The group or the monovalent heterocyclic group may have a substituent. The substituted amino group usually has about 1 to 40 carbon atoms, and specific examples thereof include methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropyl. Amino group, butylamino group, isobutylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3 , 7-dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenylamino group, dipheny Amino group, C ₁ -C ₁₂ alkoxyphenyl amino group, di (C ₁ -C ₁₂ alkoxyphenyl) amino group, di (C ₁ -C ₁₂ alkylphenyl) amino groups, 1-naphthylamino group, 2-naphthylamino group , pentafluorophenyl group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, Pirajiruamino group, triazyl amino group, phenyl -C ₁ -C ₁₂ alkylamino group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ ~ C ₁₂ alkylamino group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylamino group, di (C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkyl) amino group, di (C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkyl) amino groups, 1-naphthyl -C ₁ -C ₁₂ alkylamino group, 2-naphthyl -C ₁ -C ₁₂ alkylamino Etc. groups.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group or a monovalent heterocyclic group, and usually has 1 to 60 carbon atoms. About 3 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
Specifically, trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl group, dimethyl-i-propylsilyl group, diethyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethyl Silyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-ethylhexyl-dimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, lauryldimethylsilyl group, a phenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkylsilyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkylsilyl group, 1-naphthyl -C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl C ₁ -C ₁₂ alkylsilyl group, a phenyl -C ₁ -C ₁₂ alkyldimethylsilyl group, triphenylsilyl group, tri -p- Kishirirushiriru group, tribenzylsilyl group, diphenylmethylsilyl group, t- butyl diphenyl silyl group, Examples thereof include a dimethylphenylsilyl group.

Examples of the substituted silyloxy group include a silyloxy group (H ₃ SiO—) substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
The substituted silyloxy group usually has about 1 to 60 carbon atoms, preferably 3 to 30 carbon atoms. Specific examples thereof include trimethylsilyloxy group, triethylsilyloxy group, tri-n-propylsilyloxy group, tri- i-propylsilyloxy group, t-butylsilyldimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylylsilyloxy group, tribenzylsilyloxy group, diphenylmethylsilyloxy group, t-butyldiphenylsilyloxy group Group, dimethylphenylsilyloxy group and the like are exemplified.

Examples of the substituted silylthio group include a silylthio group (H ₃ SiS—) substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.
The substituted silylthio group usually has about 1 to 60 carbon atoms, preferably 3 to 30 carbon atoms. Specific examples thereof include trimethylsilylthio group, triethylsilylthio group, tri-n-propylsilylthio group, tri- i-propylsilylthio group, t-butylsilyldimethylsilylthio group, triphenylsilylthio group, tri-p-xylylsilylthio group, tribenzylsilylthio group, diphenylmethylsilylthio group, t-butyldiphenylsilylthio group Group, dimethylphenylsilylthio group and the like are exemplified.

The substituted silylamino group includes a silylamino group (H ₃ SiNH— or (H ₃ Si) ₂ N substituted with 1 to 6 groups selected from an alkyl group, an aryl group, an arylalkyl group, and a monovalent heterocyclic group. -). The alkyl group, aryl group, arylalkyl group, and monovalent heterocyclic group may have a substituent.
The substituted silylamino group usually has about 1 to 120 carbon atoms, preferably 3 to 60 carbon atoms. Specific examples thereof include trimethylsilylamino group, triethylsilylamino group, tri-n-propylsilylamino group, tri- i-propylsilylamino group, t-butylsilyldimethylsilylamino group, triphenylsilylamino group, tri-p-xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, t-butyldiphenylsilylamino Group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group, di (tri-n-propylsilyl) amino group, di (tri-i-propylsilyl) amino group, di (t -Butylsilyldimethylsilyl) amino group, di (triphenylsilyl) Mino group, di (tri-p-xylylsilyl) amino group, di (tribenzylsilyl) amino group, di (diphenylmethylsilyl) amino group, di (t-butyldiphenylsilyl) amino group, di (dimethylphenylsilyl) amino Examples include groups.

The monovalent heterocyclic group means a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms. Specific examples thereof include a thienyl group, C _1- C ₁₂ alkyl thienyl group, a pyrrolyl group, a furyl group, a pyridyl group, C ₁ -C ₁₂ alkyl pyridyl group, an imidazolyl group, a pyrazolyl group, a triazolyl group, an oxazolyl group, a thiazole group, a thiadiazole group and the like.

Heteroaryloxy group (Q ¹ -O- a group represented, Q ¹ represents a monovalent heterocyclic group.), Heteroarylthio groups (Q ² -S- in group represented, Q ² is a monovalent As a monovalent heterocyclic group in a heteroaryloxycarbonyl group (a group represented by Q ³ —O (C═O) —, Q ³ represents a monovalent heterocyclic group). Are exemplified by the above-described monovalent heterocyclic groups.

For example, the heteroaryl group has a carbon number of usually about 4 to 60, and specific examples thereof include thienyloxy group, C ₁ -C ₁₂ alkyl thienyl group, pyrrolyloxy group, furyloxy group, pyridyloxy group, Examples thereof include C _{1 to} C ₁₂ alkylpyridyloxy groups, imidazolyloxy groups, pyrazolyloxy groups, triazolyloxy groups, oxazolyloxy groups, thiazoleoxy groups, thiadiazoleoxy groups, and the like.

The heteroarylthio group usually has about 4 to 60 carbon atoms. Specific examples thereof include thienyl mercapto group, C _{1 to} C ₁₂ alkyl thienyl mercapto group, pyrrolyl mercapto group, furyl mercapto group, pyridyl mercapto group, C ₁ -C ₁₂ alkyl pyridyl mercapto group, imidazolylmethyl mercapto group, a pyrazolyl mercapto group, benzotriazolyl mercapto group, benzoxazolyl mercapto group, thiazole mercapto groups, such as thiadiazole mercapto groups.

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

The arylalkynyl group usually has about 8 to 50 carbon atoms, and examples of the aryl group in the arylalkynyl group include the above aryl groups.
Of the arylalkynyl groups, arylethynyl groups are preferred.

  The alkyloxycarbonyl group usually has about 2 to 20 carbon atoms, and specific examples thereof include methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, i-propyloxycarbonyl group, butoxycarbonyl group, i-butoxy Carbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxycarbonyl group, nonyloxycarbonyl group, decyloxycarbonyl group 3,7-dimethyloctyloxycarbonyl group, lauryloxycarbonyl group, trifluoromethoxycarbonyl group, pentafluoroethoxycarbonyl group, perfluorobutoxycarbo Group, perfluorohexyloxy carbonyl group, such as perfluorooctyl oxycarbonyl groups.

Aryloxycarbonyl group has a carbon number of usually about 7 to 60, and specific examples thereof include phenoxycarbonyl group, C ₁ -C ₁₂ alkoxyphenoxy group, C ₁ -C ₁₂ alkylphenoxy group, 1-naphthyl Examples include an oxycarbonyl group, 2-naphthyloxycarbonyl group, pentafluorophenyloxycarbonyl group and the like.

