WO2006011643A1

WO2006011643A1 - Polymeric compound, thin polymer film, and thin polymer film element including the same

Info

Publication number: WO2006011643A1
Application number: PCT/JP2005/014156
Authority: WO
Inventors: Masato Ueda
Original assignee: Sumitomo Chemical Company, Limited
Priority date: 2004-07-30
Filing date: 2005-07-27
Publication date: 2006-02-02
Also published as: JP2012007165A; TW200607828A; CN1989169A; KR101190933B1; GB2432837B; GB0703688D0; DE112005001823T5; CN1989169B; GB2432837A; KR20070047314A

Abstract

A polymeric compound which comprises repeating units represented by the following formula (1) and repeating units represented by the formula (2) and has a number-average molecular weight, in terms of polystyrene, of 103-108: (1) (2) wherein Ar1 and Ar2 each independently represents a trivalent aromatic hydrocarbon group or trivalent heterocyclic group; X1 and X2 each independently represents O, S, C(=O), S(=O), SO2, etc., provided that X1 is different from X2; Y represents O or S; R9 represents halogeno, alkyl, alkyloxy, etc.; m is 0 or 1; n is an integer of 1 to 6; o is an integer of 1 to 6; and p is an integer of 0 to 2.

Description

Technical description Polymer compounds, polymer thin films, and polymer thin film devices using the same

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

Background art

Thin films containing an organic material having electron transport properties or hole transport properties are expected to be applied to thin film devices such as organic thin film transistors and organic solar cells, and various studies have been made.

As a material for such a thin film, a polyphenylenevinylene derivative, a polycruolene derivative, a polyphenylene derivative, a polythiophene derivative, a polyphenylenevinylene derivative, which is a high molecular compound having an electron transporting or hole transporting molecular structure in the main chain. (App l. P y s. Let t. Vo l. 49 (1986) p. 1210; Ap l. Phy s. Let t. Vo l. 63 (1993) p. 1372; A l. Phy s. Let t. Vo l. 77 (2000) p. 406; "Semi c onduc ti ng Pol ym ers", Ed s. G. Hadz iio annou and PF van Hu tt en (200 0) Wi 1 e y-VCH).

Disclosure of the invention

An object of the present invention is to provide a novel polymer compound useful as a thin film material for polymer thin film elements such as organic thin film transistors and organic solar cells.

That is, the present invention relates to a polymer compound comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the formula (2) and having a polystyrene-equivalent number average molecular weight of 10 ³ to 10 ⁸ . Is provided.

[In the ceremony, ^! ^ Each independently represents a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and X ¹ and X ² each independently represent 0, S, C (= 〇), S (= 〇 ), S0 ₂ , C (R ¹ ) (R ² ), S i (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or P (= ○) represents (R ^8), in Ri～R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, Arukiruokishi group, an alkylthio group, § Li Ichiru group, Ariruokishi group, Ariruchio group, § reel alkyl group, § Reel alkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group , Monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, aryl 1 represents a alkenyl group, an arylethylinyl group, a strong lpoxyl group, an alkyloxy group, a sulfonyloxy group, an aralkyloxycarbonyl group, a heteroalkyloxycarbonyl group, or a cyano group. However, X ¹ and X ² are not the same. R ¹ and R ² in C (R ¹ ) (R ² ) and R ³ and R ⁴ in S i (R ³ ) (R ⁴ ) may be bonded to each other to form a ring. m represents 0 or 1, and n represents an integer from 1 to 6. However, when m = 0, X ¹ does not represent C (R ¹ ) (R ² ). Further, X ¹ and Ar ^2, A carbon atom adjacent of the carbon atoms constituting the aromatic ring of the r ¹ (hereinafter, it is Bukoto by the adjacent position to an aromatic ring) attached respectively, of m = l If, X ² and Ar ¹ is attached to adjacent positions of the aromatic ring of a r ^2, the case of m = 0, X ¹ and Ar ¹ are attached to adjacent positions of the aromatic ring of a r ^2. ]

[Where, o represents an integer from 1 to 10, p represents an integer from 0 to 2, Y represents 〇, S, C (R '°) (R ⁿ ), S i (R ¹² ) (R ¹³ ) or N (R ¹⁴ ), R ¹⁰ , R ″, R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom, a halogen atom, an alkyl group, Alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, aryl alkyl group, aryl alkyloxy group, aryl alkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue Group, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroaryl thio group, aryl alkenyl group, aryl ethynyl Represents a group, a forceloxyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxyl group or a cyano group. ! ^^ and ^{1 1} , and R ^{1 2} and R ^{1 3} may combine with each other to form a ring. R ⁹ is a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, an acyl group, Acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group , Heteroarylthio group, aryl alkenyl group, aryl alkynyl group, strong ruxoxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxy group ruponyl group, heteroaryloxy group force Represents a luponyl group or a cyano group. If R ⁹ there is more than one, they may be the same or different, and may form a ring together with R ⁹ together. ]

Furthermore, the present invention includes a repeating unit represented by the above formula (1), a repeating unit represented by the above formula (2) and a repeating unit represented by the following formula (3), wherein the number average molecular weight in terms of polystyrene is The present invention provides a polymer compound having 10 ³ to 10 ⁸ .

[In the formula, Ar ³ represents a divalent aromatic hydrocarbon group, a divalent heterocyclic group or —CR ¹⁵ = CR ¹⁶ —. R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an alkyl group Reel alkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted 05 014156

4 Silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, 'stroxyloxyl Represents a group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an arylalkyloxycarbonyl group, a heteroaryloxycarbonyl group, or a cyano group. q represents an integer from 1 to 6. Brief description of the drawings

FIG. 1 is a schematic cross-sectional view of a forward staggered organic thin film transistor according to the present invention.

FIG. 2 is a schematic cross-sectional view of a forward staggered organic thin film transistor according to the present invention. FIG. 3 is a schematic cross-sectional view of an inverted-swagger type organic thin film transistor according to the present invention.

FIG. 4 is a schematic cross-sectional view of an inverted staggered oblique organic thin film transistor according to the present invention. FIG. 5 is a schematic cross-sectional view of a solar cell according to the present invention.

FIG. 6 is a schematic cross-sectional view of the multilayer photosensor according to the present invention.

FIG. 7 is a schematic cross-sectional view of a multilayer photosensor according to the present invention.

FIG. 8 is a schematic cross-sectional view of a single-layer photosensor according to the present invention.

FIG. 9 is a schematic cross-sectional view of a single layer type electrophotographic photosensitive member according to the present invention.

FIG. 10 is a schematic cross-sectional view of a multilayer electrophotographic photosensitive member according to the present invention.

FIG. 11 is a schematic cross-sectional view of a multilayer electrophotographic photoreceptor according to the present invention.

FIG. 12 is a schematic cross-sectional view of a spatial light modulation element according to the present invention.

Explanation of symbols

1, base material

2. Polymer thin film

3, insulation film

4, gate electrode

5, source electrode

6, drain electrode

7, electrode

8, charge generation layer 9, Liquid crystal layer

1 0, Dielectric Mira Single Layer BEST MODE FOR CARRYING OUT THE INVENTION

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

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

Here, the trivalent aromatic hydrocarbon group means a remaining atomic group obtained by removing three hydrogen atoms from a benzene ring or condensed ring, and usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms, The following groups are exemplified. Among these, the remaining atomic group obtained by removing 3 hydrogen atoms from the benzene ring is most preferable. In addition, you may have a substituent on the aromatic hydrocarbon group. The carbon number of the trivalent aromatic hydrocarbon group does not include the carbon number of the substituent.

The trivalent heterocyclic group refers to the remaining atomic group obtained by removing three hydrogen atoms from the heterocyclic compound, and the carbon number is usually 4 to 60, preferably 4 to 20. The heterocyclic group may have a substituent, and the carbon number of the heterocyclic group does not include the carbon number of the substituent.

Here, the heterocyclic compound is an organic compound having a cyclic structure in which the elements constituting the ring are not only carbon atoms, but also oxygen, sulfur, nitrogen, phosphorus, boron, and key atoms. A substance containing a terror atom in the ring.

Examples of the trivalent heterocyclic group include the following.

Sl WS00Zd / lDd e io / 9ooz OAV

OAV /] dI2T / S0009

In the above formula, each R ′ is independently a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryl group, an aryloxy group, an aryl group, an aryl amino group, an aryl alkyl group, an aryl alkyl group. Represents a group, an arylalkylthio group, an arylalkylamino group, an acyloxy group, an amide group, an arylalkenyl group, an arylalkylinyl group, a monovalent heterocyclic group or a cyano group.

R "represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, a monovalent heterocyclic group, a heteroaryloxy group, or a heteroarylthio group.

Examples of the substituent that may be present on the trivalent aromatic hydrocarbon group or the trivalent heterocyclic group include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, Aryloxy group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group Group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, allylalkenyl group, arylethylinyl group, strong lpoxyl group, alkyloxycarbonyl group, aryloxycarbonyl group , Arylalkyloxy group And heteroaryloxyl sulfonyl group or cyan group. When there are a plurality of substituents, the substituents may form a ring.

In the above formula (1), X ¹ and X ² are each independently O, S, C (= O), s (= o), S 0 ₂ , C (R ¹ ) (R ² ), S i (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or? (= ○) represents (R ⁸ ). However, X ¹ and X ² are not the same.

In formula (1), Ri to R ⁸ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group. Group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent A heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group, an arylethynyl group, a carboxyl group, an alkyloxycarbonyl group, an aryloxy group, an arylalkyloxycarbonyl group. Represents a heteroaryloxycarbonyl group or a cyano group.

