JP2022020964A - Conjugate polymer, solution for forming organic semiconductor layer, organic semiconductor layer, organic thin film transistor, and cyclopentabiphenylene compound - Google Patents

Abstract

To provide a novel conjugate polymer having a high carrier movement degree and a high solubility, an organic semiconductor layer using them, and an organic thin film transistor.SOLUTION: A conjugate polymer is represented by the following formula (1). (Here, each of A, C, and E indicates a divalent coupling group containing at least one ring of a group consisting of thiophene ring, furan ring, selenophene ring, thiazole ring, thiophene ring, 2-ethenyl thiophene ring, and benzene ring. B indicates a cyclopentabiphenylene structure indicated by one kind of a group consisting of formulae (B-1) to (B-18). D indicates a fused bicyclic to fused seven cyclic divalent coupling group containing at least one kind of a group consisting of a sulfur atom, an oxygen atom, a selenium atom, and a nitrogen atom in a cyclic constituent atom. b indicates 1 to 3, and each of a, c, d, and e indicate 0 to 3, respectively, and at least one of a, c, d, and e is 1 or larger. n indicates an integer number of 2 or larger.)SELECTED DRAWING: None

Description

The present invention relates to a novel conjugate 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, and is particularly excellent in mobility and solubility. It relates to a novel conjugate polymer applicable to the device fabrication process, an organic semiconductor layer using the same, and an organic thin film. The present invention also relates to a novel cyclopentabiphenylene compound used in the synthesis of the conjugated polymer.

Organic semiconductor devices represented by organic thin film transistors have been attracting attention in recent years because they have features that are not found in inorganic semiconductor devices, such as energy saving, low cost, and flexibility. This organic semiconductor device is composed of several kinds of materials such as an organic semiconductor layer, a substrate, an insulating layer, and an electrode. Among them, the organic semiconductor layer responsible for charge carrier transfer 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, the appearance of an organic semiconductor material that gives high carrier mobility is desired.

As a method for producing an organic semiconductor layer, a vacuum vapor deposition method in which an organic material is vaporized under high temperature vacuum and a coating method in which the organic material is dissolved in an appropriate solvent and the solution is applied are generally known. Has been done. Of these, the coating method can also be carried out by using printing technology without using high temperature and high vacuum conditions. Therefore, it can be expected to significantly reduce the manufacturing cost of device manufacturing, which is an economically preferable 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 at room temperature of 0 from the viewpoint of high carrier mobility and device fabrication process. It is preferable to have 1% by weight or more.

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

Currently, as the polymer material, poly (2,5-bis (3-alkylthiophen-2-yl) thieno [3,2-b] thiophene) (see, for example, Non-Patent Document 1 and Non-Patent Document 2), Poly (2,7-bis (3-alkylthiophen-2-yl) naphthodithiophene) (see, for example, Non-Patent Document 3) and the like have been proposed.

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

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

The present invention has been made in view of the above problems, and an object of the present invention is to provide a novel coating type organic semiconductor material capable of high carrier mobility, high solubility, and annealing at a mild temperature. be.

As a result of diligent studies to solve the above problems, the present inventor has found that a novel conjugated polymer can be an organic semiconductor material that can be annealed at a mild temperature while providing high carrier mobility. , The present invention has been completed.

That is, the present invention is a conjugated polymer represented by the following formula (1).

[(Here, A, C, and E are at least 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, respectively. Indicates a divalent linking group containing a ring of. A, C and E may be the same or different, respectively.
B represents a cyclopentabiphenylene structure represented by one of the groups consisting of the following formulas (B-1) to (B-18).
D represents a divalent linking group of a condensed 2 ring to a condensed 7 ring containing at least one atom of the group consisting of a sulfur atom, an oxygen atom, a selenium atom, or a nitrogen atom in a ring-constituting atom.
b indicates 1 to 3, a, c, d, and e indicate 0 to 3, respectively, and at least one of a, c, d, and e is 1 or more. n represents an integer of 2 or more. )

(Here, R is at least one of a group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryl group having 4 to 30 carbon atoms, respectively. Species are indicated. * Indicates a binding site with other structures.)]

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a novel conjugated polymer which can provide high carrier mobility, has high solubility, and can be thermally annealed at a temperature of 140 ° C. or lower. Further, by using the conjugated polymer, it becomes possible to provide an organic thin film transistor that exhibits excellent semiconductor properties by coating on a plastic substrate, and the effect is extremely high.

It is a figure which shows the structure by the cross-sectional shape of an organic thin film transistor.