Arylalkyloxycarbonyl group has usually about 8 to 60 carbon atoms, and specific examples thereof include a phenyl -C ₁ -C ₁₂ alkoxycarbonyl group, C ₁ -C ₁₂ alkoxyphenyl -C ₁ -C ₁₂ alkoxycarbonyl group, C ₁ -C ₁₂ alkylphenyl -C ₁ -C ₁₂ alkoxycarbonyl group, 1-naphthyl -C ₁ -C ₁₂ alkoxycarbonyl group, 2-naphthyl -C ₁ -C ₁₂ alkoxycarbonyl groups.

The heteroaryloxycarbonyl group (group represented by Q ⁴ —O (C═O) —, Q ⁴ represents a monovalent heterocyclic group) usually has about 2 to 60 carbon atoms, specifically is thienyl oxycarbonyl group, C ₁ -C ₁₂ alkyl thienyl alkyloxycarbonyl group, pyrrolyl oxycarbonyl group, furyloxy group, pyridyloxy carbonyl group, C ₁ -C ₁₂ alkyl pyridyloxycarbonyl group, imidazolyloxy group, Examples include pyrazolyloxycarbonyl group, triazolyloxycarbonyl group, oxazolyloxycarbonyl group, thiazoleoxycarbonyl group, thiadiazoleoxycarbonyl group and the like.

The polymer compound of the present invention may contain two or more of the above formulas (1), (2) or (3).
The polymer compound of the present invention may contain a repeating unit other than the formula (1), the formula (2) and the formula (3) as long as the electron transport property or the hole transport property is not impaired. Further, the sum of the repeating units represented by formula (1) and formula (2), or the sum of the repeating units represented by formula (1), formula (2) and formula (3) is 10 mol% or more of all repeating units. It is preferable that it is, More preferably, it is 50 mol% or more, More preferably, it is 80 mol% or more.

  When the polymer compound of the present invention includes the formula (1) and the formula (2), the molar ratio of the formula (1) and the formula (2) is preferably in the range of 3: 1 to 1: 3. Preferably it is in the range of 2: 1 to 1: 2, more preferably about 1: 1.

  When the polymer compound of the present invention includes formula (1), formula (2) and formula (3), the molar ratio of the sum of formula (2) and formula (3) and formula (1) is from 3: 1. Those in the range of 1: 3 are preferred, more preferably those in the range of 2: 1 to 1: 2, and even more preferably about 1: 1.

The polymer compound of the present invention may be an alternating, random, block or graft copolymer, or a polymer compound having an intermediate structure thereof, such as a random copolymer having a block property. There may be. Moreover, the case where there are branches in the main chain and there are three or more terminal portions and dendrimers are also included.
Preferred are alternating, block or graft copolymers, more preferred are alternating copolymers.
Among the block or graft copolymers, those containing the structure of the formula (7) or the structure of the formula (8) in the block or graft portion are preferable.

  Among the polymer compounds of the present invention, examples of the polymer compound having the structure (7) and the polymer compound having the structure (8) include a polymer having an alternating copolymer structure represented by the following formula (7-1): And a polymer compound having a copolymer structure of the following formula (8-1).

ここに、ｔは構造（７）または構造（８）の繰り返しの数を表し、ｔは、繰り返し単位の構造により異なるが通常は 2-100,000程度であり、好ましくは5-10,000程度である。

Here, t represents the number of repetitions of the structure (7) or structure (8), and t varies depending on the structure of the repeating unit, but is usually about 2-100,000, preferably about 5-10,000.

In the polymer compound of the present invention, the repeating unit may be linked with a non-conjugated unit, or the repeating unit may contain those non-conjugated parts. Examples of the binding structure include those shown below and combinations of two or more of the following. Here, each R is independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group. , Acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, A heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group, or a cyano group, and Ar represents 6 to 60 carbon atoms Carbonization It shows the original.

  In addition, if the polymerization active group remains as it is, the terminal group of the polymer compound of the present invention may be deteriorated in characteristics and durability when used as an element, so it may be protected with a stable group. Good. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and examples thereof include a structure in which an aryl group or a heterocyclic group is bonded via a carbon-carbon bond. Specific examples include substituents described in Chemical formula 10 of JP-A-9-45478.

  The polymer compound of the present invention may have a group represented by the following formula (18), (19) or (20) at the end of the main chain.

式中、Ａｒ¹、Ａｒ²、Ｘ¹、Ｘ²およびｍは、上記と同じ意味を表す。Ｚ¹は水素原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、置換アミノ基、置換シリル基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基またはアリールアルキニル基を表す。

In the formula, Ar ¹ , Ar ² , X ¹ , X ² and m represent the same meaning as described above. Z ¹ is a hydrogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, substituted silyl group, monovalent Represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group or an arylalkynyl group;

式中、Ａｒ¹、Ａｒ²、Ｘ¹、Ｘ²、Ｚ¹およびｍは上記と同じ意味を表す。

In the formula, Ar ¹ , Ar ² , X ¹ , X ² , Z ¹ and m represent the same meaning as described above.

式中、Ｙ、Ｒ¹、Ｚ¹およびｐは上記と同じ意味を表す。

In the formula, Y, R ¹ , Z ¹ and p represent the same meaning as described above.

The number average molecular weight in terms of polystyrene of the polymer compound of the present invention is usually about 10 ³ to 10 ⁸ , preferably 10 ⁴ to 10 ⁶ .

  Solvents for the polymer compound of the present invention include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, and chloropentane. Halogenated saturated hydrocarbon solvents such as bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene, ethers such as tetrahydrofuran and tetrahydropyran Examples thereof are similar solvents. Although depending on the structure and molecular weight of the polymer compound, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

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

  A polymer compound having liquid crystallinity is useful for increasing electron mobility or hole mobility when used as a material for an organic thin film transistor, for example. In addition, it is known that a polymer compound having liquid crystallinity has optical or electrical anisotropy by being oriented. (Synthetic Metals 119 (2001) 537)

Next, a method for producing the polymer compound of the present invention will be described.
The polymer compound of the present invention can be produced, for example, by condensation polymerization using a compound represented by the following formula (21), a compound represented by (22) and a compound represented by (23) as raw materials.

式中、Ａｒ¹、Ａｒ²、Ｘ¹、Ｘ²およびｍは上記と同じ意味を表す。Ｙ¹およびＹ²はそれぞれ独立にハロゲン原子、アルキルスルホネート基、アリールスルホネート基、アリールアルキルスルホネート基、ホウ酸エステル基、スルホニウムメチル基、ホスホニウムメチル基、ホスホネートメチル基、モノハロゲン化メチル基、ホウ酸基、ホルミル基、またはビニル基を表す。

In the formula, Ar ¹ , Ar ² , X ¹ , X ² and m represent the same meaning as described above. Y ¹ and Y ² are each independently a halogen atom, alkyl sulfonate group, aryl sulfonate group, aryl alkyl sulfonate group, borate ester group, sulfonium methyl group, phosphonium methyl group, phosphonate methyl group, monohalogenated methyl group, boric acid Represents a group, a formyl group, or a vinyl group.

式中、Ｙ、Ｒ¹、Ｙ¹、Ｙ²およびｐは上記と同じ意味を表す。

In the formula, Y, R ¹ , Y ¹ , Y ² and p represent the same meaning as described above.

式中、Ａｒ³、Ｙ¹、Ｙ²およびｑは上記と同じ意味を表す。

In the formula, Ar ³ , Y ¹ , Y ² and q represent the same meaning as described above.

