DE112005001823T5 - Polymer compound, polymer thin film and polymer thin film device using them - Google Patents

Abstract

(wobei Ar¹ und Ar² jeweils unabhängig einen dreiwertigen aromatischen Kohlenwasserstoffrest oder einen dreiwertigen heterocyclischen Rest darstellen, X¹ und X² jeweils unabhängig O, S, C(=O), S(=O), SO₂, C(R¹)(R²), Si(R³)(R⁴), N(R⁵), B(R⁶), P(R⁷) oder P(=O)(R⁸) darstellen, R¹ bis R⁸ jeweils unabhängig ein Wasserstoffatom, Halogenatom, einen Alkylrest, Alkyloxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkyloxyrest, Arylalkylthiorest, Acylrest, Acyloxyrest, eine Amidgruppe, Säureimidgruppe, einen Iminrest, eine Aminogruppe, substituierte Aminogruppe, einen substituierten Silylrest, substituierten Silyloxyrest, substituierten Silylthiorest, substituierten Silylaminorest, einwertigen heterocyclischen Rest, Heteroaryloxyrest, Heteroarylthiorest, Arylalkenylrest, Arylethinylrest, eine Carboxylgruppe, einen Alkyloxycarbonylrest, Aryloxycarbonylrest, Arylalkyloxycarbonylrest, Heteroaryloxycarbonylrest oder eine Cyanogruppe darstellen. Hier sind X¹ und X² nicht identisch. R¹ und R² in C(R¹)(R²) und R³ und R⁴ in Si(R³)(R⁴) können unter Bildung eines Rings miteinander verbunden sein. m stellt 0 oder 1...Polymer compound comprising a repeating unit of the following formula (1) and a repeating unit of the following formula (2) and having a polystyrene-reduced number average molecular weight of 10 ³ to 10 ^8:

(wherein Ar ¹ and Ar ² each independently represent a trivalent aromatic hydrocarbon radical or a trivalent heterocyclic radical, X ¹ and X ^{2 are} each independently 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 ), R ¹ to R ⁸ each independently represents 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, acidimide group, imine group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group , substituted silylthio, substituted silylamino, monovalent heterocyclic, heteroaryloxy, heteroarylthio, arylalkenyl, arylethynyl, carboxyl, alkyloxycarbonyl, aryloxycarbonyl, arylalkyloxycarbonyl, heteroaryloxycarbonyl or cyano group s. Here, X ¹ and X ^{2 are} not identical. 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 linked together to form a ring. m represents 0 or 1 ...

Description

Technical field

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

State of the art

From Thin films which is an organic material with electron transportability or hole transportability are expected to be useful for polymer thin film devices such as organic thin film transistors, organic solar batteries and the like are used, and they have been variously examined.

When for such thin films materials to be used are polyphenylenevinylene derivatives, polyfluorene derivatives, Polyphenylene derivatives, polythiophene derivatives, polythienylenevinylene derivatives and the like. Known, the polymer compounds with an electron transportable or hole transportable Molecular structure in the main chain are (Appl. Phys. Lett 49 (1986), p. 1210; Appl. Phys. Lett. Vol. 63 (1993), p. 1372; Appl. Phys. Lett. Volume 77 (2000), p. 406; "Semiconducting Polymers", ed. G. Hadziioannou and P.F. van Hutten (2000) Wiley-VCH).

Disclosure of the invention

The The present invention has the object of providing a new polymer compound, which is used as the material of a thin film for polymer thin-film devices, such as organic thin-film transistors, organic Solarbattieren and the like., Are suitable.

(wobei Ar¹ und Ar² jeweils unabhängig einen dreiwertigen aromatischen Kohlenwasserstoffrest oder einen dreiwertigen heterocyclischen Rest darstellen, X¹ und X² jeweils unabhängig O, S, C(=O), S(=O), SO₂, C(R¹)(R²), Si(R³)(R⁴), N(R⁵), B(R⁶), P(R⁷) oder P(=O)(R⁸) darstellen, R¹ bis R⁸ jeweils unabhängig ein Wasserstoffatom, Halogenatom, einen Alkylrest, Alkyloxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkyloxyrest, Arylalkylthiorest, Acylrest, Acyloxyrest, eine Amidgruppe, Säureimidgruppe, einen Iminrest, eine Aminogruppe, substituierte Aminogruppe, einen substituierten Silylrest, substituierten Silyloxyrest, substituierten Silylthiorest, substituierten Silylaminorest, einen einwertigen heterocyclischen Rest, einen Heteroaryloxyrest, Heteroarylthiorest, Arylalkenylrest, Arylethinylrest, eine Carboxylgruppe, einen Alkyloxycarbonylrest, Aryloxycarbonylrest, Arylalkyloxycarbonylrest, Heteroaryloxycarbonylrest oder eine Cyanogruppe darstellen. Hier sind X¹ und X² nicht identisch. R¹ und R² in C(R¹)(R²) und R³ und R⁴ in Si(R³)(R⁴) können unter Bildung eines Rings miteinander verbunden sein. m stellt 0 oder 1 dar und n stellt eine ganze Zahl von 1 bis 6 dar. Wenn m = 0 stellt X¹ nicht C(R¹)(R²) dar. X¹ und Ar² sind an benachbarte Kohlenstoffatome unter den Kohlenstoffatomen gebunden, die den aromatischen Ring von Ar¹ bilden (nachstehend in einigen Fällen als benachbarte Stellungen des aromatischen Rings bezeichnet), und, wenn m = 1, sind X² und Ar¹ an benachbarte Stellungen des aromatischen Rings von Ar² gebunden, wenn m = 0, sind X¹ und Ar¹ an benachbarte Stellungen des aromatischen Rings von Ar² gebunden).

(wobei o eine ganze Zahl von 1 bis 10 darstellt, p eine ganze Zahl von 0 bis 2 darstellt, Y O, S, C(R¹⁰)(R¹¹), Si(R¹²)(R¹³) oder N(R¹⁴) darstellt und R¹⁰, R¹¹, R¹², R¹³ und R¹⁴ jeweils unabhängig ein Wasserstoffatom, Halogenatom, einen Alkylrest, Alkyloxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkyloxyrest, Arylalkylthiorest, Acylrest, Acyloxyrest, eine Amidgruppe, Säureimidgruppe, einen Iminrest, eine Aminogruppe, substituierte Aminogruppe, einen substituierten Silylrest, substituierten Silyloxyrest, substituierten Silylthiorest, substituierten Silylaminorest, einwertigen heterocyclischen Rest, Heteroaryloxyrest, Heteroarylthiorest, Arylalkenylrest, Arylethinylrest, eine Carboxylgruppe, einen Alkyloxycarbonylrest, Aryloxycarbonylrest, Arylalkyloxycarbonylrest, Heteroaryloxycarbonylrest oder eine Cyanogruppe darstellen. Hier können R¹⁰ und R¹¹ und R¹² und R¹³ unter Bildung eines Rings miteinander verbunden sein. R⁹ stellt ein Halogenatom, einen Alkylrest, Alkyloxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkyloxyrest, Arylalkylthiorest, Acylrest, Acyloxyrest, eine Amidgruppe, Säureimidgruppe, einen Iminrest, eine Aminogruppe, substituierte Aminogruppe, einen substituierten Silylrest, substituierten Silyloxyrest, substituierten Silylthiorest, substituierten Silylaminorest, einwertigen heterocyclischen Rest, Heteroaryloxyrest, Heteroarylthiorest, Arylalkenylrest, Arylethinylrest, eine Carboxylgruppe, einen Alkyloxycarbonylrest, Aryloxycarbonylrest, Arylalkyloxycarbonylrest, Heteroaryloxycarbonylrest oder eine Cyanogruppe dar. Wenn mehrere Reste R⁹ vorhanden sind, können sie gleich oder verschieden sein und die Reste R⁹ können unter Bildung eines Rings miteinander verbunden sein.)More specifically, the present invention provides a polymer compound containing a repeating unit of the following formula (1) and a repeating unit represented by the following formula (2) and having a polystyrene-reduced number average molecular weight of 10 ³ to 10 ⁸ .

(wherein Ar ¹ and Ar ² each independently represent a trivalent aromatic hydrocarbon radical or a trivalent heterocyclic radical, X ¹ and X ^{2 are} each independently 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 ), R ¹ to R ⁸ each independently represents 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, acidimide group, imine group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group , substituted silylthio, substituted silylamino, monohydric heterocyclic, heteroaryloxy, heteroarylthio, arylalkenyl, arylethynyl, carboxyl, alkyloxycarbonyl, aryloxycarbonyl, arylalkyloxycarbonyl, heteroaryloxycarbonyl or cyanogru ppe. Here, X ¹ and X ^{2 are} not identical. 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 linked together to form a ring. m represents 0 or 1 and n represents an integer of 1 to 6. When m = 0, X ¹ does not represent C (R ¹ ) (R ² ). X ¹ and Ar ² are bonded to adjacent carbon atoms among the carbon atoms which form the aromatic ring of Ar ¹ (hereinafter referred to as adjacent positions of the aromatic ring in some cases), and when m = 1, X ² and Ar ^{1 are} attached to adjacent positions of the aromatic ring of Ar ² when m = 0, X ¹ and Ar ^{1 are} attached to adjacent Ar ² aromatic ring positions).

(wherein o represents an integer of 1 to 10, p represents an integer of 0 to 2, YO, 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 each independently represent a hydrogen atom, halo genome atom, an alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acidimide group, imine group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted ones Silylamino, monovalent heterocyclic, heteroaryloxy, heteroarylthio, arylalkenyl, arylethynyl, carboxyl, alkyloxycarbonyl, aryloxycarbonyl, arylalkyloxycarbonyl, heteroaryloxycarbonyl or cyano. Here, R ¹⁰ and R ¹¹ and R ¹² and R ¹³ may be joined together to form a ring. R ⁹ represents halogen, alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkyloxy, arylalkylthio, acyl, acyloxy, amide, acidimide, imino, amino, substituted, substituted silyl, substituted substituted silylthio, substituted silylamino, monovalent heterocyclic, heteroaryloxy, heteroarylthio, arylalkenyl, arylethynyl, carboxyl, alkyloxycarbonyl, aryloxycarbonyl, arylalkyloxycarbonyl, heteroaryloxycarbonyl, or cyano. When multiple R ⁹ are present, they may be the same or different and R ⁹ may be joined together to form a ring.)

(wobei Ar³ einen zweiwertigen aromatischen Kohlenwasserstoffrest, einen zweiwertigen heterocyclischen Rest oder -CR¹⁵=CR¹⁶- darstellt. R¹⁵ und R¹⁶ stellen jeweils unabhängig ein Wasserstoffatom, Halogenatom, einen Alkylrest, Alkyloxyrest, Alkylthiorest, Arylrest, Aryloxyrest, Arylthiorest, Arylalkylrest, Arylalkyloxyrest, Arylalkylthiorest, Acylrest, Acyloxyrest, eine Amidgruppe, Säureimidgruppe, einen Iminrest, eine Aminogruppe, substituierte Aminogruppe, einen substituierten Silylrest, substituierten Silyloxyrest, substituierten Silylthiorest, substituierten Silylaminorest, einwertigen heterocyclischen Rest, einen Heteroaryloxyrest, Heteroarylthiorest, Arylalkenylrest, Arylethinylrest, eine Carboxylgruppe, einen Alkyloxycarbonylrest, Aryloxycarbonylrest, Arylalkyloxycarbonylrest, Heteroaryloxycarbonylrest oder eine Cyanogruppe dar. q stellt eine ganze Zahl von 1 bis 6 dar.)Further, the present invention provides a polymer compound containing a repeating unit of the above-described formula (1), a repeating unit of the above-described formula (2) and a repeating unit of the following formula (3), and a polystyrene-reduced number average molecular weight of 10 ³ to 10 ⁸ has:

(wherein Ar ^{3 represents} a divalent aromatic hydrocarbon group, a divalent heterocyclic group or -CR ¹⁵ = CR ¹⁶ -) R ¹⁵ and R ¹⁶ each independently represent 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, acidimide group, imine group, 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, arylethynyl group, one Represents carboxyl group, an alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group or a cyano group. Q represents an integer of 1 to 6.)

