CN1989169B - Polymer compound, polymer film, and polymer film element using the same - Google Patents

Abstract

A polymer compound comprising a repeating unit represented by the following formula (1) and a repeating unit represented by the following formula (2), wherein the polystyrene-equivalent number average molecular weight is 10³～10⁸，

In the formula, Ar¹And Ar²Each independently represents a 3-valent aromaticGroup of hydrocarbon radicals or heterocyclic radicals having a valence of 3, X¹And X²Each independently represents O, S, C (═ O), S (═ O), SO₂Etc. X¹And X²In contrast, Y represents O, S, R⁹Represents a halogen atom, an alkyl group, an alkoxy group or the like, m represents 0 or 1, n represents an integer of 1 to 6, o represents an integer of 1 to 6, and p represents an integer of 0 to 2.

Description

Polymer compound, polymer film, and polymer film element using the same

technical field

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 technique

Thin films made of organic materials having electron transport properties or hole transport properties are expected to be applied to thin film elements such as organic thin film transistors and organic solar cells, and various studies have been conducted.

As a material for such a film, a polymer compound having a molecular structure having electron-transporting or hole-transporting properties in the main chain, polyphenylenevinylene derivatives, polyfluorene derivatives, polyphenylene derivatives, and polyphenylene derivatives are known. Derivatives, polythiophene derivatives, polythiophene vinylidene derivatives, etc. ; Appl. Phys. Lett. Vol. 77 (2000) p. 406; "Semiconducting Polymers", Eds. G. Hadziioannou and P. F. van Hutten (2000) Wiley-VCH).

Contents of the invention

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

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

[wherein, Ar ¹ and Ar ² each independently represent a 3-valent aromatic hydrocarbon group or a 3-valent heterocyclic group, and X ¹ and X ² each independently represent O, S, C(=O), S(=O ), SO ₂ , C(R ¹ )(R ² ), Si(R ³ )(R ⁴ ), N(R ⁵ ), B(R ⁶ ), P(R ⁷ ) or P(=O)(R ⁸ ), R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkoxy group, an aryl group Alkylthio, acyl, acyloxy, amido, imido, imine residue, amino, substituted amino, substituted silyl, substituted siloxy, substituted silylthio, substituted silylamino, Monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkoxycarbonyl group, heteroaryloxycarbonyl group or cyano group. However, ^X1 and ^X2 are different. R ¹ and R 2 in C(R ¹ )(R ² ), and R ^{3 and R 4 in Si(R 3 )(R 4 ) may} combine with each other to form a ring. m represents 0 or 1, and n represents an integer of 1-6. However, when m=0, X ¹ does not represent C(R ¹ )(R ² ). In addition, X ¹ and Ar ² are respectively bonded to adjacent carbon atoms among the carbon atoms constituting the aromatic ring of Ar ¹ (hereinafter sometimes referred to as the ortho position of the aromatic ring). When m=1, X ² and Ar ¹ are bonded to Ar The ortho position of the aromatic ring of ² , when m=0, X ¹ and Ar ¹ are bound to the ortho position of the aromatic ring of Ar ² ].

[In the formula, o represents an integer of 1 to 10, p represents an integer of 0 to 2, Y represents O, S, C(R ¹⁰ )(R ¹¹ ), Si(R ¹² )(R ¹³ ) or N(R ¹⁴ ), R ¹⁰ , R ¹¹ , R ¹² , R ¹³ and R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an arane Aryl, aralkyloxy, aralkylthio, acyl, acyloxy, amido, imido, imine residue, amino, substituted amino, substituted silyl, substituted siloxy, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkoxycarbonyl group, Heteroaryloxycarbonyl or cyano. R ¹⁰ and R ¹¹ , and R ¹² and R ¹³ may combine with each other to form a ring. ^R represents a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkoxy group, an aralkylthio group, an acyl group, an acyloxy group, or an amido group , 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, arylalkenyl, arylethynyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, heteroaryloxycarbonyl or cyano. When there are multiple R ⁹ , they may be the same or different, and R ⁹ may combine with each other to form a ring].

In addition, the present invention provides a polymer compound comprising 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), in terms of polystyrene The number average molecular weight is 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 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkyloxy group, an aralkylthio group , acyl, acyloxy, amido, imido, imine residue, amino, substituted amino, substituted silyl, substituted siloxy, substituted silylthio, substituted silylamino, monovalent Heterocyclyl, heteroaryloxy, heteroarylthio, arylalkenyl, arylethynyl, carboxy, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, heteroaryloxycarbonyl or cyano. q represents an integer of 1 to 6].

Description of drawings

FIG. 1 is a schematic cross-sectional view of a forward Stagger type organic thin film transistor involved in the present invention.

FIG. 2 is a schematic cross-sectional view of a Stagger tilt organic thin film transistor involved in the present invention.

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

FIG. 4 is a schematic cross-sectional view of an organic thin film transistor of reverse Stagger tilt type 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 a laminated photosensor according to the present invention.

Fig. 7 is a schematic cross-sectional view of a laminated optical sensor according to the present invention.

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

9 is a schematic cross-sectional view of a single-layer electrophotographic photoreceptor according to the present invention.

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

11 is a schematic cross-sectional view of a laminated 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.

Symbol Description

1. Substrate

2. Polymer film

3. Insulation film

4. Gate electrode

5. Source electrode

6. Drain electrode

7. Electrodes

8. Charge generation layer

9. Liquid crystal layer

10. Dielectric mirror layer

Detailed ways

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

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

Here, the trivalent aromatic hydrocarbon group refers to an atomic group remaining after removing three hydrogen atoms from a benzene ring or a condensed ring, usually having 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms, and examples thereof include the following groups. Among them, the remaining atomic group after removing three hydrogen atoms from the benzene ring is most preferable. In addition, the aromatic hydrocarbon group may have a substituent. The carbon number of the trivalent aromatic hydrocarbon group does not include the carbon number of the substituent.

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

The heterocyclic compound mentioned here refers to an organic compound having a ring structure, in which the elements constituting the ring are not only carbon atoms, but also contain heteroatoms such as oxygen, sulfur, nitrogen, phosphorus, boron, and silicon in the ring.

As a trivalent heterocyclic group, the following groups are mentioned, for example.

In the above formula, R' each independently represents 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 arylthio group, an arylamino group, an aralkyl group, Aralkyloxy, aralkylthio, arylalkylamino, acyloxy, amido, arylalkenyl, arylalkynyl, monovalent heterocyclic group or cyano group. R" represents a hydrogen atom, an alkyl group, an aryl group, an arylalkyl group, a substituted silyl group, an acyl group, or a monovalent heterocyclic group, a heteroaryloxy group, or a heteroarylthio group.

Examples of substituents that may be present on a trivalent aromatic hydrocarbon group or a trivalent heterocyclic group include halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, and arane groups. Aryl, aralkyloxy, aralkylthio, acyl, acyloxy, amido, imido, imine residue, amino, substituted amino, substituted silyl, substituted siloxy, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkoxycarbonyl group, Heteroaryloxycarbonyl or cyano. When having a plurality of substituents, a ring may be formed between the substituents.

In the above formula, X ¹ and X ² each independently represent O, S, C(=O), S(=O), SO ₂ , C(R ¹ )(R ² ), Si(R ³ )(R ⁴ ), N(R ⁵ ), B(R ⁶ ), P(R ⁷ ), or P(=O)(R ⁸ ). However, ^X1 and ^X2 are different.

In formula (1), R ¹ to R ⁸ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkoxy group aralkylthio, acyl, acyloxy, amido, imido, imide residue, amino, substituted amino, substituted silyl, substituted siloxy, substituted silylthio, substituted silyl Amino, monovalent heterocyclyl, heteroaryloxy, heteroarylthio, arylalkenyl, arylethynyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, heteroaryloxycarbonyl or cyano.

R ¹ and R 2 in C(R ¹ )(R ² ), and R ^{3 and R 4 in Si(R 3 )(R 4 ) may} combine with each other to form a ring. In this case, as the ring structure moiety, the following structures can be specifically exemplified.

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

In said formula (1), n represents the integer of 1-6, More preferably, the integer of 1-3, More preferably, the integer of 1-2.

In the above formula (1), m represents 0 or 1, and as materials for organic thin film transistors, etc., m=1 is preferable, and n=1 and m=1 are particularly preferable.

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

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

When m=1, -X ¹ -X ² - includes groups represented by the following (4), (5), and (6).

Among these, the groups represented by the formulas (5) and (6) are preferable, and the groups represented by the formula (6) are more preferable from the viewpoint of compound stability.

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

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

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

In the above formula (2), Y represents O, S, C(R ¹⁰ )(R ¹¹ ), Si(R ¹² )(R ¹³ ), N(R ¹⁴ ), preferably O and S, more preferably S.

In addition, R ¹⁰ to R ¹⁴ each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkoxy group, an aralkyl group Thio, acyl, acyloxy, amido, imino, imine residue, amino, substituted amino, substituted silyl, substituted silyloxy, substituted silylthio, substituted silylamino, 1 valent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkoxycarbonyl group, heteroaryloxycarbonyl group or cyano group.