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

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

In the above formula (1), n represents an integer from 1 to 6, an integer from 1 to 3 is more preferable, and an integer from 1 to 2 is more preferable. In the above formula (1), m represents 0 or 1, and the organic thin film transistor material and the like are preferably m = 1, and particularly preferably n = 1 and m = 1.

Among these, X ² in formula (1) is C (R ¹ ) (R ² ), S i (R ³ ) (R ⁴ ), N (R ⁵ ), B

(R ⁶ ), P (R ⁷ ) or P (O) (R ⁸ ) is preferred, and C (R ^[ ) (R ² ) is more preferred. (In the formula, 'R ¹ ! ^ Independently represents the same meaning as above.)

Further, X ¹ in formula (1) is 〇, S, C (= 〇), S (O), S0 2, S i (R 3) (R 4), N (R 5), B (R 6 ), P (R ⁷ ) or? (= 〇) is preferably ^{(R 8), 0, S} , C (= 0), more preferably S (O) or S_〇 _2, particularly preferably from 〇 or S.

In the case of m = l, the group represented by the following (4), (5), (6) can be given as one X ¹ — X ^2- .

(Four)

(Five

(6)

Among them, from the viewpoint of the stability of the compound, the group of the formula (5) (6) is preferable, and the group of the formula (6) is more preferable. The polymer compound of the present invention contains a repeating unit of the formula (2) in addition to the repeating unit of the above formula (1). , / Ο (2)

In the formula (2), o represents an integer from 1 to 10; an integer from 1 to 6 is more preferable, and an integer from 1 to 5 is more preferable.

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

In the above formula (2), Y represents 0, S, C (R ^{1 0} ) (R ⁿ ), S i (R ^{1 2} ) (R ^{1 3} ), N (R "), and O and S are preferred S is more preferable.

R ^{1 11} to R '' are independently a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, Arylalkylthio group, acyl group, 7 siloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent Heterocyclic group, heteroaryloxy group, heteroarylthio group, arylenylalkenyl group, arylruethynyl group, strong lpoxyl group, alkyloxycarbonyl group, aralkyloxycarbonyl group, arylalkyloxycarbonyl group Represents a hetero group, heteroaryloxy group or cyan group.

In the above formula (2), R ⁹ represents a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an aryl group, an aryl alkyl group, an aryl alkyloxy group, an aryl alkylthio group, an acyl group. Group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryl Oxy group, heteroarylthio group, arylenylalkenyl group, arylethynyl group, carboxy Represents a syl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, an aryloxycarbonyl group, a heteroaryloxycarbonyl group or a cyano group, preferably a halogen atom, an alkyl group, an alkyloxy group, An alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, more preferably an alkyl group or an alkyloxy group, and R ⁹ is When there are a plurality of them, they may be the same or different, and R ⁹ may be bonded to each other to form a ring.

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

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

In the formula (3), Ar ³ is a divalent aromatic hydrocarbon group, a divalent heterocyclic group, or —CR = C

R ¹⁶ —, preferably a divalent heterocyclic group, one CR ¹⁵ ═CR ¹⁶ —, more preferably one CR ¹⁵ ═CR ¹⁶ —. Here, the divalent aromatic hydrocarbon group means a remaining atomic group obtained by removing two hydrogen atoms from a benzene ring or condensed ring, and usually has 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms. Example Examples of the trivalent aromatic hydrocarbon group shown are groups in which one hydrogen atom is added to any of the three hydrogen atoms removed. Among these, the remaining atomic group obtained by removing two hydrogen atoms from the benzene ring is most preferable. In addition, you may have a substituent on the aromatic hydrocarbon group. The carbon number of the divalent aromatic hydrocarbon group does not include the carbon number of the substituent.

The divalent heterocyclic group refers to the remaining atomic group obtained by removing two hydrogen atoms from the heterocyclic compound, and the carbon number is usually 4 to 60, preferably 4 to 20. Examples of the divalent heterocyclic group include groups in which one hydrogen atom is added to any of the trivalent heterocyclic groups exemplified above except for three hydrogen atoms. The heterocyclic group may have a substituent, and the carbon number of the heterocyclic group does not include the carbon number of the substituent.

In the above formula (3), R ¹⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group. Group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group , Substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkylenyl group, arylethylinyl group, forceloxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyl Oxycarbonyl group, heteroaryloxy group, or sulfonyl group Represents an ano group.

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

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

When the polymer compound of the present invention contains a repeating unit of the above formula (3) in addition to the repeating unit of the above formula (1) and the repeating unit of the above formula (2), Multiple repeating units may be included. When multiple repeating units of the formula (2) are included, they may be the same or different. From the viewpoint of enhancing electron transport properties or hole transport properties, those having a structure (8) in which the formulas (1), (2) and (3) are combined are preferred.

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

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

STM0 / S00Zdf / X3d Cl79llO / 900Z OAV

(0 T)

SlM0 / S00Zdf / X3d 9ΪΪ0 / 900Ζ OAV

(9 T)

STM0 / S00Zdf / X3d Cl79llO / 900Z OAV

(9 T)

STM0 / S00Zdf / X3d e io / 90oz OAV

(17)

(Wherein, 1 ^ ~1 ^9, R ¹⁵ and R ¹⁶ are as defined above. R ~ R ⁴ 'are as defined above Ri~R ^4.)

Of these, groups represented by formula (9), formula (14), formula (15), formula (17), and And a group further having a substituent on the aromatic hydrocarbon group or heterocyclic ring, and further substituted on the group represented by the formula (9), the formula (15), and these aromatic hydrocarbon group or heterocyclic ring A group having a group is more preferable. Examples of the substituent include a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an aryloxy group, an aryl alkyl group, an aryl alkyloxy group, an aryl alkylthio group, an acyl group, an acyloxy group. Amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio Group, aryl alkenyl group, aryl ethynyl group, strong ruxoxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, 7 arylalkyloxycarbonyl group, heteroaryloxycarbonyl group or cyano group, The substituents are bonded together May form a ring the above formula (1), in the formula (2) or formula (3), the halogen atom, fluorine, chlorine, bromine, iodine and the like.

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

The alkyloxy group may be linear, branched or cyclic, and may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methoxy group, a ethoxy group, Propyloxy group, i-propyloxy group, butoxy group, i-butoxy group, t-butoxy group, benzyloxy group, hexyloxy group, cyclohexyloxy group, hep Tyroxy group, Octyloxy group, 2-Ethylhexyloxy group, Nonyloxy group, Decyloxy group, 3,7-Dimethyloctyloxy group, Lauryloxy group, Trifluoromethoxy group, Pentafluoroethoxy group, Perfluorobutoxy And a perfluorinated hexyl group, a perfluorooctyl group, a methoxymethyloxy group, a 2-methoxyethyloxy group, and the like.

The alkylthio group may be linear, branched or cyclic, and may have a substituent, and usually has about 1 to 20 carbon atoms. Specific examples thereof include a methylthio group, an ethylthio group, Propylthio group, i-Propylthio group, Ptylthio group, i-Ipylthio group, t-Butylthio group, Pentylthio group, Hexylthio group, Cyclohexylthio group, Heptylthio group, Octylthio group, 2-Ethylhexylthio group, Nonylthio group, Decylthio group Group, 3,7-dimethyloctylthio group, laurylthio group, trifluoromethylthio group and the like.

The aryl group may have a substituent, and usually has about 3 to 60 carbon atoms. Specific examples thereof include a phenyl group and a ^ to 0 _{1 2} alkoxyphenyl group ₂ . It shows 1 to 12 carbon atoms. The same applies to the following. ),, ~. , _2- alkylphenyl group, 1-naphthyl group, 2-naphthyl group, pentafluorophenyl group, pyridyl group, pyridazinyl group, pyrimidyl group, birazyl group, triazyl group and the like.

The aryloxy group may have a substituent on the aromatic ring, and usually has about 3 to 60 carbon atoms. Specific examples thereof include a phenoxy group, a ^ to 0 ₁₂ alkoxyphenoxy group, ^ ~, ₂ alkylphenoxy groups, 1 naphthyloxy groups, 2-naphthyloxy groups, penufluorophenyloxy groups, pyridyloxy groups, pyridazinyloxy groups, pyrimidyloxy groups, viraziloxy groups, triazyloxy groups, etc. Illustrated.

The arylthio group may have a substituent on the aromatic ring, and usually has about 3 to 60 carbon atoms. Specific examples thereof include a phenylthio group, C 1, C ₂ C alkoxy alkoxy. Diruthio group, C, -C alkylphenylthio group, 1-naphthylthio group, 2-naphthylthio group, Examples include a pentafluorophenylthio group, a pyridylthio group, a pyridazinylthio group, a pyrimidylthio group, a pyrazylthio group, and a triazylthio group.

§ reel alkyl group may have a substituent, Ri is Der usually about 7 to 60 carbon atoms, and specific examples thereof include phenyl - Ci Cu alkyl, C, -C ₁₂ Arukokishifue two Lou C, ~ C, ₂ alkyl group, ~ dialkylphenyl- ~ dialkyl group, 1-naphthyl ~. Examples include ^ alkyl group, 2-naphthyl C, .about.C ₁₂ alkyl group and the like.