Short explanation of drawings

1 Fig. 10 is a schematic sectional view of a staggered type organic thin film transistor according to the present invention

2 Fig. 10 is a schematic cross-sectional view of a top-and-bottom organic staggered type thin-film transistor according to the present invention.

3 Fig. 10 is a schematic section of an inverted-structure organic thin-film transistor according to the present invention.

4 Fig. 12 is a schematic section of an organic top-bottom contact inverted structure thin film transistor according to the present invention.

5 Fig. 10 is a schematic section of a solar battery according to the present invention.

6 Fig. 10 is a schematic section of a laminated type optical sensor according to the present invention.

7 Fig. 10 is a schematic section of a laminated type optical sensor according to the present invention.

8th Fig. 12 is a schematic sectional view of a monolayer type optical sensor according to the present invention.

9 Fig. 10 is a schematic section of an electrophotographic photoreceptor of the monolayer Type according to the present invention.

10 Fig. 10 is a schematic sectional view of a laminated type electrophotographic photoreceptor according to the present invention.

11 Fig. 10 is a schematic sectional view of a laminated type electrophotographic photoreceptor according to the present invention.

12 Fig. 12 is a schematic section of a spatial light modulator according to the present invention.

Description of the markings

1

substratum

2

Polymer thin film

3

insulating film

4

Gate electrode

5

Source electrode

6

Drain

7

electrode

8th

charge generating layer

9

liquid crystal layer

10

dielectric mirror layer

Best embodiments the invention

The inventive polymer compound contains a repeating unit of the above-described formula (1) and a repeating unit of the above-described formula (2). Further contains the polymer compound of the invention a repeating unit of the above-described formula (1), a repeating unit of the above-described formula (2) and a repeating unit of the above-described formula (3).

In the above-described 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 radical means one atomic residue, which after removal of three hydrogen atoms from a benzene ring or condensed ring, and usually 6 to 60, preferably 6 to 20, carbon atoms and the following described residues are illustrated. Among them are at most preferably atomic radicals after cleavage of three hydrogen atoms remain from a benzene ring. The aromatic hydrocarbon radical may have a substituent. The carbon number of the trivalent aromatic hydrocarbon radicals do not close the carbon number a substituent.

Of the trivalent heterocyclic radical means an atomic radical which after splitting off three hydrogen atoms from a heterocyclic one Connection remains and usually has 4 to 60, preferably 4 to 20 carbon atoms. The heterocyclic The remainder may have a substituent thereon and the carbon number of the heterocyclic group does not close the carbon number a substituent.

Here includes the heterocyclic compound has organic compounds with a cyclic structure in which the ring-forming devices not just a carbon atom, but also heteroatoms, such as oxygen, Sulfur, nitrogen, phosphorus, boron, silicon and the like, in the ring lock in.

When trivalent heterocyclic group become, for example, the following Remains illustrated.

In the above-described formulas, R ¹ each independently represents a hydrogen atom, halogen atom, an alkyl group, alkoxy group, alkylthio group, alkylamino group, aryl group, aryloxy group, arylthio group, aryla minor, arylalkyl, arylalkyloxy, arylalkylthio, arylalkylamino, acyloxy, amide, arylalkenyl, arylalkynyl, monovalent heterocyclic, or cyano.

R '' represents a hydrogen atom, an alkyl radical, Aryl radical, arylalkyl radical, a substituted silyl group, an acyl radical, a monovalent heterocyclic radical, heteroaryloxy or Heteroarylthiorest is.

When Substituent, optionally on the trivalent aromatic hydrocarbon radical or trivalent heterocyclic radical, become halogen atoms, Alkyl radicals, an alkyloxy radical, alkylthio radicals, aryl radicals, aryloxy radicals, Arylthio radicals, arylalkyl radicals, arylalkyloxy radicals, arylalkylthio radicals, Acyl radicals, acyloxy radicals, amide groups, acid imide groups, imine radicals, Amino groups, substituted amino groups, substituted silyl groups, substituted silyloxy, substituted silylthio, substituted Silylamino radicals, monovalent heterocyclic radicals, heteroaryloxy radicals, Heteroarylthio radicals, Arylalkenylreste, Arylethinylreste, a carboxyl group, Alkyloxycarbonyl radicals, aryloxycarbonyl radicals, arylalkyloxycarbonyl radicals, Heteroaryloxycarbonyl or cyano groups illustrated. If multiple substituents are present, the substituents may be together form a ring.

In the above-described formula (1), 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 ). Here, X ¹ and X ^{2 are} not identical.

In the formula (1), R ¹ to R ⁸ each independently represent a hydrogen atom, halogen atom, an alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, an amide group, acidimide group, an imine group, an amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloy group, heteroarylthio group, arylalkenyl group, arylethynyl 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 linked together to form a ring. In this case, the following parts are particularly exemplified as the ring structure part.

When m = 0, X ¹ does not represent C (R ¹ ) (R ² ).

In of Formula (1) described above, n represents an integer from 1 to 6 and integers from 1 to 3 are more preferable and integers from 1 to 2 are more preferable.

In of the above-described formula (1) represents m is 0 or 1, and in the case of materials for organic thin film transistors it is preferred that m is 1 and especially preferred is n 1 and m is 1.

Among others, X ² in the formula (1) is preferably C (R ¹ ) (R ² ), Si (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (= O) (R ⁸ ) and more preferably C (R ¹ ) (R ² ) (wherein R ¹ to R ⁸ each independently have the same meanings as described above.) Further, X ¹ in the formula (1) is preferably 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, and particularly preferably O or S.

When m = 1, the following radicals (4), (5) and (6) are listed as -X ¹ -X ² .

Under the remainders (5) and (6) are preferred and radicals (6) are with regard to the stability of the Connection stronger prefers.

The inventive polymer compound contains a repeating unit of the formula (2) in addition to a repeating unit the above-described formula (1).

In of the formula (2) represents o an integer of 1 to 10 and whole Numbers from 1 to 6 are more preferred and integers from 1 to 5 are more preferable.

In of the above-described formula (2), p represents an integer from 0 to 2. When o is 2 or less, it is preferable that p is 0 or 1, and is further preferred that p is 0. If o 3 or more, in view of solubility, it is preferable that p Is 1 or 2 in one or more of the 5-membered rings.

In the above-described formula (2), Y represents O, S, C (R ¹⁰ ) (R ¹¹ ), Si (R ¹² ) (R ¹³ ) or N (R ¹⁴ ), and O and S are preferable and S is more preferable ,

R ¹⁰ to R ¹⁴ each independently represent a hydrogen atom, halogen atom, an alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, an amide group, acidimide group, an imine group, an amino group, substituted amino group, a substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, carboxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group or cyano group.

In the above-described formula (2), R ^{9 represents} a halogen atom, an alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, an amide group, acidimide group, an imine group, an amino group, substituted amino group a substituted silyl radical, substituted silyloxy radical, substituted silylthio radical, substituted silylamino radical, monovalent heterocyclic radical, heteroaryloxy radical, heteroarylthio radical, arylalkenyl radical, arylethynyl radical, a carboxyl group, an alkyloxycarbonyl radical, aryloxycarbonyl radical, arylalkyloxycarbonyl radical, heteroaryloxycarbonyl radical or a cyano group, preferably a halogen atom, an alkyl radical, alkyloxy radical, Alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkyloxy or arylalkylthio, and more preferably an alkyl or alkyloxy, and when plural R ⁹ are present, they may be the same or different be s and R ⁹ may be joined together to form a ring.

In the case of combining the R ⁹ with each other to form a ring, the following parts are particularly exemplified as the ring structural part.

The inventive polymer compound may be a repeat unit of formula (3) in addition to a repeating unit of the above-described formula (1) and a repeating unit of the above-described 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 or -CR ¹⁵ = CR ¹⁶ - and more preferably -CR ¹⁵ = CR ¹⁶ - represents.

Here the divalent aromatic hydrocarbon radical means one atomic residue, which after removal of two hydrogen atoms from a benzene ring or condensed ring, and usually 6 to 60, preferably 6 to 20, carbon atoms and illustrated are radicals obtained by adding a hydrogen atom to one of the parts, of which three hydrogen atoms in the above illustrated trivalent aromatic hydrocarbon radicals were split off. Of these, the most preferred are atomic radicals, after cleavage of two hydrogen atoms from a benzene ring remain. The aromatic hydrocarbon group may have a substituent exhibit. The carbon number of the divalent aromatic hydrocarbon radical includes not the carbon number of a substituent.

The divalent heterocyclic group means an atomic group remaining after eliminating two hydrogen atoms from a heterocyclic compound, and usually has 4 to 60 preferably 4 to 20 carbon atoms. As the divalent heterocyclic group, there are exemplified groups obtained by adding one hydrogen atom to one of the members from which three hydrogen atoms have been split off from the above-exemplified trivalent aromatic hydrocarbon groups. The heterocyclic group may have a substituent, and the carbon number of the heterocyclic group does not include the carbon number of a substituent.

In the above-described formula (3), R ¹⁵ and R ¹⁶ each independently represent 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, acidimide group, one Imino, amino, substituted amino, substituted silyl, substituted silyloxy, substituted silylthio, substituted silylamino, monovalent heterocyclic, heteroaryloxy, heteroarylthio, arylalkenyl, arylethynyl, carboxyl, alkyloxycarbonyl, aryloxycarbonyl, arylalkyloxycarbonyl, heteroaryloxycarbonyl or cyano.

In of the formula (3), q represents an integer of 1 to 6 and whole Numbers from 1 to 3 are more preferred and integers from 1 to 2 are more preferable.

Among the polymer compounds of the invention are those having a structure ( 7 ) obtained by combining the formula (1) and the formula (2), preferably from the viewpoint of increasing the electron transportability or hole transportability

If the polymer compounds of the invention a repeating unit as described in (3) above in addition to a repeating unit as described in (1) above and a repeating unit as described in (2) above, can several repeat units of the formula (2) may be included. If a plurality of repeating units of the formula (2) are contained, they can be the same or different. Preferred are those having a structure (8) obtained by combining the formula (1), the formula (2) and of the formula (3), in view of increasing the electron transportability or hole transportability.

Here, Y ', R ⁹ ', o 'and p' have the same meanings as Y, R ⁹ , o and p described above and may be the same or different from Y, R ⁹ , o and p.

(wobei R¹ bis R⁹, R¹⁵ und R¹⁶ die gleichen Bedeutungen wie vorstehend beschrieben aufweisen. R^1' bis R^4' weisen die gleichen Bedeutungen wie R¹ bis R⁴ auf).As examples of the structure of the above-described formula (7), structures of the following formulas (9) to (14) and structures having further a substituent on an aromatic hydrocarbon or heterocyclic group in these structures, for example, when n = 1; o = 2, 3 or 5; Y = S, illustrated. As examples of the structure of the above-described formula (8), there are exemplified structures of the following formulas (15) to (17) and structures further having a substituent on an aromatic hydrocarbon group or heterocyclic group in these structures, for example, when n = 1; o = 1; o '= 1; q = 1; Y = S; Y '= S.