In the above-mentioned formula (2), R ⁹ represents a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkoxy group, an aralkylthio group, an acyl group , acyloxy, amido, imido, imine residue, amino, substituted amino, substituted silyl, substituted siloxy, substituted silylthio, substituted silylamino, monovalent heterocycle radical, heteroaryloxy, heteroarylthio, arylalkenyl, arylethynyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, heteroaryloxycarbonyl or cyano, preferably a halogen atom, Alkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aralkylthio, more preferably alkyl, alkoxy, when there are multiple When ^R9 , they may be the same or different, and ^R9 may combine with each other to form a ring.

When R ⁹ are bonded to each other to form a ring, the following structures can be specifically exemplified as the ring structure moiety.

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

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

Among them, the so-called divalent aromatic hydrocarbon group refers to the remaining atomic group after removing two hydrogen atoms from the benzene ring or the condensed ring, usually having 6 to 60 carbon atoms, preferably 6 to 20 carbon atoms, and can be listed in the above-mentioned exemplified A trivalent aromatic hydrocarbon group in which one hydrogen atom is added to any position from which three hydrogen atoms have been removed. Among them, the remaining atomic group after removing two hydrogen atoms from the benzene ring is most preferable. In addition, the aromatic hydrocarbon group may have a substituent. The carbon number of the divalent aromatic hydrocarbon group does not include the carbon number of the substituent.

In addition, a divalent heterocyclic group refers to an atomic group remaining after removing two hydrogen atoms from a heterocyclic compound, and the number of carbon atoms is usually 4-60, preferably 4-20. Examples of the divalent heterocyclic group include groups in which one hydrogen atom is added to any position in which three hydrogen atoms are removed among the trivalent heterocyclic groups exemplified above. In addition, 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 each independently represent a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkyl group Oxygen, aralkylthio, acyl, acyloxy, amido, imido, imine residue, amino, substituted amino, substituted silyl, substituted siloxy, substituted silylthio, substituted methyl Silylamino, monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group, arylethynyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkoxycarbonyl group, heteroaryloxycarbonyl group or cyano.

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

Among the polymer compounds of the present invention, it is preferable to have a structure (7) in which formula (1) and formula (2) are combined from the viewpoint of improving electron-transport property or 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), it may contain a plurality of repeating units of the formula (2) unit. When multiple repeating units of formula (2) are contained, they may be the same or different. From the viewpoint of improving electron transport properties or hole transport properties, it is preferable to have a structure (8) in which formula (1), formula (2) and formula (3) are combined.

Wherein, Y', R ⁹ ', o', and p' represent the same meanings as Y, R ⁹ , o, and p above, and Y, R ⁹ , o, and p may be the same or different.

As an example of the structure shown in the above formula (7), for example, n=1; o=2, 3 or 5; structures shown in the following formulas (9) to (14) when Y=S and in these A structure with substituents on the aromatic hydrocarbon or heterocyclic group in the structure. In addition, as an example of the structure represented by the above-mentioned formula (8), for example, when n=1; o=1; o'=1; q=1; Y=S; Y'=S, the following formula (15 ) to (17) and structures having substituents on the aromatic hydrocarbon group or heterocyclic group in these structures.

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

Among them, preferred formula (9), formula (14), formula (15), the group shown in formula (17) and these aromatic hydrocarbon groups or the group that also has substituent on the heterocyclic ring, more preferred formula (9 ), groups represented by formula (15), and groups having substituents on these aromatic hydrocarbon groups or heterocyclic rings. Examples of substituents include halogen atoms, alkyl groups, alkoxy groups, alkylthio groups, aryl groups, aryloxy groups, arylthio groups, aralkyl groups, aralkyloxy groups, aralkylthio groups, acyl groups, and acyloxy groups. , amido group, imido group, imine residue, amino group, substituted amino group, substituted silyl group, substituted silyloxy group, substituted silylthio group, substituted silylamino group, monovalent heterocyclic group, heteroaryl Oxygen, heteroarylthio, arylalkenyl, arylethynyl, carboxyl, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, heteroaryloxycarbonyl or cyano, the substituents can be combined to form ring.

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

The alkyl group may be straight chain, branched or cyclic, and may have a substituent, and the number of carbon atoms is usually about 1 to 20. As specific examples, methyl, ethyl, propyl, isopropyl, Butyl, isobutyl, tert-butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, 2-ethylhexyl, nonyl, decyl, 3,7-dimethyloctyl, lauryl, Trifluoromethyl, pentafluoroethyl, perfluorobutyl, perfluorohexyl, perfluorooctyl, etc.

The alkoxy group may be any of straight chain, branched or cyclic, and may have a substituent, and the carbon number is usually about 1 to 20. Specific examples thereof include methoxy, ethoxy, propoxy, Isopropoxy, butoxy, isobutoxy, tert-butoxy, pentyloxy, hexyloxy, cyclohexyloxy, heptyloxy, octyloxy, 2-ethylhexyloxy, nonyloxy decyloxy, 3,7-dimethyloctyloxy, lauryloxy, trifluoromethoxy, pentafluoroethoxy, perfluorobutoxy, perfluorohexyloxy, perfluorooctyloxy , Methoxymethoxy, 2-methoxyethoxy, etc.

The alkylthio group may be any of linear, branched or cyclic, and may have a substituent, and the carbon number is usually about 1 to 20. Specific examples thereof include methylthio, ethylthio, propylthio, Isopropylthio, Butylthio, Isobutylthio, Tert-Butylthio, Pentylthio, Hexylthio, Cyclohexylthio, Heptylthio, Octylthio, 2-Ethylhexylthio, Nonylthio thiol, decylthio, 3,7-dimethyloctylthio, laurylthio, trifluoromethylthio, etc.

The aryl group may have a substituent, and generally has about 3 to 60 carbon atoms. Specific examples thereof include phenyl and C ₁ to C ₁₂ alkoxyphenyl (C ₁ to C ₁₂ represent 1 to 12 carbon atoms. The same applies hereinafter), C ₁ -C ₁₂ alkylphenyl, 1-naphthyl, 2-naphthyl, pentafluorophenyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, and the like.

The aryloxy group may have a substituent on the aromatic ring, and the carbon number is usually about 3 to 60. Specific examples thereof include phenoxy, C ₁ -C ₁₂ alkoxyphenoxy, C ₁ -C ₁₂ alkoxy ylphenoxy, 1-naphthyloxy, 2-naphthyloxy, pentafluorophenoxy, pyridyloxy, pyridazinyloxy, pyrimidinyloxy, pyrazinyloxy, triazinyloxy, etc.

The arylthio group may have a substituent on the aromatic ring, and the carbon number is usually about 3 to 60. Specific examples thereof include phenylthio, C ₁ to C ₁₂ alkoxyphenylthio, C ₁ to C ₁₂ alkane phenylthio, 1-naphthylthio, 2-naphthylthio, pentafluorophenylthio, pyridylthio, pyridazinylthio, pyrimidinylthio, pyrazinylthio, triazinylthio, etc.

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

The aralkoxy group may have a substituent, and the carbon number is usually about 7 to 60. Specific examples thereof include phenyl-C ₁ -C ₁₂ alkoxy, C ₁ -C ₁₂ alkoxyphenyl-C ₁ ~C ₁₂ alkoxy, C ₁ ~C ₁₂ alkylphenyl-C ₁ ~C ₁₂ alkoxy, 1-naphthyl-C ₁ ~C ₁₂ alkoxy, 2-naphthyl-C ₁ ~C ₁₂ Alkoxy, etc.

The aralkylthio group may have a substituent, and the carbon number is usually about 7 to 60. Specific examples thereof include phenyl-C ₁ -C ₁₂ alkylthio, C ₁ -C ₁₂ alkoxyphenyl-C ₁ ~C ₁₂ alkylthio, C ₁ ~C ₁₂ alkylphenyl-C ₁ ~C ₁₂ alkylthio, 1-naphthyl-C ₁ ~C ₁₂ alkylthio, 2-naphthyl-C ₁ ~C ₁₂ Alkylthio, etc.

The carbon number of the acyl group is usually about 2 to 20. Specific examples thereof include acetyl, propionyl, butyryl, isobutyryl, trimethylacetyl, benzoyl, trifluoroacetyl, and pentafluorobenzyl. Acyl etc.

The carbon number of the acyloxy group is usually about 2 to 20. Specific examples thereof include acetyloxy, propionyloxy, butyryloxy, isobutyryloxy, trimethylacetoxy, benzoyl Oxygen, trifluoroacetoxy, pentafluorobenzoyloxy, etc.

The carbon number of the amido group is usually about 2 to 20, preferably 2 to 18 carbon atoms. Specific examples thereof include formamido, acetylamino, propionylamino, butyrylamino, benzamido, and trifluoroacetylamino. Amino, Pentafluorobenzylamino, Di(formyl)amino, Di(acetyl)amino, Di(propionyl)amino, Di(butyryl)amino, Di(benzoyl)amino, Di(trifluoroacetyl) Amino, bis(pentafluorobenzoyl)amino, etc.