From the viewpoint of the synthesis of the compounds represented by the above (21), (22) and (23) and the ease of the condensation polymerization reaction, Y ¹ and Y ² are each independently a halogen atom, an alkyl sulfonate group or an aryl sulfonate group. , Arylalkyl sulfonate group, borate group or boric acid group is preferable.

  The polymer compound of the present invention undergoes condensation polymerization using a compound represented by the following formula (24), (25), (26) or (27) in addition to (21), (22) and (23). Therefore, the terminal structure can be preferably controlled.

式中、Ａｒ¹、Ａｒ²、Ｘ¹、Ｘ²、Ｙ²およびｍは上記と同じ意味を表す。Ｚ¹は水素原子、アルキル基、アルキルオキシ基、アルキルチオ基、アリール基、アリールオキシ基、アリールチオ基、アリールアルキル基、アリールアルキルオキシ基、アリールアルキルチオ基、置換アミノ基、置換シリル基、１価の複素環基、ヘテロアリールオキシ基、ヘテロアリールチオ基、アリールアルケニル基またはアリールアルキニル基を表す。

In the formula, Ar ¹ , Ar ² , X ¹ , X ² , Y ² and m have the same meaning as described above. Z ¹ is a hydrogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, substituted amino group, substituted silyl group, monovalent Represents a heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group or an arylalkynyl group;

式中、Ａｒ¹、Ａｒ²、Ｘ¹、Ｘ²、Ｙ¹、Ｚ¹およびｍは上記と同じ意味を表す。

In the formula, Ar ¹ , Ar ² , X ¹ , X ² , Y ¹ , Z ¹ and m represent the same meaning as described above.

式中、Ａｒ¹、Ａｒ²、Ｘ¹、Ｘ²、Ｙ²、Ｚ¹およびｍは上記と同じ意味を表す。

In the formula, Ar ¹ , Ar ² , X ¹ , X ² , Y ² , Z ¹ and m represent the same meaning as described above.

式中、Ａｒ³、Ｙ²、Ｚ¹およびｑは上記と同じ意味を表す。

In the formula, Ar ³ , Y ² , Z ¹ and q represent the same meaning as described above.

Of the compounds represented by the above formulas (24) to (27), Y ¹ to Y ² are each independently a halogen atom, an alkyl sulfonate group, an aryl from the viewpoint of the synthesis of the above compound and the ease of condensation polymerization reaction. A sulfonate group, an arylalkyl sulfonate group, a boric acid ester group or a boric acid group is preferable, and a halogen atom is more preferable.

  Examples of the alkyl sulfonate group in formulas (21) to (27) include a methane sulfonate group, an ethane sulfonate group, and a trifluoromethane sulfonate group. Examples of the aryl sulfonate group include a benzene sulfonate group and a p-toluene sulfonate group. Examples of the arylalkyl sulfonate group include a benzyl sulfonate group.

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

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

Examples of the phosphonium methyl group include groups represented by the following formula.
_{^{-CH 2 P + Ph 3 X -}} (X represents a halogen atom.)

Examples of the phosphonate methyl group include groups represented by the following formula.
-CH ₂ PO (OR ') ₂
(R ′ represents an alkyl group, an aryl group or an arylalkyl group.)

Examples of the monohalogenated methyl group include a methyl fluoride group, a methyl chloride group, a methyl bromide group, and a methyl iodide group.

The reaction method used for producing the polymer compound of the present invention includes, for example, a polymerization method by Suzuki coupling reaction, a polymerization method by Grignard reaction, a polymerization method by Ni (0) catalyst, and an oxidizing agent such as FeCl _3. Examples thereof include a method of polymerizing by oxidization, a method of electrochemically oxidative polymerization, a method of decomposing an intermediate polymer compound having an appropriate leaving group, and the like.

  Among these, polymerization by Wittig reaction, polymerization by Heck reaction, polymerization by Horner-Wadsworth-Emmons method, polymerization by Knoevenagel reaction, polymerization method by Suzuki coupling reaction, polymerization method by Grignard reaction, Ni (0) catalyst The method of polymerizing is preferable because the structure can be easily controlled. Further, a method of polymerizing by Suzuki coupling reaction, a method of polymerizing by Grignard reaction, and a method of polymerizing by Ni (0) catalyst are preferable from the viewpoint of easy availability of raw materials and easy polymerization reaction operation.

  If necessary, the monomer can be dissolved in an organic solvent and reacted, for example, with an alkali or a suitable catalyst at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point. For example, “Organic Reactions”, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, “Organic Reactions”, Vol. 27, 345-390, John Wiley & Sons, Inc., 1982, "Organic Synthesis", Collective Volume VI, 407-411, John Wiley and Sons (407-411). John Wiley & Sons, Inc.), 1988, Chem. Rev., 95, 24. 7 (1995), Journal of Organometallic Chemistry (J. Organomet. Chem.), 576, 147 (1999), Journal of Practical Chemistry (J. Prakt. Chem.), 336, 247 (1994), Macromolecular Chemistry Macromolecular Symposium (Macromol. Chem., Macromol. Symp.), Vol. 12, p. 229 (1987), etc. can be used.

  The organic solvent varies depending on the compound and reaction to be used, but it is generally preferable that the solvent to be used is sufficiently deoxygenated and the reaction proceeds in an inert atmosphere in order to suppress side reactions. Similarly, it is preferable to perform a dehydration treatment. (However, this is not the case in the case of a two-phase reaction with water such as the Suzuki coupling reaction.)

  In order to make it react, an alkali and a suitable catalyst are added suitably. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or catalyst, slowly add the alkali or catalyst solution while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, slowly add the reaction solution to the alkali or catalyst solution. And the method of adding.

  When the polymer compound of the present invention is used as a material for a polymer thin film device, the purity affects the device characteristics. Therefore, after the monomer before polymerization is purified by a method such as distillation, sublimation purification, or recrystallization. It is preferable to carry out the polymerization, and it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography after the synthesis.

  In the method for producing a polymer compound of the present invention, the respective monomers may be mixed and reacted at once, or may be divided and mixed as necessary.

  More specifically, the reaction conditions will be described. In the case of Wittig reaction, Horner reaction, Knoevengel reaction, etc., the reaction is carried out using an equivalent or more, preferably 1 to 3 equivalents of alkali with respect to the functional group of the monomer. Examples of the alkali include, but are not limited to, metal alcoholates such as potassium tert-butoxide, sodium tert-butoxide, sodium ethylate and lithium methylate, hydride reagents such as sodium hydride, and amides such as sodium amide. Etc. can be used. As the solvent, N, N-dimethylformamide, tetrahydrofuran, dioxane, toluene and the like are used. The reaction can be allowed to proceed at a reaction temperature of usually from room temperature to about 150 ° C. The reaction time is, for example, 5 minutes to 40 hours, but may be any time that allows sufficient polymerization to proceed, and it is not necessary to leave the reaction for a long time after the reaction is completed. is there. If the reaction concentration is too dilute, the reaction efficiency is poor. If the concentration is too high, it becomes difficult to control the reaction. Therefore, the concentration may be appropriately selected within the range of about 0.01 wt% to the maximum concentration to be dissolved. The range is from 1 wt% to 20 wt%. In the case of the Heck reaction, a monomer is reacted using a palladium catalyst in the presence of a base such as triethylamine. A relatively high boiling point solvent such as N, N-dimethylformamide or N-methylpyrrolidone is used, the reaction temperature is about 80 to 160 ° C., and the reaction time is about 1 to 100 hours.