(wherein R ¹ to R ⁹ , R ¹⁵ and R ^{16 have} the same meanings as described above. R ^{1 '} to R ^4' have the same meanings as R ¹ to R ⁴ ).

Under they are radicals of the formulas (9), (14), (15) and (17) and radicals with further a substituent on an aromatic hydrocarbon radical or heterocycle in these residues, and more preferred are radicals of the formulas (9) and (15) and radicals with further one substituent on an aromatic hydrocarbon radical or heterocycle in these leftovers. As a substituent, halogen atoms, alkyl groups, a Alkyloxy, alkylthio, aryl, aryloxy, arylthio, Arylalkyl radicals, arylalkyloxy radicals, arylalkylthio radicals, acyl radicals, Acyloxy, amide, acid imide, Imine radicals, amino groups, substituted amino groups, substituted Silyl radicals, substituted silyloxy radicals, substituted silylthio radicals, substituted silylamino radicals, monovalent heterocyclic radicals, Heteroaryloxy, Heteroarylthioreste, Arylalkenylreste, Arylethinylreste, a carboxyl group, alkyloxycarbonyl radicals, aryloxycarbonyl radicals, Arylalkyloxycarbonyl radicals, heteroaryloxycarbonyl radicals or cyano groups and the substituents can be formed to form a ring be connected to each other.

In The above-described formula (1), (2) or (3) are as the Halogen atom fluorine, chlorine, bromine and iodine illustrated.

Of the Alkyl may be linear, branched or cyclic, may be a Have substituents and the carbon number is usually 1 to about 20 and specific examples thereof include one Methyl group, ethyl group, propyl group, i-propyl group, butyl group, i-butyl group, tert-butyl group, Pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, 3,7-dimethyloctyl group, Lauryl group, trifluoromethyl group, pentafluoroethyl group, perfluorobutyl group, perfluorohexyl group, Perfluorooctyl group and the like.

Of the Alkyloxy may be linear, branched or cyclic, may be a Have substituents and the carbon number is usually 1 to about 20 and specific examples thereof include one Methoxy group, ethoxy group, propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, tert-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-methoxyethyloxy group and the like.

Of the Alkylthio may be linear, branched or cyclic Have substituents and the carbon number is usually 1 to about 20 and specific examples thereof include one Methylthio group, ethylthio group, propylthio group, i-propylthio group, Butylthio group, i-butylthio group, tert-butylthio group, pentylthio group, Hexylthio group, cyclohexylthio group, heptylthio group, octylthio group, 2-ethylhexylthio group, Nonylthio group, decylthio group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group and the like.

The aryl group may have a substituent, and the carbon number is usually about 3 to 60, and specific examples thereof include a phenyl group, a C ₁ -C ₁₂ alkoxyphenyl group (C ₁ -C ₁₂ means a carbon number of 1 to 12, also applicable hereinafter) C ₁ -C ₁₂ alkylphenyl, 1-naphthyl, 2-naphthyl, pentafluorophenyl, pyridyl, pyridazinyl, pyrimidyl, pyrazyl, triazyl and the like.

The aryloxy group may have a substituent on an aromatic ring and the carbon number is usually about 3 to 60, and specific examples thereof include a phenoxy group, a C ₁ -C ₁₂ alkoxyphenoxy group, C ₁ -C ₁₂ alkylphenoxy group, a 1-naphthyloxy group, 2 Naphthyloxy group, pentafluorophenyloxy group, pyridyloxy group, pyridazinyloxy group, pyrimidyloxy group, pyrazyloxy group, triazyloxy group and the like.

The arylthio group may have a substituent on an aromatic ring and the carbon number is usually about 3 to 60, and specific examples thereof include a phenylthio group, a C ₁ -C ₁₂ alkoxyphenylthio group, C ₁ -C ₁₂ alkylphenylthio group, a 1-naphthylthio group, 2 Naphthylthio group, pentafluorophenylthio group, pyridylthio group, pyridazinylthio group, pyrimidylthio group, pyrazylthio group, triazylthio group and the like.

The arylalkyl group may have a substituent, and the carbon number is usually about 7 to 60, and specific examples thereof include a phenyl-C _l -C ₁₂ -alkyl group, C ₁ -C ₁₂ -alkoxyphenyl-C ₁ -C ₁₂ -alkyl group, C ₁ - C ₁₂ alkylphenyl-C ₁ -C ₁₂ alkyl, 1-naphthyl-C ₁ -C ₁₂ alkyl, 2-naphthyl-C ₁ -C ₁₂ alkyl, and the like.

The arylalkyloxy group may have a substituent and the carbon number is usually about 7 to 60, and specific examples thereof include a phenyl-C ₁ -C ₁₂ alkoxy group, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxy group, C ₁ - C ₁₂ alkylphenyl C ₁ -C ₁₂ alkoxy, 1-naphthyl C ₁ -C ₁₂ alkoxy, 2-naphthyl C ₁ -C ₁₂ alkoxy, and the like.

The arylalkylthio radical may have a substituent and the carbon number is usually about 7 to 60, and specific examples thereof include a phenyl-C ₁ -C ₁₂ -alkylthio radical, C ₁ -C ₁₂ -alkoxyphenyl-C ₁ -C ₁₂ -alkylthio radical, C ₁ - C ₁₂ alkylphenyl C ₁ -C ₁₂ alkylthio, 1-naphthyl C ₁ -C ₁₂ alkylthio, 2-naphthyl C ₁ -C ₁₂ alkylthio, and the like.

Of the Acyl radical has a carbon number of usually about 2 to 20 and specific examples thereof include an acetyl group, propionyl group, Butyryl group, isobutyryl group, pivaloyl group, benzoyl group, Trifluoroacetyl group, pentafluorobenzoyl group and the like.

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

The Amide group has a carbon number of usually about 2 to 20, preferably 2 to 18 and specific examples thereof include Formamide group, acetamide group, propioamide group, butyramide group, Benzamide group, trifluoroacetamide group, pentafluorobenzamide group, Diformamide group, diacetamide group, dipropioamide group, dibutyramide group, Dibenzamide group, ditrifluoroacetamide group, dipentafluorobenzamide group and the like.

The acid imide includes Residues, obtained by splitting off a hydrogen atom, the to a nitrogen atom of an acid imide is bonded, and the carbon number is usually about 2 to 60, preferably 2 to 48. In particular, the following radicals are illustrated.

Of the Imine rest closes Residues obtained by splitting off a hydrogen atom of imine compounds (means organic compounds with -N = C- in the molecule. Examples include aldimines, Ketimines and compounds obtained by replacing a hydrogen atom N of these compounds through an alkyl group and the like) and the carbon number is usually about 2 to 20, preferably 2 to 18. In particular, the radicals of the following structural formulas and the like.

The substituted amino group includes amino groups substituted with one or two groups selected from alkyl groups, aryl groups, arylalkyl groups and monovalent heterocyclic groups, and the alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The substituted amino group has a carbon number of usually 1 to about 40, and specific examples thereof include a methylamino group, dimethylamino group, ethylamino group, diethylamino group, propylamino, dipropylamino, isopropylamino, diisopropylamino, butylamino, isobutylamino, tert-butylamino, pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, 2-ethylhexylamino, nonylamino, decylamino, 3,7-dimethyloctylamino, laurylamino, cyclopentylamino, dicyclopentylamino, cyclohexylamino, Dicyclohexylamino, pyrrolidyl, piperidyl, ditrifluoromethylamino, phenylamino, diphenylamino, C ₁ -C ₁₂ alkoxyphenylamino, di (C ₁ -C ₁₂ alkoxyphenyl) amino, di (C ₁ -C ₁₂ alkylphenyl) amino, 1-naphthylamino, 2-naphthylamino group, pentafluorophenylamino group, pyridylamino group, pyridazinylamino group, pyrimidylamino group, pyradylamino group, triazylamino group, a phenyl-C ₁ -C ₁₂ -alkylamino radical, C ₁ -C ₁₂ -alkoxyphenyl-C ₁ -C ₁₂ -alkylamino radical, di (C ₁ -C ₁₂ -alkoxyphenyl-C ₁ -C ₁₂ -alkyl amino, di (C ₁ -C ₁₂ alkylphenyl C ₁ -C ₁₂ alkylamino, 1-naphthyl C ₁ -C ₁₂ alkylamino, 2-naphthyl C ₁ -C ₁₂ alkylamino and the like).

Of the substituted silyl radical closes Silyl radicals substituted with 1, 2 or 3 radicals selected from Alkyl radicals, aryl radicals, Arylalkylresten and monovalent heterocyclic Radicals, one and the carbon number is usually 1 to about 60, preferably 3 to 48. The alkyl radical, aryl radical, arylalkyl radical or monovalent heterocyclic radical may have a substituent.

Specific examples thereof include a trimethylsilyl group, triethylsilyl group, tripropylsilyl group, tri-i-propylsilyl, dimethyl-i-propylsilyl, diethyl-i-propylsilyl group, tert-Butylsilyldimethylsilylgruppe, pentyldimethylsilyl group, hexyldimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, 2-Ethylhexyldimethylsilylgruppe, nonyldimethylsilyl group, decyldimethylsilyl group, 3 , 7-dimethyloctyldimethylsilyl group, lauryldimethylsilyl group, a phenyl-C ₁ -C ₁₂ -alkylsilyl radical, C ₁ -C ₁₂ -alkoxyphenyl-C ₁ -C ₁₂ -alkylsilyl radical, C ₁ -C ₁₂ -alkylphenyl-C ₁ -C ₁₂ -alkylsilyl radical, 1-naphthyl-C ₁ -C ₁₂ alkylsilyl group, 2-naphthyl-C ₁ -C ₁₂ alkylsilyl group, phenyl-C ₁ -C ₁₂ -alkyldimethylsilylrest, triphenylsilyl, tri-p-xylylsilylgruppe, tribenzylsilyl, diphenylmethylsilyl, tert-butyldiphenylsilyl Dimethylphenylsilyl group and the like.

The substituted silyloxy group includes silyloxy groups (H ₃ SiO-) substituted with 1, 2 or 3 groups selected from alkyl groups, aryl groups, arylalkyl groups and monovalent heterocyclic groups. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.

Of the substituted silyloxy has a carbon number of usually 1 to about 60, preferably 3 to 30, and specific examples close to it a trimethylsilyloxy group, triethylsilyloxy group, tri-n-propylsilyloxy group, Tri-I propylsilyloxy, tert-butylsilyldimethylsilyloxy group, triphenylsilyloxy group, Tri-p-xylylsilyloxygruppe, Tribenzylsilyloxy group, diphenylmethylsilyloxy group, tert-butyldiphenylsilyloxy group, Dimethylphenylsilyloxgruppe and the like.

The substituted silylthio group includes silylthio groups (H ₃ SiS-) substituted with 1, 2 or 3 groups selected from alkyl groups, aryl groups, arylalkyl groups and monovalent heterocyclic groups. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.