The arylalkyloxy group may have a substituent, and usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenyl ^ to ₂ alkoxy group, C, to C ₁₂ alcohol Kishifueniru - ^ ~ 0 ₁₂ alkoxy group, ^ ~ Ji ^ § Le kills phenyl over ^ ~ Ji ^ § Le Kokishi group, 1 one Nafuchiru 〇, ～〇 ₁₂ alkoxy group, such as 2-Nafuchiru ₂ an alkoxy group is exemplified The

The arylalkylthio group may have a substituent, and usually has about 7 to 60 carbon atoms. Specific examples thereof include phenyl C! C alkylthio group, C, to C ₁₂ alcohol. Kishifue two Lou 〇 ~ 〇 ₁₂ alkylthio group, ^ ~ Ji ^ Arukirufeniru - ^ ~ Ji § alkylthio group, 1 one-naphthyl - ~ 〇 ₁₂ alkylthio group, 2-Nafuchiru C, etc. -C ₁₂ § alkylthio group and the like .

The isyl group usually has about 2 to 20 carbon atoms. Specific examples thereof include an acetyl group, a propionyl group, a propylyl group, an isoptylyl group, a bivaloyl group, a benzoyl group, a trifluoroacetyl group, a pentofluorofluorobenzoyl group. And the like.

The acyloxy group usually has about 2 to 20 carbon atoms, and specific examples thereof include acetoxy group, propionyloxy group, petityloxy group, isoptyryloxy group, pivaloyloxy group, benzoyloxy group, trifluoroacetyl group. Examples thereof include an oxy group and a pen group fluoroxy group.

The amide group usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Examples include formamide group, acetoamide group, propioamide group, ptyramide group, benzamide group, trifluoroacetamide group, pentafluorene benzamide group, diformamide group, diacetamide group, dipropioamide group, dibutyroamide group, dibenzamide group, ditrifluamide group Examples include a oloacetamide group, a dipentafluorine benzamide group, and the like.

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

An imine residue is an imine compound (an organic compound having 1 N = C- in the molecule. For example, aldimine, ketimine, and hydrogen atoms on these N are substituted with alkyl groups, etc. And a residue obtained by removing one hydrogen atom from the compound, usually having about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include groups represented by the following structural formulas.

Examples of the substituted amino group include an amino group substituted with one or two groups selected from an alkyl group, an aryl group, an aryl alkyl group and a monovalent heterocyclic group. The alkyl group, aryl group, The reel alkyl group or monovalent heterocyclic group may have a substituent. The substituted amino group usually has about 1 to 40 carbon atoms. Specific examples thereof include methylamino group, dimethylamino group, ethylamino group, jetylamino group, propylamino group, dipropylamino group, isopropylamino group, diisopropylamino. Group, ptylamino group, isoptylamino group, t-butylamino group, pentylamino group, hexylamino group, cyclohexylamino group, heptylamino group, octylamino group, 2-ethylhexylamino group, nonylamino group, decylamino group, 3, 7- Dimethyloctylamino group, laurylamino group, cyclopentylamino group, dicyclopentylamino group, cyclohexylamino group, dicyclohexylamino group, pyrrolidyl group, piperidyl group, ditrifluoromethylamino group, phenyl Amino group, Jifueniruamino group, C i C! Z alkoxy Fueniruamino groups, di (C, -C _{1 2} alkoxy phenylpropyl) amino group, di (〇, ～〇 _{1 2} Al Kirufueniru) amino group, 1-Nafuchiruamino group, 2 - Nafuchiruamino group, Pentafuru Oro phenyl § amino group, Pirijiruamino group, pyridazinyl Rua amino group, Pirimijiruamino group, Birajiruamino group, Toriajiruamino group, phenylene Lou C, to d ₂ alkylamino , C, -C, ₂ alkoxy phenylalanine - C, -C, ₂ alkyl amino group, C, -C, ₂ Arukirufu Eniru - C, -C, ₂ alkyl amino group, di (C, ~ C ₁₂ alkoxy-phenylalanine - C, -C ₁₂ alkyl) amino group, di (C, ~ C, ₂ Arukirufue two Roux C, ~ C, ₂ alkyl) amino group, 1-Nafuchiru Ci C alkylamino group, 2-naphthyl - C, -C Examples include ₁₂ alkylamino groups.

Examples of the substituted silyl group include a silyl group substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an aryl alkyl group or a monovalent heterocyclic group. About 60, preferably 3 to 48 carbon atoms. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. Specifically, trimethylsilyl group, triethylsilyl group, triprovirsilyl group, tri-i-propylsilyl group, dimethyl _i-one-propylsilyl group, jetyl-i-propylsilyl group, t-butylsilyldimethylsilyl group, pentyldimethyl Silyl group, Hexyldimethylsilyl group, Heptyldimethylsilyl group, Octyldimethylsilyl group, 2-X Tylhexyludimethylsilyl group, Nonyldimethylsilyl group, Decyldimethylsilyl group, 3, 7-Dimethyloctyl Lou dimethylsilyl group, lauryldimethylsilyl group, phenylene Lou C, -C, ₂ alkyl silyl group, C, -C, ₂ Arukokishifue two Roux C, -C, ₂ alkyl silyl group, C, ~ C, ₂ alkyl Phenyl— C, ~ C, ₂ alkylsilyl group, 1-naphthyl-〇 ₁₂ alkylsilyl group, 2-naphthyl- ₂ -alkylsilyl group Group, phenyl 2-alkyldimethylsilyl group, triphenylsilyl group, tri-p-xylylsilyl group, tribenzylsilyl group, diphenylmethylsilyl group, t-butyldiphenylsilyl group, dimethylphenylsilyl group, etc. Is exemplified.

Examples of the substituted silyloxy group include a silyloxy group (H ₃ S i 0-) substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an aryl alkyl group and a monovalent heterocyclic group. It is done. The alkyl group, aryl group, arylalkyl group or monovalent heterocyclic group may have a substituent. The substituted silyloxy group usually has about 1 to 60 carbon atoms, preferably 3 to 30 carbon atoms. Specific examples thereof include a trimethylsilyloxy group, a triethylsilyloxy group, and tri-n-propyl. Birylsilyloxy group, tri-i-propylsilyloxy group, t-butylsilyldimethylsilyloxy group, triphenylsilyloxy group, tri-p-xylylsilyloxy group, tribenzylsilyloxy group, diphenylmethyl Examples thereof include a silyloxy group, t-butyldiphenylsilyloxy group, and dimethylphenylsilyloxy group. Examples of the substituted silylthio group include a silylthio group (H ₃ Si S-) substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an aryl alkyl group and a monovalent heterocyclic group. It is done. The alkyl group, aryl group, aryl alkyl group or monovalent heterocyclic group may have a substituent.

The substituted silylthio group usually has about 1 to 60 carbon atoms, preferably 3 to 30 carbon atoms. Specific examples thereof include a trimethylsilylthio group, a trisilylsilylthio group, a tri-n-propylsilylthio group, Tree i-Provir silylthio group, t-butylsilyldimethylsilylthio group, triphenylsilylthio group, tri-ρ-xylylsilylthio group, tribenzylsilylthio group, diphenylmethylsilylthio group, t-butyldiph Examples include an arylsilylthio group and a dimethylphenylsilylthio group.

'The substituted silylamino group includes a silylamino group substituted with 1 to 6 groups selected from an alkyl group, an aryl group, an arylalkyl group and a monovalent heterocyclic group (H ₃ Si NH 1 or (H ₃ S i) ₂ N—). The alkyl group, aryl group, aryl alkyl group, and monovalent heterocyclic group may have a substituent.

The substituted silylamino group usually has about 1 to 120 carbon atoms, preferably 3 to 60 carbon atoms. Specific examples thereof include trimethylsilylamino group, tribenzylsilylamino group, tri-n-propylsilylamino Group, tri-i-propyl silylamino group, t_butyl silyldimethylsilylamino group, triphenylsilylamino group, tri-p-xylylsilylamino group, tribenzylsilylamino group, diphenylmethylsilylamino group, t- Ptyldiphenylsilylamino group, dimethylphenylsilylamino group, di (trimethylsilyl) amino group, di (triethylsilyl) amino group, di (tri-n-propylsilyl)

) Amino group, Di (tri-i-proylsilyl) amino group, Di (t-butylsilyldimethylsilyl) amino group, Di (triphenylsilyl) amino group, Di (tri-ρ-xylylsilyl) amino group, Di ( Tribenzylsilyl) amino group, di (diphenylmethylsilyl) amino group, di (t_ptyldiphenylsilyl) amino group, di (dimethylphenylsilyl)

An amino group etc. are illustrated.

A monovalent heterocyclic group is a remaining atomic group obtained by removing one hydrogen atom from a heterocyclic compound, and usually has about 4 to 60 carbon atoms. Specific examples thereof include a chenyl group, C! C u alkenyl group, pyrrolyl group, furyl group, pyridyl group, 0, ~ 〇 ₁₂ alkylpyridyl group

And imidazolyl group, pyrazolyl group, triazolyl group, oxazolyl group, thiazole group, thiadiazol group and the like.

Heteroaryloxy group (group represented by O in Q, Q ¹ represents a monovalent heterocyclic group), heteroarylthio group (group represented by Q ² — S—, Q ² is 1 Represents a monovalent heterocyclic group)), heteroaryloxy group sulfonyl group (Q is a group represented by 〇 (C = 〇), Q ³ represents a monovalent heterocyclic group) Examples of the heterocyclic group include the groups exemplified in the above monovalent heterocyclic group.