  In the case of the Suzuki coupling reaction, for example, palladium [tetrakis (triphenylphosphine)] or palladium acetate is used as a catalyst, an inorganic base such as potassium carbonate, sodium carbonate, or barium hydroxide; an organic base such as triethylamine; An inorganic salt such as cesium iodide is added in an amount of not less than an equivalent amount, preferably 1 to 10 equivalents, relative to the monomer. An inorganic salt may be used as an aqueous solution and reacted in a two-phase system. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. Although depending on the solvent, a temperature of about 50 to 160 ° C. is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.

  In the case of the Grignard reaction, a halide and metal Mg are reacted in an ether solvent such as tetrahydrofuran, diethyl ether, dimethoxyethane or the like to form a Grignard reagent solution, and a monomer solution prepared separately is mixed with nickel. Alternatively, a method is exemplified in which a palladium catalyst is added while paying attention to excess reaction, and then the reaction is carried out while heating at reflux. The Grignard reagent is used in an equivalent amount or more, preferably 1 to 1.5 equivalents, more preferably 1 to 1.2 equivalents, relative to the monomer. Also in the case of polymerizing by a method other than these, the reaction can be carried out according to a known method.

  Although the method of reaction is not specifically limited, It can implement in presence of a solvent. The reaction temperature is preferably -80 ° C to the boiling point of the solvent.

  Solvents used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene and xylene, carbon tetrachloride, chloroform, dichloromethane, chlorobutane, bromobutane, chloro Halogenated saturated hydrocarbons such as pentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, halogenated unsaturated hydrocarbons such as chlorobenzene, dichlorobenzene and trichlorobenzene, methanol, ethanol, propanol, isopropanol, butanol, Alcohols such as t-butyl alcohol, carboxylic acids such as formic acid, acetic acid, propionic acid, dimethyl ether, diethyl ether, methyl-t-butyl Ether, tetrahydrofuran, tetrahydropyran, ethers such as dioxane, hydrochloric, hydrobromic, hydrofluoric, sulfuric, are such inorganic acids are exemplified such as nitric acid, may be used a single solvent or a mixed solvent.

  After the reaction, for example, it can be obtained by usual post-treatment such as quenching with water, extraction with an organic solvent, and evaporation of the solvent. The product can be isolated and purified by a method such as chromatographic fractionation or recrystallization.

Next, the polymer thin film of the present invention will be described.
The polymer thin film of the present invention includes the above-described polymer compound of the present invention.

  The film thickness of the polymer thin film of the present invention is usually about 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, and particularly preferably 20 nm to 200 nm.

  The polymer thin film of the present invention may contain one of the above polymer compounds alone, or may contain two or more of the above polymer compounds. In addition, in order to improve the electron transport property or hole transport property of the polymer thin film, a low molecular compound or a polymer compound having electron transport property or hole transport property may be mixed and used in addition to the above polymer compound. As the hole transporting material, known materials can be used, such as pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene or derivatives thereof, polyvinylcarbazole or derivatives thereof, polysilane or derivatives thereof, side chains. Or a polysiloxane derivative having an aromatic amine in the main chain, polyaniline or derivative thereof, polythiophene or derivative thereof, polypyrrole or derivative thereof, polyphenylene vinylene or derivative thereof, or polythienylene vinylene or derivative thereof, etc. Known materials can be used, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof, Or an derivative thereof, anthraquinone or a derivative thereof, tetracyanoanthraquinodimethane or a derivative thereof, a fluorenone derivative, diphenyldicyanoethylene or a derivative thereof, a diphenoquinone derivative, or a metal complex of 8-hydroxyquinoline or a derivative thereof, a polyquinoline or a derivative thereof, Examples thereof include polyquinoxaline or a derivative thereof, polyfluorene or a derivative thereof.

  Further, the polymer thin film of the present invention may contain a charge generating material in order to generate a charge by light absorbed in the polymer thin film. Known charge generating materials can be used, such as azo compounds and derivatives thereof, diazo compounds and derivatives thereof, metal-free phthalocyanine compounds and derivatives thereof, metal phthalocyanine compounds and derivatives thereof, perylene compounds and derivatives thereof, and polycyclic quinone compounds. And derivatives thereof, squarylium compounds and derivatives thereof, azurenium compounds and derivatives thereof, thiapyrylium compounds and derivatives thereof, and fullerenes such as C60 and derivatives thereof.

  Furthermore, the polymer thin film of the present invention may contain materials necessary for developing various functions. Examples thereof include a sensitizer for sensitizing the function of generating charges by absorbed light, a stabilizer for increasing stability, a UV absorber for absorbing UV light, and the like.

In addition, the polymer thin film of the present invention may contain a polymer compound material other than the polymer compound as a polymer binder in order to enhance mechanical properties. As the polymer binder, those not extremely disturbing electron transport property or hole transport property are preferable, and those which do not strongly absorb visible light are preferably used. As the polymer binder, poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-thienylenevinylene) or a derivative thereof, polycarbonate , Polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

  Although there is no restriction | limiting in the manufacturing method of the polymer thin film of this invention, For example, the method by the film-forming from the solution containing the said polymer compound, the electron transport material or hole transport material mixed as needed, and a polymer binder Is exemplified.

The solvent used for film formation from a solution is not particularly limited as long as it dissolves the polymer compound, the electron transport material or hole transport material to be mixed, and the polymer binder.
Solvents used when the polymer thin film of the present invention is formed from a solution include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene, carbon tetrachloride, chloroform, dichloromethane, Halogenated saturated hydrocarbon solvents such as dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane and bromocyclohexane, and halogenated unsaturated hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene And ether solvents such as tetrahydrofuran, tetrahydropyran and the like.
Although depending on the structure and molecular weight of the polymer compound, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.
As a film forming method from a solution, a spin coating method, a casting method, a micro gravure coating method, a gravure coating method, a bar coating method, a roll coating method, a wire bar coating method, a dip coating method, a spray coating method, a screen printing method, A coating method such as a flexographic printing method, an offset printing method, an inkjet printing method, or a dispenser printing method can be used, and a spin coating method, a flexographic printing method, an inkjet printing method, or a dispenser printing method is preferable.

The step of producing the polymer thin film of the present invention may include a step of orienting the polymer compound.
In the polymer thin film in which the polymer compound is oriented by this process, the main chain molecules or the side chain molecules are arranged in one direction, so that the electron mobility or the hole mobility is improved.
As a method for aligning polymer compounds, those known as alignment methods for liquid crystals, for example, “Fundamentals and Applications of Liquid Crystals” (Shinichi Matsumoto, Ryoko Kakuda, Industrial Research Society 1991), Chapter 5, “ “Structure and Physical Properties of Ferroelectric Liquid Crystals” (co-written by Ikuo Fukuda and Hideo Takezoe, Corona, 1990) Chapter 7, “Liquid Crystal” Vol. 3, No. 1 (1999), pages 3-16, etc. Can be used. Among them, the rubbing method, the photo-alignment method, the sharing method (shear stress application method) and the pulling coating method are simple, useful and easy to use as the alignment method, and the rubbing method and the sharing method are preferable.