Of the substituted silylthio radical has a carbon number of usually 1 to about 60, preferably 3 to 30, and specific examples close to it a trimethylsilylthio group, triethylsilylthio group, tri-n-propylsilylthio group, Tri-i-propylsilylthiogruppe, tert-butylsilyldimethylsilylthio group, triphenylsilylthio group, Tri-p-xylylsilylthiogruppe, Tribenzylsilylthio group, diphenylmethylsilylthio group, tert-butyldiphenylsilylthio group, Dimethylphenylsilylthio group and the like.

The substituted silylamino group includes silylamino groups (H ₃ SiNH- or (H ₃ Si) ₂₃ N-) substituted with 1 to 6 residues selected from alkyl groups, aryl groups, arylalkyl groups and monovalent heterocyclic groups. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent.

The substituted silylamino group has a carbon number of usually 1 to about 120, preferably 3 to 60, and specific examples thereof include a trimethylsilylamino group, triethylsilylamino group, tri-n-propylsilylamino group, tri-i-propylsilylamino group, tert-butylsilyldimethylsilylamino group, triphenylsilylamino group, tri-p -xylylsilylamino, tribenzylsilylamino, diphenylmethylsilylamino, tert-butyldiphenylsilylamino, dimethylphenylsilylamino, di (trimethylsilyl) amino, di (triethylsilyl) amino, di (tri-n-propylsilyl) amino, di (tri-i-propylsilyl) amino, di (tert-butylsilyldimethylsilyl ) amino group, di (triphenylsilyl) amino group, di (tri-p-xylylsilyl) amino group, di (tribenzylsilyl) amino group, di (diphenylmethylsilyl) amino group, di (tert-butyldiphenylsilyl) amino group, di (dimethylphenylsi lyl) amino group and the like.

The monovalent heterocyclic group means an atomic group remaining after removing one hydrogen atom from a heterocyclic compound, and the carbon number is usually about 4 to 60, and specific examples thereof include a thienyl group, a C ₁ -C ₁₂ alkylthienyl group, pyrrolyl group, furyl group, , Pyridyl group, C ₁ -C ₁₂ alkyl pyridyl, imidazolyl, pyrazolyl, triazolyl, oxazolyl, thiazole, thiadiazole and the like.

As a monovalent heterocyclic radical in the heteroaryloxy radical (radical Q ¹ -O-, Q ¹ represents a monovalent heterocyclic radical), the heteroarylthio radical (radical Q ² -S-, Q ² represents a monovalent heterocyclic radical) and the heteroaryloxycarbonyl radical (radical Q ³ -O (C = O) -, Q ³ represents a monovalent heterocyclic radical), those radicals are illustrated as illustrated for the above-described heterocyclic radical.

For example, the heteroaryloxy group has a carbon number of usually about 4 to 60, and specific examples thereof include a thienyloxy group, a C ₁ -C ₁₂ alkylthienyloxy group, a pyrrolyloxy group, furyloxy group, pyridyloxy group, a C ₁ -C ₁₂ alkyl pyridyloxy group, an imidazolyloxy group, Pyrazolyloxy group, triazolyloxy group, oxazolyloxy group, thiazoloxy group, thiadiazoloxy group and the like.

The heteroarylthio group has a carbon number of usually about 4 to 60, and specific examples thereof include a thienylmercapto group, a C ₁ -C ₁₂ alkylthienylmercapto group, a pyrrolylmercapto group, a furylmercapto group, a pyridylmercapto group, a C ₁ -C ₁₂ -alkylpyridylmercapto group, an imidazolylmercapto group, a pyrazolylmercapto group, Triazolylmercapto group, oxazolylmercapto group, thiazole mercapto group, thiadiazole mercapto group and the like.

Of the Arylalkenyl radical has a carbon number of usually about 8 to 50 and the aryl radical and the alkenyl radical in the arylalkenyl radical the same as the aryl group or alkenyl group described above. Specific Close examples of it a 1-arylvinyl radical, 2-arylvinyl, 1-aryl-1-propenyl, 2-aryl-1-propenyl, 2-aryl-2-propenyl, 3-aryl-2-propenyl and the like. Arylalkadienylreste, such as a 4-aryl-1,3-butadienyl and Like. Are also included.

Of the Arylethynyl radical has a carbon number of usually about 8 to 50 and as the aryl radical in the arylalkynyl radical are those described above Aryl radicals listed.

Of the Alkyloxycarbonyl group has a carbon number of usually about 2 to 20, and specific examples thereof include one Methoxycarbonyl group, ethoxycarbonyl group, propyloxycarbonyl group, i-propyloxycarbonyl group, Butoxycarbonyl group, i-butoxycarbonyl group, tert-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, Perfluorobutoxycarbonyl group, perfluorohexyloxycarbonyl group, perfluorooctyloxycarbonyl group and the like.

The aryloxycarbonyl group has a carbon number of usually about 7 to 60, and specific examples thereof include a phenoxycarbonyl group, a C ₁ -C ₁₂ -Alkoxyphenoxycarbonylrest, C ₁ -C ₁₂ -Alkylphenoxycarbonylrest, a 1-naphthyloxycarbonyl, 2-naphthyloxycarbonyl, Pentafluorphenyloxycarbonylgruppe and the like. one.

The arylalkyloxycarbonyl radical has a carbon number of usually about 8 to 60, and specific examples thereof include a phenyl-C ₁ -C ₁₂ alkoxycarbonyl radical, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ alkoxycarbonyl radical, C ₁ -C ₁₂ - Alkylphenyl-C ₁ -C ₁₂ alkoxycarbonyl, 1-naphthyl-C ₁ -C ₁₂ alkoxycarbonyl, 2-naphthyl-C ₁ -C ₁₂ alkoxycarbonyl and the like.

The heteroaryloxycarbonyl group (Q ⁴ -O (C = O) - group, Q ⁴ represents a monovalent heterocyclic group) has a carbon number of usually about 2 to 60, and specific examples thereof include a thienyloxycarbonyl group, a C ₁ -C ₁₂ alkylthienyloxycarbonyl group a pyrrolyloxycarbonyl group, furyloxycarbonyl group, pyridyloxycarbonyl group, a C ₁ -C ₁₂ alkylpyridyloxycarbonyl group, an imidazolyloxycarbonyl group, pyrazolyloxycarbonyl group, triazolyloxycarbonyl group, oxazolyloxycarbonyl group, thiazoloxycarbonyl group, thiadiazoloxycarbonyl group and the like.

The inventive polymer compound may each be two or more of the above-described formula (1), (2) or (3).

The inventive polymer compound may be a repeating unit other than those described above Contain formulas (1), (2) and (3) in a range that the electron transportability or Hole transportability not impaired. The sum of repeating units of the formula (1) and the formula (2) or the sum of repeating units of formula (1) which Formula (2) and Formula (3) is preferably 10 mol% or more, stronger preferably 50 mol% or more, more preferably 80 mol% or more, based on all repeat units.

If the polymer compound of the invention contains the formula (1) and the formula (2), the molar ratio of Formula (1) to formula (2) preferably in a range of 3: 1 to 1: 3, stronger preferably 2: 1 to 1: 2, more preferably about 1: 1.

If the polymer compound of the invention is the formula (1) containing the formula (2) and the formula (3) the molar ratio the sum of the formula (2) and the formula (3) of the formula (1) preferably in a range of 3: 1 to 1: 3, more preferably 2: 1 to 1: 2, more preferably about 1: 1.

The inventive polymer compound may be an alternating, random, block or graft copolymer be, in another embodiment a polymer compound having a structure that is an intermediate between them is, for example, a random copolymer, the partially blocking property. Further, those who are one Branching in the main chain and having three or more end parts, and dendrimers also included. Preference is given to alternating, Block or graft copolymers, stronger preferred are alternating copolymers. Under block or graft copolymers those are preferred which have a structure of formula (7) or a Structure of the formula (8) contained in a block or Pfropfteil.

Under the polymer compounds of the invention are used as polymer compound having the structure (7) and polymer compound having the structure (8), for example, polymer compounds having a alternating copolymer structure of the following formula (7-1) and Polymer compounds having a copolymer structure of the following formula (8-1).

Here t represents the number of repetitions of the structure (7) or the structure (8) and t is, though dependent varies from the structure of a repeat unit, usually about 2 to 100,000, preferably about 5 to 10,000.

In the polymer compound of the present invention, the repeating units may be coupled by non-conjugated units, or the unconjugated units may be contained in repeating units. As the connecting structure, those described below and those obtained by combining two or more of those described below are illustrated. Here, the Rs each independently represent a hydrogen atom, halogen atom, an alkyl radical, alkyloxy radical, alkylthio radical, aryl radical, aryloxy radical, Arylthio radical, arylalkyl radical, arylalkyloxy radical, arylalkylthio radical, acyl radical, acyloxy radical, an amide group, acidimide group, an imino radical, an amino group, substituted amino group, a substituted silyl radical, substituted silyloxy radical, substituted silylthio radical, substituted silylamino radical, monovalent heterocyclic radical, heteroaryloxy radical, heteroarylthio radical, arylalkenyl radical, arylethynyl radical , a carboxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group or a cyano group, and Ar represents a hydrocarbon group having 6 to 60 carbon atoms.

A End group of the polymer compound according to the invention can be protected with a stable residue, as when a polymerization Group remains intact, the possibility the deterioration of properties and durability in molds to a device. Those with a conjugated bond, the following a conjugated structure of the main chain are preferred and, for example, structures having an aryl group or a heterocyclic group Rest over to bond a carbon-carbon bond are illustrated. In particular, substituents are illustrated which are used in the (chemical Formula 10) in Japanese Patent Laid-Open Publication (JP-A) No. 9-45478 and the like are described.

The inventive polymer compound may be a radical of the following formula (18), (19) or (20) on a Have end of the main chain.

In the formula, Ar ¹ , Ar ² , X ¹ , X ² and m have the same meanings as described above. Z ¹ represents hydrogen, alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkyloxy, arylalkylthio, substituted amino, substituted silyl, monovalent heterocyclic, heteroaryloxy, heteroarylthio, arylalkenyl or arylethynyl.

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

In the formula, Y, R ¹ , Z ¹ and p have the same meanings as described above.

The polymer compound of the present invention has a polystyrene reduced number average molecular weight of about 10 ³ to 10 ⁸ , preferably 10 ⁴ to 10 ⁶ on.

When solvent for the inventive polymer bond become solvents based on an unsaturated Hydrocarbons, such as toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene and the like, solvents based on a halogenated saturated hydrocarbon, such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, Chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, Chlorocyclohexane, bromocyclohexane and the like., Solvents based on a halogenated unsaturated hydrocarbon, such as chlorobenzene, dichlorobenzene, trichlorobenzene and the like, solvents ether-based, such as tetrahydrofuran, tetrahydropyran and the like. Illustrated. Dependent on the structure and molecular weight of the polymer compound The polymer compound can usually in an amount of 0.1% by weight or more in these solvents solved become.

Under the polymer compounds of the invention For example, polymer compounds having liquid crystallinity are preferable. Polymer compound with liquid crystallinity means that the polymer compound of a molecule containing the polymer compound contains a liquid crystalline Phase shows. The liquid crystalline Phase can be measured by a polarizing microscope and differential scanning calorimetry, X-ray scattering measurement and the like. Be determined.

The Polymer compound with liquid crystallinity is when For example, as a material for organic thin film transistors is used to increase the electron mobility or hole mobility suitable. From the polymer compound having liquid crystallinity, it is known that they orient optical or electronic anisotropy shows (Synthetic Meals 119 (2001) 537).

The Process for the preparation of the polymer compound of the invention is described below.