For example, hetero § reel O alkoxy group has a carbon number of usually 4-6 0 degree, and specific examples thereof include Cheniruokishi group, d ~ C _{1 2} alkyl chain alkenyl O alkoxy group, Piroriruokishi group, Furiruokishi group, Pirijiruokishi group , O, to O _{1 2} alkylpyridyloxy group, imidazolyloxy group, pyrazolyloxy group, triazolyloxy group, oxazolyloxy group, thiazoloxy group, thiadiazoleoxy group and the like are exemplified.

The heteroarylthio group usually has about 4 to 60 carbon atoms, and specific examples thereof include a benzyl mercapto group, a d to C ₁₂ alkyl benzyl mercapto group, a pyrrolyl mercapto group, and a furyl mercapto group. , Pyridyl mercapto group, ^ ~ ji ^ alkyl pyridyl mel Examples include a capto group, an imidazolyl mercapto group, a virazolyl mercapto group, a triazolyl mercapto group, an oxazolyl mercapto group, a thiazole mercapto group, and a thiadiazole mercapto group.

The aryl alkenyl group usually has about 8 to 50 carbon atoms, and the aryl group and alkenyl group in the aryl alkenyl are the same as the above-described aryl group and alkenyl group, respectively. . Specific examples thereof include 1-aryl vinyl group, 2-aryl vinyl group, 1-aryl group, 1-propylenyl group, 2-aryl group, 1-propylenyl group, 2-aryl group, 2-propylenyl group. Group, 3-aryl-2-propylenyl group and the like. Also included are aryl alkadenyl groups such as 4-aryl 1,3-butadenyl.

The arylenetin group usually has about 8 to 50 carbon atoms, and examples of the aryl group in the aryl alkynyl group include the above aryl group.

The alkyloxy group is usually about 2 to 20 carbon atoms. Specific examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, a propyloxycarbonyl group, an i-propyloxycarbonyl group, a butoxycarbonyl group. I-butoxycarbonyl group, t-butoxycarbonyl group, pentyloxycarbonyl group, hexyloxy group sulfonyl group, cyclohexyloxycarbonyl group, heptyloxycarbonyl group, octyloxycarbonyl group, 2-ethylhexyloxy group Xyloxycarbonyl group, Nonyloxy group, Decyloxycarbonyl group, 3,7-Dimethyloctyloxycarbonyl group, Lauroxycarbonyl group, Trifluoromethoxycarbonyl group, Penyufluoroethoxycarbonyl group Group, perfluorobutokki Karuponiru group, Kishiruokishi force Ruponiru group to path one Furuo port, etc. Pafuruo clever speech lipped Ruo carboxymethyl Cal Poni Le groups.

The aryloxy group sulfonyl group usually has about 7 to 60 carbon atoms. Specific examples thereof include a phenoxycarbonyl group, ~ Ji ^ alkoxy off enoki deer Lupo group, C, ~ C _{1 2} alkyl full enoki deer Lupo group, 1-naphthyl O carboxymethyl Cal Poni group, 2-naphthyl Examples of arylalkyloxy-powered sulfonyl groups include methoxycarbonyl groups, pentafluorophenyloxycarbonyl groups, etc. The carbon number of arylalkyloxy groups is usually about 8 to 60 carbon atoms. C ₁₂ alkoxycarbonyl alkenyl group, C, -C ₁₂ Arukokishifu Eniru C, -C, ₂ alkoxy Cal Poni group, C, ~ C ₁₂ Arukirufue two Roux C, ~ C _{I 2} alkoxy Cal Poni group, 1-Nafuchiru C, ~ C ₁₂ alkoxy Cal Poni group, such as 2-na Fuchiru ~ Ji ^ alkoxy Cal Poni Le groups.

Heteroalkyloxycarbonyl group (group represented by Q ⁴ -0 (C = 0) —, Q ⁴ represents a monovalent heterocyclic group) has usually about 2 to 60 carbon atoms. Are: a phenyloxycarbonyl group, a _2- alkylphenyloxycarbonyl group, a pyrrolyloxy group, a furonoxycarbonyl group, a pyridyloxycarbonyl group, a Ci to C ₁₂ alkylpyridoxycarbonyl group, an imidazolyl group. Examples thereof include a xyloxy group, a pyrazolyloxycarbonyl group, a triazolyloxycarbonyl group, an oxazolyloxycarbonyl group, a thiazoleoxycarbonyl group, and a thiadiazoleoxycarbonyl group.

The polymer compound of the present invention may contain two or more of the above formulas (1), (2) or (3).

The polymer compound of the present invention may contain a repeating unit other than those represented by formula (1), formula (2) and formula (3) as long as the electron transport property or the hole transport property is not impaired. In addition, the sum of the repeating units represented by formula (1) and formula (2), or the sum of the repeating units represented by formula (1), formula (2) and formula (3) is 10 mol% or more of all the repeating units. Is preferably 50 mol% or more, more preferably 80 mol% or more, when the polymer compound of the present invention contains the formula (1) or the formula (2), ), The molar ratio of formula (2) is preferably in the range of 3: 1 to 1: 3, more preferably 2: 1 to 1: It is in the range of 2, more preferably about 1: 1.

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

In addition, the polymer compound of the present invention may be an alternating, random, block or graft copolymer, or a polymer compound having an intermediate structure thereof, for example, a random copolymer having a block property. There may be. Also, if the main chain is branched and there are 3 or more terminal parts, dendrimers are included. Preferred are alternating, block or graft copolymers, and more preferred are alternating copolymers. Among the block or graft copolymers, those containing the structure of the formula (7) or the structure of the formula (8) in the block or graft portion are preferable.

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

, T represents the number of repetitions of structure (7) or structure (8), U or Usually, it is about 2-100,000, preferably about 5-10,000 depending on the structure of the position. In the polymer compound of the present invention, the repeating unit may be linked by a non-conjugated unit, or the repeating unit may contain those non-conjugated parts. Examples of the binding structure include those shown below, and combinations of two or more of the following. Here, each R is independently a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an aryloxy group, an arylalkyloxy group, an arylalkyloxy group, an arylalkylthio group. Group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, Heteroaryloxy group, heteroarylthio group, arylenylalkenyl group, arylethylinyl group, strong ruxoxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryloxycarbonyl group Group or cyan group, A r is Shows the prime 6 6 0 hydrocarbon radical.

R R R R

I I I I

-0- -S- One N One -B- -Si— -C-

I I

R R

0 0 0 0 0

II II II II II

One C One -C-0- -0-C- -N-C- -C-N- i

0 0 0 0

II II II II

-zC, no,, shi

R! 1 1 Ar, N N: Ar:; N- C C C QT

II II II II

In addition, the terminal group of the polymer compound of the present invention has a polymerization active group as it is. Since the properties and durability may be reduced, it may be protected with a stable group. Those having a conjugated bond continuous with the conjugated structure of the main chain are preferable, and examples thereof include a structure in which the aryl group or the heterocyclic group is bonded via a carbon-carbon bond. Specific examples include substituents described in Chemical Publication No. 10 of JP-A No. 914-154547.

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

In the formula, A r A r ² , X ¹ , X ² and m represent the same meaning as above. Z ¹ represents a hydrogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, an arylalkyl group, an arylalkyloxy group, an arylalkylthio group, a substituted amino group, a substituted silyl group, 1 A valent heterocyclic group, a heteroaryloxy group, a heteroarylthio group, an arylalkenyl group or an arylethynyl group;

, Z ¹ and m have the same meaning as above.

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

The number average molecular weight in terms of polystyrene of the polymer compound of the present invention is usually from about 10 ³ to about I 0 ⁸ , and preferably from about 10 ⁴ to about L 0 ⁶ .

Solvents for the polymer compound of the present invention include toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene and other unsaturated hydrocarbon solvents, carbon tetrachloride, Chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, black pentane, bromopentane, black hexane, bromohexane, chlorocyclohexane, bromocyclohexane, and other halogenated saturated hydrocarbon solvents, black benzene, Examples thereof include halogenated unsaturated hydrocarbon hydrocarbon solvents such as dichlorobenzene and trichlorobenzene, and ether solvents such as tetrahydrofuran and tetrahydropyran. Although it depends on the structure and molecular weight of the polymer compound, it can usually be dissolved in these solvents in an amount of 0.1% by weight or more.

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

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

Next, a method for producing the polymer compound of the present invention will be described.

The polymer compound of the present invention is produced, for example, by condensation polymerization using a compound represented by the following formula (2 1), a compound represented by (2 2), and a compound represented by (2 3) as raw materials. be able to.

In the formula, A r ′, A r ² , X ¹ , X ² and m represent the same meaning as described above. Y ¹ and Y ² are each independently a halogen atom, an alkyl sulfonate group, an aryl sulfonate group, an aryl alkyl sulfonate group, a borate ester group, a sulfone methyl group, a phospho nmethyl group, a phosphonate methyl group, or a monohalogenated methyl group. Group, boric acid group, holmi Represents a vinyl group or a vinyl group.

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

In the formula, Ar ³ , YY ² and q have the same meaning as described above.

From the viewpoint of the synthesis of the compounds represented by the above (21), (22) and (23) and from the point of view of condensation polymerization reaction, Y ¹ and Y ² are each independently a halogen atom, an alkyl sulfonate group, an aryl. A sulfonate group, an arylalkyl sulfonate group, a borate ester group or a borate group is preferred.

In addition to (21), (22) and (23), the polymer compound of the present invention comprises condensation polymerization using a compound represented by the following formula (2 4), (25), (26) or (27) Thus, the terminal structure can be preferably controlled.