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

The photo-alignment method is a method of providing an alignment function by forming an alignment film on a substrate and irradiating polarized UV light or obliquely irradiating UV light. Examples of the alignment film include polyimide, polyamide, and polyvinyl cinnamate, and a commercially available alignment film for liquid crystal can also be used.
In the rubbing method or the photo-alignment method, the alignment can be performed by sandwiching the aligned polymer compound material between the substrates subjected to the above-described treatment. At this time, it is necessary that the temperature of the substrate is a liquid crystal phase or isotropic phase. The temperature may be set before or after the polymer compound material is sandwiched between the substrates. Alternatively, the polymer compound material may be simply applied on a substrate that has been subjected to an alignment treatment. To apply the polymer compound, place the polymer compound on the substrate and set the temperature to Tg or higher, or set to a temperature that shows a liquid crystal phase or isotropic phase, and coat it in one direction with a rod or prepare a solution dissolved in an organic solvent. And it can carry out by the method of apply | coating by spin coating or flexographic printing.

The sharing method is a method in which another substrate is placed on the polymer compound material placed on the substrate, and the upper substrate is shifted in one direction at a temperature at which it becomes a liquid crystal phase or an isotropic phase. At this time, a substrate having a higher degree of orientation can be obtained by using a substrate that has been subjected to an orientation treatment as described in the rubbing method or the photo-alignment method. As the substrate, glass, a polymer film, or the like can be used. What is displaced by stress may be a metal rod or the like instead of the substrate.

The pull-up coating method is a method in which a substrate is dipped in a polymer compound solution and pulled up. The organic solvent used in the polymer compound solution and the substrate pulling rate are not particularly limited, but can be selected and adjusted according to the degree of orientation of the polymer compound.

The step of orienting the polymer compound is performed after the step of forming the polymer compound into a thin film, such as a rubbing method or a sharing method. There is a case. Moreover, the process of creating alignment film may be included before the process of making a high molecular compound into a thin film.

  Since the polymer thin film of the present invention has an electron transport property or a hole transport property, by controlling the transport of electrons or holes injected from the electrode or charges generated by light absorption, an organic thin film transistor, an organic solar cell, It can be used for various polymer thin film elements such as an optical sensor, an electrophotographic photosensitive member, a spatial modulation element, and a photorefractive element. When the polymer thin film is used in these polymer thin film elements, it is preferable to use the polymer thin film by aligning it by an orientation treatment because the electron transport property or hole transport property is improved.

The application of the polymer thin film of the present invention to an organic thin film transistor will be described.
As the structure of the organic thin film transistor of the present invention, the source electrode and the drain electrode are usually provided in contact with an active layer made of a polymer compound, and a gate electrode is provided with an insulating layer in contact with the active layer interposed therebetween. The structure of FIGS. 1-4 is illustrated, for example.

  The organic thin film transistor is usually formed on a support substrate. The material of the support substrate is not particularly limited as long as the characteristics as an organic thin film transistor are not impaired, but a glass substrate, a flexible film substrate, or a plastic substrate can also be used.

  The organic thin film transistor can be manufactured by a known method, for example, a method described in JP-A-5-110069.

  When forming the active layer, it is very advantageous and preferable to use an organic solvent-soluble polymer compound, and therefore, using the method for producing a polymer thin film of the present invention described above, A polymer thin film can be formed.

  The insulating layer in contact with the active layer is not particularly limited as long as it is a material having high electrical insulation, and a known one can be used. For example, SiOx, SiNx, Ta2O5, polyimide, polyvinyl alcohol, polyvinylphenol and the like can be mentioned. From the viewpoint of lowering the voltage, a material having a high dielectric constant is preferable.

  When an active layer is formed on an insulating layer, the surface of the insulating layer is treated with a surface treatment agent such as a silane coupling agent to improve the interface characteristics between the insulating layer and the active layer. It is also possible to form. Examples of the surface treatment agent include long-chain alkylchlorosilanes, long-chain alkylalkoxysilanes, fluorinated alkylchlorosilanes, and fluorinated alkylalkoxysilanes. Prior to the treatment with the surface treatment agent, the surface of the insulating layer may be treated with ozone UV or O 2 plasma.

A sealed organic thin film transistor formed by sealing after forming an organic thin film transistor is preferable.
Thereby, an organic thin-film transistor is interrupted | blocked from air | atmosphere and the fall of the characteristic of an organic thin-film transistor can be suppressed.
Examples of the sealing method include a method of covering with a UV curable resin, a thermosetting resin or an inorganic SiONx film, and a method of bonding a glass plate or film with a UV curable resin or a thermosetting resin. In order to effectively cut off from the atmosphere, it is preferable to perform the steps from the preparation of the organic thin film transistor to the sealing without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum).

  FIG. 5 is a diagram illustrating the application of the polymer thin film of the present invention to a solar cell as a representative example. One is used in a structure in which a polymer thin film is disposed between a pair of transparent or translucent electrodes. As an electrode material, a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or transparent conductive film thereof can be used. In order to obtain a high open circuit voltage, each electrode is preferably selected so that the difference in work function is large. In the polymer thin film, a carrier generating agent, a sensitizer and the like can be added and used in order to increase photosensitivity. As the substrate, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.

  6-8 is a figure explaining the application to the optical sensor of the polymer thin film of this invention as a representative example. One is used in a structure in which a polymer thin film is disposed between a pair of transparent or translucent electrodes. A charge generation layer that absorbs light and generates charges can also be used. As an electrode material, a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or transparent conductive film thereof can be used. In the polymer thin film, a carrier generating agent, a sensitizer and the like can be added and used in order to increase photosensitivity. As the substrate, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.

  9 to 11 are diagrams for explaining the application of the polymer thin film of the present invention to an electrophotographic photoreceptor as a representative example. Used in a structure in which a polymer thin film is disposed on an electrode. A charge generation layer that absorbs light and generates charges can also be used. As the electrode material, metals such as aluminum, gold, silver, and copper can be used. In the polymer thin film, a carrier generating agent, a sensitizer and the like can be added and used in order to increase photosensitivity. As the base material, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used, and a base material and an electrode can be used by using a metal such as aluminum.

FIG. 12 is a diagram illustrating the application of the polymer thin film of the present invention to a spatial light modulator as a representative example. It is used in a structure in which a polymer thin film, a dielectric layer mirror, and a liquid crystal layer are disposed between a pair of transparent or translucent electrodes. The dielectric layer mirror is preferably composed of a dielectric multilayer film, and is designed to have a low-reflectance wavelength region and a high-reflectivity wavelength region, and the boundary thereof rises sharply. Various liquid crystal materials can be used for the liquid crystal layer, but ferroelectric liquid crystal is preferably used.
As the electrode material, a semi-transparent film such as aluminum, gold, silver, copper, or a transparent conductive film having high conductivity can be used. As the substrate, a transparent or translucent material such as a glass substrate or a plastic substrate can be used.

Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples.
Here, for the number average molecular weight, the number average molecular weight in terms of polystyrene was determined by gel permeation chromatography (GPC) using chloroform as a solvent.