Hereinafter, a conjugated polymer which is one aspect of the present invention will be described in detail.

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

In formula (1), A, C, and E are each independently at least 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. The divalent linking group containing the ring of the species is shown. Due to its high mobility and high solubility, the linking group preferably comprises at least one of the group consisting of a thiophene ring, a furan ring, a selenophene ring and a thiazole ring, and more preferably contains a thiophene ring. A, C and E may be the same or different from each other.

Examples of the linking group represented by A, C, and E include the following formulas (A-1) to (A-9).

(Here, R ¹ and R ² are independently composed of a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryl group having 4 to 30 carbon atoms. Indicates at least one species in the group. R ¹ and R ² may be the same or different, respectively. * Indicates a binding site with another structure.)

Since the linking group represented by A, C, and E is a conjugated polymer exhibiting high mobility, at least one of the group consisting of (A-1) to (A-4) is preferable, and (A-1). )-(A-3), at least one of the group is more preferable.

In the formulas (A-1) to (A-9), R ¹ and R ² are independent of each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. It represents one of a group consisting of aryl groups having 4 to 30 carbon atoms, and is either an alkyl group having 1 to 30 carbon atoms or an aryl group having 4 to 30 carbon atoms because it is a conjugated polymer exhibiting high mobility. Is preferable.

As the halogen atom in R ¹ and R ² , for example, one of a group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom is shown, and since it is stable, either a fluorine atom or a chlorine atom is preferable.

Examples of the alkyl group having 1 to 30 carbon atoms in R ¹ and R ² include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group and an undecyl group. Linear alkyl group such as group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group, isopropyl group, isobutyl group, isovaleryl group, 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, 4-octyldodecyl group, 4-decyltetradecyl group, 4-decylhexadecyl group, 4-cyclohexylbutyl group, 8-cyclohexyloctyl group and other branched alkyl groups, cyclopentyl group, cyclohexyl group, cycloheptyl group, 3 -Cyclic alkyl groups such as a decylcyclopentyl group and a 4-decylcyclohexyl group can be mentioned. Among them, since it is a conjugated polymer that exhibits particularly high mobility and high solubility, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, and a pentadecyl group. , Hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group, henicosyl group, docosyl group and other linear alkyl groups having 6 to 24 carbon atoms, or 2-ethylhexyl group, 3-ethylheptyl group, 3-ethyldecyl, 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 a branched alkyl group having 8 to 26 carbon atoms such as a decyltetradecyl group, a 4-hexyldecyl group, a 4-octyldecyl group, a 4-octyldodecyl group, a 4-decyltetradecyl group, and a 4-decylhexadecyl group. One of the groups is preferable, and one of the group consisting of a linear alkyl group having 10 to 22 carbon atoms or a branched alkyl group having 10 to 24 carbon atoms is more preferable.

The alkyl group having 1 to 30 carbon atoms can replace at least one hydrogen atom with a fluorine atom. Further, the alkyl group having 1 to 30 carbon atoms can replace one to three carbon atoms with an oxygen atom.

Examples of the alkoxy group having 1 to 30 carbon atoms in R ¹ and R ² include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group and a nonyloxy group. Decyloxy group, undecyloxy group, dodecyloxy group, tridecyloxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, icosyloxy group, henikosyl Linear alkoxy group such as oxy group, 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 Cyclic alkoxy groups such as cyclohexyloxy groups can be mentioned. Among them, since it is a conjugated polymer showing particularly high mobility and high solubility, hexyloxy group, heptyloxy group, octyloxy group, nonyloxy group, decyloxy group, undecyloxy group, dodecyloxy group and tridecyl Directly of 6 to 24 carbon atoms such as oxy group, tetradecyloxy group, pentadecyloxy group, hexadecyloxy group, heptadecyloxy group, octadecyloxy group, nonadecyloxy group, icosyloxy group, henicosyloxy group, docosyloxy group, etc. Chain alkyloxy group, or 2-ethylhexyloxy group, 3-ethylheptyloxy group, 3-ethyldecyloxy group, 2-hexyldecyloxy group, 2-octyldecyloxy group, 2-octyldodecyloxy group, 2-decyl Dodecyloxy group, 2-decyltetradecyloxy group, 3-hexyldecyloxy group, 3-octyldecyloxy group, 3-octyldodecyloxy group, 3-decyltetradecyloxy group, 4-hexyldecyloxy group, 4- One of a group consisting of branched alkoxy groups having 8 to 26 carbon atoms such as an octyldecyloxy group, a 4-octyldodecyloxy group, a 4-decyltetradecyloxy group, and a 4-decylhexadecyloxy group is preferable, and the group having 8 carbon atoms is preferable. One of a group consisting of a linear alkoxy group of ~ 22 or a branched alkoxy group having 10 to 24 carbon atoms is more preferable.

