JP7342565B2 - Conjugated polymer, organic semiconductor layer forming solution, organic semiconductor layer, and organic thin film transistor - Google Patents

Description

The present invention relates to a novel conjugated polymer that can be applied to electronic materials such as organic semiconductor materials, an organic semiconductor layer using the same, and an organic thin film transistor. The present invention relates to a novel conjugated polymer applicable to device manufacturing processes, an organic semiconductor layer using the same, and an organic thin film transistor.

Organic semiconductor devices, typified by organic thin film transistors, have attracted attention in recent years because they have characteristics that inorganic semiconductor devices do not have, such as energy saving, low cost, and flexibility. This organic semiconductor device is composed of several types of materials such as an organic semiconductor layer, a substrate, an insulating layer, and an electrode, among which the organic semiconductor layer, which is responsible for charge carrier movement, plays a central role in the device. Since the performance of an organic semiconductor device depends on the carrier mobility of the organic semiconductor material constituting the organic semiconductor layer, it is desired to develop an organic semiconductor material that provides high carrier mobility.

Generally known methods for producing an organic semiconductor layer include a vacuum evaporation method in which an organic material is vaporized under high-temperature vacuum, and a coating method in which an organic material is dissolved in an appropriate solvent and the solution is applied. It is being Among these, the coating method can also be carried out using printing technology without using high temperature and high vacuum conditions. Therefore, it can be expected to significantly reduce the manufacturing cost of device fabrication, making it an economically preferable process.

From the viewpoint of high carrier mobility and device manufacturing process, the organic semiconductor material used in such a coating method has a carrier mobility of 0.1 cm ² /V・sec or more and a solubility of 0 at room temperature. .1% by weight or more.

Here, polymer semiconductors are generally known to have superior film forming properties compared to low-molecular semiconductors, but it is difficult to improve the crystallinity of thin films compared to low-molecular semiconductors. There is a problem with low carrier mobility compared to small molecule semiconductors. Thermal annealing is an effective method for improving the crystallinity and molecular orientation of the thin film, but in consideration of the heat resistance of the plastic substrate, it is preferable to perform the annealing at a temperature of 140° C. or lower.

Currently, as polymeric materials, poly(2,5-bis(3-alkylthiophenyl-2-)thieno[3,2-b]thiophene) (for example, see Non-Patent Documents 1 and 2), poly (2,7-bis(3-alkylthiophenyl-2-)naphthodithiophene) (see, for example, Non-Patent Document 3) and the like have been proposed.

However, the annealing temperature of poly(2,5-bis(3-alkylthiophenyl-2-)thieno[3,2-b]thiophene) described in Non-Patent Document 2 is 150°C; The annealing temperature of the described poly(2,7-bis(3-alkylthiophenyl-2-)naphthodithiophene) is also 150°C, and annealing at a milder temperature has been desired.

Nature Materials, 2006, vol. 5, pp. 328-333 Journal of Applied Physics, 2009, Volume 105, Pages 024516-1 to 024516-5 Journal of the American Chemical Society, 2011, Volume 133, Pages 6852-6860

The present invention has been made in view of the above problems, and its purpose is to provide a novel coated organic semiconductor material that has high carrier mobility, high solubility, and can be annealed at a mild temperature. be.

As a result of intensive studies to solve the above problems, the present inventors discovered that a new conjugated polymer provides high carrier mobility and is an organic semiconductor material that has high solubility and can be annealed at mild temperatures. , we have completed the present invention.

That is, the present invention relates to a conjugated polymer containing a monomer unit having a benzocyclobutene skeleton, an organic semiconductor layer, and an organic thin film transistor using the same.

The conjugated polymer containing a monomer unit having a benzocyclobutene skeleton of the present invention is not limited in any way as long as it contains a benzocyclobutene skeleton in the monomer unit, but a biphenylene skeleton is preferred because it is stable.

The conjugated polymer containing a monomer unit having a benzocyclobutene skeleton is more specifically represented by the following general formula (1).

(Here, A, C, and E are each independently one of the group consisting of a thiophene ring, a furan ring, a selenophene ring, a thiazole ring, a thienothiophene ring, a 2-ethenylthiophene ring, or a benzene ring. B represents a 3- to 7-ring divalent linking group containing at least one benzocyclobutene skeleton; D represents at least one sulfur atom, oxygen atom, selenium atom, or nitrogen atom; Represents a divalent linking group of fused 2- to 7-ring atoms containing atoms as ring constituent atoms. b represents 1 to 3, a, c, d, e are 0 to 3, and a, c, d , at least one of e is 1 or more. n represents an integer of 2 or more.)

The present invention will be explained in detail below.

The conjugated polymer of the present invention is represented by the above general formula (1).

A, C, and E in general formula (1) are each independently one member of the group consisting of a thiophene ring, a furan ring, a selenophene ring, a thiazole ring, a thienothiophene ring, a 2-ethenylthiophene ring, or a benzene ring. represents a divalent linking group. Because of high mobility and high solubility, one type from the group consisting of a thiophene ring, a furan ring, a selenophene ring, and a thiazole ring is preferred, and a thiophene ring is more preferred.

Examples of A, C, and E in general formula (1) include those shown in the group consisting of general formulas (A-1) to (A-9) below.

(Here, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, a carbon Indicates an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, or an aryl group having 4 to 30 carbon atoms. * indicates a bonding site with another structure.)

A, C, and E are preferably one of the group consisting of (A-1) to (A-4) because they are conjugated polymers exhibiting high mobility; ) is more preferable.

The halogen atom in R ¹ and R ² is, for example, one of the group consisting of fluorine atom, chlorine atom, bromine atom, and iodine atom, and fluorine atom and chlorine atom are preferred because they are stable.

Examples of the alkyl group having 1 to 30 carbon atoms in R ¹ and R ² include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, and undecyl group. groups, straight chain alkyl groups such as dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl yellow, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, isopropyl, isobutyl, isovaleryl, Isohexyl group, 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl group, 2-hexyldecyl group, 2-hexylundecyl group, 2-octyldecyl group, 2-octyldodecyl group, 2-decyltetradecyl group , 2-decylhexadecyl group, 3-hexyldecyl group, 3-octyldecyl group, 3-octyldodecyl group, 3-decyltetradecyl group, 3-decylhexadecyl group, 4-hexyldecyl group, 4-octyldecyl group group, branched alkyl group such as 4-octyldodecyl group, 4-decyltetradecyl group, 4-decylhexadecyl group, 4-cyclohexylbutyl group, 8-cyclohexyloctyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 3 Examples include cyclic alkyl groups such as -decylcyclopentyl group and 4-decylcyclohexyl group. Among them, conjugated polymers exhibit particularly high mobility and high solubility, so they include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, and pentadecyl groups. , straight chain alkyl groups having 68 to 24 carbon atoms such as hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, and 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl group, 2-hexyldecyl group, 2-octyldecyl group, 2-octyldodecyl group, 2-decyldodecyl group, 2-decyltetradecyl group, 3-hexyldecyl group, 3-octyldecyl group, 3-octyldodecyl group, 3 - Consists of branched alkyl groups having 8 to 26 carbon atoms such as decyltetradecyl group, 4-hexyldecyl group, 4-octyldecyl group, 4-octyldodecyl group, 4-decyltetradecyl group, 4-decylhexadecyl group One type of the group consisting of a straight chain alkyl group having 10 to 22 carbon atoms or a branched alkyl group having 10 to 24 carbon atoms is more preferable.

In addition, in the alkyl group having 1 to 30 carbon atoms, at least one hydrogen atom can be replaced with a fluorine atom. Further, in the alkyl group having 1 to 30 carbon atoms, one to three carbon atoms can be substituted with oxygen atoms.

Examples of the alkoxy group having 1 to 30 carbon atoms in R ¹ and R ² include methoxy group, ethoxy group, propoxy group, butoxy group, pentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, Decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, icosyloxy group, henicosyl Linear alkoxy groups such as oxy group and docosyloxy group, isopropoxy group, isobutoxy group, isovaleroxy group, isohexyloxy group, 2-ethylhexyloxy group, 3-ethylheptyloxy group, 3-ethyldecyloxy group, 2-hexyl Decyloxy group, 2-octyldecyloxy group, 2-octyldodecyloxy group, 2-decyltetradecyloxy group, 2-decylhexadecyloxy group, 3-hexyldecyloxy group, 3-octyldecyloxy group, 3- Octyldodecyloxy group, 3-decyltetradecyloxy group, 3-decylhexadecyloxy group, 4-hexyldecyloxy group, 4-octyldecyloxy group, 4-octyldodecyloxy group, 4-decyltetradecyloxy group, Branched alkoxy groups such as 4-decylhexadecyloxy group, 4-cyclohexylbutyloxy group, 8-cyclohexyloctyloxy group, cyclopentyloxy group, cyclohexyloxy group, cycloheptyloxy group, 3-decylcyclopentyloxy group, 4-decyl Examples include cyclic alkoxy groups such as cyclohexyloxy. Among them, conjugated polymers exhibit particularly high mobility and high solubility, so octyloxy groups, nonyloxy groups, decyloxy groups, undecyloxy groups, dodecyloxy groups, tridecyloxy groups, tetradecyloxy groups, Straight chain alkyloxy groups having 8 to 24 carbon atoms such as pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, icosyloxy group, henicosyloxy group, docosyloxy group, and 2- Ethylhexyloxy group, 3-ethylheptyloxy group, 3-ethyldecyloxy group, 2-hexyldecyloxy group, 2-octyldecyloxy group, 2-octyldodecyloxy group, 2-decyldodecyloxy group, 2-decyltetra Decyloxy group, 3-hexyldecyloxy group, 3-octyldecyloxy group, 3-octyldodecyloxy group, 3-decyltetradecyloxy group, 4-hexyldecyloxy group, 4-octyldecyloxy group, 4-octyl One member of the group consisting of branched alkoxy groups having 8 to 26 carbon atoms such as dodecyloxy group, 4-decyltetradecyloxy group, and 4-decylhexadecyloxy group is preferred, and linear alkoxy groups having 10 to 22 carbon atoms or More preferred is one of the group consisting of branched alkoxy groups having 10 to 24 carbon atoms.

In addition, in the alkoxy group having 1 to 30 carbon atoms, at least one hydrogen atom can be replaced with a fluorine atom. Further, in the alkyl group having 1 to 30 carbon atoms, one to three carbon atoms can be substituted with oxygen atoms.

Examples of the acyl group having 1 to 30 carbon atoms in R ¹ and R ² include formyl group, acetyl group, propionyl group, butyryl group, valeryl group, hexanoyl group, heptanoyl group, octanoyl group, nonanoyl group, decanoyl group, and undecanoyl group. straight-chain acyl groups such as dodecanoyl group, tridecanoyl group, tetradecanoyl group, pentadenoyl group, hexidecanoyl group, heptadecanoyl group, octadecanoyl group, nonadecanoyl group, icosilyl group, heniicosilyl group, docosilyl group, isobutyryl group , 2-ethylhexanoyl group, 3-ethylheptanoyl group, 3-ethyldecanoyl group, 2-hexyldecanoyl group, 2-octyldecanoyl group, 2-octyldodecanoyl group, 2-decyltetradecanoyl group , 2-decylhexadecanoyl group, 3-hexyldecanoyl group, 3-octyldecanoyl group, 3-octyldodecanoyl group, 3-decyltetradecanoyl group, 3-decylhexadecanoyl group, 4-hexyldecanoyl group Branched alkyl groups such as noyl group, 4-octyldecanoyl group, 4-octyldodecanoyl group, 4-decyltetradecanoyl group, 4-decylhexadecanoyl group, 4-cyclohexylbutyryl group, 8-cyclohexyloctanoyl group, etc. Examples include groups.

In the acyl group having 1 to 30 carbon atoms, at least one hydrogen atom can be replaced with a fluorine atom. Furthermore, in the acyl group having 1 to 30 carbon atoms, one to three carbon atoms can be substituted with oxygen atoms.

Examples of the alkenyl group having 2 to 30 carbon atoms in R ¹ and R ² include ethenyl group, propenyl group, butenyl group, 2-methylpropenyl group, pentenyl group, 2-methylbutenyl group, hexenyl group, and 2-methylpentenyl group. , heptenyl group, octenyl group, 2-ethylhexenyl group, nonel group, 2-ethylheptenyl group, decenyl group, dodecenyl group, cyclopentenyl-1-group, cyclohexenyl-1-group, cycloheptenyl-1- group One type is mentioned.