・C₈H₁₇MgBrの調製
100ml 3口フラスコにマグネシウム 1.33gを取り、フレームドライ、アルゴン置換した。これにTHF10ml、1-ブロモオクタン2.3mlを加え、加熱し、反応を開始させた。2.5時間還流した後に室温まで放冷した。
・Grignard反応
窒素置換した300ml3口フラスコに化合物1 1.00gをとり、10mlのTHFに懸濁させた。0℃に冷却し、上記で調製したC8H17MgBr溶液を加えた。冷浴をはずし、還流下、5時間攪拌した。反応液を放冷後、水10ml、塩酸を加えた。塩酸を加える前は懸濁液であったが、添加後は2相の溶液となった。分液後、有機相を水、飽和食塩水で洗浄した。硫酸ナトリウムで乾燥し、溶媒を留去したところ、1.65gの粗生成物を得た。シリカゲルカラムクロマトグラフィーにより精製（ヘキサン：酢酸エチル＝20：1）し、1.30gの化合物2を得た。

窒素置換した25ml 2口フラスコに化合物2 0.20ｇを取り、4mlのトルエンに溶解した。
この溶液にp-トルエンスルホン酸・１水和物0.02g（0.06mmol）を加え、100℃で11時間攪拌した。反応液を放冷後、水、4N NaOH水溶液、水、飽和食塩水の順に洗浄し、溶媒を留去したところ、0.14gの化合物3を得た。

窒素雰囲気下、反応容器に上記化合物３ 1.0g（1.77mmol）、ビス（ピナコレート）ジボロン 0.945g（3.72mmol）、〔1,1'-ビス（ジフェニルホスフィノ）フェロセン〕パラジウムジクロリド 0.078g（0.11mmol）、1,1'-ビス（ジフェニルフォスフィノ）フェロセン 0.059g（0.11mmol）および1,4-ジオキサン 15mlを入れ、アルゴンガスを30分間バブリングした。その後、酢酸カリウム 1.043g（10.6mmol）を加え、窒素雰囲気下95℃で13.5時間反応させた。反応終了後、反応液をろ過して不溶物を除いた。アルミナショートカラムで精製し、溶媒を除去後。トルエンに溶解させ、活性炭を加えて攪拌、ろ過した。ろ液を再度アルミナショートカラムで精製し、活性炭を加えて攪拌、ろ過した。トルエンを完全に除去した後、ヘキサン2.5mlを加えて再結晶することにより、下記に示す化合物３−ａ 0.28gを得た。

Reference synthesis example 1
6.65 g of 2,7-dibromo-9-fluorenone was placed in a nitrogen-substituted 500 ml three-necked flask and dissolved in 140 ml of a mixed solvent of trifluoroacetic acid: chloroform = 1: 1. To this solution was added sodium perborate monohydrate and stirred for 20 hours. The reaction solution was filtered through celite and washed with toluene. The filtrate was washed with water, sodium bisulfite and saturated brine, and then dried over sodium sulfate. After distilling off the solvent, 6.11 g of crude product was obtained.
The crude product was recrystallized from toluene and further recrystallized from chloroform to obtain 1.19 g of Compound 1.

・ Preparation of C ₈ H ₁₇ MgBr
In a 100 ml three-necked flask, 1.33 g of magnesium was taken, flame dried, and purged with argon. To this, 10 ml of THF and 2.3 ml of 1-bromooctane were added and heated to start the reaction. After refluxing for 2.5 hours, the mixture was allowed to cool to room temperature.
Grignard reaction 1.00 g of Compound 1 was placed in a nitrogen-substituted 300 ml three-necked flask and suspended in 10 ml of THF. After cooling to 0 ° C., the C8H17MgBr solution prepared above was added. The cold bath was removed and the mixture was stirred for 5 hours under reflux. The reaction solution was allowed to cool, and 10 ml of water and hydrochloric acid were added. It was a suspension before the addition of hydrochloric acid, but it became a two-phase solution after the addition. After separation, the organic phase was washed with water and saturated brine. Drying with sodium sulfate and evaporation of the solvent gave 1.65 g of crude product. Purification by silica gel column chromatography (hexane: ethyl acetate = 20: 1) gave 1.30 g of compound 2.

In a 25 ml two-necked flask purged with nitrogen, 0.20 g of Compound 2 was taken and dissolved in 4 ml of toluene.
To this solution, 0.02 g (0.06 mmol) of p-toluenesulfonic acid monohydrate was added and stirred at 100 ° C. for 11 hours. The reaction solution was allowed to cool, then washed with water, 4N NaOH aqueous solution, water and saturated brine in this order, and the solvent was distilled off to obtain 0.14 g of Compound 3.

Under a nitrogen atmosphere, 1.0 g (1.77 mmol) of the above compound 3, 0.945 g (3.72 mmol) of bis (pinacolato) diboron, 0.078 g (0.11 mmol) of [1,1′-bis (diphenylphosphino) ferrocene] palladium dichloride in a reaction vessel. ), 0.059 g (0.11 mmol) of 1,1′-bis (diphenylphosphino) ferrocene and 15 ml of 1,4-dioxane were added, and argon gas was bubbled for 30 minutes. Thereafter, 1.043 g (10.6 mmol) of potassium acetate was added and reacted at 95 ° C. for 13.5 hours under a nitrogen atmosphere. After completion of the reaction, the reaction solution was filtered to remove insoluble matters. After purification with an alumina short column and removing the solvent. It was dissolved in toluene, activated carbon was added, and the mixture was stirred and filtered. The filtrate was purified again with an alumina short column, added with activated carbon, stirred and filtered. After complete removal of toluene, recrystallization was carried out by adding 2.5 ml of hexane to obtain 0.28 g of compound 3-a shown below.

上記化合物４を用い、参考合成例１と同様の方法により下記に示す化合物４−ａを得た。

Reference synthesis example 2
Compound 4 shown below was obtained by the method described in JP-A-2004-043544.

Compound 4-a shown below was obtained in the same manner as in Reference Synthesis Example 1 using Compound 4 above.

Example 1
<Synthesis of Polymer Compound A>
0.62 g of the above compound 3-a, 0.29 g of 5,5′-dibromo-2,2′-bithiophene and 0.36 g of Aliquat 336 (manufactured by ACROS ORGANICS) were charged into a reaction vessel. Thereafter, the reaction was performed in a nitrogen atmosphere until the reaction. To the previous reaction vessel, 9.3 g of toluene deaerated by bubbling with argon gas in advance was added. Next, a solution prepared by dissolving 0.39 g of potassium carbonate in 9.6 g of ion-exchanged water previously deaerated by bubbling with an argon gas was added to the mixed solution. Subsequently, 2.1 mg of tetrakis (triphenylphosphine) palladium (0) was added. All reactions were performed under a nitrogen atmosphere. After reacting under reflux conditions for 16.3 hours, 18.4 mg of bromobenzene was added and reacted under reflux conditions for 2 hours. Furthermore, 19.0 mg of 2-phenyl-1,3,2-dioxaborinane was added and reacted under reflux conditions for 2 hours. After the reaction, the two-phase solution was cooled and the aqueous layer was removed. Since the organic solvent layer was very viscous, chloroform was added and diluted. The mixed solution was poured into methanol and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. This precipitate was dried under reduced pressure and then dissolved in chloroform. This solution was purified by passing through a column packed with silica and alumina. Next, this solution was poured into methanol and reprecipitated, and the produced precipitate was recovered. This precipitate was dried under reduced pressure to obtain 0.53 g of polymer compound A.
The number average molecular weight in terms of polystyrene of this polymer compound A was 1.2 × 10 ⁶ .