Examples of the imido group include residues obtained by removing a hydrogen atom bonded to the nitrogen atom from imide, and usually have about 2 to 60 carbon atoms, preferably 2 to 48 carbon atoms. Specific examples include groups shown below.

As an imine residue, it refers to an organic compound derived from an imine compound (referring to an organic compound having -N=C- in the molecule. As an example, aldimine, ketimine, and their N-hydrogen atoms are alkane In a compound substituted with a radical, etc.), a residue from which one hydrogen atom has been removed usually has about 2 to 20 carbon atoms, preferably 2 to 18 carbon atoms. Specific examples include groups represented by the following structural formulas, and the like.

Examples of substituted amino groups include amino groups substituted with 1 or 2 groups selected from alkyl, aryl, aralkyl and monovalent heterocyclic groups. A heterocyclic group may have a substituent. The carbon number of the substituted amino group is usually about 1 to 40, and specific examples thereof include methylamino, dimethylamino, ethylamino, diethylamino, propylamino, dipropylamino, and isopropylamino. , diisopropylamino, butylamino, isobutylamino, tert-butylamino, pentylamino, hexylamino, cyclohexylamino, heptylamino, octylamino, 2-ethylhexylamino, nonylamino , decylamino, 3,7-dimethyloctylamino, laurylamino, cyclopentylamino, dicyclopentylamino, cyclohexylamino, dicyclohexylamino, pyrrolidinyl, piperidinyl, di( Trifluoromethyl)amino, phenylamino, diphenylamino, C ₁ -C ₁₂ alkoxyphenylamino, di(C ₁ -C ₁₂ alkoxyphenyl)amino, di(C ₁ -C ₁₂ Alkylphenyl)amino, 1-naphthylamino, 2-naphthylamino, pentafluorophenylamino, pyridylamino, pyridazinylamino, pyrimidinylamino, pyrazinylamino, triazinylamino, phenyl -C ₁ ~C ₁₂ alkylamino, C ₁ ~C ₁₂ alkoxyphenyl-C ₁ ~C ₁₂ alkylamino, C ₁ ~C ₁₂ alkylphenyl-C ₁ ~C ₁₂ alkylamino, di (C ₁ ~C ₁₂ alkoxyphenyl-C ₁ ~C ₁₂ alkyl)amino, di(C ₁ ~C ₁₂ alkylphenyl-C ₁ ~C ₁₂ alkyl)amino, 1-naphthyl-C ₁ -C ₁₂ alkylamino, 2-naphthyl-C ₁ -C ₁₂ alkylamino, etc.

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 aralkyl group, or a monovalent heterocyclic group, and the carbon number is usually about 1 to 60. , preferably having 3 to 48 carbon atoms. In addition, the alkyl group, aryl group, aralkyl group or monovalent heterocyclic group may have a substituent.

Specifically, trimethylsilyl, triethylsilyl, tripropylsilyl, triisopropylsilyl, dimethylisopropylsilyl, diethylisopropyl Silyl, tert-butylsilyldimethylsilyl, pentyldimethylsilyl, hexyldimethylsilyl, heptyldimethylsilyl, octyldimethylsilyl, 2-Ethylhexyl-dimethylsilyl, nonyldimethylsilyl, decyldimethylsilyl, 3,7-dimethyloctyl-dimethylsilyl, lauryl Dimethylsilyl, phenyl-C ₁ ~C ₁₂ alkylsilyl, C ₁ ~C ₁₂ alkoxyphenyl-C ₁ ~C ₁₂ alkylsilyl, C ₁ ~C ₁₂ alkyl Phenyl-C ₁ ~C ₁₂ alkylsilyl, 1-naphthyl-C ₁ ~C ₁₂ alkylsilyl, 2-naphthyl-C ₁ ~C ₁₂ alkylsilyl, phenyl-C ₁ -C ₁₂ alkyl dimethylsilyl, triphenylsilyl, tri(p-xylyl)silyl, tribenzylsilyl, diphenylmethylsilyl, tert-butyl Diphenylsilyl group, dimethylphenylsilyl group and the like.

Examples of the substituted siloxy group include silyloxy (H ₃ SiO—) substituted with 1, 2 or 3 groups selected from an alkyl group, an aryl group, an aralkyl group, and a monovalent heterocyclic group. In addition, the alkyl group, aryl group, aralkyl group or monovalent heterocyclic group may have a substituent.

The carbon number of the substituted silyloxy group is usually about 1 to 60, preferably 3 to 30 carbon atoms. Specific examples thereof include trimethylsilyloxy, triethylsilyloxy, tri-n-propyl Silyloxy, triisopropylsilyloxy, tert-butylsilyldimethylsilyloxy, triphenylsilyloxy, tris(p-xylyl)silyloxy, tribenzylmethylsilyloxy Siloxy, diphenylmethylsilyloxy, tert-butyldiphenylsilyloxy, dimethylphenylsilyloxy, and the like.

Examples of the substituted silylthio group include silylthio groups (H ₃ SiS—) substituted with 1, 2 or 3 groups selected from alkyl groups, aryl groups, aralkyl groups, and monovalent heterocyclic groups. In addition, the alkyl group, aryl group, aralkyl group or monovalent heterocyclic group may have a substituent.

The carbon number of the substituted silylthio group is usually about 1 to 60, preferably 3 to 30 carbons. Specific examples thereof include trimethylsilylthio, triethylsilylthio, tri-n-propyl Silylthio, Triisopropylsilylthio, tert-Butylsilyldimethylsilylthio, Triphenylsilylthio, Tris(p-Xylyl)silylthio, Tribenzylmethyl Silylthio, diphenylmethylsilylthio, tert-butyldiphenylsilylthio, dimethylphenylsilylthio and the like.

Examples of the substituted silylamino group include silylamino (H ₃ SiNH- or (H ₃ Si) ₂ N-). In addition, the alkyl group, aryl group, aralkyl group, and monovalent heterocyclic group may have a substituent.

The carbon number of the substituted silylamino group is usually about 1 to 120, preferably 3 to 60. Specific examples thereof include trimethylsilylamino, triethylsilylamino, tri-n-propyl Silylamino, triisopropylsilylamino, tert-butylsilyldimethylsilylamino, triphenylsilylamino, tri(p-xylyl)silylamino, tribenzylmethyl Silylamino, diphenylmethylsilylamino, tert-butyldiphenylsilylamino, dimethylphenylsilylamino, bis(trimethylsilyl)amino, bis(triethylsilyl) ylsilyl)amino, bis(tri-n-propylsilyl)amino, bis(triisopropylsilyl)amino, bis(tert-butylsilyldimethylsilyl)amino, bis(triphenyl ylsilyl)amino, bis(tri(p-xylyl)silyl)amino, bis(tribenzylsilyl)amino, bis(diphenylmethylsilyl)amino, bis(tert-butyl (diphenylsilyl)amino, bis(dimethylphenylsilyl)amino, etc.

The so-called monovalent heterocyclic group refers to the remaining atomic group after removing one hydrogen atom from the heterocyclic compound, and the carbon number is usually about 4 to 60. Specific examples thereof include thienyl, C ₁ to C ₁₂ Alkylthienyl, pyrrolyl, furyl, pyridyl, C ₁ -C ₁₂ alkylpyridyl, imidazolyl, pyrazolyl, triazolyl, oxazolyl, thiazolyl, thiadiazolyl, etc.

As heteroaryloxy (group represented by Q ¹ -O-, Q ¹ represents a monovalent heterocyclic group), heteroarylthio group (group represented by Q ² -S-, Q ² represents a monovalent Heterocyclic group), heteroaryloxycarbonyl (group represented by Q ³ -O(C=O)-, Q ³ represents a monovalent heterocyclic group), the monovalent heterocyclic group can include the above-mentioned monovalent The group exemplified in the heterocyclic group.

For example, the carbon number of the heteroaryloxy group is usually about 4 to 60. Specific examples thereof include thienyloxy, C ₁ -C ₁₂ alkylthienyloxy, pyrroleoxy, furyloxy, pyridyloxy, C ₁ -C ₁₂ alkylpyridyloxy, imidazolyloxy, pyrazolyloxy, triazolyloxy, oxazolyloxy, thiazolyloxy, thiadiazolyloxy and the like.

The carbon number of the heteroarylthio group is usually about 4 to 60. Specific examples thereof include thiophenethiol, _C1 - _C12 alkylthiophenethiol, pyrrolethiol, furanthiol, pyridinethiol, _C1 - _C12 alkane Pyridine mercapto, imidazole mercapto, pyrazole mercapto, triazole mercapto, oxazole mercapto, thiazole mercapto, thiadiazole mercapto, etc.

The carbon number of the arylalkenyl group is usually about 8 to 50, and the aryl group and the alkenyl group in the arylalkenyl group are the same as the aryl group and the alkenyl group described above, respectively. Specific examples thereof include 1-aryl vinyl, 2-aryl vinyl, 1-aryl-1-propenyl, 2-aryl-1-propenyl, 2-aryl-2-propenyl , 3-aryl-2-propenyl, etc. In addition, arylalkadienyl groups such as 4-aryl1,3-butadienyl are also included.