In the alkenyl group having 2 to 30 carbon atoms, at least one hydrogen atom can be replaced with a fluorine atom.

Examples of the alkynyl group having 2 to 30 carbon atoms in R ¹ and R ² include ethynyl group, propynyl group, butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, dodecynyl group, trimethylsilyl group. Examples include one of the group consisting of ethynyl group, triethylsilylethynyl group, and tert-butyldimethylsilylethynyl group.

In the alkynyl group having 2 to 30 carbon atoms, at least one hydrogen atom can be replaced with a fluorine atom.

The aryl group having 4 to 30 carbon atoms in R ¹ and R ² includes a heteroaryl group having 4 to 30 carbon atoms. Examples of the aryl group having 4 to 30 carbon atoms include phenyl group; p-tolyl group, p-(hexyl)phenyl group, p-(octyl)phenyl group, p-(decyl)phenyl group, p-(2 -ethylhexyl) phenyl group; 2-furyl group, 2-thienyl group; 5-fluoro-2-furyl group, 5-methyl-2-furyl group, 5-ethyl-2-furyl group, 5 -(propyl)-2-furyl group, 5-(butyl)-2-furyl group, 5-(pentyl)-2-furyl group, 5-(hexyl)-2-furyl group, 5-(octyl)-2 -furyl group, 5-(2-ethylhexyl)-2-furyl group, 5-fluoro-2-thienyl group, 5-methyl-2-thienyl group, 5-ethyl-2-thienyl group, 5-(propyl)- 2-thienyl group, 5-(butyl)-2-thienyl group, 5-(pentyl)-2-thienyl group, 5-(hexyl)-2-thienyl group, 5-(octyl)-2-thienyl group, 5 A group consisting of alkyl-substituted heteroaryl groups such as -(2-ethylhexyl)-2-thienyl group, 5-(2-hexylundecyl)-2-thienyl group, and 5-(2-octyldodecyl)-2-thienyl group. One type can be mentioned.

In the aryl group having 4 to 30 carbon atoms, at least one hydrogen atom can be replaced with a fluorine atom.

B in the general formula (1) represents a divalent linking group of 3 to 7 fused rings containing at least one benzocyclobutene skeleton. All rings constituting the fused 3-ring to 7-fused ring are 4- to 8-membered rings. Specific examples of the 4- to 8-membered ring include a cyclobutene ring, a thiophene ring, a furan ring, a selenophene ring, a thiazole ring, an oxazole ring, a pyrrole ring, an imidazole ring, a benzene ring, a pyridine ring, and a cyclooctatetraene ring. At least one member of the group consisting of a cyclobutene ring, a thiophene ring, a furan ring, a selenophene ring, and a benzene ring is preferred because of its high mobility. In particular, a 4- to 6-membered ring is preferred because of its high solubility, and at least one member of the group consisting of a cyclobutene ring, a thiophene ring, a furan ring, a selenophene ring, and a benzene ring is more preferred.

The number of benzocyclobutene skeletons constituting B is preferably one, and more preferably a biphenylene skeleton. This makes B more stable.

Examples of B include at least one member of the group consisting of those shown in the following general formulas (B-1) to (B-25).

(Here, X represents an oxygen atom, a sulfur atom, a selenium atom, or one of the group consisting of C=C, and ^Y represents a carbon atom or a nitrogen atom. Indicates one type of the group consisting of C=C or NH. * indicates a bonding site with another structure.)

B is preferably at least one member of the group consisting of (B-1) to (B-19) because it is a conjugated polymer exhibiting high mobility and high solubility, and (B-6) to (B-15). ) is more preferred.

X represents an oxygen atom, a sulfur atom, a selenium atom, or one of the group consisting of C=C, and since it is a conjugated polymer that exhibits high mobility, one of the group consisting of an oxygen atom, a sulfur atom, and a selenium atom is Preferably, a sulfur atom is more preferable.

Y represents either a carbon atom or a nitrogen atom, and is preferably a sulfur atom since it results in a conjugated polymer exhibiting high mobility.

X ¹ represents one type of the group consisting of an oxygen atom, a sulfur atom, a selenium atom, C═C, or NH, and C═C is preferable because it results in a stable conjugated polymer.

In the above general formulas (B-1) to (B-25), the hydrogen atom on carbon and the hydrogen atom of NH are halogen atoms, alkyl groups having 1 to 30 carbon atoms, alkoxy groups having 1 to 30 carbon atoms, carbon It can be substituted with one member of the group consisting of an acyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, or an aryl group having 4 to 30 carbon atoms.

The halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, carbon Specific examples of the aryl group having numbers 4 to 30 include, for example, a halogen atom in R ¹ and R ² of the above general formulas (A-1) to (A-9), an alkyl group having 1 to 30 carbon atoms, and a carbon number Specific examples include one of the group consisting of alkenyl groups having 2 to 30 carbon atoms, alkynyl groups having 2 to 30 carbon atoms, and aryl groups having 4 to 30 carbon atoms.

From the viewpoint of high mobility and high solubility, the substitutable group for the hydrogen atom on carbon and the hydrogen atom of NH is preferably an alkyl group having 1 to 30 carbon atoms, and the above-mentioned linear chain having 6 to 24 carbon atoms. One type of the group consisting of an alkyl group or a branched alkyl group having 8 to 26 carbon atoms is more preferable, and one type of the group consisting of a straight chain alkyl group having 10 to 22 carbon atoms or a branched alkyl group having 10 to 24 carbon atoms is particularly preferable. preferable.

D in the general formula (1) represents a divalent linking group of 2- to 7-ring condensed rings containing at least one sulfur atom, oxygen atom, selenium atom, or nitrogen atom as a ring-constituting atom. All rings constituting the fused 2-ring to 7-fused ring are 4- to 8-membered rings. Specific examples of the 4- to 8-membered ring include a cyclobutene ring, a thiophene ring, a furan ring, a selenophene ring, a thiazole ring, an oxazole ring, a pyrrole ring, an imidazole ring, a benzene ring, a pyridine ring, and a cyclooctatetraene ring. At least one member of the group consisting of a cyclobutene ring, a thiophene ring, a furan ring, a selenophene ring, and a benzene ring is more preferable. .

Examples of D include those shown in the following general formulas (D-1) to (D-64).

(Here, * indicates a binding site with another structure.)

Since D is a conjugated polymer exhibiting high mobility and high solubility, at least one member of the group consisting of (D-1) to (D-14) and (D-52) to (D-64) is selected. Preferably, at least one member of the group consisting of (D-52) to (D-64) is more preferable.

In the above general formulas (D-1) to (D-64), the hydrogen atoms on carbon and the hydrogen atoms of SiH ₂ and NH are halogen atoms, alkyl groups having 1 to 30 carbon atoms, and hydrogen atoms having 1 to 30 carbon atoms. It may be substituted with one of the group consisting of an alkoxy group, an acyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, or an aryl group having 4 to 30 carbon atoms. can.

The halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, carbon Specific examples of the aryl group having numbers 4 to 30 include, for example, a halogen atom in R ¹ and R ² of the above general formulas (A-1) to (A-8), an alkyl group having 1 to 30 carbon atoms, a carbon number A specific example is one of the group consisting of an alkoxy group having 1 to 30 carbon atoms, an acyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 30 carbon atoms, and an aryl group having 4 to 30 carbon atoms. It can be mentioned as follows.

From the viewpoint of high mobility and high solubility, the hydrogen atom on the carbon and the substitutable group for the hydrogen atom of SiH ₂ and NH are preferably an alkyl group having 1 to 30 carbon atoms, and the above-mentioned alkyl group having 6 to 30 carbon atoms. One of the group consisting of a straight chain alkyl group having 24 carbon atoms or a branched alkyl group having 8 to 26 carbon atoms is more preferable; One type is particularly preferred.

In general formula (1), a, c, d, and e represent 0 to 3, and at least one of a, c, d, and e is 1 or more. n represents an integer of 2 or more.

Since a, c, d, and e have high mobility, 0 to 2 are preferable. When a and c are 1, d and e are preferably 0, and when c, d and e are 1, a is preferably 0.

In general formula (1), b represents 1 to 3, and 1 is preferable because it has higher mobility.

The conjugated polymer represented by the general formula (1) is a compound in which n, which is a repeating unit, is 2 or more. Although n is not particularly limited as long as it is an integer of 2 or more, it is preferably 4 or more for high mobility, preferably 300 or less for high solubility, and more preferably 200 or less.

The molecular weight of the conjugated polymer is preferably 2,000 to 1,000,000, more preferably 4,000 to 300,000, since it is suitable for obtaining an organic thin film transistor with higher carrier mobility. Particularly preferred is 10,000 to 150,000. In the present invention, the molecular weight of the polymer refers to the weight average molecular weight (Mw) in terms of polystyrene, and is measured by gel permeation chromatography (GPC).

Specific examples of the conjugated polymer represented by the general formula (1) of the present invention include the following.

As a method for producing the conjugated polymer represented by general formula (1) of the present invention, any production method can be used as long as it is possible to produce the conjugated polymer.

Examples of the method for producing the conjugated polymer include a method in which compounds represented by the following general formulas (2) and (3) are used and a coupling reaction is performed.
Z ¹ -(B)b-Z ² (2)
Z ³ -(C)c-(D)d-(E)e-(A)a-Z ⁴ (3)
(Here, A, B, C, D, E, a, b, c, d, and e are A, B, C, D, E, a, b, c, d in the above general formula (1). , and have the same meaning as e. Z ¹ to Z ⁴ each independently represent a halogen atom, trifluorosulfonyloxy, trimethylsulfonyloxy, trialkyltin, triaryltin, dialkoxyboron, dihydroxyboron, Indicates zinc halide, dimethylfluorosilicon, difluoromethylsilicon, triethoxysilicon, trimethoxysilicon, or magnesium halide.However, two of Z ¹ to Z ⁴ are halogen, trifluorosulfonyloxy, trimethylsulfonate. Honyloxy is selected from the group consisting of trialkyltin, triaryltin, dialkoxyboron, dihydroxyboron, zinc halide, dimethylfluorosilicon, difluoromethylsilicon, triethoxysilicon, trimethoxysilicon, (One selected from the group consisting of magnesium halides.)

The coupling reaction is an aryl-aryl coupling reaction, and because it has a high yield, it is a group consisting of Stille coupling reaction, Suzuki coupling reaction, Negishi coupling reaction, Kumada coupling reaction, and Hiyama coupling reaction. At least one of the following is preferred, and at least one of Stille coupling reaction and Suzuki coupling reaction is more preferred.

Z ¹ to Z ⁴ in general formulas (2) and (3) each independently represent a halogen atom, trifluorosulfonyloxy, trimethylsulfonyloxy, trialkyltin, triaryltin, dialkoxyboron, dihydroxyboron. , zinc halide, dimethylfluorosilicon, difluoromethylsilicon, triethoxysilicon, trimethoxysilicon, or magnesium halide.

The halogen atom is one of the group consisting of a bromine atom, an iodine atom, a chlorine atom, and a fluorine atom, and at least one of a bromine atom and an iodine atom is preferred because of its high reactivity.

The trialkyltin alkyl group represents an alkyl group having 1 to 10 carbon atoms, and includes, for example, at least one member of the group consisting of trimethyltin, triethyltin, tripropyltin, tributyltin, trihexyltin, and tricyclohexyltin. At least one of trimethyltin and tributyltin is preferred because of their availability.

The triaryltin aryl group represents an aryl group having 6 to 10 carbon atoms, such as triphenyltin, tri(o-tolyl)tin, tri(m-tolyl)tin, tri(p-tolyl)tin, At least one member of the group consisting of trinaphthyltin can be mentioned.

The alkoxy group of the dialkoxyboron represents an alkoxy group having 1 to 10 carbon atoms, and includes, for example, a group consisting of dimethoxyboron, diethoxyboron, dipropyloxyboron, diisopropyloxyboron, dibutoxyboron, and dihexyloxyboron. It shows at least one kind of. Note that two alkoxy groups can be combined to form a ring, such as a 4,4,5,5-tetramethyldioxoborolanyl group. As the dialkoxyboron, 4,4,5,5-tetramethyldioxobororanyl group and 1,3,2-dioxaborinanyl group are preferable from the viewpoint of high reactivity.

Examples of the zinc halide include ClZn, BrZn, and IZn.

Examples of the magnesium halide include ClMg, BrMg, and IMg.