Example 2

<Synthesis of polymer compound B>
0.73 g of the above compound 4-a, 0.32 g of 5,5′-dibromo-2,2′-bithiophene and 0.40 g of Aliquat 336 were charged into a reaction vessel. Thereafter, the reaction was performed in a nitrogen atmosphere until the reaction. To the previous reaction vessel, 10.4 g of toluene deaerated by bubbling with argon gas in advance was added. Next, a solution prepared by dissolving 0.44 g of potassium carbonate in 10.7 g of ion-exchanged water previously deaerated by bubbling with an argon gas was added to the mixed solution. Subsequently, 2.3 mg of tetrakis (triphenylphosphine) palladium (0) was added. All reactions were performed under a nitrogen atmosphere. After reacting under reflux conditions for 15 hours, 20.4 mg of bromobenzene was added and reacted under reflux conditions for 2 hours. Furthermore, 21.1 mg of 2-phenyl-1,3,2-dioxaborinane was added and reacted under reflux conditions for 2 hours. After the reaction, the two-phase solution was cooled and the organic solvent layer was poured into methanol and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. This precipitate was dried under reduced pressure and then dissolved in chloroform. This solution was purified by passing through a column packed with silica and alumina. Next, this solution was poured into methanol and reprecipitated, and the produced precipitate was recovered. This precipitate was dried under reduced pressure to obtain 0.56 g of polymer compound B.
The number average molecular weight in terms of polystyrene of this polymer compound B was 3.9 × 10 ⁵ .

Example 3
<Preparation of polymer thin film element and evaluation of organic thin film transistor characteristics>
Purchase a high-concentrated n-type silicon substrate surface that will be the gate electrode, with a 200-nm thick silicon oxide film that will be the insulating layer by thermal oxidation, and ultrasonically wash with alkaline detergent, ultrapure water, and acetone. After that, the surface was cleaned by ozone UV irradiation. The substrate was immersed in a 5 mM octane solution of octadecyltrichlorosilane in a nitrogen atmosphere for 12 hours to silane-treat the surface of the silicon substrate, and then the substrate was rinsed in the order of octane and chloroform. 0.018 g of the polymer compound A was weighed, and chloroform was added to make 5.3 g. After filtering through a 3 μm membrane filter, this coating solution was used to coat the surface-treated substrate with a film thickness of 70 nm by spin coating. A polymer thin film containing the polymer compound A was formed. An Au electrode was vapor-deposited on the polymer thin film by a vacuum deposition method to form a source electrode and a drain electrode having a channel width of 2 mm and a channel length of 20 μm.
When the gate electrode V _G was changed to 0 to −80 V and the source-drain voltage V _SD was changed to 0 to −80 V in the nitrogen atmosphere, the organic thin film transistor characteristics were measured. A −Vg characteristic was obtained, and a drain current of −1.4 μA was obtained at V _g = −80 V and V _Sd = −80 V. The field-effect mobility obtained from the Isd-Vg characteristic was 1 × 10 ⁻³ cm ² / Vs, and the current on / off ratio was 1 × 10 ⁶ .

Reference synthesis example 3
<Synthesis of polymer compound C>
After charging 0.96 g of the compound 3 and 0.55 g of 2,2′-bipyridyl in a reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this was added 80 g of tetrahydrofuran (THF) (dehydrated solvent) deaerated previously by bubbling with an argon gas. Next, 1.05 g of bis (1,5-cyclooctadiene) nickel (0) {Ni (COD) 2} is added to this mixed solution, and the mixture is stirred at room temperature for 10 minutes, and then at 60 ° C. for 1.5 hours. Reacted. The reaction was performed in a nitrogen gas atmosphere. After the reaction, this solution was cooled, poured into a mixed solution of methanol 100 ml / ion exchanged water 200 ml, and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. This precipitate was dried under reduced pressure and then dissolved in chloroform. The solution was filtered to remove insoluble matters, and then the solution was purified by passing through a column filled with alumina. Next, this solution was poured into methanol and reprecipitated, and the produced precipitate was recovered. This precipitate was dried under reduced pressure to obtain 0.5 g of polymer compound C.
The number average molecular weight in terms of polystyrene of this polymer compound C was 7.3 × 10 ⁵ .

Comparative Example 1
<Preparation of polymer thin film element and evaluation of organic thin film transistor characteristics>
A polymer thin film containing polymer compound C having a thickness of 50 nm is formed on the surface-treated substrate by the same method as in Example 3 except that polymer compound C is used instead of polymer compound A by spin coating. did. An Au electrode was deposited on the polymer thin film by a vacuum deposition method to form a source electrode and a drain electrode having a channel width of 2 mm and a channel length of 20 μm, and a polymer thin film element 2 was produced.
The organic thin film transistor characteristics were measured on the prepared polymer thin film element 2 by changing the gate voltage V _G to 0 to −80 V and the source-drain voltage V _SD to 0 to −80 V in a nitrogen atmosphere. When V _g = −80 V and V _Sd = −60 V, the drain current was as low as −0.8 nA.

Example 4
<Preparation of polymer thin film element and evaluation of solar cell characteristics>
A suspension of poly (3,4) ethylenedioxythiophene / polystyrene sulfonic acid (manufactured by Bayer, Baytron P AI 4083) is applied to a glass substrate with an ITO film having a thickness of 150 nm by sputtering using a 0.2 μm membrane filter. After filtration, a thin film having a thickness of 70 nm was formed by spin coating, and dried on a hot plate at 200 ° C. for 10 minutes. Thereafter, a polymer thin film having a thickness of 50 nm was formed by spin coating using a 0.2 wt% chloroform solution of polymer compound A at room temperature. Further, this was dried at 60 ° C. under reduced pressure for 1 hour, and then, as an electrode, lithium fluoride was equivalent to about 0.4 nm, then calcium was deposited at 5 nm, and aluminum was further deposited at 180 nm to form a polymer using polymer compound A A thin film element 3 was produced. The degree of vacuum during vapor deposition was 1 × 10 ⁻⁴ Pa or less. When the voltage-current characteristics were measured while irradiating the obtained polymer thin film element 3 with a xenon lamp, solar cell characteristics with a short-circuit current of 43 μA / cm ² and an open-circuit voltage of 1.75 V were obtained.

Example 5
<Preparation of polymer thin film element and evaluation of solar cell characteristics>
Using the polymer compound B instead of the polymer compound A, a polymer thin film element 4 was produced in the same manner as in Example 5. When the voltage-current characteristics were measured while irradiating the obtained polymer thin film element 4 with a xenon lamp, a short-circuit current of 38 μA / cm ² and an open-circuit voltage of 1.15 V were obtained.