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

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

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

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

Among the compounds represented by the above formulas (24) (27), in view of of Chasse of synthesis and on the condensation polymerization reaction of the above compound, Υ "~Υ ² are each independently a halogen atom, an alkyl sulfonate group, § Preferably, it is a reel sulfonate group, an arylalkyl sulfonate group, a boric acid ester group or a boric acid group, more preferably a halogen atom. Examples of the alkyl sulfonate group in formulas (21) to (27) include a methane sulfonate group. , Ethane sulfonate group, trifluoromethane sulfonate group, etc. are exemplified, as aryl sulfonate group, benzene sulfonate group, ρ-toluene sulfonate group, etc. are exemplified, and as aryl alkyl sulfonate group, Examples include a benzyl sulfonate group.

Examples of the boric acid ester group include groups represented by the following formulae.

Examples of the sulfomethylmethyl group include groups represented by the following formulae.

(X represents a halogen atom. ') Examples of the phosphonium methyl group include groups represented by the following formulae.

(X represents a halogen atom.)

Examples of the phosphonate methyl group include groups represented by the following formulae.

— CH ₂ P〇 (OR ') (R 'represents an alkyl group, an aryl group or an aryl group.)

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

Moreover, as a reaction method used for manufacture of the polymer compound of the present invention, for example,

Polymerization method by Suz uk i coupling reaction, Polymerization method by Grignard reaction, Polymerization method by N i (0) catalyst, Polymerization method by oxidizing agent such as FeC 1 ₃ , Electrochemical oxidation polymerization Or a method by decomposition of an intermediate polymer compound having an appropriate leaving group.

Among these, polymerization by the Wi ttig reaction, polymerization by the Heck reaction, polymerization by the Horn er-Wadswort h_Emmons method, polymerization by Knevene 1 anti-j center, and polymerization by the Suz uk i coupling reaction The method of polymerizing by the Grignard reaction and the method of polymerizing by the Ni (0) catalyst are preferable because the structure control is difficult. Furthermore, a method of polymerizing by a Suzuk i coupling reaction, a method of polymerizing by a Grignard reaction, and a method of polymerizing by a Ni (0) catalyst are preferred from the standpoint of obtaining raw materials and the convenience of the polymerization reaction operation.

If necessary, the monomer can be dissolved in an organic solvent, and the reaction can be carried out, for example, using an alkali or a suitable catalyst at a temperature not lower than the melting point of the organic solvent and not higher than the boiling point. For example, “Organic Reactions”, Vol. 14, 270-490, John Wiley & Sons, Inc., 1965, “Orga Nick Reactions ", 27, 345-390, John Wiley & Sons, Inc., 1982," Organic Synthesis (Organic Synthesis) " ic Syn t he ses) ", Collective Vol. 6 (Collective Vo 1 ume VI), 407-411, John Wiley & Sons, Inc., 1988, Chemical Review (Chem Rev.), 95, 2457 (1995), Journal of Organomet. Chem., 576, 147 (1999), Journal of Practical Chemistry (J. Prac t. Ch em.), 336, 247 (1994), Macromolecular Chemistry, Macromolecular Symposium (Mak romo l. Ch em. ), Vol. 12, p. 229 (1987), etc., can be used.

Although the organic solvent varies depending on the compound and reaction used, it is generally preferable that the solvent used is sufficiently deoxygenated to allow the reaction to proceed in an inert atmosphere in order to suppress side reactions. Similarly, it is preferable to perform a dehydration treatment. (However, this does not apply in the case of a two-phase reaction with water, such as the Suz uk i force pulling reaction.) Appropriate catalyst is appropriately added for the reaction. These may be selected according to the reaction used. The alkali or catalyst is preferably one that is sufficiently dissolved in the solvent used in the reaction. As a method of mixing the alkali or the catalyst, the reaction solution is slowly added under stirring in an inert atmosphere such as argon or nitrogen, and the solution of the catalyst or catalyst is added slowly. The method of adding the reaction solution slowly is exemplified. When the polymer compound of the present invention is used as a material for a polymer thin film device, the purity affects the device characteristics, so the monomer before polymerization was purified by methods such as distillation, sublimation purification, and recrystallization. Polymerization is preferably performed later, and after the synthesis, it is preferable to carry out a purification treatment such as reprecipitation purification and fractionation by chromatography.

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

More specifically, the reaction conditions are described. In the case of the Witig reaction, the Horner reaction, the Kno evengel reaction, etc., an alkali equivalent to the functional group of the monomer, preferably 1 to 3 equivalents, is added. To react. The alkali is not particularly limited, For example, metal alcoholates such as potassium tert-butoxide, sodium tert-butoxide, sodium ethylate and lithium methylate, hydride reagents such as sodium hydride, amides such as sodium amide and the like can be used. As the solvent, N, N-dimethylformamide, tetrahydrofuran, dioxane, toluene or the like is used. The reaction can be carried out usually at room temperature to about 1550 ° C. The reaction time is, for example, 5 minutes to 40 hours, but it is sufficient that the polymerization proceeds sufficiently, and it is not necessary to leave the reaction for a long time after the reaction is completed. 4 hours. The concentration at the time of the reaction is poor if the reaction is too dilute, and if it is too high, it becomes difficult to control the reaction. Is in the range of 0.1 wt% to 2 O wt%. In the case of the Heck reaction, the monomer is reacted in the presence of a base such as triethylamine using a palladium catalyst. N, N-dimethylformamide N-methylpyrrolidone and other solvents with relatively high boiling points are used, the reaction temperature is about 80 to 160 ° C, and the reaction time is about 1 hour to 100 hours. is there.

In the case of Suzuki coupling reaction, for example, palladium [tetraxphosphine (triphenylphosphine)], palladium acetates, etc. are used as catalysts, inorganic bases such as potassium carbonate, sodium carbonate, barium hydroxide, organic bases such as trigelylamine, The reaction is carried out by adding an inorganic salt such as cesium fluoride in an equivalent amount or more, preferably 1 to 10 equivalents, relative to the monomer. The inorganic salt may be reacted as an aqueous solution in a two-phase system. Examples of the solvent include N, N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. Although depending on the solvent, a temperature of about 50 to 160 ° C. is preferably used. The temperature may be raised to near the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours

In the case of the G rignard reaction, the halide and metal Mg are reacted in an ether solvent such as tetrahydrofuran, jetyl ether, or dimethochetan. An example is a method in which an ard reagent solution is mixed with a separately prepared monomer solution, nickel or palladium catalyst is added while paying attention to excess reaction, and then the mixture is heated and refluxed. The Grignard reagent is used in an amount equivalent to or more, preferably 1 to 1.5 equivalents, more preferably 1 to 1.2 equivalents, relative to the monomer. In the case of polymerizing by a method other than these, the reaction can be carried out according to a known method.

Although the method of reaction is not particularly limited, it can be carried out in the presence of a solvent. The reaction temperature is preferably from −80 ° C. to the boiling point of the solvent.

Solvents used in the reaction include saturated hydrocarbons such as pentane, hexane, heptane, octane, and cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, and xylene, carbon tetrachloride, chloroform, dichloromethane, Halogenated saturated hydrocarbons such as chlorobutane, bromobutane, black-opened pentane, bromopentane, black-opened hexane, bromohexane, black-opened cyclohexane, and bromocyclohexane, black-opened benzene, dichlorobenzene, and trichloro-opened benzene Halogenated unsaturated hydrocarbons such as methanol, ethanol, propanol, isopropanol, butanol, alcohols such as t-butyl alcohol, carboxylic acids such as formic acid, acetic acid, propionic acid, dimethyl ether, jetyl ether Examples include ethers such as ether, methyl t-butyl ether, tetrahydrofuran, tetrahydropyran, and dioxane, and inorganic acids such as hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, and nitric acid. May be used

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

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

The thickness of the polymer thin film of the present invention is usually about 1 nm to 100 m, preferably Is from 2 nm to l 00 00 nm, more preferably from 5 nm to 500 nm, and particularly preferred is 2 0 ηπ! ~ 200 nm.

The polymer thin film of the present invention may contain one of the above polymer compounds alone, or may contain two or more of the above polymer compounds. Further, in order to enhance the electron transport property or hole transport property of the polymer thin film, a low molecular compound or a polymer compound having electron transport property or hole transport property may be used in addition to the above polymer compound. As the hole transporting material, known materials can be used, such as pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, oligothiophene or its derivatives, polyvinylcarbazol or its derivatives, polysilane or the like. Is a derivative thereof, a polysiloxane derivative having an aromatic amine in the side chain or the main chain, polyaniline or a derivative thereof, polythiophene or a derivative thereof, polypyrrole or a derivative thereof, polyphenylenevinylene or a derivative thereof, or polyphenylene pinylene or Derivatives thereof are exemplified, and known materials can be used as electron transporting materials, such as oxadiazole derivatives, anthraquinodimethane or derivatives thereof, benzoquinone or derivatives thereof. Derivatives, naphthoquinone or derivatives thereof, anthraquinone or derivatives thereof, tetracyananthraquinodimethane or derivatives thereof, fluorenone derivatives, diphenyldicyanethylene or derivatives thereof, diphenoquinone derivatives, or 8-hydroxyquinoline or derivatives thereof Examples include metal complexes, polyquinoline or derivatives thereof, polyquinoxaline or derivatives thereof, polyfluorene or derivatives thereof, and the like.