Among Z ¹ to Z ⁴ , two are selected from the group consisting of halogen atoms, trifluorosulfonyloxy, and trimethylsulfonyloxy, and the remaining two are trialkyltin, triaryltin, dialkoxyboron, selected from the group consisting of dihydroxyboron, zinc halide, dimethylfluorosilicon, difluoromethylsilicon, triethoxysilicon, trimethoxysilicon, or magnesium halide. For example, due to their high reactivity, Z ¹ and Z ² may be trialkyltin, triaryltin, dialkoxyboron, dihydroxyboron, zinc halide, dimethylfluorosilicon, difluoromethylsilicon, triethoxysilicon, trimethoxysilicon, Preferably, Z ³ and Z ⁴ are selected from the group consisting of magnesium halides, and Z 3 and Z 4 are selected from the group consisting of halogen atoms, trifluorosulfonyloxy, and trimethylsulfonyloxy.

For the Stille coupling reaction, Suzuki coupling reaction, Negishi coupling reaction, Kumada coupling reaction, and Hiyama coupling reaction, which are methods for producing the conjugated polymer of general formula (1), a zero-valent palladium compound or a divalent palladium compound is used. At least one of the catalysts is used. Examples of the zero-valent palladium compound include at least one of the group consisting of tris(dibenzylideneacetone)dipalladium, bis(dibenzylideneacetone)palladium, tetrakis(triphenylphosphine)palladium, and bis{tri(tert-butyl)phosphine}palladium. Examples of divalent palladium compounds include dichlorobis(triphenylphosphine)palladium, {1,2-bis(diphenylphosphino)ethane}palladium dichloride, and {1,3-bis(diphenylphosphine)palladium. Examples include at least one member of the group consisting of {1,1'-bis(diphenylphosphino)ferrocene}palladium dichloride, {1,1'-bis(diphenylphosphino)ferrocene}palladium dichloride, and palladium acetate. Furthermore, at least one phosphine selected from the group consisting of tri(o-tolyl)phosphine, triphenylphosphine, and tri(tert-butyl)phosphine may be added to the palladium compound.

Moreover, a nickel compound can also be used as a catalyst. The nickel compound includes bis(1,5-cyclooctadienyl)nickel, {1,2-bis(diphenylphosphino)ethane}nickel dichloride, and {1,3-bis(diphenylphosphino)propane}nickel dichloride. At least one member of the group consisting of:

A copper compound may be added to the palladium compound and nickel compound. Examples of the copper compound include monovalent copper such as copper(I) iodide, copper(I) chloride, copper(I) bromide, and copper(I) acetate; copper(II) chloride, copper(II) bromide; ), copper(II) iodide, copper(II) acetate, copper(II) acetylacetonate, and other divalent coppers, among which monovalent copper is preferable, and copper(I) iodide is more preferable. preferable.

In the aryl-aryl coupling reaction, a base may be added to promote the reaction. Examples of the base include inorganic bases such as potassium phosphate, sodium phosphate, cesium carbonate, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, potassium hydroxide, sodium hydroxide, and sodium tert-butoxide; triethylamine; , trimethylamine, tributylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, diisopropylamine, and pyridine.

In the aryl-aryl coupling reaction, a fluoride may be added to promote the reaction. Suitable examples of the fluoride include tetrabutylammonium fluoride, potassium fluoride, hookanatrim, cesium fluoride, and lithium fluoride.

The coupling reaction using the compounds represented by the general formulas (2) and (3) is preferably carried out in a solvent. The solvent is not particularly limited, and examples include toluene, xylene, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, tetrahydrofuran (hereinafter abbreviated as THF), diethyl ether, methyl-tert-butyl ether, dioxane, ethylene glycol dimethyl ether, At least one member of the group consisting of hexane, cyclohexane, ethanol, water, N,N-dimethylformamide (hereinafter abbreviated as DMF), N-methylpyrrolidone (hereinafter abbreviated as NMP), triethylamine, piperidine, pyrrolidine, and diisopropylamine. Further, these solvents may be used alone or in a mixture of two or more thereof, for example, a two- or three-component system such as toluene/water or toluene/ethanol/water can be used.

The amount of the palladium catalyst and nickel catalyst to be used is in the range of 0.1 to 20 mol%, preferably in the range of 0.5 to 10 mol%, based on the compound of general formula (2).

The amount of phosphine used is 0.9 to 8.0 equivalents, preferably 1.0 to 3.0 equivalents, relative to the palladium compound.

The amount of the copper compound to be used is in the range of 0.5 to 30 mol%, preferably in the range of 1 to 20 mol%, based on the compound of general formula (2).

The amount of the base used is 0.8 to 2.5 equivalents, preferably 1.2 to 2.2 equivalents, relative to the compound of general formula (2).

The amount of the compound of general formula (3) to be used is 0.8 to 1.3 equivalents, preferably 0.9 to 1.2 equivalents, and 1.0 to 1.1 equivalents, relative to the compound of general formula (2). Equivalents are more preferred.

The temperature during the reaction is 10 to 160°C, particularly preferably 30 to 140°C, and even more preferably 40 to 120°C. The reaction time is 1 to 72 hours, preferably 2 to 48 hours.

Furthermore, the produced conjugated polymer of general formula (1) can be purified by existing methods such as Soxhlet extraction and reprecipitation.

As a method for producing the compound represented by the above general formula (2), for example, in the case of a skeleton in which X in the above general formula (B-5) is a sulfur atom and Y is CH, the following steps A1 to F1 may be used. It can be manufactured by the following method.

(Step A1); In the presence of a palladium catalyst, 1-bromo-4-fluorophenyl-2-zinc chloride derived from 1-bromo-4-fluoro-2-iodobenzene and 2-bromo-4-fluoro- A process for producing 2,2'-dibromo-4,5'-difluorobiphenyl from 1-iodobenzene.
(Step B1); 2,6- A process for producing difluorobiphenylene.
(Step C1); 2,6-difluoro-1,5-dihalobiphenylene is produced by treating 2,6-difluorobiphenylene obtained in step B1 with lithium diisopropylamide (hereinafter abbreviated as LDA)/halogenation. Process.
(Step D1); In the presence of a palladium/copper catalyst, 1,5-bis(tri- A process for producing alkylsilylethynyl)-2,6-difluorobiphenylene.
(Step E1): A step of producing an unsubstituted dithienobiphenylene derivative by subjecting the 1,5-bis(trialkylsilylethynyl)-2,6-difluorobiphenylene obtained in Step D1 to a reaction with sodium sulfide.
(Step F1); After reacting the unsubstituted dithienobiphenylene derivative obtained in the step E1 with butyllithium, it is treated with trialkyltin chloride to produce 2,7-bis(trialkyltin)dithienobiphenylene. Process.

Details of each step of A1 to F1 are shown below.

In the A1 step, 1-bromo-4-fluorophenyl-2-zinc chloride derived from 1-bromo-4-fluoro-2-iodobenzene and 2-bromo-4-fluoro- This is a process for producing 2,2'-dibromo-4,5'-difluorobiphenyl from cross-coupling of 1-iodobenzene.

1-Bromo-4-fluorophenyl-2-zinc chloride is produced by converting iodine from 1-bromo-4-fluoro-2-iodobenzene into magnesium halide using an organometallic reagent such as ethylmagnesium chloride or isopropylmagnesium bromide. After exchange (preparation of 1-bromo-4-fluorophenyl-2-magnesium halide), it can be prepared by metal exchange with zinc chloride. Moreover, it is also possible to use magnesium metal instead of the organometallic reagent.

The conditions for preparing 1-bromo-4-fluorophenyl-2-magnesium halide include, for example, a temperature range of -80°C to 20°C in a solvent such as THF or diethyl ether. 1-Bromo-4-fluorophenyl-2-zinc chloride can be prepared by reacting a solution of the magnesium salt (1-bromo-4-fluorophenyl-2-magnesium halide) with zinc chloride. Zinc chloride may be used as it is or may be a solution in THF or diethyl ether. The reaction temperature between the magnesium salt and zinc chloride can be carried out within the range of -80°C to 30°C.

Examples of the palladium catalyst in step A1 include tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, and the like, and the reaction temperature includes a range of 20°C to 80°C.

The B1 step is performed by converting the 2,2'-dibromo-4,5'-difluorobiphenyl obtained in the A1 step into a dilithium salt with 2 equivalents or more of butyllithium, and intramolecularly cyclizing it with copper(II) chloride. This is a process for producing 2,6-difluorobiphenylene.

The conditions for preparing the dilithium salt include, for example, using 2 to 3 equivalents of butyllithium or tert-butyllithium in a solvent such as THF or diethyl ether at a temperature range of -80°C to 20°C. can.

Copper (II) chloride is used in an amount of 1 to 3 equivalents based on the dilithium salt, and the intramolecular cyclization reaction can be carried out at a temperature range of -80°C to 30°C. Note that copper (II) bromide can also be used instead of copper (II) chloride.

In the C1 step, the 2,6-difluorobiphenylene obtained in the B1 step is reacted with LDA to generate dilithium salts at the 1st and 5th positions, and then halogenated to produce 2,6-difluoro-1,5 - This is a process for producing dihalobiphenylene.

Conditions for the reaction with LDA include, for example, using 2 to 4 equivalents of LDA in a solvent such as THF or diethyl ether at a temperature range of -80°C to 20°C. The reaction between the dilithium salt and the halogenating agent can be carried out at a temperature of -80°C to 30°C.

Instead of LDA, butyllithium, butyllithium/tetramethylethylenediamine, butyllithium/2,2,6,6-tetramethylpiperidine can be used, and as the halogenating agent, iodine, 1-chloro-2-iodoethane , N-iodosuccinimide, bromotrichloromethane, tetrabromomethane, 1,2-dibromotetrachloroethane, N-bromosuccinimide (hereinafter abbreviated as NBS), and N-fluorobenzenesulfonimide. I can do it.

In the D1 step, in the presence of a palladium catalyst and a copper catalyst, 1,5-bis( This is a process for producing (trialkylsilylethynyl)-2,6-difluorobiphenylene.

Examples of the palladium catalyst in this case include tetrakis(triphenylphosphine)palladium, dichlorobis(triphenylphosphine)palladium, etc., and copper catalysts include copper(I) iodide, copper(I) bromide, copper chloride, etc. (I) etc. can be mentioned. Furthermore, Sonogashira coupling can be carried out in a solvent such as triethylamine, diisopropylamine, diisopropylethylamine, piperidine, or pyridine at a temperature range of 20°C to 80°C. Note that toluene, THF, etc. may be added as a solvent.

Examples of the trialkylsilylacetylene in step D1 include trimethylsilylacetylene, triethylsilylacetylene, tert-butyldimethylsilylacetylene, and the like.

The E1 step is a step of producing an unsubstituted dithienobiphenylene derivative by reacting 1,5-bis(trialkylsilylethynyl)-2,6-difluorobiphenylene obtained in the D1 step with sodium sulfide.

The reaction can be carried out, for example, in a solvent such as dimethyl sulfoxide (hereinafter abbreviated as DMSO), DMF, NMP, etc. at a temperature range of 40 to 200°C.

Note that this step can also be carried out using known reaction conditions for synthesizing a benzothiophene ring from 2-haloalkynylbenzene (eg, Organic Letters, 2009, Vol. 11, pp. 2473-2475).

In the F1 step, the unsubstituted dithienobiphenylene derivative obtained in the E1 step is reacted with butyllithium, and then treated with trialkyltin chloride to produce 2,7-bis(trialkyltin)dithienobiphenylene. It is a process.

The conditions for preparing the dilithium salt of a dithienobiphenylene derivative by reacting with butyllithium include, for example, using 2 to 5 equivalents of butyllithium in a solvent such as THF or diethyl ether at a temperature range of -80°C to 40°C. It can be implemented. The reaction between the dilithium salt and trialkyltin chloride can be carried out at a temperature in the range of -80°C to 40°C.

Instead of butyllithium, sec-butyllithium, tert-butyllithium, butyllithium/tetramethylethylenediamine, butyllithium/2,2,6,6,-tetramethylpiperidine, etc. can be used, and as trialkyltin chloride, For example, trimethyltin chloride, triethyltin chloride, tripropyltin chloride, tributyltin chloride, trihexyltin chloride, tricyclohexyltin chloride, triphenyltin chloride, etc. can be used.

The following reaction scheme shows a specific method for producing (B-5-a) which is preferable since the number of reaction steps is small.

Among the compounds of general formula (2), for example, in the case of a skeleton in which X of the above general formula (B-6) is a sulfur atom and Y is CH, it is produced by a method that involves the following steps A2 to E2. be able to.