The carbon number of the arylethynyl group is usually about 8 to 50, and examples of the aryl group in the arylethynyl group include the above-mentioned aryl groups.

The carbon number of the alkoxycarbonyl group is usually about 2 to 20. Specific examples thereof include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, and isobutoxycarbonyl. Carbonyl, tert-butoxycarbonyl, benzyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, heptyloxycarbonyl, octyloxycarbonyl, 2-ethylhexyloxycarbonyl, nonyloxycarbonyl, decyloxy ylcarbonyl, 3,7-dimethyloctyloxycarbonyl, lauryloxycarbonyl, trifluoromethoxycarbonyl, pentafluoroethoxycarbonyl, perfluorobutoxycarbonyl, perfluorohexyloxycarbonyl, perfluoro Octyloxycarbonyl, etc.

The carbon number of the aryloxycarbonyl group is usually about 7 to 60. Specific examples thereof include phenoxycarbonyl, C ₁ to C ₁₂ alkoxyphenoxycarbonyl, C ₁ to C ₁₂ alkylphenoxycarbonyl, 1-naphthyloxycarbonyl, 2-naphthyloxycarbonyl, pentafluorophenoxycarbonyl and the like.

The carbon number of the aralkoxycarbonyl group is usually about 8 to 60. Specific examples thereof include phenyl-C _{1 -C 12} alkoxycarbonyl, C ₁ -C ₁₂ alkoxyphenyl-C ₁ -C ₁₂ Alkoxycarbonyl, C ₁ ~C ₁₂ alkylphenyl-C ₁ ~C ₁₂ alkoxycarbonyl, 1-naphthyl-C ₁ ~C ₁₂ alkoxycarbonyl, 2-naphthyl-C ₁ ~C ₁₂ Alkoxycarbonyl, etc.

Heteroaryloxycarbonyl (a group represented by Q ⁴ -O(C=O)-, Q ⁴ represents a monovalent heterocyclic group) usually has a carbon number of about 2 to 60, and specific examples include thienyloxycarbonyl, C ₁ -C ₁₂ alkylthienyloxycarbonyl, pyrroleoxycarbonyl, furyloxycarbonyl, pyridyloxycarbonyl, C ₁ -C ₁₂ alkylpyridyloxycarbonyl, imidazolyloxycarbonyl, pyrazolyloxycarbonyl, tri Azolyloxycarbonyl, oxazolyloxycarbonyl, thiazolyloxycarbonyl, thiadiazolyloxycarbonyl and the like.

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

The polymer compound of the present invention may contain repeating units other than formula (1), formula (2) and formula (3) within the range that does not impair electron transport properties or hole transport properties. In addition, the total of repeating units represented by formula (1), formula (2) or the total of repeating units represented by formula (1), formula (2) and formula (3) is preferably 10 mol % or more of all repeating units , more preferably 50 mol% or more, still more preferably 80 mol% or more.

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

When the macromolecular compound of the present invention contains formula (1), formula (2) and formula (3), the total molar ratio of formula (2) and formula (3) and formula (1) is preferably in 3:1～1: 3, more preferably 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, and may be a polymer compound having an intermediate structure of these, for example, a random copolymer having a block property. In addition, the case where the main chain has branches, three or more terminal parts, and dendrimers are also included. Alternating, block or graft copolymers are preferred, alternating copolymers are more preferred. In the block or graft copolymer, it is preferable that the block or graft portion contains the structure of formula (7) or the structure of formula (8).

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, for example, a polymer compound having an alternating copolymer structure of the following formula (7-1) . A polymer compound having a copolymer structure of the following formula (8-1).

Wherein, t represents the repeating number of structure (7) or structure (8), and t varies depending on the structure of the repeating unit, and is usually about 2-100000, preferably about 5-10000.

In addition, in the polymer compound of the present invention, the repeating unit may be connected by non-conjugated units, and these non-conjugated moieties may be included in the repeating unit. As a bonding structure, the bonding structure shown below, the bonding structure which combined 2 or more of the bonding structures shown below, etc. are mentioned. Wherein, R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkoxy group, an aralkylthio group, an acyl group , acyloxy, amido, imido, imine residue, amino, substituted amino, substituted silyl, substituted siloxy, substituted silylthio, substituted silylamino, monovalent heterocycle group, heteroaryloxy group, heteroarylthio group, aryl alkenyl group, arylethynyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, aralkoxycarbonyl group, heteroaryloxycarbonyl group or cyano group, Ar represents carbon number 6 ~60 hydrocarbyl groups.

In addition, the terminal group of the polymer compound of the present invention may be protected with a stable group because the characteristics and durability of the device may be reduced if the polymerization active group remains. It preferably has a conjugated bond connected to a conjugated structure of the main chain, for example, a structure bonded to an aryl group or a heterocyclic group through a carbon-carbon bond. Specifically, the substituent shown in Formula 10 of JP-A-9-45478, etc. are mentioned.

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

In the formula, Ar ¹ , Ar ² , X ¹ , X ² and m have the same meanings as above. ^Z represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkoxy group, an aralkylthio group, a substituted amino group, a substituted silyl group, Monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group or arylethynyl group.

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

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

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

As the solvent of the polymer compound of the present invention, unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decahydronaphthalene, n-butylbenzene, carbon tetrachloride, chloroform, di Chloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane and other halogenated saturated hydrocarbon solvents, chlorine Halogenated unsaturated hydrocarbon solvents such as benzene, dichlorobenzene, and trichlorobenzene, ether solvents such as tetrahydrofuran and tetrahydropyran, etc. It varies depending on the structure and molecular weight of the polymer compound, but usually 0.1% by weight or more is dissolved in these solvents.

Among the polymer compounds of the present invention, polymer compounds having liquid crystallinity are preferred. 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 used, for example, to improve electron mobility or hole mobility when used as a material of an organic thin film transistor. In addition, it is known that polymer compounds having liquid crystallinity become optically or electrically anisotropic by aligning them. (Synthetic Metals 119(2001)537)

The method for producing the polymer compound of the present invention will be described below.

The polymer compound of the present invention can be produced, for example, by polycondensation using a compound represented by the following formula (21), a compound represented by (22) and a compound represented by (23) as raw materials.

In the formula, Ar ¹ , Ar ² , X ¹ , X ² and m have the same meanings as above. ^Y1 and ^Y2 each independently represent a halogen atom, an alkylsulfonate group, an arylsulfonate group, an arylalkylsulfonate group, a borate group, a sulfonium methyl group, a phosphonium methyl group, a phosphonic acid Estermethyl, monohalomethyl, boronic acid, formyl, or vinyl.

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

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

From the viewpoint of the synthesis of the compounds represented by the above (21), (22) and (23) and the ease of the polycondensation reaction, ^Y1 and ^Y2 are preferably each independently a halogen atom, an alkylsulfonate group, An arylsulfonate group, an arylalkylsulfonate group, a borate group or a boronic acid group.

The polymer compound of the present invention is preferably polycondensed by using a compound represented by the following formula (24), (25), (26) or (27) in addition to (21), (22) and (23), and its The terminal structure is controlled.

In the formula, Ar ¹ , Ar ² , X ¹ , X ² , Y ² and m have the same meanings as above. ^Z represents a hydrogen atom, an alkyl group, an alkoxy group, an alkylthio group, an aryl group, an aryloxy group, an arylthio group, an aralkyl group, an aralkoxy group, an aralkylthio group, a substituted amino group, a substituted silyl group, Monovalent heterocyclic group, heteroaryloxy group, heteroarylthio group, arylalkenyl group or arylethynyl group.

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

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

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

Among the compounds represented by the above formulas (24) to (27), Y ¹ to Y ² are preferably each independently a halogen atom, an alkyl sulfonate group, arylsulfonate group, arylalkylsulfonate group, borate group or boronic acid group, more preferably a halogen atom.

As the alkylsulfonate group in formulas (21) to (27), mesylate group, ethanesulfonate group, trifluoromethanesulfonate group, etc. can be mentioned, and as the arylsulfonate group, Examples thereof include a benzenesulfonate group, a p-toluenesulfonate group, and the like, and examples of the arylalkylsulfonate group include a benzylsulfonate group and the like.

As a borate ester group, the group represented by the following formula is mentioned.

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

-CH ₂ S ⁺ Me ₂ X ^- , -CH ₂ S ⁺ Ph ₂ X ^- (X represents a halogen atom)

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

-CH ₂ P ⁺ Ph ₃ X ^- (X represents a halogen atom)

As a phosphonate methyl group, the group represented by the following formula is mentioned.

-CH ₂ PO(OR') ₂

(R' represents alkyl, aryl or arylalkyl)

Examples of the monohalomethyl group include fluoromethyl, chloromethyl, bromomethyl and iodomethyl.

In addition, as the reaction method used in the production of the polymer compound of the present invention, for example, a method of polymerization by Suzuki coupling reaction, a method of polymerization by Grignard reaction, a method of polymerization by Ni(O) catalyst, a method of polymerization by FeCl ₃ A method of polymerizing with an oxidizing agent, a method of electrochemically oxidative polymerization, or a method of decomposing an intermediate high molecular compound having a suitable leaving group.