The alkoxy group having 1 to 30 carbon atoms can replace at least one hydrogen atom with a fluorine atom. Further, the alkyl group having 1 to 30 carbon atoms can replace one to three carbon atoms with an oxygen atom.

Examples of the aryl group having 4 to 30 carbon atoms in R ¹ and R ² include a phenyl group; a p-tolyl group, a p- (hexyl) phenyl group, a p- (octyl) phenyl group and a p- (decyl) phenyl group. , P- (dodecyl) phenyl group, p- (tetradecyl) phenyl group, p- (hexadecyl) phenyl group, p- (octadecyl) phenyl group, p- (2-ethylhexyl) phenyl group and other alkyl substituted phenyl groups; 2 -Frill 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-frill group, 5- (pentyl) -2-frill group, 5- (hexyl) -2-frill group, 5- (octyl) -2-fryl group, 5- (tetradecyl) -2-frill Group, 5- (hexadecyl) -2-fryl group, 5- (2-ethylhexyl) -2-fryl 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- (decyl) -2-thienyl group, 5- (dodecyl) -2-thienyl group, 5- (tetradecyl) -2-thienyl group, 5- (hexadecyl) -2-thienyl Group, 5- (octadecyl) -2-thienyl group, 5- (2-ethylhexyl) -2-thienyl group, 5- (2-hexylundecyl) -2-thienyl group, 5- (2-octyldodecyl)- 2-thienyl group, 4- (tetradecyl) -2-thienyl group, 4- (hexadecyl) -2-thienyl group, 4- (octadecyl) -2-thienyl group, 4- (2-ethylhexyl) -2-thienyl group , 4- (2-Hexylundecyl) -2-thienyl group, 4- (2-octyldodecyl) -2-thienyl group and the like can be mentioned as one of a group consisting of an alkyl substituted heteroaryl group.

The aryl group having 4 to 30 carbon atoms is preferably a heteroaryl group having 4 to 30 carbon atoms.

The aryl group having 4 to 30 carbon atoms can replace at least one hydrogen atom with a fluorine atom.

In the formula (1), B represents a cyclopentabiphenylene structure represented by one of the groups consisting of the above formulas (B-1) to (B-18).

Since B is a conjugated polymer exhibiting high mobility and high solubility, (B-1), (B-5), (B-6), (B-8), (B-11), (B). At least one of the group consisting of -13) is preferable.

In the formulas (B-1) to (B-18), R is 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, or 4 to 4 carbon atoms. Since it represents one of the group consisting of 30 aryl groups and is a conjugated polymer exhibiting high mobility, either an alkyl group having 1 to 30 carbon atoms or an aryl group having 4 to 30 carbon atoms is preferable.

From the viewpoint of high mobility and high solubility, the alkyl group having 1 to 30 carbon atoms is more preferably either a linear alkyl group having 6 to 24 carbon atoms or a branched alkyl group having 8 to 26 carbon atoms. Either a linear alkyl group having a number of 10 to 22 or a branched alkyl group having 10 to 24 carbon atoms is particularly preferable.

Specific examples of the halogen atom as an example of R, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and an aryl group having 4 to 30 carbon atoms are, for example, the above-mentioned formula (A-1). It can be considered in the same manner as R ¹ and R ² of (A to 9), from a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and an aryl group having 4 to 30 carbon atoms. A specific example of at least one of the groups can be mentioned.

In the formula (1), D represents a divalent linking group containing a condensed 2 ring to a condensed 7 ring containing at least one of the group consisting of a sulfur atom, an oxygen atom, a selenium atom, or a nitrogen atom. All the rings constituting the condensed 2-ring to condensed 7-ring are 4- to 8-membered rings. Specific examples of the 4- to 8-membered ring include, for example, a cyclobutene ring, a hydrocyclopenta 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, and a cyclo. Octatetraene ring, pyridine ring, thiadiazole ring, ketopyrol ring, triazole ring, oxadiazole ring, imide ring and the like can be mentioned. , Hydrocyclopenta ring, thiophene ring, furan ring, selenophene ring, benzene ring, pyridine ring, thiadiazole ring, ketopyrol ring, triazole ring, oxadiazole ring, succinimide ring, glutarimide ring. Is even more preferable.

Examples of the linking group represented by D include the following formulas (D-1) to (D to 71).