(Step A2); In the presence of a palladium catalyst, 1-bromo-3-fluorophenyl-2-zinc chloride derived from 1-bromo-3-fluoro-2-iodobenzene and 2-bromo-1-fluoro- A process for producing 2,2'-dibromo-3,6'-difluorobiphenyl from 3-iodobenzene.
(Step B2); 2,2'-dibromo-3,6'-difluorobiphenyl obtained in Step A2 is dilithiated with butyllithium and reacted with a halogenating agent to produce 1-fluoro-5-halobiphenylene. The process of doing.
(Step C2): A step of producing 1,5-bis(dialkoxyethylthio)biphenylene by reacting 1-fluoro-5-halobiphenylene obtained in Step B2 with sodium sulfide and haloacetaldehyde dialkyl acetal.
(Step D2); A step of producing an unsubstituted dithienobiphenylene derivative by treating the 1,5-bis(dialkoxyethylthio)biphenylene obtained in Step C2 with polyphosphoric acid.
(Step E2); Step of producing a 2,7-bis(trialkyltin)biphenylene derivative by reacting the unsubstituted dithienobiphenylene derivative obtained in step D2 with butyllithium and then treating it with trialkyltin chloride. .

Details of each step of A2 to E2 are shown below.

The A2 step is the same as the reagents and reaction conditions of the A1 step, except for using 1-bromo-3-fluoro-2-iodobenzene and 2-bromo-1-fluoro-3-iodobenzene. to produce 2,2'-dibromo-3,6'-difluorobiphenyl.

In the B2 step, the 2,2'-dibromo-3,6'-difluorobiphenyl obtained in the A2 step is dilithiated with 2 equivalents or more of butyllithium, and after the generated benzyne is intramolecularly cyclized, a halogenating agent is added. 1-fluoro-5-halobiphenylene is produced by reacting with.

The conditions for the dilithiation include, for example, using 2 to 3 equivalents of butyllithium or tert-butyllithium in a solvent such as THF or diethyl ether at a temperature range of -80°C to 20°C.

The halogenating agent is used in an amount of 1 to 3 equivalents based on 2,2'-dibromo-3,6'-difluorobiphenyl, and the intramolecular cyclization reaction can be carried out at a temperature range of -80°C to 30°C. Examples of the halogenating agent include hexachloroethane, carbon tetrachloride, N-chlorosuccinimide, 1,2-dibromotetrachloroethane, bromotrichloromethane, tetrabromomethane, NBS, iodine, 1-chloro-2-iodoethane, N-iodo Examples include succinimide and N-fluorobenzenesulfonimide.

In the C2 step, 1-fluoro-5-halobiphenylene obtained in the B2 step is reacted with sodium sulfide, and further reacted with a haloacetaldehyde dialkyl acetal to produce 1,5-bis(dialkoxyethylthio)biphenylene. do. The reaction is carried out, for example, in a solvent such as DMSO, DMF, NMP, etc. at a temperature range of 40 to 200°C. Examples of the haloacetaldehyde dialkyl acetal include bromoacetaldehyde dimethyl acetal, bromoacetaldehyde diethylacetal, chloroacetaldehyde dimethyl acetal, and chloroacetaldehyde diethylacetal.

The D2 step is a step of treating 1,5-bis(2,2-dialkoxyethylthio)biphenylene obtained in the C2 step with polyphosphoric acid.

The conditions for cyclization with polyphosphoric acid include, for example, using 1 to 5 times the weight of polyphosphoric acid in a solvent such as chlorobenzene, toluene, or xylene at a temperature range of 100° C. to 150° C.

The E2 step is a step of producing 2,7-bis(trialkyltin)dithienobiphenylene from the unsubstituted dithienobiphenylene derivative obtained in the D2 step using the reagents and reaction conditions of the above F1 step. The 2,7-bis(trialkyltin)dithienobiphenylene can be produced using the reagents, reaction conditions, etc. of the above F1 step.

The following reaction scheme shows a specific method for producing (B-6-a) which is preferable since the number of reaction steps is small.

Among the compounds of general formula (2), for example, when X in the above general formula (B-6) is a sulfur atom, Y is CH, and has an alkyl group at the 4th and 9th positions, E3 to It can be manufactured by a method that involves the process of G3.

(Step E3); Step of producing 4,9-diacyldithienobiphenylene by introducing acyl groups into the 4 and 9 positions of the unsubstituted dithienobiphenylene derivative obtained in the above step D2 by Friedel-Crafts acylation. .
(Step F3); A step of reducing 4,9-diacyldithienobiphenylene obtained in step E3 to produce 4,9-dialkyldithienobiphenylene.
(G3 step); After reacting the 4,9-dialkyldithienobiphenylene obtained in the F3 step with butyllithium, it was treated with trialkyltin chloride, and 2,7-bis(trialkyltin)-4,9 - A process for producing dialkyldithienobiphenylene.

Details of each step of E3 to G3 are shown below.

The E3 step is a step in which the unsubstituted dithienobiphenylene derivative obtained in the D2 step is treated with acid chloride in the presence of aluminum chloride to diacylate the 4- and 9-positions.
The acid chloride is an acid chloride having 1 to 30 carbon atoms, such as decanoyl chloride, dodecanoyl chloride, tetradecanoyl chloride, hexadecanoyl chloride, heptadecanoyl chloride, octadecanoyl chloride, etc. can. The reaction is preferably carried out at -50°C to 40°C in a solvent such as dichloromethane, tetrachloroethane, toluene, or chlorobenzene.

The F3 step is a step in which 4,9-diacyldithienobiphenylene obtained in the E3 step is reduced using a reducing agent to produce 4,9-dialkyldithienobiphenylene. Examples of the reducing agent include sodium borohydride/aluminum chloride, lithium aluminum hydride/aluminum chloride, diborane, etc., in a solvent such as THF, tert-butyl ethyl ether, toluene, etc., at 0°C to 60°C. It can be carried out in a temperature range of

In the G3 step, the 4,9-dialkyldithienobiphenylene obtained in the F3 step is converted into 2,7-bis(trialkyltin)-4,9-dialkyldi-phenylene using the reagents and reaction conditions of the F1 step. This is a process for producing thienobiphenylene, and can be carried out using the reagents, reaction conditions, etc. of the above F1 process.

The following reaction scheme shows a specific method for producing (B-6-b), which is preferable since the number of reaction steps is small.

(Here, R represents a hydrogen atom or an alkyl group having 1 to 29 carbon atoms.)

Among the compounds of general formula (2), for example, in the case of a skeleton in which X in the above general formula (B-13) is a sulfur atom and Y is CH, it is produced by a method that involves the following steps C4 to F4. be able to.
(Step C4): A step of halogenating the 2,6-difluorobiphenylene obtained in the above steps A1 and B1 to produce 2,6-dihalo-3,7-difluorobiphenylene.
(Step D4); In the presence of a palladium/copper catalyst, 2,6-bis(trialkyl A process for producing silylethynyl)-3,7-difluorobiphenylene.
(Step E4); A step of producing unsubstituted dithienobiphenylene by subjecting the 2,6-bis(trialkylsilylethynyl)-3,7-difluorobiphenylene obtained in Step D4 to a reaction with sodium sulfide.
(Step F4); After reacting the unsubstituted dithienobiphenylene obtained in step E4 with butyllithium, it is treated with trialkyltin chloride to produce a 2,7-bis(trialkyltin)dithienobiphenylene derivative. Process.

Details of each step from C4 to F4 are shown below.

In the C4 step, for example, the 2,6-difluorobiphenylene obtained in the above B1 step is reacted with a halogenating agent to halogenate the 3- and 7-positions to produce 2,6-dihalo-3,7-difluoro. This is a process for producing biphenylene.

Conditions for the reaction with the halogenating agent include, for example, using 2 to 4 equivalents of the halogenating agent in a solvent such as DMF, NMP, DMSO, etc., within a temperature range of 20° C. to 70° C.

As the halogenating agent, halogenating agents such as NBS, bromine, iodine, and N-iodosuccinimide can be used.

In the D4 and E4 steps, an unsubstituted dithienobiphenylene derivative is prepared using the reagents and reaction conditions of the above D1 and E1 steps, except that 2,6-dihalo-3,7-difluorobiphenylene is used in the D4 step. can be manufactured.

In the F4 step, 2,7-bis(trialkyltin)dithienobiphenylene can be produced from the unsubstituted dithienobiphenylene derivative obtained in the E4 step using the reagents and reaction conditions of the above F1 step. can.

The following reaction scheme shows a specific method for producing (B-13-a) which is preferable since the number of reaction steps is small.

Furthermore, the produced compound of general formula (2) can be purified by subjecting it to column chromatography, etc. In this case, the separating agent may be silica gel, activated alumina, and the solvent may be hexane, heptane, Examples include toluene, dichloromethane, and chloroform.

The produced compound of general formula (2) can be decolorized and purified in a solution by subjecting it to activated carbon, zeolite, activated alumina, etc. At that time, hexane, heptane, toluene, dichloromethane, chloroform, etc. can be used as the solvent. can be mentioned.

Further, the produced compound of general formula (2) may be further purified by recrystallization, and the purity can be improved by increasing the number of recrystallizations. The number of times of recrystallization is preferably 2 to 5 times from the viewpoint of high purity and high yield. Purity can be improved by increasing the number of recrystallizations. Examples of the solvent used for recrystallization include hexane, heptane, octane, toluene, xylene, chloroform, chlorobenzene, dichlorobenzene, etc., and a mixture of these in any proportion may be used.

In the recrystallization method, a solution of an aromatic compound is prepared by heating (the concentration of the solution at this time is preferably in the range of 0.01 to 10.0% by weight, and 0.05 to 10.0% by weight in order to efficiently remove impurities). The aromatic compound crystals are precipitated and isolated by cooling the solution. The final cooling temperature during isolation is determined to improve purity and recovery rate. Therefore, the temperature is preferably in the range of -20°C to 40°C. In addition, when measuring purity, it is possible to analyze by liquid chromatography.

The compound represented by the above general formula (3) can be synthesized by a known production method. Alternatively, commercially available products can be used as they are.

The conjugated polymer of the present invention can be made into an organic semiconductor layer forming solution containing the conjugated polymer by dissolving it in a suitable solvent. As the solvent, any solvent may be used as long as it can dissolve the conjugated polymer represented by the general formula (1), and when forming the organic semiconductor layer, the drying rate of the solvent may be adjusted to a suitable An organic solvent having a boiling point of 100° C. or higher at normal pressure is preferable because it can be used as an organic solvent.

There are no particular limitations on the solvent that can be used in the present invention, and examples include aromatic solvents such as toluene, mesitylene, o-xylene, isopropylbenzene, pentylbenzene, cyclohexylbenzene, 1,2,4-trimethylbenzene, tetralin, and indane. Group hydrocarbons; anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole, ethyl phenyl ether, butylphenyl ether, 1,2- Aromatic ethers such as methylenedioxybenzene, 1,2-ethylenedioxybenzene; chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 1,2-difluorobenzene, Aromatic halogen compounds such as 1,3-difluorobenzene and 1,4-difluorobenzene; thiophene, 3-chlorothiophene, 2-chlorothiophene, 3-methylthiophene, 2-methylthiophene, benzothiophene, 2-methylbenzothiophene , 2,3-dihydrobenzothiophene, furan, 3-methylfuran, 2-methylfuran, 2,5-dimethylfuran, benzofuran, 2-methylbenzofuran, 2,3-dihydrobenzofuran, thiazole, oxazole, benzothiazole, benzo Heteroaromatics such as oxazole and pyridine; Saturated hydrocarbons such as hexane, cyclohexane, heptane, octane, nonane, decane, undecane, dodecane, and decalin; dipropylene glycol dimethyl ether, dipropylene glycol diacetate, dipropylene glycol methyl- n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,3-butylene glycol diacetate, 1,6-hexanediol diacetate, ethylene glycol Glycols such as monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; dimethyl phthalate, diethyl phthalate, dimethyl terephthalate, phenyl acetate, cyclohexanol acetate, At least one member of the group consisting of esters such as 3-methoxybutyl acetate, tetrahydrofurfuryl acetate, tetrahydrofurfuryl propionate, and γ-butyrolactone; and cyclic ethers such as THF and 2-methoxymethyltetrahydrofuran may be mentioned. Among them, toluene, o-xylene, mesitylene, 1,2,4-trimethylbenzene, tetralin, indane, octane, nonane, decane, anisole, 2-methylanisole, 3 are preferred because they have an appropriate drying speed. -Methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole, ethyl phenyl ether, butylphenyl ether, 1,2-methylenedioxybenzene, 1,2-ethylenedioxybenzene , chlorobenzene, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 3-methylthiophene, benzothiazole, more preferably toluene, o-xylene, mesitylene, tetralin, indan, At least one member of the group consisting of octane, nonane, decane, anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, and 2,6-dimethylanisole.