Among them, polymerization using the Wittig reaction, polymerization using the Heck reaction, polymerization using the Horner-Wadsworth-Emmons method, polymerization using the Knoevenagel reaction, polymerization using the Suzuki coupling reaction, and polymerization using the Grignard reaction are preferred because the structure is easy to control. A method of polymerization, a method of polymerization using a Ni(O) catalyst. In view of the ease of obtaining raw materials and the simple and convenient operation of the polymerization reaction, it is more preferred to use the Suzuki coupling reaction for polymerization, the Grignard reaction for polymerization, and the Ni(O) catalyst for polymerization.

The monomer is dissolved in an organic solvent as necessary, and reacted at a temperature above the melting point and below the boiling point of the organic solvent using, for example, a base or a suitable catalyst. For example, Organic Reactions, Vol. 14, pp. 270-490, John Wiley & Sons, Inc., 1965, "Organic Reactions", Vol. 27, pp. 345-390, John Wiley & Sons, Inc. , 1982, "Organic Syntheses", Collective Volume VI, pp. 407-411, John Wiley & Sons, Inc., 1988, "Chem. Rev.", Vol. 95, pp. 2457 (1995), "J. Organomet.Chem.", Vol. 576, p. 147 (1999), "J.Prakt.Chem.", Vol. 336, p. 247 (1994), "Makromol.Chem., Macromol.Symp.", p. Known methods described in Vol. 12, p. 229 (1987) and the like.

The organic solvent varies depending on the compound used and the reaction, but in general, in order to suppress side reactions, it is preferable that the solvent used is sufficiently deoxidized and the reaction proceeds under an inert atmosphere. In addition, it is preferable to perform dehydration treatment in the same manner. (However, there is no such limitation in the case of a reaction in a two-phase system with water such as a Suzuki coupling reaction).

For the reaction, an appropriate base, an appropriate catalyst is added. They can be selected according to the reaction used. The base or catalyst is preferably sufficiently dissolved in the solvent used for the reaction. As a method of mixing the base or the catalyst, a solution of the base or the catalyst is gradually added while stirring the reaction solution under an inert atmosphere such as argon or nitrogen, or conversely, a method of slowly adding the reaction solution to the solution of the base or the catalyst .

When the polymer compound of the present invention is used as a material for polymer thin film elements, since its purity affects the characteristics of the element, it is preferable to use methods such as distillation, sublimation purification, and recrystallization to refine the monomer before polymerization and then polymerize it. , In addition, after the synthesis, it is preferable to carry out purification treatment such as reprecipitation purification, separation by chromatography, and the like.

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

More specifically, the reaction conditions will be described. In the case of Wittig reaction, Horner reaction, Knoevengel reaction, etc., the reaction is carried out using an equivalent or more, preferably 1 to 3 equivalents, of the base with respect to the functional group of the monomer. The base is not particularly limited, and for example, metal alkoxides such as potassium tert-butoxide, sodium tert-butoxide, sodium ethoxide and lithium methoxide, 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 and the like can be used. The reaction temperature is usually about room temperature to 150°C for the reaction. The reaction time is, for example, 5 minutes to 40 hours, which may be sufficient time for the polymerization to proceed, and is preferably 10 minutes to 24 hours because it does not need to be left for a long time after the reaction is completed. If the concentration during the reaction is too dilute, the reaction efficiency will be poor, and if it is too concentrated, the reaction will be difficult to control. Therefore, it can be appropriately selected in the range of about 0.01 wt% to the maximum concentration of dissolution, usually in the range of 0.1 wt% to 20 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. A solvent with a higher boiling point such as N,N-dimethylformamide and N-methylpyrrolidone is used, the reaction temperature is about 80-160°C, and the reaction time is about 1 hour-100 hours.

In the case of the Suzuki coupling reaction, for example, palladium [tetrakis(triphenylphosphine)], palladium acetate, etc. are used as catalysts, and inorganic compounds such as potassium carbonate, sodium carbonate, and barium hydroxide are added in an equivalent amount or more, preferably 1 to 10 equivalents, to the monomer. Alkali, organic bases such as triethylamine, and inorganic salts such as cesium fluoride. The reaction can be carried out in a two-phase system with an inorganic salt as an aqueous solution. Examples of the solvent include N,N-dimethylformamide, toluene, dimethoxyethane, tetrahydrofuran and the like. Depending on the solvent, it is preferable to use a temperature of about 50 to 160°C. The temperature may be raised to around the boiling point of the solvent and refluxed. The reaction time is about 1 hour to 200 hours.

In the case of the Grignard reaction, a solution of the Grignard reagent is obtained by reacting a halide with metal Mg in an ether solvent such as tetrahydrofuran, diethyl ether, or dimethoxyethane, and mixing it with a separately prepared monomer solution. Pay attention to the method of reacting after adding a nickel or palladium catalyst while raising the temperature to reflux. The Grignard reagent is used in an equivalent amount or more, preferably 1 to 1.5 equivalents, more preferably 1 to 1.2 equivalents, based on the monomer. When superposition|polymerization is performed by the method other than these, it can also make it react according to a well-known method.

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

As the solvent used in the reaction, saturated hydrocarbons such as pentane, hexane, heptane, octane, cyclohexane, unsaturated hydrocarbons such as benzene, toluene, ethylbenzene, xylene, carbon tetrachloride, chloroform, Dichloromethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane and other halogenated saturated hydrocarbons, chlorobenzene, dichlorobenzene, Halogenated unsaturated hydrocarbons such as trichlorobenzene, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, and tert-butanol, carboxylic acids such as formic acid, acetic acid, and propionic acid, dimethyl ether, diethyl ether, methyl ether, etc. Ethers such as tert-butyl ether, tetrahydrofuran, tetrahydropyran, and dioxane, and inorganic acids such as hydrochloric acid, bromic acid, hydrofluoric acid, sulfuric acid, and nitric acid, etc., can be used as a single solvent or a mixed solvent of these.

After the reaction, it can be obtained by, for example, quenching with water, extraction with an organic solvent, and usual post-treatment such as distilling off the solvent. Isolation and purification of the product can be performed by methods such as fractionation using chromatography and recrystallization.

The polymer film of the present invention will be described below.

The polymer film of the present invention is characterized by containing the above-mentioned polymer compound of the present invention.

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

The polymer film of the present invention may contain one kind of the above-mentioned high-molecular compound alone, or may contain two or more kinds of the above-mentioned high-molecular compound. In addition, in order to improve the electron-transport property or hole-transport property of the polymer thin film, a low-molecular compound or a high-molecular compound having electron-transport property or hole-transport property other than the above-mentioned polymer compounds may be mixed and used. Known materials can be used as the hole-transporting material, for example, pyrazoline derivatives, arylamine derivatives, 1,2-stilbene derivatives, triphenyldiamine derivatives, oligothiophene or its derivatives, polyvinylcarbazole or its derivatives, polysilane or its derivatives, polysiloxane derivatives with aromatic amines in the side chain or main chain, polyaniline or its derivatives, polythiophene or its Derivatives, polypyrrole or its derivatives, polyphenylene vinylene or its derivatives, or polythienyl vinylene or its derivatives, etc., as the electron transport material, known materials can be used, including For example, oxadiazole derivatives, anthraquinone dimethane or its derivatives, benzoquinone or its derivatives, naphthoquinone or its derivatives, anthraquinone or its derivatives, tetracyanoanthraquinone dimethane or its derivatives, fluorene Ketone derivatives, diphenyldicyanoethylene or its derivatives, bisphenoquinone derivatives, or metal complexes of 8-hydroxyquinoline or its derivatives, polyquinoline or its derivatives, polyquinoline Oxaline or its derivatives, polyfluorene or its derivatives, etc.

In addition, the polymer thin film of the present invention may contain a charge generating material in order to generate charges from absorbed light in the polymer thin film. Known materials can be used as the charge generating material, and examples include azo compounds and their derivatives, diazo compounds and their derivatives, metal-free phthalocyanine compounds and their derivatives, metal phthalocyanine compounds and their derivatives, perylene compounds and its derivatives, polycyclic quinone compounds and their derivatives, squalilium (squalilium) compounds and their derivatives, azulenium (aronium) compounds and their derivatives, thiopyrylium compounds and their derivatives, fullerenes such as C60 classes and their derivatives.

In addition, the polymer film of the present invention may contain materials necessary for realizing various functions. For example, a sensitizer for sensitizing the function of generating charge by absorbed light, a stabilizer for increasing stability, a UV absorber for absorbing UV light, and the like can be cited.

Furthermore, in order to improve mechanical properties, the polymer film of the present invention may contain a polymer compound material other than the above polymer compounds as a polymer binder. As the polymer binder, one that does not extremely hinder electron transport or hole transport is preferable, and a polymer binder that does not absorb visible light strongly is preferably used. Examples of the polymer binder include poly(N-vinylcarbazole), polyaniline or its derivatives, polythiophene or its derivatives, poly(p-phenylene vinylene) or its derivatives, poly (2,5-thienylene vinylene) or its derivatives, polycarbonate, polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane, etc. .