The inventive polymer compound For example, by condensation polymerization using a compound of the following formula (21), a compound of the following formula (22) and a compound of the following formula (23) are prepared as starting materials.

In the formula, Ar ¹ , Ar ² , X ¹ , X ² and m have the same meanings as described above. Y ¹ and Y ² each independently represent a halogen atom, an alkylsulfonate residue, arylsulfonate residue, arylalkylsulfonate residue, a borate group, sulfonylmethyl group, phosphoniummethyl group, phosphonate methyl group, monohalogenated methyl group, boric acid group, formyl group or vinyl group.

In the formula, Y, R ¹ , Y ¹ , Y ² and p have the same meanings as described above.

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

Preferably, Y ¹ and Y ² each independently represent a halogen atom, an alkylsulfonate residue, arylsulfonate residue, arylalkylsulfonate residue, a borate group or boric acid group with respect to the synthesis of compounds of the above-described formulas (21), (22) and (23) and ease of the condensation polymerization reaction ,

The polymer compound of the present invention can be synthesized by using a compound of the following Formula (24), (25), (26) or (27) in addition to (21), (22) and (23) are condensation polymerized to successfully control their final structure.

In the formula, Ar ¹ , Ar ² , X ¹ , X ² , Y ² and m have the same meanings as described above. Z ¹ represents a hydrogen atom, an 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 heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group or represents arylethynyl.

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

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

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

In the compounds of the above-described formulas (24) to (27), Y ¹ and Y ² each preferably independently represent a halogen atom, an alkylsulfonate residue, arylsulfonate residue, arylalkylsulfonate residue, a borate group or boric acid group, more preferably a halogen atom in view of the synthesis of those described above Compounds and simplicity of a condensation polymerization reaction.

When Alkyl sulfonate groups in the formulas (21) to (27) become a methanesulfonate group, Ethanesulfonate group, trifluoromethanesulfonate group and the like, As Arylsulfonatrest a benzenesulfonate, p-toluenesulfonate and the like, and as the arylalkylsulfonate residue, a Benzylsulfonatgruppe and the like. Illustrates.

When Borate group are illustrated residues of the following formulas.

As the sulfonylmethyl group, groups of the following formulas are exemplified.
-CH ₂ S ⁺ Me ₂ X ^- , -CH ₂ S ⁺ Ph ₂ X ^- (X represents a halogen atom)

As phosphoniummethyl group, radicals of the following formula are illustrated.
-CH ₂ P ⁺ Ph ₃ X ^- (X represents a halogen atom)

As Phosphonatmethylgruppe radicals of the following formula are illustrated.
-CH ₂ PO (OR ') ₂
(R 'represents an alkyl radical, aryl radical or arylalkyl radical)

When monohalogenated methyl group are a methyl fluoride group, methyl chloride group, Methyl bromide group and methyl iodide group illustrated.

As a reaction method to be used for producing the polymer compound of the present invention, there are used, for example, a method of polymerization with the Suzuki coupling reaction, a method of polymerization with the Grignard reaction, a method of polymerization using a Ni (0) catalyst, a method of polymerization using an oxidizing agent such as FeCl ₃ and the like, a method of electrochemical oxidation polymerization, a method of decomposing a polymer compound as an intermediate with a suitable releasing group and the like.

From they are methods of polymerization by the Wittig reaction, Polymerization by the Heck reaction, polymerization by the Homer-Wadsworth-Emmons reaction, polymerization by the Knoevenagel reaction and polymerization by the Suzuki coupling reaction and a process the polymerization by the Grignard reaction and a process the polymerization using a Ni (0) catalyst, because the structure control is easy. Further, a method polymerization by the Suzuki coupling reaction, a process the polymerization by the Grignard reaction and a process polymerization using a Ni (0) catalyst because of the easy availability of Starting substances and simplicity of a polymerization reaction process prefers.

One Monomer is, if necessary, in an organic solvent solved, and may be at temperatures not lower than the melting point and not higher as the boiling point of the organic solvent using of, for example, an alkali or a suitable catalyst be implemented. For example, you can known methods described in "Organic Reactions", Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, "Organic Reactions ", volume 27, pp. 345-390, John Wiley & Sons, Inc., 1982, "Organic Syntheses, Collective Volume VI, pp. 407-411, John Wiley & Sons, Inc., 1988, "Chemical Rev. ", Vol. 95, P. 2457 (1995) J. Organomet. Chem., Vol. 576, p. 147 (1999), J. Prakt. Chem., Vol. 336, p. 247 (1994), Makromol. Chem., Macromol. Symp., Vol. 12, p. 229 (1987) and the like.

Preferably For example, the organic solvent to be used becomes sufficiently one Deoxidation treated and the reaction goes under one inert atmosphere to suppress side reactions, in general this depends varies from the compounds and reactions that use are. A drainage treatment is preferably performed for the same reason (except at Reactions with water in a two-phase system, such as the Suzuki coupling reaction).

To the Carry out the reaction becomes an alkali or a suitable catalyst Appropriately added. these can advantageously dependent be chosen by the implementation to be used. As alkali or Catalyst are those which are sufficiently in an in the reaction to be used solvent to solve. As a method of mixing an alkali or a catalyst are illustrated by a solution of a Alkali or a catalyst slowly while stirring the reaction liquid under an inert atmosphere, such as argon, nitrogen and the like is added, or in contrast, the reaction liquid slowly to a solution an alkali or a catalyst is added.

If the polymer compound of the invention as material for used a polymer thin film device is influenced their purity is the property of the device, so it is preferable that a monomer prior to polymerization with a method such as Distillation, sublimation purification, recrystallization and the like the polymerization is purified, and it is preferred that after the synthesis a cleaning treatment, such as Wiederausfällungsreinigung, Chromatography fractionation and the like. Is performed.

in the Process for the preparation of the polymer compound of the invention may be Monomers can be mixed and reacted in one batch or, if required, split and mixed.

With respect to certain reaction conditions, in the case of the Wittig reaction, Horner reaction, Knoevenagel reaction and the like, an alkali is used and reacted in an amount of one equivalent, preferably 1 to 3 equivalents, based on functional groups in monomers. The alkali is not particularly limited and, for example, metal alcoholates such as potassium tert-butoxide, sodium tert-butoxide, sodium methylate, lithium methylate and the like, hydride reagents such as sodium hydride and the like, amides such as sodium amide and the like can be used. As the solvent, N, N-dimethylformamide, tetrahydrofuran, dioxane, toluene and the like can be used. The reaction may usually proceed at reaction temperatures from room temperature to about 150 ° C. The reaction time is, for example, from 5 minutes to 40 hours and times for a sufficient progress of the polymerization are possible, and since it is not required to stand for a long time after completion of the reaction, the reaction time is preferably 10 minutes to 24 hours. If the concentration in the reaction is too low, the reaction efficiency is poor, and if it is too large, the control of the reaction becomes difficult, the concentration may suitably be in a range of about 0.01 wt% to the maximum soluble concentration and usually in a range of 0.1 wt .-% to 20 wt .-% can be selected. In the case of the Heck reaction, the monomers are reacted in the presence of a base such as triethylamine and the like using a palladium catalyst. A relatively high boiling point solvent such as N, N-dimethylformamide, N-methylpyrrolidone and the like 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 become palladium [tetrakis (triphenylphosphine)], Palladiumacetate and the like. For example, used as a catalyst and an inorganic base such as potassium carbonate, sodium carbonate, Barium hydroxide and the like, an organic base such as triethylamine and the like, and an inorganic salt such as cesium fluoride and the like in an amount of one equivalent or more, preferably 1 to 10 equivalents, and implemented. It may also be possible be that an inorganic salt in the form of an aqueous solution used and implemented in the two-phase system. As a solvent N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. Illustrates. Dependent from the solvent Temperatures of about 50 to 160 ° C are suitably used. It may also be possible that the temperature is close to the boiling point of a solvent elevated is to bring about reflux. The implementation period is about 1 hour to 200 hours.

in the Case of the Grignard reaction, methods are illustrated those containing a halide and metallic Mg in a solvent ether-based, such as tetrahydrofuran, diethyl ether, dimethoxyethane and the like., to give a Grignard reagent solution obtained with a separately prepared monomer solution is mixed, and a Nickel or palladium catalyst is added while monitoring for excessive reaction is, then the temperature is increased and the reaction below backflow causes. The Grignard reagent is used in an amount of one equivalent or more, preferably 1 to 1.5 equivalents, more preferably 1 to 1.2 equivalents, based on the monomers used. Also in the case of polymerization With other methods than this method, the reaction according to known Procedure performed become.

The Reaction process is not particularly limited and the reaction can in the presence of a solvent carried out become. The reaction temperature is preferably -80 ° C until Boiling point of the solvent.

When solvents to be used in the reaction become saturated hydrocarbons, such as pentane, hexane, heptane, octane, cyclohexane and the like, unsaturated hydrocarbons, such as benzene, toluene, ethylbenzene, xylene and the like, halogenated saturated hydrocarbons, such as carbon tetrachloride, chloroform, dichloromethane, chlorobutane, Bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, Bromocyclohexane and the like, halogenated unsaturated hydrocarbons, such as chlorobenzene, dichlorobenzene, trichlorobenzene and the like, alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, tert-butyl alcohol and the like, carboxylic acids, like formic acid, Acetic acid, propionic and the like, ethers, such as dimethyl ether, diethyl ether, methyl tert-butyl ether, Tetrahydrofuran, tetrahydropyran, dioxane and the like, inorganic acids, like hydrochloric acid, hydrobromic, Hydrofluoric acid, Sulfuric acid, nitric acid and the like, and these may be in the form of a single solvent or mixed solvent be used.

To the implementation can usual post-treatments carried out be, such as quenching with water before extraction with an organic solvent and distilling off the solvent and the like. Isolation and purification of the product can be achieved by methods like fractionation by chromatography, recrystallization and Like., Performed become.

When next becomes the polymer thin film of the present invention.

The polymer thin film according to the invention is characterized in that it has the above be described polymer compound of the present invention.

The Thickness of the polymer thin film according to the invention is usually about 1 nm to 100 μm, preferably 2 nm to 1000 nm, more preferably 5 nm to 500 nm, in particular preferably 20 nm to 200 nm.

Of the inventive polymer thin film can one which is one of the polymer compounds described above contains individually or may be one having two or more of those described above Contains polymer compounds. To increase the electron transportability or hole transportability of the Polymer thin film may be a low molecular weight compound or polymer compound with electron transportability or hole transportability also mixed in and in addition to the polymer compounds described above. As hole transport material can known materials are used and illustrated Pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, Oligothiophene or its derivatives, polyvinylcarbazole or its Derivatives, polysilane or its derivatives, polysiloxane with an aromatic amine in the side chain or main chain, polyaniline or its derivatives, polythiophene or its derivatives, polypyrrole or its derivatives, polyphenylenevinylene or its derivatives, polythienylenevinylene or its derivatives and the like, and as an electron transport material can known materials are used and illustrated Oxadiazole derivatives, anthraquinodimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its derivatives, anthraquinone or its derivatives, tetracyanoanthraquinodimethane or its derivatives, Fluorenone derivatives, diphenyldicyanoethylene or its derivatives, diphenoquinone derivatives, Metal complexes of 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoxaline or its derivatives, polyfluorene or its derivatives and the like.