Note that the solvent used in the present invention can be used alone or in a mixture of two or more solvents having different properties such as boiling point, polarity, and solubility parameters.

The temperature at which the conjugated polymer represented by general formula (1) is mixed and dissolved in a solvent is preferably in the range of 0 to 80°C, and preferably in the range of 10 to 60°C, for the purpose of promoting dissolution. It is more preferable to carry out the process using

Furthermore, the time for dissolving and mixing the conjugated polymer represented by general formula (1) in an organic solvent is preferably 1 minute to 1 hour in order to obtain a homogeneous solution.

In the present invention, when the concentration of the conjugated polymer represented by general formula (1) in the organic semiconductor layer forming solution of the present invention is in the range of 0.1 to 10.0% by weight, handling becomes easy and the organic semiconductor layer can be formed. The efficiency during formation is more excellent. Further, when the viscosity of the organic semiconductor layer forming solution is in the range of 0.3 to 20 mPa·s, more suitable coating properties will be exhibited.

The solution can be prepared at a relatively low temperature because the conjugated polymer itself has moderate cohesiveness, and is oxidation resistant, so it can be suitably applied to the production of organic thin films by coating. . That is, since there is no need to remove air from the atmosphere, the coating process can be simplified. Furthermore, the solution can be used, for example, for polystyrene, poly(α-methylstyrene), poly(4-methylstyrene), poly(1-vinylnaphthalene), poly(2-vinylnaphthalene), poly(styrene-block-butadiene-block). -styrene), poly(styrene-block-isoprene-block-styrene), poly(vinyltoluene), poly(styrene-co-2,4-dimethylstyrene), poly(chlorostyrene), poly(styrene-co-α) -methylstyrene), poly(styrene-co-butadiene), poly(ethylene-conorbornene), polyphenylene ether, polycarbonate, polycarbazole, polytriarylamine, poly(9,9-dioctylfluorene-co-dimethyltriaryl) amine), poly(N-vinylcarbazole), polymethyl methacrylate, poly(styrene-co-methyl methacrylate), polyethyl methacrylate, poly n-propyl methacrylate, polyisopropyl methacrylate, poly n-butyl methacrylate , polyphenyl methacrylate, polymethyl acrylate, polyethyl acrylate, polyacrylic n-propyl, etc., preferably polystyrene, poly(α-methylstyrene), poly(ethylene-conorbornene), At least one polymer of the group consisting of polymethyl methacrylate can also be present as binder. The concentration of these polymer binders is preferably 0.001 to 10.0% by weight for appropriate solution viscosity.

The glass transition temperature (Tg) of the polymer binder is preferably 105°C or higher, more preferably 120°C or higher, and more preferably 130°C or higher, since it is more suitable for handling process temperatures during electronic device manufacturing. It is particularly preferable that

Further, the molecular weight of the polymer is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000, since it is suitable for obtaining an organic thin film transistor with higher carrier mobility. , 20,000 to 100,000 are particularly preferred. In the present invention, the molecular weight of the polymer refers to the weight average molecular weight (Mw) in terms of polystyrene.

The polymer has an effect as a general polymer binder and improves the film formability of the obtained organic semiconductor layer, and insulating polymers and semiconducting polymers can also be used.

Examples of the semiconducting polymer include polytriarylamine and poly(9,9-dioctylfluorene-co-dimethyltriarylamine).

In addition to the polymers mentioned above, specific examples of polymers that can be used as a polymer binder in the present invention include polar cyclic polyolefins, polysulfones, acrylonitrile-styrene copolymers, methyl methacrylate-styrene copolymers, etc. Examples include polymers.

More specifically, the polar cyclic polyolefins are preferably polymers represented by the following general formula (4).

(Here, R ³ to R ⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkyloxycarbonyl group having 2 to 20 carbon atoms. , an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, an amino group, or an aryloxycarbonyl group having 1 to 20 carbon atoms. Represents one type of the group consisting of alkylamino groups, and X ² is a halogen atom, an alkyloxycarbonyl group having 2 to 20 carbon atoms, an aryloxycarbonyl group having 7 to 20 carbon atoms, a cyano group, a nitro group, or a 1-carbon group. Represents one member of the group consisting of an alkoxy group having ~20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms. p is an integer of 20 to 5,000. , and q and r each independently represent an integer of 0 to 2. Bonds consisting of solid lines and dotted lines indicate single bonds or double bonds.)

In general formula (4), R ³ to R ⁵ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, and an alkyloxy group having 2 to 20 carbon atoms. Carbonyl group, aryloxycarbonyl group having 7 to 20 carbon atoms, cyano group, nitro group, alkoxy group having 1 to 20 carbon atoms, aryloxy group having 6 to 20 carbon atoms, hydroxyl group, amino group, or 1 to 20 carbon atoms At least one member of the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms is preferred because of its high heat resistance.

Examples of the alkyl group having 1 to 20 carbon atoms in R ³ to R ⁵ include straight chain or branched alkyl groups such as methyl group, ethyl group, propyl group, butyl group, isobutyl group, sec-butyl group, and pentyl group. It will be done. Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, p-tolyl group, p-(hexyl)phenyl group, p-(octyl)phenyl group, and p-(2-ethylhexyl)phenyl group. Examples of the alkyloxycarbonyl group having 2 to 20 carbon atoms include methyloxycarbonyl group, ethyloxycarbonyl group, and propyloxycarbonyl group. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms include phenoxycarbonyl group and 4-methylphenoxycarbonyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include methoxy group, ethoxy group, and propoxy group. Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group and 4-methylphenoxy. Examples of the alkylamino group having 1 to 20 carbon atoms include a methylamino group, an ethylamino group, and a propylamino group. Among these, for high heat resistance, the substituent R ³ is preferably a methyl group, ethyl group, or n-propyl group, and the substituents R ⁴ and R ⁵ are preferably a hydrogen atom.

In the general ^formula (4), It represents an aryloxy group having 6 to 20 carbon atoms, a hydroxyl group, an amino group, or an alkylamino group having 1 to 20 carbon atoms.

Examples of the alkyloxycarbonyl group having 2 to 20 carbon atoms in the substituent X ² include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, butoxycarbonyl group, hexyloxycarbonyl group, cyclohexyloxycarbonyl group, etc. Examples of the aryloxycarbonyl group having numbers 7 to 20 include phenoxycarbonyl group, 4-methylphenoxycarbonyl group, 2,4-dimethylphenoxycarbonyl group, and 4-ethylphenoxycarbonyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group and an ethoxy group. Examples of the aryloxy group having 6 to 20 carbon atoms include phenoxy group and 4-methylphenoxy. Examples of the alkylamino group having 1 to 20 carbon atoms include a methylamino group, an ethylamino group, and a propylamino group. In view of high solubility and high heat resistance, an alkyloxycarbonyl group having 2 to 20 carbon atoms is preferred.

p represents an integer of 20 to 5,000, and is preferably 40 to 2,000, since it is suitable for obtaining an organic thin film transistor with higher carrier mobility. q represents an integer of 0 to 2, preferably 1. r represents an integer of 0 to 2, preferably 0 or 1. More preferably, it is 0.

Bonds formed by solid lines and dotted lines indicate single bonds or double bonds, and are preferably single bonds for thermal stability.

The polysulfones used as the polymer binder in the present invention are not particularly limited as long as they have a polysulfone structure, and more specifically include at least one of the group consisting of polysulfones shown below as polysulfones 1 to 5.

(Here, the substituents R ⁶ to R ⁹ each independently represent an alkyl group having 1 to 20 carbon atoms, and s represents an integer of 10 to 20,000.)

The alkyl group having 1 to 20 carbon atoms in the substituents R ⁶ to R ⁹ is, for example, a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a pentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, Examples include straight chain or branched alkyl groups such as nonyl group, decyl group, dodecyl group, tetradecyl group, octadecyl group, 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl group, and 2-hexyldecyl group.

s represents an integer of 10 to 20,000, preferably an integer of 10 to 10,000.

The acrylonitrile-styrene copolymer used as a polymer binder in the present invention is a copolymer of acrylonitrile and styrene in any ratio, and exhibits good electrical properties, with a change in threshold voltage when bias stress is applied. The weight ratio of acrylonitrile to styrene is preferably from 10:90 to 50:50, and more preferably from 20:80 to 40:60, since reliability is improved, such as a smaller size.

The methyl methacrylate-styrene copolymer used as a polymer binder in the present invention is a copolymer of methyl methacrylate and styrene in any ratio, and exhibits good electrical properties and changes in threshold voltage when bias stress is applied. The molar ratio of methyl methacrylate to styrene is preferably 1:99 to 90:10, more preferably 1:99 to 70:30, since reliability is improved, such as a smaller value.

The polymer used as the polymer binder in the present invention can be one whose surface energy has been adjusted with a surface treatment agent. As a surface treatment agent, a silane coupling agent can be used, and specific examples thereof include 1,1,1,3,3,3-hexamethyldisilazane, phenyltrimethoxysilane, octyltrichlorosilane, Examples include β-phenethyltrichlorosilane and β-phenethyltrimethoxysilane. As the polymer binder used in the present invention, one type of polymer can be used alone, or a mixture of two or more types of polymers can be used. Furthermore, it is also possible to use a mixture of polymers of different molecular weights.

The conjugated polymer of general formula (1) of the present invention may form a block copolymer with the polymer binder shown above.

The coating method for forming an organic semiconductor layer using the solution for forming an organic semiconductor layer of the present invention is not particularly limited as long as it is a method that can form an organic semiconductor layer, such as spin coating, drop casting, dip coating, etc. Simple coating methods such as coating, cast coating, etc. Printing methods such as dispenser, inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing, and offset printing can be mentioned. Spin coating, drop casting, and inkjet are preferable because they allow for.

After applying the organic semiconductor layer forming solution of the present invention, by drying and removing the solvent, it is possible to form an organic semiconductor layer using the organic semiconductor layer forming solution.

When drying and removing the solvent from the applied organic semiconductor layer, there are no particular restrictions on the drying conditions, and for example, the solvent can be dried and removed under normal pressure or reduced pressure.

Although there is no particular restriction on the temperature at which the organic solvent is dried and removed from the applied organic semiconductor layer, it is possible to efficiently dry and remove the organic solvent from the applied organic semiconductor layer and form an organic semiconductor layer. It is preferable to carry out at a temperature range of 10 to 150°C.

When drying and removing the organic solvent from the applied organic semiconductor layer, by adjusting the vaporization rate of the organic solvent to be removed, it becomes possible to promote the growth of the orientation of the conjugated polymer represented by the general formula (1).

There is no limit to the thickness of the organic semiconductor layer formed using the solution for forming an organic semiconductor layer of the present invention, and since good carrier movement can be obtained, it is preferably in the range of 1 nm to 1 μm, and preferably in the range of 10 nm to 300 nm. It is more preferable that

Further, the obtained organic semiconductor layer may be subjected to an annealing treatment at 40 to 200° C. after forming the organic semiconductor layer.

The organic semiconductor layer formed from the organic semiconductor layer forming solution of the present invention can be used as an organic semiconductor device comprising the organic semiconductor layer, particularly an organic thin film transistor comprising the organic semiconductor layer.

An organic thin film transistor can be obtained by laminating an organic semiconductor layer provided with a source electrode and a drain electrode and a gate electrode on a substrate via an insulating layer, and the organic semiconductor layer of the present invention is added to the organic semiconductor layer. By using an organic semiconductor layer formed from a solution, it is possible to obtain an organic thin film transistor that exhibits excellent semiconductor and electrical characteristics.

FIG. 1 shows a cross-sectional structure of a general organic thin film transistor. Here, (A) is a bottom gate-top contact type, (B) is a bottom gate-bottom contact type, (C) is a top gate-top contact type, and (D) is a top gate-bottom contact type. 1 is an organic thin film transistor, 1 is an organic semiconductor layer, 2 is a substrate, 3 is a gate electrode, 4 is a gate insulating layer, 5 is a source electrode, and 6 is a drain electrode, formed from the organic semiconductor layer forming solution of the present invention. The organic semiconductor layer can be applied to any organic thin film transistor.