In addition, the polymer thin film of the present invention may contain a charge generation material in order to generate charges by light absorbed in the polymer thin film. Known charge generating materials can be used, such as azo compounds and derivatives thereof, diazo compounds and derivatives thereof, metal-free phthalocyanine compounds and derivatives thereof, metal phthalocyanine compounds and derivatives thereof, perylene compounds and derivatives thereof, Examples include polycyclic quinone compounds and derivatives thereof, squarylium compounds and derivatives thereof, azurenium compounds and derivatives thereof, thiapyrylium compounds and derivatives thereof, and fullerenes such as C 60 and derivatives thereof.

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

In addition, the polymer thin film of the present invention may contain a high molecular compound material other than the above polymer compound as a polymer binder in order to enhance mechanical properties. As the polymer binder, those not extremely disturbing the electron transport property or hole transport property are preferable, and those not strongly absorbing to visible light are preferably used. Examples of the polymer binder include poly (N-vinylcarbazole), polyaniline or a derivative thereof, polythiophene or a derivative thereof, poly (p-phenylenevinylene) or a derivative thereof, poly (2,5-cenylenepinylene) Alternatively, derivatives thereof, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polychlorinated pierce, polysiloxane and the like are exemplified.

The method for producing the polymer thin film of the present invention is not limited. For example, the polymer compound, an electron transporting material or a hole transporting material mixed as necessary, and a method by film formation from a solution containing a polymer binder Is exemplified.

The solvent used for film formation from a solution is not particularly limited as long as it dissolves the polymer compound, the electron transport material or hole transport material to be mixed, and the polymer binder.

Solvents used when the polymer thin film of the present invention is formed from a solution include unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decalin, n-butylbenzene, carbon tetrachloride, and black mouth form. Halogenated saturated hydrocarbon solvents such as dichloromethane, dichloroethane, chlorobutane, bromobutane, black mouth pentane, bromopentane, black mouth hexane, bromohexane, chlorocyclohexane, bromocyclohexane, black mouth benzene, dichlorobenzene, trichloro Examples thereof include halogenated unsaturated hydrocarbon solvents such as benzene, and ether solvents such as tetrahydrofuran and tetrahydropyran. Although it depends on the structure and molecular weight of the polymer compound, it can usually be dissolved in these solvents by 0.1% by weight or more.

Examples of film formation methods from solution include spin coating, casting, and microgravity. Coating method, gravure coating method, bar coating method, roll coating method, wire bar coating method, dip coating method, spray coating method, screen printing method, flexographic printing method, offset printing method, inkjet printing method, dispenser printing A coating method such as a spin coating method, a flexographic printing method, an ink jet printing method, or a dispenser printing method is preferable.

The step of producing the polymer thin film of the present invention may include a step of orienting the polymer compound.

In the polymer thin film in which the polymer compound is oriented by this process, the main chain molecules or the side chain molecules are arranged in one direction, so that the electron mobility or the hole mobility is improved.

As a method of aligning polymer compounds, those known as alignment methods for liquid crystals, such as “Fundamentals and applications of liquid crystals” (Shinichi Matsumoto, Ryoko Kakuda, Industrial Research Committee, 1991) Chapter 5, “ “Structure and Physical Properties of Ferroelectric Liquid Crystal” (Co-authored by Ikuo Fukuda and Hideo Takezoe, Corona, 1990) Chapter 7, “Liquid Crystal” Vol. 3 No. 1 (1999) 3-16 pages, etc. Can be used. Of these, the lapping method, photo-alignment method, shearing method (shear stress application method) and pull-up coating method are simple, useful and easy to use as the alignment method. The rubbing method and the sharing method are preferred. This is a method of rubbing lightly. As the substrate, glass, a high molecular film or the like can be used. Cloths such as gauze, polyester, cotton, nylon, and rayon can be used as the cloth for rubbing the substrate. In addition, if a separate alignment film is formed on the substrate, the alignment performance becomes higher. Here, examples of the alignment film include polyimide, polyamide, PVA, polyester, and nylon, and a commercially available alignment film for liquid crystal can also be used. The alignment film can be formed by spin coating or flexographic printing. The cloth used for rubbing can be appropriately selected according to the alignment film used.

The photo-alignment method is a method of providing an alignment function by forming an alignment film on a substrate and irradiating it with polarized UV light or obliquely irradiating UV light. Examples of the alignment film include polyimide, polyamide, and polyvinyl cinnamate. Commercially available alignment films for liquid crystals can also be used.

In the rubbing method or photo-alignment method, the polymer aligned between the substrates subjected to the above-described treatment Orientation can be achieved by sandwiching the compound material. At this time, it is necessary for the substrate to have a liquid crystal phase or isotropic phase temperature. The temperature may be set before or after the polymer compound material is sandwiched between the substrates. Alternatively, the polymer compound material may be simply applied on a substrate that has been subjected to an alignment treatment. The polymer compound can be applied by placing the polymer compound on a substrate and setting the temperature to Tg or higher, or a temperature that exhibits a liquid crystal phase or an isotropic phase, and coating in one direction with a rod or a solution dissolved in an organic solvent. It can be prepared and applied by spin coating or flexographic printing.

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

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

The step of orienting the polymer compound is performed at the same time as the step of thinning the polymer compound, such as the pull-up coating method, when it is performed after the step of thinning the polymer compound, such as the rubbing method or the sharing method. There is a case. In addition, a step of creating an alignment film may be included before the step of thinning the polymer compound.

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

The application of the polymer thin film of the present invention to an organic thin film transistor will be described.

As the structure of the organic thin film transistor of the present invention, the source electrode and the drain electrode are usually provided in contact with the active layer made of a polymer compound, and further, the insulating film in contact with the active layer is provided. It suffices if the gate electrode is provided with the edge layer interposed therebetween. For example, the structures of FIGS.

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

The organic thin film transistor can be manufactured by a known method, for example, a method described in JP-A No. 5-110.09.

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

The insulating layer in contact with the active layer is not particularly limited as long as it is a material having high electrical insulation, and a known one can be used. For example, S i O x, S i N x, Ta 2 0 5, polyimide, polyvinyl alcohol, polypinylphenol and the like can be mentioned. From the viewpoint of lowering the voltage, a material having a high dielectric constant is preferable.

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

A sealed organic thin film transistor obtained by sealing an organic thin film transistor after forming the organic thin film transistor is preferable. As a result, the organic thin film transistor is shielded from the atmosphere, and deterioration of the characteristics of the organic thin film transistor can be suppressed. Examples of the sealing method include a method of covering with a UV curable resin, a thermosetting resin or an inorganic Si ONX film, and a method of bonding a glass plate or film with a UV curable resin or a thermosetting resin. . In order to effectively cut off from the atmosphere, it is preferable to carry out the steps from the preparation of the organic thin film transistor to the sealing without exposure to the atmosphere (for example, in a dry nitrogen atmosphere or in a vacuum). FIG. 5 is a diagram illustrating the application of the polymer thin film of the present invention to a solar cell as a representative example. One is used in a structure in which a polymer thin film is disposed between a pair of transparent or translucent electrodes. As the electrode material, a metal such as aluminum, gold, silver, copper, alkali metal, alkaline earth metal, or a translucent film or transparent conductive film thereof can be used. In order to obtain a high open-circuit voltage, it is preferable to select each electrode so that the difference in work function is large. In the polymer thin film, a carrier generating agent, a sensitizer and the like can be added to increase photosensitivity. As the base material, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.

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

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

FIG. 12 is a diagram illustrating the application of the polymer thin film of the present invention to a spatial light modulator as a representative example. Used in a structure in which a polymer thin film, a dielectric layer mirror, and a liquid crystal layer are disposed between a pair of transparent or translucent electrodes. The dielectric layer mirror is preferably composed of a dielectric multilayer film, and has a low reflectance wavelength region and a high reflectance wavelength region, and is designed so that the boundary rises sharply. Various liquid crystal materials can be used for the liquid crystal layer, but it is preferable to use a ferroelectric liquid crystal. Highly conductive electrode materials such as aluminum, gold, silver, copper and other translucent films A transparent conductive film can be used. As the substrate, a transparent or translucent material such as a glass substrate or a plastic substrate can be used.

EXAMPLES Examples will be shown below for illustrating the present invention in more detail, but the present invention is not limited to these examples. Here, regarding the number average molecular weight, the polystyrene-reduced number average molecular weight was determined by gel permeation chromatography (GPC) using black mouth form as a solvent. Reference synthesis example 1

2. 65 g of 2,7-dibromo-9-fluorenone was placed in a nitrogen-substituted 500 ml three-necked flask and dissolved in 140 ml of a mixed solvent of trifluoroacetic acid: chloroform form = 1: 1. To this solution, sodium perborate monohydrate was added and stirred for 20 hours. The reaction solution was filtered through celite and washed with toluene. The filtrate was washed with water, sodium hydrogen sulfite, and saturated brine, and then dried over sodium sulfate. After distilling off the solvent, 6. l lg of crude product was obtained.

This crude product was recrystallized from toluene and further recrystallized from black mouth form to obtain 1.19 g of Compound 1.

• Preparation of C ₈ ¾ ₇ MgBr

Magnesium 1.33 g was placed in a 100 ml three-necked flask, flame-dried, and purged with argon. To this was added 10 ml THF and 2.3 ml 卜 promooctane and heated to start the reaction. 2. After refluxing for 5 hours, the mixture was allowed to cool to room temperature.