The method for producing the polymer thin film of the present invention is not particularly limited, and examples thereof include a method of forming a film from a solution containing the above-mentioned polymer compound, an electron-transporting material or a hole-transporting material mixed as necessary, and a polymer binder. .

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

As the solvent used when forming the polymer film of the present invention from a solution, unsaturated hydrocarbon solvents such as toluene, xylene, mesitylene, tetralin, decahydronaphthalene, n-butylbenzene, etc., tetrachloride Carbon, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane, etc. Hydrocarbon solvents, chlorobenzene, dichlorobenzene, trichlorobenzene and other halogenated unsaturated hydrocarbon solvents, tetrahydrofuran, tetrahydropyran and other ether solvents, etc. Although it varies depending on the structure and molecular weight of the polymer compound, usually 0.1% by weight or more can be dissolved in these solvents.

Examples of methods for forming a film from a solution include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire rod coating, dip coating, and spray coating. Coating methods such as screen printing, flexographic printing, offset printing, inkjet printing, and dispenser printing, preferably spin coating, flexographic printing, inkjet printing, and dispenser printing.

In the step of producing the polymer film of the present invention, a step of orienting the polymer compound may be included.

The polymer thin film in which the polymer compound is oriented by this process has improved electron mobility or hole mobility because main chain molecules or side chain molecules are aligned in one direction.

As a method for orienting a polymer compound, for example, Chapter 5, "Strong Liquid Crystal" (Shoichi Matsumoto, Ichiyo Kakuda, 1991) of "Basics and Applications of Liquid Crystals" known as an alignment method for liquid crystals can be used. "Structure and Physical Properties of Dielectric Liquid Crystals" (Atsuo Fukuda, Hideo Takesoe, co-authored, Corona Corporation, 1990) Chapter 7, "Liquid Crystals" Vol. 3 No. 1 (1999) pp. 3-16 etc. The method described. Among them, the rubbing method, the photo-alignment method, the shearing method (applied shear stress method), and the lift coating method are convenient and useful as orientation methods, and are easy to use, and the rubbing method and the shearing method are preferable.

The rubbing method refers to a method of lightly rubbing the surface of the substrate with a cloth or the like. As the substrate, glass, a polymer film, or the like can be used. As the cloth for rubbing the substrate, cloth such as gauze, polyester, cotton, nylon, and rayon can be used. Furthermore, if an alignment film is additionally formed on the substrate, alignment performance is further improved. Among them, polyimide, polyamide, PVA, polyester, nylon, etc. are mentioned as an alignment film, and a commercially available alignment film for liquid crystals can also be used. The alignment film can be formed by spin coating, flexographic printing, or the like. The cloth used for rubbing can be appropriately selected according to the alignment film to be used.

The so-called photo-alignment method refers to a method in which an alignment film is formed on a substrate and irradiated with polarized UV light or UV light at an oblique incidence to have an alignment function. As an alignment film, polyimide, polyamide, polyvinyl cinnamate, etc. are mentioned, and a commercially available alignment film for liquid crystals can also be used.

In the rubbing method or the photo-alignment method, orientation can be achieved by sandwiching the oriented polymer compound material between the substrates subjected to the above-mentioned treatment. At this time, it is necessary to bring the substrate to a temperature at which the material becomes a liquid crystal phase or an isotropic phase. The temperature setting may be performed before clamping the polymer compound material to the substrate or after clamping. In addition, coating of the polymer compound material may be performed only on the substrate subjected to the orientation treatment. The coating of the polymer compound is carried out by placing the polymer compound on the substrate, setting it to a temperature above Tg or showing a liquid crystal phase or an isotropic phase, and coating it in one direction with a rod or the like, or preparing and dissolving it in A solution in an organic solvent is applied by spin coating, flexographic printing, or the like.

The so-called shearing method refers to a method in which another substrate is placed on the polymer compound material placed on the substrate, and the upper substrate is moved in one direction at a temperature at which it becomes a liquid crystal phase or an isotropic phase. At this time, a higher degree of orientation can be obtained by using a substrate subjected to an orientation treatment as described in the above-mentioned rubbing method and photo-alignment method as the substrate. As the substrate, glass, a polymer film, or the like can be used, and the object to be removed by stress may be not the substrate but a metal rod or the like.

The so-called lift-coating method refers to a method in which a substrate is dipped in a solution of a polymer compound and lifted up. The organic solvent used in the polymer compound solution and the lifting speed of the substrate are not particularly limited, and can be selected and adjusted according to the degree of orientation of the polymer compound.

The process of orienting the polymer compound includes performing after the process of forming the polymer compound into a thin film such as the rubbing method and the shearing method, and also includes performing it simultaneously with the process of forming the polymer compound into a thin film such as the lift coating method. . In addition, a step of forming an alignment film may be included before the step of making the polymer compound into a thin film.

Since the polymer thin film of the present invention has electron transport or hole transport properties, it can be used in organic thin film transistors and organic solar cells by controlling the transport of electrons or holes injected from electrodes or charges generated by light absorption. , photosensors, electrophotographic photoreceptors, spatial modulation elements, photorefractive elements and other polymer thin film elements. When this polymer film is used for these polymer film elements, it is preferable to use it by orientation treatment to orient it because electron-transport property or hole-transport property improves.

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 arranged in contact with the active layer made of a polymer compound, and the gate electrode may be further sandwiched between the insulating layer in contact with the active layer. For example, The structure of Figures 1 to 4.

Organic thin film transistors are usually formed on a support substrate. The material of the supporting substrate is not particularly limited as long as it does not hinder the properties of the organic thin film transistor, and a glass substrate, a flexible film substrate, and a plastic substrate can also be used.

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

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

The insulating layer in contact with the active layer is not particularly limited as long as it is a material with high electrical insulating properties, and known materials can be used. Examples thereof include SiOx, SiNx, Ta ₂ O ₅ , polyimide, polyvinyl alcohol, polyvinyl phenol, and the like. From the viewpoint of lowering the voltage, a material with a high dielectric constant is preferable.

When forming the active layer on the insulating layer, in order to improve the interface properties between the insulating layer and the active layer, the surface of the insulating layer can also be treated with a surface treatment agent such as a silane coupling agent, and the active layer can be formed after surface modification. Examples of the surface treatment agent include long-chain alkylchlorosilanes, long-chain alkylalkoxysilanes, fluoroalkylchlorosilanes, fluoroalkylalkoxysilanes, and the like. Before the treatment with the surface treatment agent, the surface of the insulating layer can also be treated with ozone UV, _O2 plasma in advance.

After the organic thin film transistor is produced, it is preferably a packaged organic thin film transistor formed by packaging. Accordingly, the organic thin film transistor is blocked from the air, and the deterioration of the characteristics of the organic thin film transistor can be suppressed.

The encapsulation method includes a method of covering with UV curable resin, thermosetting resin, inorganic SiONx film, etc., a method of bonding a glass plate or film with UV curable resin, thermosetting resin, etc., and the like. In order to effectively block the organic thin film transistor from the atmosphere, it is preferable to carry out the steps from the production to the packaging of the organic thin film transistor without exposure to the atmosphere (for example, in a dry nitrogen atmosphere, in a vacuum, etc.).

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

6 to 8 are diagrams illustrating representative examples of the application of the polymer thin film of the present invention to an optical sensor. It is used in a structure where a polymer thin film is arranged between a pair of electrodes, one of which is transparent or translucent. A charge generation layer that absorbs light and generates charges may also be inserted. As the electrode material, metals such as aluminum, gold, silver, copper, alkali metals, and alkaline earth metals, or semitransparent films or transparent conductive films thereof can be used. In order to increase the photosensitivity, a carrier generating agent, a sensitizer, etc. can be added to the polymer film. As the base material, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used.

9 to 11 are diagrams illustrating representative examples of application of the polymer film of the present invention to an electrophotographic photoreceptor. It is used with a structure in which a polymer film is arranged on an electrode. A charge generation layer that absorbs light and generates charges may also be inserted. As the electrode material, metals such as aluminum, gold, silver, and copper can be used. In order to increase the photosensitivity, a carrier generating agent, a sensitizer, etc. can be added to the polymer film. As the base material, a silicon substrate, a glass substrate, a plastic substrate, or the like can be used, and a metal such as aluminum can also be used so that both the substrate and the electrode can be used.

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

Examples are shown below to describe the present invention in more detail, but the present invention is not limited to these Examples.

Here, the number average molecular weight was calculated|required the number average molecular weight of polystyrene conversion by gel permeation chromatography (GPC) using chloroform as a solvent.

Reference Synthesis Example 1

6.65 g of 2,7-dibromo-9-fluorenone was put into a 500 ml 3-necked flask replaced with nitrogen, and dissolved in 140 ml of a mixed solvent of trifluoroacetic acid:chloroform=1:1. Sodium perborate monohydrate was added to the solution and stirred for 20 hours. The reaction solution was filtered through celite and washed with toluene. The filtrate was washed with water, sodium bisulfite, and saturated brine, and dried over sodium sulfate. After the solvent was distilled off, 6.11 g of a crude product was obtained.