The substrate according to the present invention is not particularly limited and includes, for example, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, fluorinated cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, Plastic substrates such as polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyether sulfone, polyphenylene sulfide, cellulose triacetate; glass, quartz, aluminum oxide, silicon, highly doped silicon , inorganic material substrates such as silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; and metal substrates such as gold, copper, chromium, titanium, and aluminum. Note that when highly doped silicon is used for the substrate, the substrate can also serve as a gate electrode.

The gate electrode according to the present invention is not particularly limited, and examples thereof include aluminum, gold, silver, copper, highly doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, graphene, carbon nanotubes, etc. and organic materials such as doped conductive polymers (eg, PEDOT-PSS).

Moreover, the above-mentioned inorganic materials can be used without any problem as metal nanoparticle ink. In this case, the solvent is a polar solvent such as water, methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, etc.; a carbon number solvent such as hexane, heptane, octane, decane, dodecane, tetradecane, etc. 6 to 14 aliphatic hydrocarbon solvents; toluene, xylene, mesitylene, ethylbenzene, pentylbenzene, hexylbenzene, octylbenzene, cyclohexylbenzene, tetralin, indane, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, Preferably, the solvent is an aromatic hydrocarbon solvent having 7 to 14 carbon atoms, such as 1,2-dimethylanisole, 2,3-dimethylanisole, and 3,4-dimethylanisole. After applying the nanoparticle ink, it is preferable to perform an annealing treatment in a temperature range of 80° C. to 200° C. to improve conductivity.

The gate insulating layer according to the present invention is not particularly limited and includes, for example, silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide, titanium Inorganic materials such as barium acid and bismuth titanate; polymethyl methacrylate, polymethyl acrylate, polyimide, polyamic acid polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), polyethylene terephthalate, polyethylene Phthalate, polyethyl cinnamate, polymethyl cinnamate, polyethyl crotonate, polyethersulfone, polypropylene-co-1-butene, polyisobutylene, polypropylene, polycyclopentane, polycyclohexane, polycyclohexane-ethylene copolymer, Polyfluorinated cyclopentane, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene copolymer, BCB resin (trade name: Cyclotene, manufactured by Dow Chemical Company), Cytop (trademark), Teflon (trademark), Parylene C, etc. Polymer insulating materials such as Parylene (trademark) can be mentioned, and since the manufacturing method is simple, a polymer insulating material (polymer gate insulating layer) to which a coating method can be applied is preferable.

The polymer gate insulating layer can also be used after photo-crosslinking.

The solvent used to dissolve the polymer material is not particularly limited, and examples thereof include aliphatic hydrocarbon solvents having 6 to 14 carbon atoms such as hexane, heptane, octane, decane, dodecane, and tetradecane; THF, and 1,2-dimethoxy. Ether solvents such as ethane and dioxane; alcohol solvents such as ethanol, isopropyl alcohol, 1-butanol, 2-butanol, 2-ethylhexanol, and tetrahydrofurfuryl alcohol; acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone, acetophenone, etc. Ketone solvents; ester solvents such as ethyl acetate, γ-butyrolactone, cyclohexanol acetate, 3-methoxybutyl acetate, tetrahydrofurfuryl acetate, and tetrahydrofurfuryl propionate; amide solvents such as DMF and NMP; dipropylene glycol Dimethyl ether, dipropylene glycol diacetate, dipropylene glycol methyl-n-propyl ether, dipropylene glycol methyl ether acetate, 1,4-butanediol diacetate, 1,3-butylene glycol diacetate, 1,6-hexane diol diacetate Glycol solvents such as acetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate; perfluorohexane, perfluorooctane, 2-(pentafluoroethyl) ) Hexane, 3-(pentafluoroethyl)heptane, and other fluorinated solvents.

The concentration of the polymeric insulating material is, for example, 0.1-10.0% by weight at a temperature of 20-40°C. There is no limit to the thickness of the insulating layer obtained at this concentration, and from the viewpoint of insulation resistance, it is preferably 100 nm to 1 μm, more preferably 150 nm to 900 nm.

The surface of these gate insulating layers is coated with, for example, octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, or phenyltrichlorosilane. Silanes such as chlorosilane and phenyltrimethoxysilane; phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid, and octylphosphonic acid; and silylamines such as hexamethyldisilazane may be used. In general, surface treatment of the gate insulating layer increases the crystal grain size of the organic semiconductor material and improves molecular orientation, resulting in favorable effects such as improvement in carrier mobility, current on/off ratio, and reduction in threshold voltage. Get results.

The material for the source electrode and drain electrode of the organic thin film transistor of the present invention is not particularly limited, and the same material as the gate electrode can be used, the material may be the same as or different from the gate electrode material, or a different material can be used. may be laminated. Further, in order to increase carrier injection efficiency, these electrode materials can also be subjected to surface treatment. Examples of the surface treatment agent used for surface treatment include benzenethiol, pentafluorobenzenethiol, 4-fluorobenzenethiol, and 4-methoxybenzenethiol.

For fast operation, the organic thin film transistor of the present invention preferably has a carrier mobility of 0.10 cm ² /V·sec or more. Further, for high switching characteristics, it is preferable that the current on/off ratio is 1.0×10 ⁵ or more.

The conjugated polymer of the present invention can be used for organic semiconductor layers in organic thin film transistors such as electronic paper, organic EL displays, liquid crystal displays, IC tags (RFID tags), pressure sensors, and biosensors; for organic semiconductor layers in organic thin film solar cells; It can be used for electronic materials such as EL display materials; organic semiconductor laser materials; and photonic crystal materials.

The novel conjugated polymers of the present invention provide high carrier mobility, are highly soluble, and can be thermally annealed at temperatures below 140°C. Therefore, it is possible to provide an organic thin film transistor that exhibits excellent semiconductor characteristics by coating on a plastic substrate, and the effect is extremely high.

is a diagram showing a structure according to a cross-sectional shape of an organic thin film transistor;

EXAMPLES Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples.

¹ H NMR spectra, gas chromatography-mass spectra (GCMS), and liquid chromatography-mass spectra (LCMS) analyzes were used to identify the products.

< ^1H NMR spectrum analysis>
Device; manufactured by JEOL, (product name) Delta V5 (400MHz)
Measurement temperature: 23℃ (if no temperature specified)
<Gas chromatography-mass spectrum analysis>
Equipment: Manufactured by Shimadzu Corporation, (product name) QP-2010 Ultra
Column; manufactured by Agilent, (trade name) DB-1, 30m.
MS ionization; electron impact (EI) method (70 electron volts)
<Direct introduction mass spectrometry analysis>
Equipment: Manufactured by Shimadzu Corporation, (product name) QP-2010 Ultra
MS ionization; electron impact (EI) method (70 electron volts)
<Liquid chromatography-mass spectrum (LCMS) analysis>
Equipment: Bruker Daltonics, (product name) microTOF focus
MS ionization: atmospheric pressure chemical ionization (APCI) method LC conditions: conditions described in the liquid chromatography analysis section below

The progress of the reaction was confirmed using thin layer chromatography, gas chromatography (GC), and liquid chromatography (LC) analysis. The purity of the biphenylene derivative was also measured using liquid chromatography analysis.

<Thin layer chromatography analysis>
PLC silica gel 60F254 0.5 mm for thin layer chromatography manufactured by Merck was used, and hexane or/and toluene, ethyl acetate, and toluene were used as developing solvents.
<Gas chromatography analysis>
Equipment: Manufactured by Shimadzu Corporation, (product name) GC2014
Column: manufactured by Agilent, (trade name) DB-1, 30m
<Liquid chromatography analysis>
Equipment: Tosoh (controller: PX-8020, pump: CCPM-II, degasser: SD-8022)
Column: manufactured by Tosoh, (product name) ODS-100V, 5 μm, 4.6 mm x 250 mm
Column temperature: 33℃
Eluent; dichloromethane:acetonitrile = 2:8 (volume ratio)
Flow rate: 1.0 ml/min Detector: UV (manufactured by Tosoh, (trade name) UV-8020, wavelength: 254 nm).
<High temperature GPC analysis>
Equipment: Tosoh HLC-8321GPC/HT
Column: Tosoh TSK gel GMHHR-H (20) HT, 7.8 mm x 300 mm, 3 columns Column temperature: 140°C
Eluent: 1,2,4-trichlorobenzene Flow rate: 1.0 ml/min Detector: RI

A DSC (differential scanning calorimeter) was used to measure the melting point of the conjugated polymer.
<DSC measurement>
Device: Manufactured by SII Nano Technology, model: DSC6220
Temperature increase/decrease rate: 10°C/min
Scanning range: -10℃~300℃

Synthesis Example 1 (Synthesis of 2,2'-dibromo-4,5'-difluorobiphenyl) (Step A1)
Under a nitrogen atmosphere, 3.95 g (13.1 mmol) of 1-bromo-4-fluoro-2-iodobenzene (Tokyo Kasei Kogyo) and 15 ml of THF (dehydration grade) were added to a 100 ml Schlenk reaction vessel. This solution was cooled to 0° C., and 6.8 ml (13.6 mmol) of a THF solution of ethylmagnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. This mixture was aged at 0° C. for 15 minutes to prepare 1-bromo-4-fluorophenyl-2-magnesium chloride.

Meanwhile, 2.42 g (17.7 mmol) of zinc chloride (Wako Pure Chemical Industries, Ltd.) and 19 ml of THF (dehydration grade) were added to another 100 ml Schlenk reaction vessel under a nitrogen atmosphere, and the mixture was cooled to 0°C. The previously prepared 1-bromo-4-fluorophenyl-2-magnesium chloride solution was added dropwise into the obtained white fine slurry solution using a Teflon (registered trademark) cannula, and then 2 ml of THF (dehydrated grade) was added. A 100 ml Schlenk reaction vessel and a Teflon (registered trademark) cannula were charged into the reactor while being washed using the reactor. The resulting mixture was stirred while gradually heating up to room temperature. 3.18 g (10.5 mmol) of 2-bromo-4-fluoro-1-iodobenzene (Tokyo Kasei Kogyo) and tetrakis ( 115 mg (0.0995 mmol, 0.948 mol% based on 2-bromo-4-fluoro-1-iodobenzene) of palladium (triphenylphosphine) (Tokyo Kasei Kogyo) was added. After carrying out the reaction at 50° C. for 7 hours, the container was cooled with water and the reaction was stopped by adding 1M hydrochloric acid. Toluene and brine were added, the organic phase was separated, the organic phase was washed with brine, and dried over anhydrous sodium sulfate. It was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane). 3.48 g of a colorless oil of 2,2'-dibromo-4,5'-difluorobiphenyl was obtained (yield 94%).
MS m/z: 350 (M ⁺ +2, 51%), 348 (M ⁺ , 100%), 346 (M ⁺ -2, 53).
^1H NMR ( _CDCl3 ): δ=7.62 (dd, J=8.7Hz, 5.4Hz, 1H), 7.43 (dd, J=8.2Hz, 2.3Hz, 1H), 7. 27-7.19 (m, 1H), 7.11 (dt, J=8.2Hz, 2.7Hz, 1H), 7.04-6.96 (m, 2H).

Synthesis Example 2 (Synthesis of 2,6-difluorobiphenylene) (Step B1)
Under a nitrogen atmosphere, 3.30 g (9.48 mmol) of 2,2'-dibromo-4,5'-difluorobiphenyl synthesized in Synthesis Example 1 and 160 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reaction vessel. This mixture was cooled to −78° C., and 12.5 ml (20.0 mmol) of a hexane solution of butyl lithium (Tokyo Kasei Kogyo, 1.6 M) was added dropwise. This mixture was aged at -78°C for 1 hour. To this, 3.75 g (27.9 mmol) of copper (II) chloride (manufactured by Wako Pure Chemical Industries, Ltd.) was added at -78°C. The resulting mixture was stirred while gradually heating up to room temperature. After adding 1M hydrochloric acid to the reaction mixture, toluene was added and the phases were separated. The organic phase was washed twice with brine and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane). 1.48 g of a pale yellow solid of 2,6-difluorobiphenylene was obtained (yield 91%).
MS m/z: 188 (M ⁺ , 100%).
¹ H NMR (CDCl ₃ ): δ=6.56 (dd, J=11Hz, 4.0Hz, 2H), 6.42-6.35 (m, 4H).