• Grignard reaction

1 l.OOg of the compound was placed in a nitrogen-substituted 300 ml three-necked flask and suspended in 10 ml of THF. Cool to 0 and add the C8H17MgBr solution prepared above. The cold bath was removed and the mixture was stirred for 5 hours under reflux. The reaction mixture was allowed to cool, and 10 ml of water and hydrochloric acid were added. Before adding hydrochloric acid, it was a suspension, but after the addition, it became a two-phase solution. After separation, the organic phase was washed with water and saturated brine. After drying over sodium sulfate and distilling off the solvent, 1.65 g of crude product was obtained. Silica gel color 1.30 g of compound purified by chromatography (hexane: ethyl acetate = 20: 1)

2 got.

Nitrogen-substituted 25 ml 2-neck flask was charged with 0.20 g of compound 2 and dissolved in 4 ml of toluene. To this solution, 0.02 g (0.06 mmol) of p-toluenesulfonic acid monohydrate was added and stirred at 100 ° C. for 11 hours. The reaction solution was allowed to cool, then washed with water, an aqueous NaOH solution, water and saturated brine in this order, and the solvent was distilled off to obtain 0.14 g of compound 3.

In a nitrogen atmosphere, 3 l.Og (1.77 ol) of the above compound, 0.945 g (3.72 mmol) of bis (pinacolate) dipolone, [1, -bis (diphenylphosphino) phenol] 0.078 g of palladium dichloride (0. llmmol), Ι, -bis (diphenylphosphino) pheucose 0.059g (0.11 匪 ol) and 1,4-dioxane 15ml were added, and argon gas was bubbled for 30 minutes. Thereafter, 1.043 g (10.6 mmol) of potassium acetate was added, and the mixture was reacted at 95 ° C. for 13.5 hours in a nitrogen atmosphere. After completion of the reaction, the reaction solution was filtered to remove insoluble matters. After purification with an alumina short column and removal of the solvent. Dissolved in toluene, added activated carbon, stirred and filtered. The filtrate was purified again with an alumina short column, activated carbon was added, and the mixture was stirred and filtered. After completely removing toluene, 2.5 ml of hexane was added and recrystallized to obtain 0.28 g of compound 3-a shown below.

Reference synthesis example 2

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

4 Using the above compound 4, the following compound 4-a was obtained in the same manner as in Reference Synthesis Example 1.

Example 1

A reaction vessel was charged with 0.62 g of the above compound 3-a, 0.59 g of 5,5 '1 jib mouth moe, 2,29 g of pitifen, and 0.36 g of Aliquat 336 (manufactured by ACROS 0RGANICS). Thereafter, the reaction was performed in a nitrogen atmosphere until the reaction. To the previous reaction vessel, 9.3 g of toluene deaerated beforehand by publishing with argon gas was added. Next, 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 degassed by publishing with argon gas in advance. Subsequently, tetrakis (triphenylphosphine) palladium (0) 2. lmg was added. All reactions were performed under a nitrogen atmosphere. After reacting for 16.3 hours under reflux conditions, 18.4 mg of bromobenzene was added and reacted under reflux conditions for 2 hours. Furthermore, 2-phenyl-1,1,3,2-dioxapolynan 19. Omg was added and reacted under reflux conditions for 2 hours. After the reaction, the two-phase solution was cooled and the aqueous layer was removed. Since the organic solvent layer was very viscous, it was diluted by adding black mouth form. This mixed solution Was poured into methanol and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. This precipitate was dried under reduced pressure and then dissolved in black mouth form. This solution was purified by passing through a column packed with silica and alumina. Next, this solution was poured into methanol and re-precipitated, and the generated precipitate was recovered. This precipitate was dried under reduced pressure to obtain 0.53 g of polymer compound A.

The polystyrene reduced number average molecular weight of the polymer compound A was 1. 2x l 0 ^6.

Example 2

The above-mentioned compound 4_a 0.73 g and 5, 5 '1 jib mouth moe 2, 2, —bitiophen 0 · 328 and 11311 & {336 0.40 g were charged into a reaction vessel. Thereafter, the reaction was performed in a nitrogen atmosphere until the reaction. To the previous reaction vessel, 10.4 g of toluene that had been deaerated in advance by argon gas was added. Next, a solution prepared by dissolving 0.44 g of potassium carbonate in 10.7 g of ion-exchanged water previously deaerated by argon gas coupling was added to the mixed solution. Subsequently, 2.3 mg of tetrakis (triphenylphosphine) palladium (0) was added. All reactions were performed under a nitrogen atmosphere. After reacting under reflux conditions for 15 hours, 20.4 mg of bromobenzene was added, and reacted under reflux conditions for 2 hours. Furthermore, 2-phenyl-2-1,3,2-dioxapolynan (21. lmg) was added and reacted under reflux conditions for 2 hours. After the reaction, the two-phase solution was cooled, and the organic solvent layer was poured into methanol and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. This sediment was dried under reduced pressure and then dissolved in black mouth form. This solution was purified by passing through a column packed with silica and alumina. Next, this solution was poured into methanol and reprecipitated, and the generated precipitate was recovered. This precipitate was dried under reduced pressure to obtain 0.56 g of polymer compound B. The polystyrene reduced number average molecular weight of the polymer compound B was 3. 9x l 0 ^5.

Example 3

Purchase a highly doped n-type silicon substrate surface that will be the gate electrode and thermally oxidized the surface of the silicon oxide film that will form an insulating layer of 200 nm, and use ultrasonic detergent with alkaline detergent, ultrapure water, and acetone. After cleaning, the surface was cleaned by ozone UV irradiation. The substrate was immersed in a 5 mM octane solution of octadecyltrichlorosilane in a nitrogen atmosphere for 12 hours to silane-treat the surface of the silicon base plate, and then the substrate was rinsed in the order of octane and black mouth form. Polymer Compound A is weighed out to 0.018 g, added to form mouthpiece to make 5.3 g, filtered through a 3 zm membrane filter, and then applied to the surface-treated substrate using this coating solution. A polymer thin film containing polymer compound A having a thickness of 70 nm was formed by spin coating. An Au electrode was deposited on the polymer thin film by a vacuum deposition method to form a source electrode and a drain electrode having a channel width of 2 mm and a channel length of 20 to produce a polymer thin film element 1.

The organic thin film transistor characteristics were measured by changing the gate voltage V _c from 0 to 80 V and the source-drain voltage V _SD from 0 to 80 V in a nitrogen atmosphere. As a result, good I sd-Vg characteristics were obtained, and a drain current of -1.4〃A was obtained at V _g = -80 V and V _Sd = -80 V. The field-effect mobility obtained from I sd Vg characteristic is ^{^{1 X 10- 3 cm 2 / Vs}} , the on-off ratio of the current was 1 X 10 ^6. Reference synthesis example 3

After charging 0.96 g of the compound 3 and 0.55 g of 2,2′-pipyridyl in a reaction vessel, the inside of the reaction system was replaced with nitrogen gas. Pre-publish with argon gas Then, 80 g of degassed tetrahydrofuran (THF) (dehydrated solvent) was added. Next, 1.05 g of bis (1,5-cyclooctagen) nickel (0) {N i (COD) 2} was added to this mixed solution and stirred at room temperature for 10 minutes, then at 60 ° C And reacted for 1.5 hours. The reaction was performed in a nitrogen gas atmosphere. After the reaction, this solution was cooled and then poured into a mixed solution of methanol 100 ml Z ion exchanged water 200 ml and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration. This precipitate was dried under reduced pressure and then dissolved in black mouth form. The solution was filtered to remove insoluble matters, and then the solution was purified by passing through a column packed with alumina. Next, this solution was poured into methanol and reprecipitated, and the generated precipitate was recovered. This precipitate was dried under reduced pressure to obtain 0.5 g of polymer compound C.

The number average molecular weight in terms of polystyrene of this polymer compound C was 7.3 × 10 ⁵ .

Comparative Example 1

Except for using polymer compound C instead of polymer compound A, polymer compound C having a film thickness of 5 Onm was applied by spin coating on the surface-treated substrate in the same manner as in Example 3. A high molecular weight thin film was formed. On the polymer thin film, an Au electrode was deposited by a vacuum deposition method to form a source electrode and a drain electrode having a channel width of 2 mm and a channel length of 20 m, and a polymer thin film element 2 was produced.

The organic thin film transistor characteristics were measured by changing the gate voltage V _G from 0 to 80 V and the source-drain voltage V _SD from 0 to 80 V in a nitrogen atmosphere. When V _g = —80 V and V _sd = —60 V, the drain current was as low as 0.8 nA.

Example 4 Preparation of polymer thin film element and evaluation of solar cell characteristics>

A suspension of poly (3,4) ethylenedioxythiophene polystyrene sulfonic acid (Bayer, Baytron P AI 4083) on a glass substrate with a 150 nm thick ITO film deposited by sputtering is 0.2. After filtration through a membrane filter, a thin film was formed with a thickness of 70 nm by spin coating, and dried on a hot plate at 200 ° C. for 10 minutes. Thereafter, a polymer thin film was formed to a thickness of 50 nm by spin coating using a 0.2% 1:% chloroform solution of polymer compound A at room temperature. Furthermore, after drying this at 60 ° C under reduced pressure for 1 hour, lithium fluoride was equivalent to about 0.4 nm, then 5 nm of calcium and 180 nm of aluminum were further deposited as an electrode, and polymer compound A was used. Polymer thin film element 3 was fabricated. The degree of vacuum in vapor deposition was less than all 1 X 10- ⁴ P a. When the voltage-current characteristics were measured while irradiating the obtained polymer thin film element 3 with a xenon lamp, solar cell characteristics with a short-circuit current of 43 A / cm ² and an open-circuit voltage of 1.75 V were obtained. Example 5

A polymer thin film element 4 was produced in the same manner as in Example 5 using the polymer ich compound B instead of the polymer ich compound A. When the voltage-current characteristics were measured while irradiating the obtained polymer thin film element 4 with a xenon lamp, a short-circuit current of 3 S ^ A / cm ^{2 and an} open-circuit voltage of 1.15 V were obtained.