Of the inventive polymer thin film can a charge generating material for generating charge by absorbed Light in the polymer thin film contain. As the charge generating material, known materials can be used and illustrate azo compounds and derivatives thereof, diazo compounds and derivatives thereof, non-metal phthalocyanine compounds and derivatives thereof, metal phthalocyanine compounds and derivatives thereof, perylene compounds and derivatives thereof, polycyclic compounds quinine-based and derivatives thereof, squarylium compounds and derivatives thereof, azulenium compounds and derivatives thereof, thiapyrylium compounds and derivatives thereof, fullerenes such as C60 and the like, and derivatives thereof.

Further the polymer thin film of the invention can substances included, which required to obtain various functions are. For example, sensitizers are used to sensitize one Function for generating charge by an absorbed light, Stabilizers to increase stability, UV absorber for absorbing UV light and the like. Illustrates.

Of the inventive polymer thin film can also as polymer binder a material of a polymer compound, which differs from the polymer compounds described above, to improve a mechanical property. As polymer binder are those that have electron transportability or hole transportability do not extremely inhibit, preferably and those that do not have strong absorption for visible Show light, are preferably used. Illustrated as Polymer binders are poly (N-vinylcarbazole), polyaniline or its derivatives, polythiophene or its derivatives, poly (p-phenylenevinylene) or its derivatives, poly (2,5-thienylenevinylene) or its derivatives, polycarbonate, polyacrylate, polymethylacrylate, Polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

The Process for the preparation of the polymer thin film according to the invention is not particularly limited and illustrates methods in which a film is made from a solution is formed, which is the polymer compound described above and an electron transport material or hole transport material and contains a polymer binder, which are to be mixed if necessary.

The for the Film formation from a solution solvents to be used is not particularly limited with the proviso that it is the polymer compound described above and an electron transportable Material or hole transportable material and a polymer binder that triggers are to be mixed.

As the solvent to be used in the case of forming the polymer thin film of the present invention, unsaturated hydrocarbon-based solvents such as toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene and the like are used halogenated sown Hydrocarbon such as carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane and the like., Solvents based on a halogenated unsaturated hydrocarbon such as chlorobenzene, dichlorobenzene, trichlorobenzene and the like., Solvent Ether base such as tetrahydrofuran, tetrahydropyran and the like. The polymer compound may usually be dissolved in an amount of 0.1% by weight or more in these solvents, depending on the structure and the molecular weight of the polymer compound.

When Process for film formation from a solution may include coating processes, such as a spin coating method, casting method, microgravure coating method, Gravure coating process, knife coating process, roll coating process, Wire bar coating method, dip coating method, spray coating method, Screen printing, flexographic printing, offset printing, ink jet printing, Dispenserdruckverfahren and the like. To be illustrated and a Spin coating method, flexographic printing method, ink jet printing method and dispensing printing methods are preferred.

The Process for the preparation of the polymer thin film according to the invention may include a method of orienting a polymer compound.

Of the Polymer thin film, which contains a polymer compound oriented by this method shows improvement in terms of electron mobility or hole mobility, since main chain molecules or Side chain molecules align themselves along one direction.

When Methods for orienting a polymer compound may include methods used as the liquid crystal orientation method known, for example, in "ekisho no kiso to oyo" (Shoichi Matsumoto, Ichiyoshi Kadota collaboration, Kogyo Chosakai 1991), Chapter 5, "kyoyudensei ekisho no kozo to bussei "(Atsuo Fukuda, Hideo Takezoe collaboration, Coronasha 1990), Chapter 7, "ekisho" Vol. 3, No. 1 (1999), P.3 to 16 Shearing Method (Method of Applying Shear Stress) and Hochziehbeschichtungsverfahren simple and as an orientation method suitable and are easily used, and a rubbing method and a shearing process is preferred.

The Friction method is a method of lightly rubbing the surface of a Substrate with a substance and the like. As the substrate, glass, Polymer film and the like. Be used. As a substance for rubbing a substrate can Gauze, polyester, cotton, nylon, rayon and the like. When an orientation film is formed separately on a substrate becomes, takes the orientation ability further to. Here are used as orientation film polyimide, polyamide, PVA, polyester, nylon and the like listed, and commercially available Orientation films for a liquid crystal can also be used. The orientation film can with a Spin coating process, flexographic printing and the like. Be formed. The cloth used for rubbing may be according to the orientation film to be used suitably chosen become.

The Photo alignment method is a method in which an orientation film formed on a substrate and with polarized UV light or irradiated with UV light at an inclined angle of incidence, for orientation function to rent. The orientation film is polyimide, polyamide, polyvinyl cinnamate and the like, and commercially available orientation films for liquid crystal can also be used.

at the rubbing method or photo-alignment method may be an orientation by interposing a material of an oriented polymer compound between substrates, the treatment described above have been achieved. In this case, it is necessary Adjust the substrate temperature to that at which the material in liquid crystalline Phase or isotropic phase is present. The temperature can be before interim a material of a polymer compound between substrates or be set after interim. It is also possible that the material of the polymer compound is only applied to a substrate which has undergone the orientation treatment. The application a polymer compound can be carried out by methods in which a polymer compound is placed on a substrate and on a temperature of Tg or higher is set, or in which a liquid crystalline phase or isotropic Phase is shown, and the polymer compound is along a Direction by a rod or the like. Plotted, in another embodiment becomes a polymer compound in an organic solvent solved, a solution produced by spin coating, flexographic printing and the like. is applied.

The shearing process is a process wherein on a material of a polymer compound, on a sub is applied, another substrate is deposited, and the upper substrate is translated along a direction at temperatures that cause a liquid crystalline phase or isotropic phase. In this case, when substrates subjected to the orientation treatment as described in the above-described rubbing method and photo-alignment method are used, those having a higher degree of orientation are obtained. As the substrate, glass, polymer film and the like may be used, and the object to be displaced by the stress may not be a substrate but a metal rod and the like.

The Hochziehbeschichtungsverfahren is a technology, wherein a substrate in a solution immersed in a polymer compound, then pulled up. The in the solution the organic compound to be used in the polymer compound and the pulling-up speed are not particularly limited and may be according to the degree the orientation of the polymer compound can be selected and adjusted.

The Method for orienting a polymer compound includes one Case of performing according to a method of forming a polymer compound into a Thin film, such as a rubbing method, a shearing method and the like, and a case simultaneous execution with the method of molding a polymer compound into a thin film, such as a pull-up coating method and the like. In another embodiment may provide a method of producing an orientation film a method of molding a polymer compound into a thin film be.

There the inventive polymer thin film electron transportability or hole transport capability, can he for various polymer thin-film devices, like organic thin-film transistors, organic Solar batteries, optical sensors, photoreceptors for electrophotography, spatial Light modulators, photorefractive devices and the like, by controlling the transport of electrons or holes from an electrode or charges generated by light absorption will be used. When the polymer thin film for these polymer thin film devices is used, it is preferred to apply the film with an orientation treatment before use, since then the electron transportability or hole transportability is further improved.

Of the Use of the polymer thin film according to the invention for organic Thin-film transistors will be described.

In the structure of the organic thin film transistor of the present invention, it is common for a source electrode and a drain electrode to be provided adjacent to an active layer made of a polymer compound, and further advantageously to provide a gate electrode having an insulating layer adjacent thereto includes the active layer, and the structures in the 1 to 4 are illustrated.

Of the organic thin-film transistor becomes common on a supportive Substrate formed. The material of the supporting substrate is not particularly limited with the proviso that it does not disturb the property as an organic thin-film transistor, and a glass substrate and flexible film substrate and plastic substrate can also be used.

Of the organic thin-film transistor can by known methods, for example, one in JP-A No. 5-110069 described method can be produced.

at Forming an active layer is the use of one in an organic one solvent soluble Polymer compound very advantageous and in terms of production preferably, such a polymer thin film as the active layer using the above-described Process for the preparation of the polymer thin film according to the invention be formed.

The insulating layer adjacent to the active layer is not particularly limited, provided that it is a material having high electrical insulation, and known materials can be used. For example, SiO x, SiN x, Ta ₂ O ₅ , polyimide, polyvinyl alcohol, polyvinyl phenol and the like are listed. In terms of voltage reduction, stronger dielectrics are preferred.

In forming an active layer on an insulating layer, it is also possible to perform a surface modification by treating the surface of the insulating layer with a surface treating agent such as a silane coupling agent and the like to improve an interfacial property between the insulating layer and the active layer before forming the active layer , As a surface treatment Long-chain alkylchlorosilanes, long-chain alkylalkoxysilanes, fluorinated alkylchlorosilanes, fluorinated alkylalkoxysilanes and the like are listed. It is also possible to treat the surface of the insulation layer with ozone UV or O ₂ plasma prior to treatment with a surface treatment agent.

Prefers is a sealed organic thin film transistor passing through Producing an organic thin film transistor and then Isolating the manufactured transistor is obtained. This is the organic thin film transistor before atmospheric Air protected and a deterioration of the property of the organic thin film transistor can be suppressed become.

When Sealing methods become a method of covering with UV curing Resins, thermosetting Resins, inorganic SiONx films and the like, a method of sticking of glass substrates or films with UV-curing resins, thermosetting Resins and the like listed. For protection against atmospheric To carry out air effectively, is preferred, the method of producing an organic thin film transistor to Sealing without exposure to atmospheric air (for example in a dried nitrogen atmosphere, in vacuo and the like).

5 Fig. 14 is a view illustrating an application of the solar battery polymer thin film of the present invention as a typical example. A structure is used in which a polymer thin film is interposed between a pair of electrodes, one of which is transparent or semitransparent. As the electrode material, metals such as aluminum, gold, silver, copper, alkali metals, alkaline earth metals and the like, or semitransparent films and transparent conductive films thereof may be used. To obtain a higher open circuit voltage, it is preferable that electrodes be selected so that a difference in workfunction is higher. For increasing the photosensitivity, a carrier generator, sensitizer and the like may be added and used in a polymer thin film. As the substrate material, a silicon substrate, glass substrate, plastic substrate and the like can be used.

6 to 8th FIG. 11 is views illustrating an application of the polymer thin film for an optical sensor according to the present invention as a typical example. A structure is used in which a polymer thin film is interposed between a pair of electrodes, one of which is transparent or semitransparent. A charge generating layer that absorbs light and generates charge may also be inserted and used. As the electrode material, metals such as aluminum, gold, silver, copper, alkali metals, alkaline earth metals and the like, or semitransparent films and transparent conductive films thereof may be used. For increasing the photosensitivity, a carrier generator, sensitizer and the like may be added and used in a polymer thin film. As the substrate material, a silicon substrate, glass substrate, plastic substrate and the like can be used.

9 to 11 are views illustrating the application of the polymer thin film for an electrophotographic photoreceptor of the present invention as a typical example. A structure is used in which a polymer thin film is placed on an electrode. A charge-generating layer that absorbs light and generates charge can also be inserted and used. As the electrode material, metals such as aluminum, gold, silver, copper and the like can be used. For increasing the photosensitivity, a carrier generator, sensitizer and the like may be added and used in a polymer thin film. As the substrate material, a silicon substrate, glass substrate, plastic substrate and the like may be used, and it is also possible that a metal such as aluminum and the like may be used simultaneously as a substrate material and an electrode.