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

· Modulation of C ₈ H ₁₇ MgBr

Get 1.33g of magnesium and put it into a 100ml 3-neck flask, carry out flame drying and argon replacement. 10 ml of THF and 2.3 ml of 1-bromooctane were added thereto, followed by heating to start the reaction. After reflux for 2.5 hours, cool to room temperature.

·Grignard reaction

1.00 g of compound 1 was put into a 300 ml 3-necked flask replaced with nitrogen, and suspended in 10 ml of THF. After cooling to 0°C, the above-prepared C ₈ H ₁₇ MgBr solution was added. The cooling bath was removed and stirred at reflux for 5 hours. After cooling the reaction solution, 10 ml of water and hydrochloric acid were added. It was a suspension before the addition of hydrochloric acid, but it became a two-phase solution after the addition. After liquid separation, the organic phase was washed with water and saturated brine. After drying with sodium sulfate, the solvent was distilled off to obtain 1.65 g of a crude product. Purification was carried out by silica gel column chromatography (hexane:ethyl acetate=20:1) to obtain 1.30 g of the compound.

Take 0.20 g of compound 2 and put it into a 25 ml 2-necked flask replaced with nitrogen, and dissolve it in 4 ml of toluene. 0.02 g (0.06 mmol) of p-toluenesulfonic acid monohydrate was added to this solution, and it stirred at 100 degreeC for 11 hours. After the reaction solution was left to cool, it was washed with water, 4N NaOH aqueous solution, water, and saturated brine in this order, and the solvent was distilled off to obtain 0.14 g of Compound 3.

Under a nitrogen atmosphere, 1.0 g (1.77 mmol) of the above compound 3, 0.945 g (3.72 mmol) of bispinacolate diboron, [1,1'-bis(diphenylphosphino) Ferrocene]palladium dichloride 0.078g (0.11mmol), 1,1'-bis(diphenylphosphino)ferrocene 0.059g (0.11mmol) and 1,4-dioxane 15ml, with argon Bubble for 30 minutes. Then, 1.043 g (10.6 mmol) of potassium acetate was added, and it was made to react at 95 degreeC in nitrogen atmosphere for 13.5 hours. After completion of the reaction, the reaction solution was filtered to remove insoluble matter. Purify with an alumina short column, remove the solvent, dissolve in toluene, add activated carbon, stir, and filter. The filtrate was refined again with an alumina short column, and activated carbon was added to stir and filter. After the toluene was completely removed, 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.

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

Example 1

<Synthesis of Polymer Compound A>

0.62 g of the above compound 3-a, 0.29 g of 5,5'-dibromo-2,2'-bithiophene and 0.36 g of Aliquat336 (manufactured by ACROS ORGANICS) were charged into a reaction vessel. Thereafter, until the reaction was performed under nitrogen atmosphere. In the previous reaction container, 9.3 g of toluene deaerated by bubbling with argon gas was put in advance. Then, a solution obtained by dissolving 0.39 g of potassium carbonate in 9.6 g of ion-exchanged water degassed by bubbling argon beforehand was added to the mixed solution. Next, 2.1 mg of tetrakis(triphenylphosphine)palladium(0) was added. All reactions were carried out under nitrogen atmosphere. After reacting under reflux conditions for 16.3 hours, 18.4 mg of bromobenzene was added and reacted under reflux conditions for 2 hours. Further, 19.0 mg of 2-phenyl-1,3,2-dioxabororane was added, and the mixture was reacted under reflux for 2 hours. After the reaction, the biphasic solution was cooled, and the aqueous layer was removed. The organic solvent layer was very viscous, so chloroform was added for dilution. This mixed solution was poured into methanol, and stirred for about 1 hour. Then, the resulting precipitate was recovered by filtration. This precipitate was dried under reduced pressure, and dissolved in chloroform. This solution was purified by passing through a column packed with silica and alumina. Then, this solution was poured into methanol for reprecipitation, and the generated precipitate was recovered. This precipitate was dried under reduced pressure to obtain 0.53 g of polymer compound A.

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

Example 2

<Synthesis of Polymer Compound B>

The above-mentioned compound 4-a 0.73g and 5,5'-dibromo-2,2'-bithiophene 0.32g and Aliquat3360.40g were charged into a reaction vessel. Thereafter, until the reaction was performed under nitrogen atmosphere. Into the preceding reaction container, 10.4 g of toluene deaerated by bubbling with argon gas was added. Then, a solution obtained by dissolving 0.44 g of potassium carbonate in 10.7 g of ion-exchanged water degassed by bubbling argon beforehand was added to the mixed solution. Next, 2.3 mg of tetrakis(triphenylphosphine)palladium(O) was added. All reactions were carried out under 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. Further, 21.1 mg of 2-phenyl-1,3,2-dioxabororane was added and reacted under reflux for 2 hours. After the reaction, the two-phase solution was cooled, and the organic solvent layer was poured into methanol, followed by stirring for about 1 hour. Then, the resulting precipitate was recovered by filtration. This precipitate was dried under reduced pressure, and dissolved in chloroform. This solution was purified by passing through a column packed with silica and alumina. Then, this solution was poured into methanol for reprecipitation, and the generated precipitate was recovered. This precipitate was dried under reduced pressure to obtain 0.56 g of polymer compound B.

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

Example 3

<Fabrication of Polymer Thin Film Devices and Evaluation of Properties of Organic Thin Film Transistors>

Use thermal oxidation to form a 200nm silicon oxide film as an insulating layer on the surface of a highly doped n-type silicon substrate that will become a gate electrode, purchase it, and perform ultrasonic cleaning with alkaline detergent, ultrapure water, and acetone , using ozone UV irradiation to wash the surface. The substrate was immersed in a 5 mM octadecyltrichlorosilane solution of octadecyltrichlorosilane in a nitrogen atmosphere for 12 hours to perform silane treatment on the surface of the silicon substrate, and then rinse the substrate in the order of octane and chloroform. Weigh 0.018 g of polymer compound A, add chloroform to obtain 5.3 g, filter it with a 3 μm membrane filter, use this coating solution, and form a film thickness of 70 nm on the above-mentioned surface-treated substrate by spin coating. Polymer thin film of polymer compound A. Au electrodes were vapor-deposited on the polymer thin film by vacuum evaporation method to form a source electrode and a drain electrode with a groove width of 2 mm and a groove length of 20 μm, and the polymer thin film element 1 was produced.

For the polymer thin film device 1 made, the gate voltage V _G was changed to 0 to -80V in a nitrogen atmosphere, and the voltage V _SD between the source electrode and the drain electrode was changed to 0 to -80V, and the characteristics of the organic thin film transistor were measured, and the results were obtained. Good Isd-Vg characteristics, at V _g =-80V, V _sd =-80V, a leakage current of -1.4μA is obtained. In addition, the electric field effect mobility obtained from the Isd-Vg characteristic was 1×10 ^-3 cm ² /Vs, and the current switching ratio was 1×10 ⁶ .

Reference Synthesis Example 3

<Synthesis of Polymer Compound C>

After putting 30.96 g of the above-mentioned compound and 0.55 g of 2,2'-bipyridine into the reaction vessel, the inside of the reaction system was replaced with nitrogen gas. To this was added 80 g of tetrahydrofuran (THF) (dehydration solvent) degassed by bubbling with argon beforehand. Then, 1.05 g of bis(1,5-cyclooctadiene)nickel (O){Ni(COD)2} was added to this mixed solution, and after stirring at room temperature for 10 minutes, it was made to react at 60 degreeC for 1.5 hours. In addition, the reaction was carried out in a nitrogen atmosphere. After the reaction, the solution was cooled, poured into a mixed solution of 100 ml of methanol/200 ml of ion-exchanged water, and stirred for about 1 hour. Then, the resulting precipitate was recovered by filtration. This precipitate was dried under reduced pressure, and dissolved in chloroform. After the solution was filtered to remove insoluble matter, the solution was purified by passing through a column filled with alumina. Then, this solution was poured into methanol for reprecipitation, and the generated precipitate was recovered. This precipitate was dried under reduced pressure to obtain 0.5 g of polymer compound C.

The polymer compound C had a polystyrene-equivalent number average molecular weight of 7.3×10 ⁵ .

Comparative example 1

<Fabrication of Polymer Thin Film Devices and Evaluation of Properties of Organic Thin Film Transistors>

Except for using polymer compound C instead of polymer compound A, in the same manner as in Example 3, a polymer thin film containing polymer compound C with a film thickness of 50 nm was formed on the above-mentioned surface-treated substrate by spin coating. Au electrodes were vapor-deposited on the polymer thin film by vacuum evaporation method to form a source electrode and a drain electrode with a groove width of 2 mm and a groove length of 20 μm, and the polymer thin film element 2 was produced.

For the fabricated polymer thin film device 2, the gate voltage _VG was varied from 0 to -80V and the source-drain voltage _VSD was varied from 0 to -80V in a nitrogen atmosphere, and the characteristics of the organic thin film transistor were measured. At V _g =-80V and V _sd =-60V, the leakage current is -0.8nA, which is a low level.