Synthesis Example 3 (Synthesis of 2,6-difluoro-1,5-diiodobiphenylene) (Step C1)
Under a nitrogen atmosphere, 516 mg (5.10 mmol) of diisopropylamine and 9 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reaction vessel. This mixture was cooled to −40° C., and 3.1 ml (5.0 mmol) of a hexane solution of butyl lithium (Tokyo Kasei Kogyo, 1.6 M) was added dropwise to prepare LDA. This mixture was cooled to -78°C, 380 mg (2.02 mmol) of 2,6-difluorobiphenylene synthesized in Synthesis Example 2 was added little by little, and the mixture was stirred at -78°C to -60°C for 2.5 hours. did. The resulting mixture was heated to -78°C, and a solution consisting of 1.26 g (4.96 mmol) of iodine and 4 ml of THF (dehydration grade) was added dropwise. The resulting mixture was stirred while gradually heating up to room temperature. After the reaction mixture was cooled to 0° C., water and toluene were added and the phases were separated. The aqueous phase was extracted with toluene, and the combined organic phases were washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The resulting residue was purified by silica gel column chromatography (solvent: hexane) to obtain 471 mg of a pale yellow solid of 2,6-difluoro-1,5-diiodobiphenylene (yield: 53%).
^1H NMR ( _CDCl3 ): δ=6.68 (dd, J=7.3Hz, 3.6Hz, 2H), 6.44 (dd, J=9.6Hz, 7.3Hz, 2H).

Synthesis Example 4 (Synthesis of 2,6-difluoro-1,5-bis(trimethylsilylethynyl)biphenylene) (Step D1)
Under a nitrogen atmosphere, 752 mg (1.71 mmol) of 2,6-difluoro-1,5-diiodobiphenylene synthesized in Synthesis Example 3 and 24 dichlorobis(triphenylphosphine)palladium (Wako Pure Chemical Industries) were placed in a 100 ml Schlenk reaction vessel. .7 mg (0.0352 mol), 14.5 mg (0.0761 mmol) of copper(I) iodide (Wako Pure Chemical Industries), 10 ml of toluene, and 15 ml of triethylamine were added. Furthermore, 506 mg (5.15 mmol) of trimethylsilylacetylene (Tokyo Kasei Kogyo) was added. This mixture was reacted at 25° C. for 3.5 hours. Toluene and water were added to the obtained reaction mixture, and after phase separation, the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane). 641 mg of a yellow solid of 2,6-difluoro-1,5-bis(trimethylsilylethynyl)biphenylene was obtained (yield 98%). Purity was found to be 95.6% by GC analysis.
¹ H NMR (CDCl ₃ ): δ=6.60-6.57 (q, J=4.1 Hz, 2H), 6.46-6.41 (dd, J=7.32 Hz, 2H), 0. 26 (s, 18H).

Synthesis Example 5 (Synthesis of unsubstituted dithienobiphenylene derivative) (Step E1)
Under a nitrogen atmosphere, 458 mg (1.20 mmol) of 2,6-difluoro-1,5-bis(trimethylsilylethynyl)biphenylene synthesized in Synthesis Example 4 and sodium sulfide nonahydrate (Wako Pure Chemical Industries, Ltd.) were placed in a 200 ml eggplant flask. ) 1.01 g (4.19 mmol) and 15 ml of DMSO (Wako Pure Chemical Industries) were added. The mixture was heated to 70°C and stirred for 5 hours. After cooling the resulting reaction mixture to 0°C, water and dichloromethane were added. After phase separation, the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane/dichloromethane) to obtain 161 mg of a yellow solid of an unsubstituted dithienobiphenylene derivative (yield: 51%). The purity was 83.5% by LC analysis.
MS m/z: 264 (M ⁺ , 100%)
¹ H NMR (CDCl ₃ ): δ=7.31-7.29 (d, J=6.0 Hz, 2H), 7.19-7.17 (d, J=7.8 Hz, 2H), 6. 94-6.93 (d, J = 5.5 Hz, 2H), 6.66-6.64 (d, J = 7.3 Hz, 2H).

Synthesis Example 6 (Synthesis of B-5-a) (Step F1)
In a nitrogen atmosphere, 160 mg (0.605 mmol) of the unsubstituted dithienobiphenylene derivative synthesized in Synthesis Example 5 and 20 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reaction vessel. 1.5 ml (2.4 mmol) of a hexane solution of butyl lithium (Tokyo Kasei Kogyo, 1.6 M) was added to this at -78°C, stirred at 25°C for 15 minutes, and then cooled to -78°C again. . To this was added 520 mg (2.60 mmol) of trimethyltin chloride (Tokyo Kasei Kogyo). After the resulting mixture was heated to room temperature, water and toluene were added and the phases were separated. The organic phase was washed with brine and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 324 mg of an orange solid B-5-a (yield 91%).

Synthesis Example 7 (Synthesis of 2,7-dibromodithienobiphenylene derivative)
In Synthesis Example 6, the same operation as in Synthesis Example 6 was repeated except that 1,2-dibromotetrachloroethane was used instead of trimethyltin chloride to obtain an orange solid of 2,7-dibromodithienobiphenylene derivative. rate 90%).
^1H NMR ( _CDCl3 ): δ = 7.02 (dd, J = 7.3Hz, 0.9Hz, 2H), 6.96 (d, J = 0.9Hz, 2H), 6.58 (d, J=7.3Hz, 2H).

Synthesis Example 8 (Synthesis of 2,6-dibromo-3,7-difluorobiphenylene) (C4 step)
Under a nitrogen atmosphere, 351 mg (1.86 mmol) of 2,6-difluorobiphenylene synthesized in Synthesis Example 2 and 7 ml of DMF (dehydrated grade) were added to a 100 ml Schlenk reaction vessel. To this, 954 mg (5.36 mmol) of NBS (Wako Pure Chemical Industries) was added at room temperature. After stirring at 40° C. for 10 hours, the resulting reaction mixture was cooled to room temperature. Water and toluene were added and the phases were separated. The organic phase was washed twice with water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained residue was recrystallized from a mixed solvent of hexane:toluene=1:2 to obtain 302 mg of yellow needle crystals of 2,6-dibromo-3,7-difluorobiphenylene (yield: 47%).
^1H NMR ( _CDCl3 ): δ=6.82 (d, J=5.9 Hz, 2H), 6.49 (d, J=6.4 Hz, 2H).

Synthesis Example 9 (Synthesis of 2-bromo-1-fluoro-3-iodobenzene)
Under a nitrogen atmosphere, 5.76 g (56.9 mmol) of diisopropylamine and 115.0 ml of THF (dehydrated grade) were added to a 500 ml Schlenk reaction vessel. This solution was cooled to −50° C., and 34.0 ml (54.4 mmol) of a hexane solution of butyl lithium (Tokyo Kasei Kogyo, 1.6 M) was added dropwise to prepare LDA. The mixture was cooled to -78°C, 11.5 g (51.8 mmol) of 1-fluoro-3-iodobenzene (Tokyo Kasei Kogyo) was added, and the mixture was maintained at -78°C for 2 hours. A solution prepared by dissolving 34.4 g (103.6 mmol) of tetrabromomethane (Tokyo Kasei Kogyo) in 160.0 ml of THF (dehydration grade) was added dropwise thereto at -78°C, and the temperature was gradually raised to room temperature. Water and toluene were added to the resulting reaction mixture, and the phases were separated. The organic phase was dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: hexane). 3.0 g of methanol (Wako Pure Chemical Industries) was added and the temperature was raised to 50°C to recrystallize to obtain 7.43 g of a white solid of 2-bromo-1-fluoro-3-iodobenzene (yield: 43 %).
MS m/z: 302 (M ⁺ +2, 75%), 300 (M ⁺ , 78%), 175 (M ⁺ +2-I, 38%), 173 (M ⁺ -I, 39%), 94 (M ⁺ -BrI, 100%).
¹ H NMR (CDCl ₃ ): δ = 7.68-7.64 (m, 1H), 7.12-7.08 (m, 1H), 7.05-7.00 (m, 1H).

Synthesis Example 10 (Synthesis of 2,2'-dibromo-3,6'-difluorobiphenyl) (Step A2)
Under a nitrogen atmosphere, 4.89 g (16.3 mmol) of 1-bromo-3-fluoro-2-iodobenzene (Wako Pure Chemical Industries, Ltd.) and 50.0 ml of THF (dehydration grade) were added to a 200 ml Schlenk reaction vessel. This solution was cooled to 0° C., and 8.4 ml (19.8 mmol) of a THF solution of ethylmagnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. This mixture was aged at 0° C. for 20 minutes to prepare 2-bromo-6-fluorophenylmagnesium chloride.

Meanwhile, 3.28 g (24.1 mmol) of zinc chloride (Wako Pure Chemical Industries, Ltd.) and 30 ml of THF (dehydration grade) were added to another 300 ml Schlenk reaction vessel under a nitrogen atmosphere, and the mixture was cooled to 0°C. The previously prepared 2-bromo-6-fluorophenylmagnesium chloride solution was added dropwise into the obtained white fine slurry solution using a Teflon (registered trademark) cannula, and then 100 ml was added using 2 ml of THF (dehydration grade). The Schlenk reaction vessel and Teflon (registered trademark) cannula were charged while being washed. The resulting mixture was stirred while gradually heating up to room temperature. 3.51 g (11.7 mmol) of 2-bromo-1-fluoro-3-iodobenzene synthesized in Synthesis Example 9 and tetrakis(triphenyl 1.40 g (1.2 mmol, 10 mol % based on 2-bromo-1-fluoro-3-iodobenzene) of palladium (Tokyo Kasei Kogyo) was added. After carrying out the reaction at 60° C. for 3 hours, the reaction was stopped by cooling the container with water and adding 1M hydrochloric acid. Toluene was added, the organic phase was separated, and the organic phase was dried over anhydrous sodium sulfate. It was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane). 2.98 g of a colorless solid of 2,2'-dibromo-3,6'-difluorobiphenyl was obtained (yield 73%).
¹ H NMR (CDCl ₃ ): δ = 7.50 (d, J = 8.2 Hz, 1H), 7.42 to 7.36 (m, 1H), 7.33 to 7.26 (m, 1H) , 7.23 to 7.18 (m, 1H), 7.17 to 7.12 (m, 1H), 7.05 to 6.96 (d, J = 7.3Hz, 1H).

Synthesis Example 11 (Synthesis of 1-fluoro-5-chlorobiphenylene) (Step B2))
Under a nitrogen atmosphere, 2.94 g (8.44 mmol) of 2,2'-dibromo-3,6'-difluorobiphenyl synthesized in Synthesis Example 10 and 50 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reaction vessel. This mixture was cooled to −78° C., and 13.2 ml (21.1 mmol) of a hexane solution of butyl lithium (Tokyo Kasei Kogyo, 1.6 M) was added dropwise. This mixture was heated to -35°C, then cooled again to -78°C, and 2.98g (12.6mmol) of hexachloroethane (Tokyo Kasei Kogyo) was added. The resulting mixture was stirred while gradually heating up to room temperature. After adding water to the reaction mixture, it was extracted with toluene. The organic phase was washed with saturated brine and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane). 1.27 g of a pale yellow solid of 1-fluoro-5-chlorobiphenylene was obtained (yield 73%).
MS m/z: 204 (M ⁺ , 100%).
¹ H NMR (CDCl ₃ ): δ = 6.81 (m, 1H), 6.76-6.67 (m, 2H), 6.62-6.58 (m, 2H), 6.53 (t , J=8.6Hz.1H).

Synthesis Example 12 Synthesis of (1,5-bis(2,2-dimethoxyethylthio)biphenylene) (C2 step)
Under a nitrogen atmosphere, 502 mg (2.45 mmol) of 1-fluoro-5-chlorobiphenylene synthesized in Synthesis Example 11 and 2.83 g (11. 8 mmol) and 50 ml of NMP (Wako Pure Chemical Industries) were added. The mixture was stirred at 120°C for 5 hours. 3.88 g (22.9 mmol) of bromoacetaldehyde dimethyl acetal (Tokyo Kasei Kogyo) was added to the resulting mixture, and the mixture was stirred at 100° C. for 1 hour. Furthermore, 2.75 g (11.5 mmol) of sodium sulfide nonahydrate was added, and the mixture was stirred at 120° C. for 5 hours. The resulting reaction mixture was cooled with ice, and water and toluene were added. After phase separation, extraction was performed with toluene, and the combined organic phases were dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was concentrated under reduced pressure using a Kugelrohr (120 Pa, 97° C.). 1.77 g of the obtained residue was purified by silica gel column chromatography (solvent: toluene/ethyl acetate = 20/0 to 20/1) to obtain a yellow viscous mixture of 1,5-bis(2,2-dimethoxyethylthio)biphenylene. 892 mg of liquid was obtained (yield 92%).
¹ H NMR (CDCl ₃ ): δ = 6.74 to 6.67 (m, 4H), 6.54 (dd, J = 5.5Hz, 1.4Hz, 2H), 4.53 (t, J = 5.9Hz, 2H), 3.38 (s, 12H), 3.10 (d, J=5.9, Hz, 4H).