12 Fig. 14 is a view illustrating the application of the polymer thin film for a spatial light modulator as a typical example. A structure is used in which a polymer thin film, dielectric layer mirror, and a liquid crystal layer are interposed between a pair of transparent or semitransparent electrodes. The dielectric layer mirror is preferably made of a dielectric multi-layered film, and the arrangement is made such that a low refractive index wavelength region and a high refractive index wavelength region are present, and the limit thereof rises steeply. Various liquid crystalline materials may be used in the liquid crystal layer, and ferroelectric liquid crystals are preferably used. As the electrode material, semiconductor flame and transparent conductive films of aluminum, gold, silver, copper and the like which exhibit high electrical conductivity can be used. As the substrate material, transparent or semitransparent materials such as glass substrates, plastic substrates and the like can be used.

Examples for illustrating the present invention will be more specifically described below but the present invention is not limited to them.

Here became one with respect to the number-average molecular weight Polystyrene number average molecular weight with gel permeation chromatography (GPC) using chloroform as a solvent.

Reference Synthesis Example 1

In one purged with nitrogen 500 ml three-necked flasks were charged with 6.65 g of 2,7-dibromo-9-fluorenone and dissolved in 140 ml of a mixed solvent of trifluoroacetic acid Chloroform = 1: 1 dissolved. To this solution sodium perborate monohydrate was added and the mixture became 20 Hours stirred. The reaction liquid was filtered through celite and washed with toluene. The filtrate was washed with water, sodium hydrogen sulfite and saturated brine, then over Dried sodium sulfate. After distilling off the solvent were obtained 6.11 g of a coarse product.

This crude product was recrystallized from toluene, further from chloroform recrystallized to obtain 1.19 g of Compound 1.

Preparation of C ₈ H ₁₇ MgBr

In To a 100 ml three-necked flask was added 1.33 g of magnesium and flame-dried and purged with argon. To this was added 10 ml of THF and Add 2.3 ml of 1-bromooctane and heat the mixture to start the reaction. After 2.5 hours under reflux one left the reaction liquid cool to room temperature.

Grignard reaction

Into a 300 ml three-necked flask purged with nitrogen was added 1.00 g of Compound 1 and suspended in 10 ml of THF. The suspension was cooled to 0 ° C and the C ₈ H ₁₇ MgBr solution prepared above added. A cooling bath was removed and the reaction liquid was stirred at reflux for 5 hours. The reaction liquid was allowed to cool and 10 ml of water and hydrochloric acid were added. The liquid was a suspension prior to the addition of hydrochloric acid, but after the addition was converted to a two phase solution. After liquid separation, the organic phase was washed with water and saturated brine. This phase was dried over sodium sulfate and the solvent was distilled off to obtain 1.65 g of a coarse product. The crude product was purified by silica gel column chromatography (hexane: ethyl acetate = 20: 1) to obtain 1.30 g of Compound 2.

In one purged with nitrogen 25 ml of two-necked flask were added 0.20 g of compound 2 and dissolved in Dissolved 4 ml of toluene. To this solution were 0.02 g (0.06 mmol) of p-toluenesulfonic acid monohydrate and the mixture was stirred at 100 ° C for 11 hours. The reaction liquid was left cooling down, then it became watery, 4 n aqueous NaOH solution, Water and saturated saline solution washed in this order and the solvent was distilled off, wherein 0.14 g of compound 3 was obtained.

Under a nitrogen atmosphere, 1.0 g (1.77 mmol) of the above Compound 3 described above, 0.945 g (3.72 mmol) of bis (pinacolate) diboron, 0.078 g (0.11 mmol) of [1,1'-bis (diphenylphosphino) ferrocene] palladium dichloride, 0.059 g (0.11 mmol) of 1, 1'-Bis (diphenylphosphino) ferrocene and 15 ml of 1,4-dioxane and argon gas was blown into this mixture for 30 minutes. Thereafter, 1.043 g (10.6 mmol) of potassium acetate was added and reacted under a nitrogen atmosphere at 95 ° C for 13.5 hours. After completion of the reaction, the reaction liquid was filtered to remove the insoluble substances. The product was purified by a short alumina column, the solvent was distilled off, then the residue was dissolved in toluene and activated charcoal was added, and the mixture was stirred and filtered. The filtrate was again purified through a short column of alumina and charcoal was added and the mixture was stirred and filtered. Toluene was completely removed, then 2.5 ml of hexane was added and recrystallization was carried out to obtain 0.28 g of Compound 3-a described below.

Reference Synthesis Example 2

The Compound 4 shown below was treated with a compound disclosed in JP-A No. 2004-043544 obtained described method.

Under Use of the compound 4 described above became a compound 4-a shown below in the same manner as in the reference synthesis example 1 received.

example 1

Synthesis of polymer compound A

0.62 g of Compound 3-a described above, 0.29 g of 5,5'-dibromo-2,2'-bithiophene and 0.36 g of Aliquat 336 (manufactured by ACROS ORGANICS) were placed in a reaction vessel. Thereafter, the manipulations were carried out under a nitrogen atmosphere until the reaction. In the reaction vessel described above, 9.3 g of toluene was introduced, which had previously been deaerated while blowing argon gas. Then, to this mixed solution was added a solution prepared by dissolving 0.39 g of potassium carbonate in 9.6 g of ion-exchanged water which had been previously deaerated while bubbling argon gas. Subsequently, 2.1 mg of tetrakis (triphenylphosphine) palladium (0). The reactions were all carried out under a nitrogen atmosphere. The mixture was reacted under reflux conditions for 16.3 hours, then 18.4 mg of bromobenzene was added and the mixture was refluxed 2 Hours implemented. Further, 19.0 mg of 2-phenyl-1,3,2-dioxabolinane was added, and the mixture was reacted under reflux conditions for 2 hours. After the reaction, this two-phase solution was cooled and the aqueous layer was removed. Since the organic solvent layer was very viscous, chloroform was added for dilution. This mixed solution was poured into methanol, and the mixture was stirred for about 1 hour. Then, the precipitate formed was recovered by filtration. This precipitate was dried under reduced pressure, then dissolved in chloroform. This solution was purified by passage through a column filled with silica and alumina. Then, this solution was poured into methanol to cause re-precipitation, and the precipitate formed was recovered. This precipitate was dried under reduced pressure to obtain 0.53 g of a polymer compound A.

This polymer compound A had a polystyrene-reduced number average molecular weight of 1.2 × 10 ⁶ .

Polymerverbindung A

Polymer compound A

Example 2

Synthesis of polymer compound B

0.73 g of Compound 4-a described above, 0.32 g of 5,5'-dibromo-2,2'-bithiophene and 0.40 g of Aliquat 336 were charged to a reaction vessel. Thereafter, manipulations were performed under a nitrogen atmosphere until the reaction. Into the reaction vessel described above was added 10.4 g of toluene which had been previously deaerated while bubbling argon gas. Then into this mixed solution was added a solution prepared by dissolving 0.44 g of potassium carbonate in 10.7 g of ion-exchanged water which had been previously deaerated while blowing with argon gas. Subsequently, 2.3 mg of tetrakis (triphenylphosphine) palladium (0). The reactions were all carried out under a nitrogen atmosphere. The mixture was refluxed 15 Reacted hours, then 20.4 mg of bromobenzene were added and the mixture was refluxed 2 Hours implemented. Further, 21.1 mg of 2-phenyl-1,3,2-dioxabolinane was added and the mixture was refluxed 2 Hours implemented. After the reaction, this two-phase solution was cooled, and the organic solvent layer was poured into methanol, and the mixture was stirred for about 1 hour. Then, the precipitate formed was recovered by filtration. This precipitate was dried under reduced pressure, then dissolved in chloroform. This solution was purified by passage through a column filled with silica and alumina. Then, this solution was poured into methanol to cause re-precipitation, and the precipitate formed was recovered. This precipitate was dried under reduced pressure to obtain 0.56 g of Polymer Compound B.

This polymer compound B had a polystyrene-reduced number average molecular weight of 3.9 × 10 ⁵ .

Polymerverbindung B

Polymer compound B

Example 3

Preparation of Polymer Thin Film Device and judgment of the property of the organic thin film transistor

An n-type silicon substrate doped in high concentration was formed as a gate electrode having a surface on which 200 nm of silicon oxide as an insulating layer by thermal oxidation was obtained and washed with an alkali detergent, ultrapure water and acetone under ultrasonic waves , then the surface was washed by irradiation with ozone UV. The substrate was immersed in a 5nM octane solution of octadecyltrichlorosilane for 12 hours in a nitrogen atmosphere to perform silane treatment on the surface of the silicon substrate, followed by rinsing the substrate with octane and chloroform in this order. 0.018 g of polymer compound A was weighed and chloroform was added to obtain a weight of 5.3 g, and the mixture was filtered through a 3 μm film filter, then using this coating liquid, a polymer thin film having a thickness of 70 nm was prepared containing the polymer compound A was formed on the above-described surface-treated substrate by a spin coating method. On the polymer thin film For example, an Au electrode was evaporated by a vacuum vapor 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, using the polymer thin film device 1 was produced.

In the prepared polymer thin film device, in a nitrogen atmosphere, a gate voltage V _G varying from 0 to -80 V was applied, and a source-drain voltage V _SD varying from 0 to -80 V was applied the property of the organic thin film transistor was measured to show excellent Isd-Vg property, and the drain current was -1.4 μA at V _g = -80 V and V _sd = -80 V. Derived from the Isd Vg Property obtained electron field mobility was 1 × 10 ^-3 cm ² / Vs and the on / off ratio of the current was 1 × 10 ⁶ .

Reference Synthesis Example 3

Synthesis of the polymer compound C

0.96 g of Compound 3 described above and 0.55 g of 2,2'-bipyridyl were placed in a reaction vessel, then an atmosphere in the reaction system was purged with a nitrogen gas. To this was added 80 g of tetrahydrofuran (THF) (dehydrated solvent) previously deaerated while bubbling with argon gas. Next, to this mixed solution was added 1.05 g of bis (1,5-cyclooctadieny) nickel (0) {Ni (COD) ₂ }, and the mixture was stirred at room temperature for 10 minutes, then at 60 ° C for 1.5 hours implemented. The reaction was carried out in a nitrogen gas atmosphere. After the reaction, this solution was cooled, then poured into a mixed solution of methanol, 100 ml / ion exchanged water, 200 ml, and the mixture was stirred for about 1 hour. Then, the precipitate formed was recovered by filtration. This precipitate was dried under reduced pressure, then dissolved in chloroform. This solution was filtered to remove the insoluble substances, then this solution was purified by passage through an alumina-filled column. Then, this solution was poured into methanol to cause re-precipitation, and the precipitate formed was recovered. This precipitate was dried under reduced pressure to obtain 0.5 g of polymer compound C.

This polymer compound C had a polystyrene-reduced number average molecular weight of 7.3 × 10 ³ .

Polymerverbindung C

Polymer compound C

Comparative Example 1

Preparation of Polymer Thin Film Device and evaluation of the properties of the organic thin film transistor

A polymer thin film having a thickness of 50 nm and containing the polymer compound C was formed by a spin coating method on the above-described surface-treated substrate in the same manner as in Example 3 except that Polymer Compound C was used in place of Polymer Compound A. On the polymer thin film, an Au electrode was vapor-deposited by a vacuum evaporation method to form a source electrode and a drain electrode having a channel width of 2 mm and a channel length of 20 μm, using a polymer thin-film device 2 was produced.

In the prepared polymer thin film device, in a nitrogen atmosphere, a gate voltage V _G varying from 0 to -80 V was applied, and a source-drain voltage V _SD varying from 0 to -80 V was applied the property of the organic thin film transistor was measured. The drain current was -0.8 μA at V _g = -80 V and V _sd = -60 V.