Example 6

The above compound 3—a 1.13 g and 1,2—di (5-jib mouth mo 2—chenyl) ethene 0.60 g (eg, M. Fu jieta l., Synthetic Meters, 55-57) , 2136-2139 (1993)) and Aliquat 336 0.69 g were charged into a reaction vessel. Thereafter, the reaction was performed in a nitrogen atmosphere until the reaction. In the previous reaction vessel, 19.4 g of toluene deaerated in advance by publishing with argon gas was added. Next, a solution obtained by dissolving 0.74 g of potassium carbonate in 20.0 g of ion-exchanged water deaerated by bubbling with argon gas in advance was added to the mixed solution. Then tetrakis (triphenylphosphine) palladium (0) 3.9 mg was added. All reactions were performed under a nitrogen atmosphere. After reacting under reflux conditions for 15 hours, 34.7 mg of promobenzene was added and reacted under reflux conditions for 2 hours. Furthermore, 35.8 mg of 2-phenylene 1,3,2-dioxapolynan was added and reacted under reflux conditions for 2 hours. After the reaction, the two-phase solution was cooled, and the organic solvent layer was poured into methanol and stirred for about 1 hour. Next, the produced precipitate was recovered by filtration.

This precipitate was dried under reduced pressure to obtain 1.00 g of polymer compound D. This polymer compound D has a polystyrene-reduced number average molecular weight of 1 × 10 ⁶ or more.

Example 7

Preparation of polymer thin film element and evaluation of organic thin film transistor characteristics>

The polymer compound D was weighed out to 0.008 g, and dichlorobenzene was added to make 2 g to prepare a coating solution. We purchase a highly doped n-type silicon substrate that will be the gate electrode, which has been oxidized by thermal oxidation to form a 200 nm silicon oxide film that will be the insulating layer, and will be ultra-clean with alkaline detergent, ultrapure water, and acetone. After sonic cleaning, the surface was cleaned by ozone UV irradiation. An Au electrode was deposited on the substrate by vacuum deposition to form a source electrode and a drain electrode having a channel width of 2 mm and a channel length of 20 jLim. The substrate with the electrode was set on a spin coater, and 1 (11 ^ (; 11 ^ 1 ^ 1011511 & 2311601¾ © 5) was dropped, and then the substrate was spun at 2000 rpm, and the substrate surface was treated with HMDS. Using a coating solution of the polymer compound D, apply the polymer compound D so as to cover the space between the source electrode and the drain electrode using a needle pen with an inner diameter of 100 m, using a dispenser-printing method (Shot Mini, manufactured by Musashi Engineering). A thin film having a thickness of 700 ηηι was formed, and then baked at 120 ° C. for 30 minutes in a nitrogen atmosphere to prepare a polymer thin film element 5.

When the gate voltage V _G was changed from 0 to 1-60 V and the source-drain voltage V _SD was changed from 0 to 1-60 V in vacuum, the organic thin film transistor characteristics were measured. Good I sd— Vg characteristics are obtained, and when V _g = —60 V and V _sd = — 60 V, A drain current of 0.6 Α was obtained. The field effect mobilities obtained from I sd V g characteristic is ^{^{5 X 1 0 4 cm 2 /}} Vs, the on-off ratio of the current was 1 X 1 0 ^3. Industrial use "δί ability

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

Claims

The scope of the claims

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

[Wherein, A r ¹ and A r ² each independently represent a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group, and X ¹ and X ² each independently represent ◯, S, C (= 0), S (= 0), S0 ₂ , C (R ¹ ) (R ² ), S i (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P ( R ⁷ ) or? (= 0) represents (R ⁸ ), and each R ′ R ⁸ independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylalkyl group, an aryl alkyl group, Aryloxyloxy group, aryloxylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group Group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylenetinyl group, strong ruxoxyl group, alkyloxyroxynyl group, aryloxycarbonyl group , Arylalkyloxycarbonyl group, heteroalkyloxycarbonyl group or cyano group Represent. However, X ¹ and X ² are not the same. R ′ and R ² in C (R ¹ ) (R ² ) and R ³ and R ⁴ in S i (R ³ ) (R ⁴ ) may be bonded to each other to form a ring. m represents 0 or 1, and n represents an integer from 1 to 6. However, when m = 0, X ¹ does not represent C (R ¹ ) (R ² ). Also, attached to adjacent positions of the aromatic ring of X ¹ and Ar Ar ^1, the case of m = l, X ² and A r ¹ is engaged binding at the adjacent position to an aromatic ring of A r ^2, the case of m = 0 X ¹ and Ar ¹ are bonded to the adjacent positions of the aromatic ring of Ar ² . ] (R ⁹ )

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丫 'o (2)

[In the formula, o represents an integer from 1 to 10, p represents an integer from 0 to 2, Y represents 〇, S, C (R ¹⁰ ) (R ¹¹ ), S i (R ¹² ) ( R ¹³ ) or N (R ¹⁴ ), and when there are a plurality of Y, they may be the same or different, and R ^1D , R ¹ R ¹² , R ¹³ and R ¹⁴ are each independently , Hydrogen atom, halogen atom, alkyl group, alkyloxy group, alkylthio group, aryl group, aryloxy group, arylthio group, arylalkyl group, arylalkyloxy group, arylalkylthio group, acyl group, 7 Siloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryl group Xyl group, heteroarylthio group, aryl It represents a rualkenyl group, an arylruetynyl group, a strong lpoxyl group, an alkyloxycarbonyl group, an aryloxy group, an arylalkyloxycarbonyl group, a heteroalkyloxycarbonyl group, or a cyano group. R ^1D and R ^M , R ¹² and R ¹³ may be bonded to each other to form a ring, and R ⁹ is a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an aryl group, Reel alkyl group, arylalkyloxy group, arylalkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted Silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroary —Luthio group, aryloxyalkenyl group, arylethynyl group, strong oxyloxy group, alkyloxycarbonyl group, aralkyloxycarbonyl group, aralkylalkyloxy group, heteroaryloxy group, or cyano group To express. If R ⁹ is more, they may be the same or different, and may form a ring together with R ⁹ together. ]

2. A repeating unit represented by the above formula (1), a repeating unit represented by the above formula (2), and a repeating unit represented by the following formula (3), and having a number average molecular weight in terms of polystyrene of 10 ³ to 10 polymer compound according to claim 1, characterized in that the ^8.

No q (3)

[In the formula, Ar ³ represents a divalent aromatic hydrocarbon group, a divalent heterocyclic group or —CR ¹⁵ = CR ¹⁶ —. Ri ⁵ and R ¹⁶ are each independently a hydrogen atom, a halogen atom, an alkyl group, an alkyloxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arylalkyl group, an arylalkyloxy group, an Reel alkylthio group, acyl group, acyloxy group, amide group, acid imide group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group , Heteroaryloxy group, heteroarylthio group, arylenylalkenyl group, arylethynyl group, forceloxyl group, alkyloxycarbonyl group, aryloxycarbonyl group, arylalkyloxycarbonyl group, heteroaryl group Represents a ryloxycarbonyl group or a cyano group. q represents an integer from 1 to 6. ]

3. The X ¹ in formula (1), 0, S, C ( 〇), S (O) or polymer compound according to claim 1 or 2, characterized in that S_〇 _2.

4. X ^{2 in} formula (1) is C (R ¹ ) (R ² ), S i (R ³ ) (R ⁴ ), N (R ⁵ ), B (R ⁶ ), P (R ⁷ ) or The polymer compound according to claim 1, wherein the polymer compound is P (◯) (R ⁸ ). (In the formula, shaku ¹ ~! ^ Each independently represents the same meaning as above.)

5. The polymer compound according to any one of claims 1 to 4, wherein A r ¹ and A r ^{2 in the} formula (1) are each independently a trivalent aromatic hydrocarbon group. .

6. The polymer compound according to any one of claims 1 to 5, wherein Y in the formula (2) is S. .

7. The polymer compound according to any one of claims 2 to 6, wherein Ar ³ in the formula (3) is one CR ¹⁵ = CR ¹⁶ —. (In the formula, R ¹⁵ and R ¹⁶ represent the same meaning as described above.)

8. The polymer compound according to any one of claims 1 to 7, wherein the total of the repeating units represented by the formulas (1) and (2) is 10 mol% or more of all repeating units.

9. The polymer compound according to claim 1, which has liquid crystallinity.

10. A polymer thin film comprising the polymer compound according to claim 1 and having a thickness in a range of 1 nm to 100 zm.

11. The method for producing a polymer thin film according to claim 10, wherein a spin coating method, an ink jet printing method, a dispenser printing method or a flexographic printing method is used.

12. The method for producing a polymer thin film according to claim 10, further comprising a step of orienting the polymer by a rubbing method or a sharing method.

13. A polymer thin film element comprising the polymer thin film according to claim 10.

14. An organic thin film transistor comprising the polymer thin film according to claim 10.

15. An organic solar cell comprising the polymer thin film according to claim 10.

16. An optical sensor comprising the polymer thin film according to claim 10.

17. An electrophotographic photoreceptor comprising the polymer thin film according to claim 10.

18. A spatial light modulator comprising the polymer thin film according to claim 10.