Example 4

<Fabrication of polymer thin film elements and evaluation of solar cell characteristics>

On a glass substrate coated with an ITO film at a thickness of 150 nm by sputtering, a suspension of poly(3,4)ethylenedioxythiophene/polystyrenesulfonic acid (manufactured by Bayer, Baytron PAI 4083) was sprayed with 0.2 After filtration with a μm membrane filter, a 70 nm thick film was formed by spin coating and dried on a hot plate at 200 °C for 10 min. Then, a 50 nm-thick polymer film was formed by spin coating at room temperature using a 0.2 wt % chloroform solution of the polymer compound A. Furthermore, after drying it under reduced pressure at 60°C for 1 hour, as an electrode, about 0.4 nm of lithium fluoride was vapor-deposited, then 5 nm of calcium was vapor-deposited, and then 180 nm of aluminum was vapor-deposited, and polymer compound A was used to produce The polymer thin film element 3. The degree of vacuum during vapor deposition was all 1×10 ^-4 Pa or less. Voltage-current characteristics were measured while irradiating the obtained polymer thin film element 3 with a xenon lamp. As a result, solar cell characteristics were obtained with a short-circuit current of 43 μA/cm ² and an open voltage of 1.75 V.

Example 5

<Fabrication of polymer thin film elements and evaluation of solar cell characteristics>

The polymer thin film element 4 was produced in the same manner as in Example 5, using the polymer compound B instead of the polymer compound A. The voltage-current characteristics were measured while irradiating the obtained polymer thin film element 4 with a xenon lamp. As a result, a short-circuit current of 38 μA/cm ² and an open voltage of 1.15 V were obtained.

Example 6

<Synthesis of Polymer Compound D>

1.13 g of the above compound 3-a and 0.60 g of 1,2-bis(5-dibromo-2-thienyl)ethylene (for example, in M.Fuji et al., Synthetic Metals, 55-57, 2136-2139 ( 1993) and recorded the synthetic method) and Aliquat 336 0.69g into the reaction vessel. Thereafter, until the reaction was performed under nitrogen atmosphere. 19.4 g of toluene degassed by bubbling with argon gas was added to the previous reaction container. Then, a solution obtained by dissolving 0.74 g of potassium carbonate in 20.0 g of ion-exchanged water degassed by bubbling argon beforehand was added to the mixed solution. Next, 3.9 mg of tetrakis(triphenylphosphine)palladium(0) was added. All reactions were carried out under nitrogen atmosphere. After reacting under reflux conditions for 15 hours, 34.7 mg of bromobenzene was added and reacted under reflux conditions for 2 hours. Further, 35.8 mg of 2-phenyl-1,3,2-dioxabororane was added and reacted under reflux for 2 hours. After the reaction, the two-phase solution was cooled, and the organic solvent layer was poured into methanol, followed by stirring for about 1 hour. Then, the resulting precipitate was recovered by filtration.

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

Example 7

<Fabrication of Polymer Thin Film Devices and Evaluation of Properties of Organic Thin Film Transistors>

0.008 g of polymer compound D was weighed, and dichlorobenzene was added to obtain 2 g to prepare a coating liquid. Use thermal oxidation to form a 200nm silicon oxide film as an insulating layer on the surface of a highly doped n-type silicon substrate that will become a gate electrode, purchase it, and perform ultrasonic cleaning with alkaline detergent, ultrapure water, and acetone , using ozone UV irradiation to wash the surface. Au electrodes were vapor-deposited on the substrate by a vacuum evaporation method to form a source electrode and a drain electrode with a groove width of 2 mm and a groove length of 20 μm. This electrode-attached substrate was fixed on a spin coater, hexamethyldisilazane (HMDS) manufactured by Aldrich was dropped thereon, and then rotated at 2000 rpm to treat the surface of the substrate with HMDS. Using the coating solution of the above-mentioned polymer compound D, the dispenser printing method (Shot Mini manufactured by Musashi Engineering Co., Ltd.) was used to coat the polymer compound D with a needle tip with an inner diameter of 100 μm so as to cover the gap between the source electrode and the drain electrode to form a film with a thickness of 700 nm. film. Then, it was baked at 120° C. for 30 minutes in a nitrogen atmosphere to produce a polymer thin film element 5 .

For the polymer thin film element 5 made, the gate voltage V _G is changed to 0 ~ -60V in vacuum, the voltage V _SD between the source electrode and the drain electrode is changed to 0 ~ -60V, and the characteristics of the organic thin film transistor are measured, and the results are good. According to the Isd-Vg characteristic of V _g =-60V, V _sd =-60V, the leakage current is -0.6μA. In addition, the field effect mobility obtained from the Isd-Vg characteristic was 5×10 ^-4 cm ² /Vs, and the current on-off ratio was 1×10 ³ .

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

Claims (15)

1. macromolecular compound, it is characterized in that: contain the repeating unit shown in repeating unit shown in the following formula (7) or the formula (8), and the repeating unit shown in formula (7) or the formula (8) add up to 50 moles of whole repeating units more than the %, the number-average molecular weight of polystyrene conversion is 10 ³～10 ⁸,

In the formula, Ar ¹And Ar ²Represent the aromatic hydrocarbyl of 3 valencys or the heterocyclic radical of 3 valencys independently of one another, X ¹And X ²Represent independently of one another O, S, C (=O), S (=O), SO ₂, C (R ¹) (R ²) or N (R ⁵), Ar ³The heterocyclic radical of aromatic hydrocarbyl, the divalent of expression divalent or-CR ¹⁵=CR ¹⁶-, R ¹, R ², R ⁵, R ¹⁵And R ¹⁶Heterocyclic radical, heteroaryloxy, heteroarylthio or the cyano group of representing hydrogen atom, halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aromatic alkylthio, 1 valency independently of one another, still, X ¹And X ²Difference, C (R ¹) (R ²) in R ¹And R ²Can mutually combine and form ring, m represents 0 or 1, and n represents 1～6 integer, still, during m=0, X ¹Do not represent C (R ¹) (R ²), in addition, X ¹And Ar ²Be incorporated into Ar ¹The ortho position of aromatic nucleus, during m=1, X ²With Ar ¹Be attached to Ar ²The ortho position of aromatic nucleus, during m=0, X ¹With Ar ¹Be attached to Ar ²The ortho position of aromatic nucleus;

O represents 1～10 integer, and p represents 0～2 integer, and Y represents S, R ⁹Heterocyclic radical, heteroaryloxy, heteroarylthio or the cyano group of expression halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aromatic alkylthio, 1 valency have a plurality of R ⁹The time, they are identical or different, in addition, and R ^{9 it}Between can mutually combine and form ring, q represents 1～6 integer,

The integer of o ' expression 1～10, the integer of P ' expression 0～2, Y ' represents S, R ⁹' heterocyclic radical, heteroaryloxy, heteroarylthio or the cyano group of expression halogen atom, alkyl, alkoxyl group, alkylthio, aryl, aryloxy, arylthio, aralkyl, aralkoxy, aromatic alkylthio, 1 valency, a plurality of R are arranged ⁹' time, they are identical or different, in addition, and R ⁹' between can mutually combine and form ring.

2. macromolecular compound according to claim 1 is characterized in that: the X of formula (7) or formula (8) ¹For O, S, C (=O), S (=O) or SO ₂

3. macromolecular compound according to claim 1 and 2 is characterized in that: the X of formula (7) or formula (8) ²Be C (R ¹) (R ²) or N (R ⁵), in the formula, R ¹, R ²And R ⁵Represent implication same as described above independently of one another.

4. macromolecular compound according to claim 1 and 2 is characterized in that: the Ar of formula (7) or formula (8) ¹And Ar ²Be the aromatic hydrocarbyl of 3 valencys independently of one another.

5. macromolecular compound according to claim 1 and 2 is characterized in that: Ar in the formula (8) ³For-CR ¹⁵=CR ¹⁶-, in the formula, R ¹⁵And R ¹⁶Represent implication same as described above.

6. macromolecular compound according to claim 1 and 2 is characterized in that: have liquid crystal liquid crystal property.

7. macromolecule membrane, it is characterized in that: contain each described macromolecular compound in the claim 1～6, thickness is in the scope of 1nm～100 μ m.

8. the manufacture method of the described macromolecule membrane of claim 7 is characterized in that: use spin-coating method, ink jet printing method, divider print process or flexographic printing method.

9. the manufacture method of the described macromolecule membrane of claim 7 is characterized in that: comprise the operation that adopts rubbing manipulation or shearing method to make macromolecular orientation.

10. a macromolecule membrane element is characterized in that: comprise the described macromolecule membrane of claim 7.

11. an OTFT is characterized in that: comprise the described macromolecule membrane of claim 7.

12. an organic solar batteries is characterized in that: comprise the described macromolecule membrane of claim 7.

13. optical sensor: it is characterized in that: comprise the described macromolecule membrane of claim 7.

14. an Electrophtography photosensor is characterized in that: comprise the described macromolecule membrane of claim 7.

15. a spatial optical modulation element is characterized in that: comprise the described macromolecule membrane of claim 7.

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