Example 4

Preparation of Polymer Thin Film Device and judgment of the property of a solar battery

On a glass substrate having an ITO film with a thickness of 150 nm formed by a sputtering method, a suspension of poly (3,4) ethylenedioxythiophene / polystyrenesulfonic acid (manufactured by Bayer, Baytron PAI 4083) through a 0.2 Filtered membrane filter, then a thin film with a thickness of 70 nm was formed by spin coating and dried on a hot plate at 200 ° C for 10 minutes. Then, a polymer thin film having a thickness of 50 nm was spin-coated at room temperature using a 0.2 wt% chloroform solution of the polymer compound A. Further, this was dried under reduced pressure at 60 ° C for 1 hour, then deposited with lithium fluoride to a thickness of about 0.4 nm, then evaporated with a thickness of 5 nm thick, further deposited aluminum with a thickness of 180 nm as electrodes, wherein a polymer thin film device 3 was prepared using polymer compound A. The degrees of vacuum evacuation were all 1 × 10 ^-4 Pa or less. While the obtained polymer thin film device 3 was irradiated with a xenon lamp, the voltage-current property was measured, whereby the solar battery characteristics of a short-circuit current of 43 uA / cm ² and an open circuit voltage of 1.75 V was obtained.

Example 5

Preparation of Polymer Thin Film Device and judgment of the property of the solar battery

A polymer thin film device 4 was prepared in the same manner as in Example 5 using polymer compound B instead of polymer compound A. Under irradiation of the obtained polymer thin film device 4 with a xenon lamp, the characteristic voltage-current was measured, whereby a short-circuit current of 38 uA / cm ² and an open circuit voltage of 1.15 V was obtained.

Example 6

Synthesis of the polymer compound D

1.13 g of Compound 3-a described above, 0.60 g of 1,2-di (5-dibromo-2-thienyl) ethene (Synthetic method is described, for example, in M. Fuji et al., Synthetic Metals, 55-57 , 2136-2119 (1993)) and 0.69 g of Aliquat 336 were placed in a reaction vessel. Thereafter, the manipulations were carried out under a nitrogen atmosphere until the reaction. Into the reaction vessel described above was added 19.4 g of toluene which had been previously deaerated while bubbling argon gas. Then, to this mixed solution was added a solution prepared by dissolving 0.74 g of potassium carbonate in 20.0 g of ion-exchanged water which had been previously deaerated while bubbling argon gas. Subsequently, 3.9 mg of tetrakis (triphenylphosphine) palladium (0). The reactions were all performed under a nitrogen atmosphere. The mixture was refluxed 15 Reacted hours, then 34.7 mg of bromobenzene were added and the mixture was refluxed 2 Hours implemented. Further, 35.8 mg of 2-phenyl-1,3,2-dioxabolinane was added and the mixture was refluxed 2 Hours implemented. After the reaction, this two-phase solution was cooled, and the organic solvent layer was poured into methanol, and the mixture was stirred for about 1 hour. Then, the precipitate formed 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-reduced number average molecular weight of 1 × 10 ⁶ or more.

Polymerverbindung D

Polymer compound D

Example 7

Preparation of Polymer Thin Film Device and judgment of the property of the organic thin film transistor

0.008 g of the polymer compound D was weighed and dichlorobenzene was added to obtain a weight of 2 g to prepare a coating liquid. An n-type silicon substrate doped in high concentration as a gate electrode having a surface on which 200 nm of a silicon oxide as an insulating layer was formed by thermal oxidation was obtained, and with an alkali detergent, ultrapure water and acetone under ultrasonic waves washed, then the surface was washed by irradiation with UV ozone. On the substrate, an Au electrode was vapor-deposited by a vacuum evaporation 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 the electrodes was placed on a spin coater and hexamethyldisilazane (HMDS) manufactured by Aldrich was dropped, then spun at 2000 rpm, and the surface of the substrate was treated with HMDS. Using the above-described coating liquid of the polymer compound D, the polymer compound D was coated so that a part between the source electrode and the drain electrode was covered by using a needle tip having an inner diameter of 100 μm with a dispenser printing method (manufactured by Musashi Engineering, Shot Mini) to form a thin film with a thickness of 700 nm. Then, the film was cured at 120 ° C for 30 minutes in a nitrogen atmosphere to form a polymer thin film device 5 manufacture.

In the manufactured polymer thin-film device 5 In the vacuum, a gate voltage V _G varying from 0 to -60 V was applied, and a source-drain voltage V _SD varying from 0 to -60 V was applied, and the characteristic of the organic thin-film transistor was measured , wherein excellent Isd-Vg property was found and the drain current was -0.6 μA at V _g = -60 V and V _sd = -60 V. The electron field effect mobility obtained from the Isd-Vg property was 5 × 10 5 ^-4 cm ² / Vs and the on / off ratio of the current was 1 × 10 ³ .

Industrial applicability

The inventive polymer compound is as a material of a thin film for one Polymer thin film device suitable.

Summary

(wobei Ar¹ und Ar² jeweils unabhängig einen dreiwertigen aromatischen Kohlenwasserstoffrest oder einen dreiwertigen heterocyclischen Rest darstellen, X¹ und X² jeweils unabhängig O, S, C(=O), S(=O), SO₂ oder dgl. darstellen und X¹ und X² nicht identisch sind. Y stellt O, S dar und R⁹ stellt ein Halogenatom, einen Alkylrest, Alkyloxyrest oder dgl. dar. m stellt 0 oder 1 dar und n stellt eine ganze Zahl von 1 bis 6 dar. o stellt eine ganze Zahl von 1 bis 6 dar und p stellt eine ganze Zahl von 0 bis 2 dar).A polymer compound comprising a repeating unit of the following formula (1) and a repeating unit represented by the following formula (2) and having a polystyrene-reduced number average molecular weight of 10 ³ to 10 ⁸ :

(wherein Ar ¹ and Ar ² each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, X ¹ and X ² each independently represent O, S, C (= O), S (= O), SO ₂ or the like, and X ¹ and X ² are not identical. Y represents O, S, and R ⁹ represents a halogen atom, an alkyl group, alkyloxy group, or the like.. m represents 0 or 1 and n represents an integer 1 to 6 o represents an integer of 1 to 6 and p represents an integer of 0 to 2).

Claims (18)

Polymer compound comprising a repeating unit of the following formula (1) and a repeating unit of the following formula (2) and having a polystyrene-reduced number average molecular weight of 10 ³ to 10 ^8:

(wherein Ar ¹ and Ar ² each independently represent a trivalent aromatic hydrocarbon radical or a trivalent heterocyclic radical, X ¹ and X ^{2 are} each independently 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 ), R ¹ to R ⁸ each independently represents 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, acidimide group, imine group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group , substituted silylthio, substituted silylamino, monovalent heterocyclic, heteroaryloxy, heteroarylthio, arylalkenyl, arylethynyl, carboxyl, alkyloxycarbonyl, aryloxycarbonyl, arylalkyloxycarbonyl, heteroaryloxycarbonyl or cyano group s. Here, X ¹ and X ^{2 are} not identical. 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 linked together to form a ring. m represents 0 or 1 and n represents an integer of 1 to 6. When m = 0, X ¹ does not represent C (R ¹ ) (R ² ). X ¹ and Ar ² are at adjacent positions of the aromatic ring of Ar ¹ , and when m = 1, X ² and Ar ^{1 are} attached to adjacent Ar ² aromatic ring positions; when m = 0, X ¹ and Ar ^{1 are} attached to adjacent Ar ² aromatic ring positions .)

(wherein o represents an integer of 1 to 10, p represents an integer of 0 to 2, YO, S, C (R ¹⁰ ) (R ¹¹ ), Si (R ¹² ) (R ¹³ ) or N (R ¹⁴ ), and when plural Y are present, they may be the same or different and R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ^{14 are} each independently hydrogen, halogen, alkyl, alkyloxy, alkylthio, aryl, aryloxy, arylthio , Arylalkyl, arylalkyloxy, arylalkylthio, acyl, acyloxy, amide, acidimide, imino, substituted, amino, substituted, substituted, substituted, substituted, substituted, substituted, silylamino, monovalent, heteroaryloxy, heteroarylthio, arylalkenyl, arylethynyl, represent a carboxyl group, an alkyloxycarbonyl radical, aryloxycarbonyl radical, arylalkyloxycarbonyl radical, heteroaryloxycarbonyl radical or a cyano group, here R ¹⁰ and R ¹¹ and R ¹² and R ^{13 are} mutually connected to form a ring, and R ⁹ represents a halogen atom, an alkyl group, alkyloxy group, alkylthio group, acyl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, an amide group, acidimide group, an imine group, an amino group , substituted amino, substituted silyl, substituted silyloxy, substituted silylthio, substituted silylamino, monovalent heterocyclic, heteroaryloxy, heteroarylthio, arylalkenyl, arylethynyl, carboxyl, alkyloxycarbonyl, aryloxycarbonyl, arylalkyloxycarbonyl, heteroaryloxycarbonyl or cyano. When multiple R ^{9 is} present they may be the same or different and the R ^9s may be linked together to form a ring.). A polymer compound according to claim 1, which comprises a repeating unit of the above-described formula (1), a repeating unit of the above-described formula (2) and a repeating unit of the following formula (3) and has a polystyrene-reduced number average molecular weight of 10 ³ to 10 ⁸ :

(wherein Ar ^{3 represents} a divalent aromatic hydrocarbon group, a divalent heterocyclic group or -CR ¹⁵ = CR ¹⁶ -) R ¹⁵ and R ¹⁶ each independently represent 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, acidimide group, imine group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylal kenyl, arylethynyl, carboxyl, alkyloxycarbonyl, aryloxycarbonyl, arylalkyloxycarbonyl, heteroaryloxycarbonyl or cyano. q represents an integer of 1 to 6). A polymer compound according to claim 1 or 2, wherein X ¹ in the formula (1) is O, S, C (O), S (O) or SO ₂ . A polymer compound according to any one of claims 1 to 3, wherein 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 (wherein R ¹ to R ⁸ each independently have the same meanings as described above). A polymer compound according to any one of claims 1 to 4, wherein Ar ¹ and Ar ² in the formula (1) each independently represent a trivalent aromatic hydrocarbon group. Polymer compound according to one of claims 1 to 5, wherein Y in the formula (2) is S. A polymer compound according to any one of claims 2 to 6, wherein Ar ³ in the formula (3) is -CR ¹⁵ = CR ¹⁶ - (wherein R ¹⁵ and R ^{16 have} the same meanings as described above). Polymer compound according to one of claims 1 to 7, wherein the sum of the repeating units of the formulas (1) and (2) 10 mol% or more, based on all repeating units, is. Polymer compound according to one of claims 1 to 8, which has liquid crystallinity. Polymer thin film, which comprises the polymer compound according to any one of claims 1 to 9 and a film thickness from 1 nm to 100 μm having. Process for the preparation of the polymer thin film according to claim 10 using a spin coating method, Ink jet printing process, dispenser printing process or flexographic printing process. Process for the preparation of the polymer thin film according to claim 10, comprising a method of orienting a Polymers with a rubbing or shearing process. Polymer thin film device, comprising the polymer thin film according to claim 10. Organic thin film transistor, comprising the polymer thin film according to claim 10. An organic solar battery comprising the polymer thin film Claim 10. Optical sensor comprising the polymer thin film after Claim 10. An electrophotographic photoreceptor comprising the polymer thin film according to claim 10. Territorial A light modulator comprising the polymer thin film of claim 10.