Synthesis Example 13 (Synthesis of unsubstituted dithienobiphenylene derivative) (Step D2)
Under a nitrogen atmosphere, 1.02 g of polyphosphoric acid (Wako Pure Chemical Industries, Ltd.) and 10 ml of chlorobenzene (Sigma-Aldrich, dehydrated grade) were added to a 100 ml Schlenk reaction vessel. After gently refluxing the mixture at 130°C, 302 mg (0.769 mmol) of 1,5-bis(2,2-dimethoxyethylthio)biphenylene synthesized in Synthesis Example 12 and 5 ml of chlorobenzene (Sigma-Aldrich, dehydrated grade) were added. A solution consisting of was added dropwise over 2 hours. The resulting mixture was stirred at 130° C. for 6 hours, cooled on ice, and water and toluene were added. After phase separation, the organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane/toluene = 10/0 to 10/2) to obtain 112 mg of a yellow-orange solid of an unsubstituted dithienobiphenylene derivative ( yield 55%).
MS m/z: 264 (M ⁺ ).
^1H NMR ( _CDCl3 ): δ=7.19 (d, J=6.5 Hz, 2H), 7.18 (d, J=5.5 Hz, 2H), 7.03 (d, J=5. 5Hz, 2H), 6.72 (d, J=7.5Hz, 2H).

Synthesis Example 14 (Synthesis of B-6-a) (Step E2)
Under a nitrogen atmosphere, 68.7 mg (0.259 mmol) of the unsubstituted dithienobiphenylene derivative synthesized in Synthesis Example 13 and 8 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reaction vessel. To this, 0.56 ml (0.90 mmol) of a hexane solution of butyllithium (Tokyo Kasei Kogyo, 1.6M) was added at -78°C, and the mixture was stirred at -78°C for 15 minutes and then at 25°C for 15 minutes. . The mixture was cooled again to −78° C., and 220 mg (1.10 mmol) of trimethyltin chloride (Tokyo Kasei Kogyo) was added thereto. After the resulting mixture was heated to room temperature, water and toluene were added and the phases were separated. The organic phase was washed with brine and water, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain 145 mg of an orange solid B-6-a (yield 95%).
^1H NMR ( _CDCl3 ): δ=7.16 (d, J=7.4Hz, 2H), 7.09 (s, 2H), 6.67 (d, J=7.4Hz, 2H), 0 .42 (s, 18H).

Synthesis Example 15 (Synthesis of 2,7-dibromodithienobiphenylene derivative)
The same procedure as in Synthesis Example 14 was repeated except that 1,2-dibromotetrachloroethane (Tokyo Kasei Kogyo) was used instead of trimethyltin chloride to obtain an orange solid of 2,7-dibromodithienobiphenylene derivative. was obtained (yield 95%).
¹ H NMR ( _CDCl3 ): δ=7.07 (d, J=7.5 Hz, 2H), 7.05 (s, 2H), 6.64 (d, J=7.5 Hz, 2H).

Synthesis Example 16 Synthesis of (4,9-dioctanoyldithienobiphenylene) (Step E3)
Under a nitrogen atmosphere, 64.0 mg (0.242 mmol) of the unsubstituted dithienobiphenylene derivative synthesized in Synthesis Example 13 and 10 ml of dichloromethane (dehydrated grade) were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to -20°C, and 113 mg (0.847 mmol) of aluminum chloride (Wako Pure Chemical Industries) was added. The mixture was cooled to -20°C, and 118 mg (0.726 mmol) of octanoyl chloride (Tokyo Kasei Kogyo) was added. The mixture was gradually warmed to room temperature and stirred at room temperature for 30 hours. The resulting reaction mixture was quenched with water and extracted with dichloromethane. The organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane/toluene = 3/1 to 0/1) to obtain 102 mg of an orange solid of 4,9-dioctanoyldithienobiphenylene. (yield 82%).
^1H NMR ( _CDCl3 ): δ=8.21 (d, J=5.5Hz, 2H), 7.55 (d, J=5.5Hz, 2H), 7.29 (s, 2H), 2 .97 (t, J=7.3Hz, 4H), 1.75 (m, 4H), 1.39-1.25 (m, 16H), 0.90 (t, J=7.0Hz, 6H) .

Synthesis Example 17 Synthesis of (4,9-dioctyldithienobiphenylene) (Step F3)
Under a nitrogen atmosphere, 86.0 mg (0.166 mmol) of 4,9-dioctanoyldithienobiphenylene synthesized in Synthesis Example 16 and 8 ml of THF (dehydrated grade) were added to a 100 ml Schlenk reaction vessel. The mixture was ice-cooled, and 113 mg (0.845 mmol) of aluminum chloride (Wako Pure Chemical Industries) and 72.2 mg (1.91 mmol) of sodium borohydride (Wako Pure Chemical Industries) were added. The mixture was heated to 40°C and stirred for 2 hours. The resulting reaction mixture was ice-cooled, quenched with water, and extracted with toluene. The organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the resulting residue was purified by silica gel column chromatography (solvent: hexane) to obtain 61 mg of an orange solid of 4,9-dioctyldithienobiphenylene (yield 76%).
^1H NMR ( _CDCl3 ): δ=7.14 (d, J=2.2Hz, 4H), 6.57 (s, 2H), 2.73 (d, J=7.6Hz, 4H), 1 .63 (m, 4H), 1.36-1.22 (m, 20H), 0.89 (t, J=7.1Hz, 6H).

Example 1 (Synthesis of conjugated polymer, compound 1)
Under a nitrogen atmosphere, in a 100 ml Schlenk reaction vessel, 90.3 mg (0.153 mmol) of (B-6-a) synthesized in Synthesis Example 14, 5,5'-dibromo-4,4'-ditetradecyl-2,2' - Bithiophene (Sigma-Aldrich) 109 mg (0.152 mmol), tris(dibenzylideneacetone)dipalladium (Tokyo Kasei Kogyo) 2.8 mg (0.00305 mmol), tri-o-tolylphosphine (Tokyo Kasei Kogyo) 3.9 mg (0.0128 mmol) and 10 ml of chlorobenzene (dehydrated grade) were added. The mixture was heated to 130°C and stirred for 46 hours. The resulting reaction mixture was cooled to 40° C. and poured into a mixed solution of 100 ml of methanol and 2 ml of hydrochloric acid. The resulting slurry liquid was filtered, and the resulting solid was subjected to Soxhlet extraction. Low molecular weight substances were removed by extraction and washing with methanol, hexane, and chloroform. Thereafter, the mixture was extracted with chlorobenzene, and the resulting extracted solution was poured into methanol to obtain 90 mg of a red solid conjugated polymer (compound 1).
High temperature GPC revealed that Mw=46,000, Mn=25,000, and PDI=1.84.

Example 2 (Preparation of organic semiconductor layer forming solution)
In a nitrogen atmosphere, 1.0 mg of the conjugated polymer (Compound 1) synthesized in Example 1 and 332 mg of chlorobenzene (Sigma-Aldrich, dehydrated grade) were added to a 10 ml sample tube, and after heating and dissolving at 50°C, the mixture was dissolved at room temperature ( 25° C.) to prepare an organic semiconductor layer forming solution. The solution state was maintained even after 10 hours at 25° C. (concentration of Compound 1 was 0.30% by weight), confirming that the compound was suitable for film formation by spin coating and inkjet.

Example 3 (Production of organic semiconductor layer and organic thin film transistor)
Using the organic semiconductor layer forming solution obtained in Example 2, a top gate-bottom contact type p-type organic thin film transistor was manufactured. Table 1 shows the materials and film forming methods of each component. The thickness of the thin film of the conjugated polymer (compound 1) was 48 nm.

As a result of evaluating the transfer characteristics of the transistor element, the carrier mobility of holes was 0.10 cm ² /V·sec, and the current on/off ratio was 1.5×10 ⁵ .

Further, this organic thin film transistor was annealed at 140° C. for 15 minutes, and then its electrical properties were measured. The carrier mobility of holes was 0.22 cm ² /V·sec, the current on/off ratio was 2.8×10 ⁶ , and the performance was improved by thermal annealing at 140° C.

Example 4 (Synthesis of conjugated polymer, compound 1)
The same synthesis as in Example 1 was performed except that the heating temperature of the mixture was 120°C. 105 mg of a red solid conjugated polymer (compound 1) was obtained.
High temperature GPC revealed that Mw=21,000, Mn=10,000, and PDI=2.1.

Example 5 (Preparation of organic semiconductor layer forming solution)
A solution was prepared in the same manner as in Example 2, except that the conjugated polymer (Compound 1) synthesized in Example 4 was used instead of Compound 1 synthesized in Example 2. The solution state was maintained even after 10 hours at 25° C. (concentration of Compound 1 was 0.30% by weight), confirming that the compound was suitable for film formation by spin coating and inkjet.

Example 6 (Production of organic semiconductor layer and organic thin film transistor)
The same device fabrication as in Example 3 was performed except that the solution for forming an organic semiconductor layer obtained in Example 5 was used instead of the solution for forming an organic semiconductor layer obtained in Example 2. As a result of evaluating the transfer characteristics of the obtained transistor element, the carrier mobility of holes was 0.14 cm ² /V·sec, and the current on/off ratio was 1.8×10 ⁵ .
Further, this organic thin film transistor was annealed at 140° C. for 15 minutes, and then its electrical properties were measured. The carrier mobility of holes was 0.29 cm ² /V·sec, the current on/off ratio was 2.9×10 ⁶ , and the performance was improved by thermal annealing at 140° C.

Comparative example 1
(Preparation of organic semiconductor layer forming solution)
Under a nitrogen atmosphere, in a 10 ml sample tube, using poly{2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene} (Sigma-Aldrich), the same procedure as in Example 2 was carried out. An organic semiconductor layer forming solution was prepared by the method described above. The solution state was maintained even after 10 hours at 25°C (0.30% by weight), confirming that the compound was suitable for film formation by drop casting and inkjet.

(Production of organic semiconductor layer and organic thin film transistor)
Poly{2,5-bis(3-tetradecylthienyl-2-)thieno[3,2-b]thiophene} with a film thickness of 53 nm was prepared using the organic semiconductor layer forming solution in the same manner as in Example 3. A bottom gate-top contact type p-type organic thin film transistor was fabricated.
As a result of evaluating the transfer characteristics of the transistor element, the carrier mobility of holes was 0.03 cm ² /V·sec, and the current on/off ratio was 3.0×10 ⁴ .
Further, this organic thin film transistor was annealed at 140° C. for 15 minutes, and then its electrical properties were measured. As a result, the carrier mobility was 0.02 cm ² /V·sec and the current on/off ratio was 3.2×10 ⁴ , with no improvement observed.

The conjugated polymer of the present invention has high carrier mobility, excellent solubility, and can be thermally annealed at a mild temperature of 140°C or less, so it can be used as an organic thin film semiconductor device material, typified by organic thin film transistors having plastic substrates. can be expected to be applied.

(A): Bottom gate - top contact type organic thin film transistor (B): Bottom gate - bottom contact type organic thin film transistor (C): Top gate - top contact type organic thin film transistor (D): Top gate - bottom contact type organic thin film transistor 1: Organic semiconductor layer 2: Substrate 3: Gate electrode 4: Gate insulating layer 5: Source electrode 6: Drain electrode

Claims (4)

A conjugated polymer containing a monomer unit having a benzocyclobutene skeleton, which is a conjugated polymer represented by the following general formula (1) .
(Here, A, C, and E represent a divalent linking group of a thiophene ring , and B represents a structure represented by one of the group consisting of the following general formulas (B-6) to (B-8). and D represents a divalent linking group of 2 to 7 fused rings containing at least one sulfur atom, oxygen atom, selenium atom, or nitrogen atom as a ring constituent atom. a, b, c represent 1 ; , d, and e are 0. n indicates an integer of 2 or more.)
(Here, X represents one type of the group consisting of oxygen atoms and sulfur atoms , and Y represents a carbon atom . * represents a bonding site with another structure.) An organic semiconductor layer forming solution containing the conjugated polymer according to claim 1. An organic semiconductor layer formed by using the solution for forming an organic semiconductor layer according to claim 2. An organic thin film transistor comprising the organic semiconductor layer according to claim 3.