Example 6
<Synthesis of polymer compound D>
1.13 g of the above compound 3-a and 0.60 g of 1,2-di (5-dibromo-2-thienyl) ethene (for example, M. Fuji et al., Synthetic Metals, 55-57, 2136-2139 (1993) ) And Aliquat 336 (0.69 g) were charged into a reaction vessel. Thereafter, the reaction was performed in a nitrogen atmosphere until the reaction. To the previous reaction vessel, 19.4 g of toluene deaerated previously by bubbling with argon gas was added. Next, a solution prepared by dissolving 0.74 g of potassium carbonate in 20.0 g of ion-exchanged water previously deaerated by bubbling with an argon gas was added to the mixed solution. Subsequently, 3.9 mg of tetrakis (triphenylphosphine) palladium (0) was added. All reactions were performed under a nitrogen atmosphere. After reacting under reflux conditions for 15 hours, 34.7 mg of bromobenzene was added and reacted under reflux conditions for 2 hours. Further, 35.8 mg of 2-phenyl-1,3,2-dioxaborinane was added and reacted under reflux conditions for 2 hours. After the reaction, the two-phase solution was cooled and the organic solvent layer was poured into methanol and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration.
This precipitate was dried under reduced pressure to obtain 1.00 g of polymer compound D. This polymer compound D has a polystyrene-equivalent number average molecular weight of 1 × 10 ⁶ or more.

Example 7
<Preparation of polymer thin film element and evaluation of organic thin film transistor characteristics>
0.008 g of the polymer compound D was weighed, and dichlorobenzene was added to make 2 g to prepare a coating solution. Purchase a high-concentrated n-type silicon substrate surface that will be the gate electrode, with a 200-nm thick silicon oxide film that will be the insulating layer by thermal oxidation, and ultrasonically wash with alkaline detergent, ultrapure water, and acetone. After that, the surface was cleaned by ozone UV irradiation. An Au electrode was deposited on the substrate by a vacuum deposition method to form a source electrode and a drain electrode having a channel width of 2 mm and a channel length of 20 μm. The substrate with electrodes was set on a spin coater, and Hexamethyldisilazane (HMDS) manufactured by Aldrich was dropped, followed by spinning at 2000 rpm, and the substrate surface was treated with HMDS. Using the coating solution of the polymer compound D, the polymer compound D is applied so as to cover between the source electrode and the drain electrode by a dispenser printing method (Shot Mini manufactured by Musashi Engineering) using a needle tip with an inner diameter of 100 μm, A thin film having a thickness of 700 nm was formed. Then, it baked for 30 minutes at 120 degreeC in nitrogen atmosphere, and the polymer thin film element 5 was created.
When the organic thin film transistor characteristics were measured by changing the gate voltage V _G to 0 to −60 V and the source-drain voltage V _SD to 0 to −60 V in the vacuum on the prepared polymer thin film element 5, a good Isd− Vg characteristics were obtained, and a drain current of −0.6 μA was obtained at V _g = −60 V and V _Sd = −60 V. The field-effect mobility obtained from the Isd-Vg characteristic was 5 × 10 ⁻⁴ cm ² / Vs, and the current on / off ratio was 1 × 10 ³ .

DESCRIPTION OF SYMBOLS 1, Base material 2, Polymer thin film 3, Insulating film 4, Gate electrode 5, Source electrode 6, Drain electrode 7, Electrode 8, Charge generation layer 9, Liquid crystal layer 10, Dielectric mirror layer

Claims (14)

A polymer comprising a polymer compound comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the formula (2), and having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ A polymer thin film element comprising a thin film.

[Wherein, Ar ¹ and Ar ² each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and X ¹ and X ² each independently represent O, S, C ( = O), S (= O), SO ₂ , C (R ¹ ) (R ² ), Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) Or P (═O) (R ⁸ ), wherein R ^{1 to} R ⁸ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, aryl Alkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group Group, monovalent heterocyclic group, hetero An aryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group or cyano group is represented. R ¹ and R ² in C (R ¹ ) (R ² ) and R ³ and R ⁴ in Si (R ³ ) (R ⁴ ) may be bonded to each other to form a ring. m represents 0 or 1, and n represents an integer of 1 to 6. However, when m = 0, X ¹ does not represent C (R ¹ ) (R ² ), and when m = 1, X ¹ and X ² are not the same. X ¹ and Ar ² are each bonded to adjacent carbon atoms constituting the ring of Ar ¹ , and when m = 1, X ² and Ar ¹ are carbon atoms constituting the ring of Ar ^2. Are bonded to adjacent carbon atoms, and when m = 0, X ¹ and Ar ¹ are bonded to adjacent carbon atoms among the carbon atoms constituting the ring of Ar ² . ]

[Wherein, o represents an integer from 1 to 10, p represents an integer from 0 to 2,
Y represents O, S, C (R ¹⁰ ) (R ¹¹ ), Si (R ¹² ) (R ¹³ ) or N (R ¹⁴ ), and when a plurality of Y are present, they may be the same or different. R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, Arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted Silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylalkynyl group, carboxyl group, alkyl Le oxycarbonyl group, an aryloxycarbonyl group, arylalkyloxy group, represents a heteroaryloxy group or a cyano group, also R ¹⁰ and R ^11, R ¹² and R ¹³ are bonded to each other to form a ring Well, R ⁹ is a halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, Acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl Group, arylalkynyl group, carboxyl group, alkynyl Represents a ruoxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group or a cyano group; If R ⁹ is more, they may be the same or different, and may form a ring together with R ⁹ together. ] The polymer compound includes a repeating unit represented by the above formula (1), a repeating unit represented by the above formula (2), and a repeating unit represented by the following formula (3), and the number average molecular weight in terms of polystyrene is 10 The polymer thin film element according to claim 1, wherein the polymer thin film element is ³ to 10 ⁸ .

[In the formula, Ar ³ represents a divalent aromatic hydrocarbon group, a divalent heterocyclic group or —CR ¹⁵ ═CR ¹⁶ —. R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl Group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group Represents a heteroarylthio group, an arylalkenyl group, an arylalkynyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group or a cyano group. q represents an integer of 1 to 6. ] 3. The polymer thin film element according to claim 1, wherein X ^{1 in the} formula (1) is O, S, C (O), S (O), or SO ₂ . X ^{2 in} formula (1) is C (R ¹ ) (R ² ), Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (O The polymer thin film element according to claim 1, wherein the polymer thin film element is (R ⁸ ).
(Wherein R ^{1 to} R ⁸ each independently represent the same meaning as described above.) The polymer thin film element according to claim 1, wherein Ar ¹ and Ar ^{2 in} the formula (1) are each independently a trivalent aromatic hydrocarbon group. Y in Formula (2) is S, The polymer thin film element in any one of Claims 1-5 characterized by the above-mentioned. Ar < ³ > in Formula (3) is -CR < ¹⁵ > = CR < ¹⁶ >-, The polymer thin film element in any one of Claims 2-6 characterized by the above-mentioned. (In the formula, R ¹⁵ and R ¹⁶ represent the same meaning as described above.)   The polymer thin film element according to any one of claims 1 to 7, wherein the total of the repeating units represented by the formulas (1) and (2) is 10 mol% or more of all repeating units.   The polymer thin film element according to claim 1, wherein the polymer compound has liquid crystallinity.   The polymer thin film element according to claim 1, wherein the polymer thin film element is an organic thin film transistor.   The polymer thin film element according to any one of claims 1 to 9, wherein the polymer thin film element is an organic solar cell.   The polymer thin film element according to claim 1, wherein the polymer thin film element is an optical sensor.   The polymer thin film element according to claim 1, wherein the polymer thin film element is an electrophotographic photosensitive member.   The polymer thin film element according to claim 1, wherein the polymer thin film element is a spatial light modulation element.

Images