(Here, R ³ is at least a group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryl group having 4 to 30 carbon atoms, respectively. 1 type is indicated. * Indicates a binding site with another structure.)

Since the linking group represented by D is a conjugated polymer exhibiting high mobility and high solubility, it is a group consisting of (D-1) to (D-14) and (D-52) to (D-71). At least one is preferable, and at least one of the group consisting of (D-52) to (D-71) having acceptor properties is more preferable.

In the formulas (D-1) to (D to 71), R ³ independently has a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or 4 to 4 carbon atoms. Since it represents one of the group consisting of 30 aryl groups and is a conjugated polymer exhibiting high mobility, either an alkyl group having 1 to 30 carbon atoms or an aryl group having 4 to 30 carbon atoms is preferable.

Specific examples of the halogen atom as an example of R ³ , an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and an aryl group having 4 to 30 carbon atoms are, for example, the above-mentioned formula (A-1). It can be considered in the same manner as R ¹ and R ² of (A-9), from a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and an aryl group having 4 to 30 carbon atoms. A specific example of at least one of the groups can be mentioned.

From the viewpoint of high mobility and high solubility, the alkyl group having 1 to 30 carbon atoms is more preferably either a linear alkyl group having 6 to 24 carbon atoms or a branched alkyl group having 8 to 26 carbon atoms. Either a linear alkyl group having a number of 10 to 22 or a branched alkyl group having 10 to 24 carbon atoms is particularly preferable.

In the 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.

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

In the formula (1), b represents 1 to 3 and has high mobility, so 1 is preferable.

In equation (1), n represents an integer of 2 or more.

The conjugate polymer represented by the formula (1) is a compound having two or more repeating units n. The n is not particularly limited as long as it is an integer of 2 or more, but is preferably 4 or more because of its high mobility, preferably 300 or less, and even more preferably 250 or less because of its high solubility.

The molecular weight of the conjugated polymer of the present invention is preferably 2,000 to 1,000,000, and more preferably 4,000 to 300,000 because it is suitable for obtaining an organic thin film transistor having a higher carrier mobility. It is preferable, and 10,000 to 150,000 is particularly preferable. In the present invention, the molecular weight of the polymer refers to the polystyrene-equivalent weight average molecular weight (Mw).

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

The cyclopentabiphenylene compound, which is one aspect of the present invention, will be described in detail below.

The cyclopentabiphenylene compound of the present invention is represented by the following formulas (B'-1) to (B'-18).

(Here, R is at least one of a group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryl group having 4 to 30 carbon atoms, respectively. Species are indicated. X independently indicates at least one of a group consisting of a hydrogen atom, a halogen atom, a trialkyltin, a dialkoxyboron, a dihydroxyboron, or an alkyl group having 1 to 30 carbon atoms.)

Since the cyclopentabiphenylene compound of the present invention is a monomer of a conjugated polymer exhibiting high mobility and high solubility, the formulas (B'-1), (B'-5), (B'-6), (B) At least one of the group consisting of'-8), (B'-11) and (B'-13) is preferable.

In formulas (B'-1) to (B'-18), R is 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, or an alkoxy group having 1 to 30 carbon atoms. An alkyl group having 1 to 30 carbon atoms or an aryl group having 4 to 30 carbon atoms is preferable because it represents one of a group consisting of 4 to 30 aryl groups and serves as a monomer of a conjugated polymer exhibiting high mobility. ..

From the viewpoint of high mobility and high solubility, the alkyl group having 1 to 30 carbon atoms is more preferably either a linear alkyl group having 6 to 24 carbon atoms or a branched alkyl group having 8 to 26 carbon atoms. Either a linear alkyl group having a number of 10 to 22 or a branched alkyl group having 10 to 24 carbon atoms is particularly preferable.

Specific examples of the halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and an aryl group having 4 to 30 carbon atoms as examples of the R are, for example, the above-mentioned formula (A-1). )-(A-9) can be considered in the same manner as R ¹ and R ² , a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, and an aryl group having 4 to 30 carbon atoms. A specific example of at least one of the group consisting of can be mentioned.

In formulas (B'-1) to (B'-18), X is independently a group consisting of a hydrogen atom, a halogen atom, a trialkyltin, a dialkoxyboron, or an alkyl group having 1 to 30 carbon atoms. One of the group consisting of a hydrogen atom, a halogen atom, a trialkyltin, a dialkoxyboron, and a dihydroxyboron is preferable because it shows at least one kind and becomes a monomer having good reactivity.

As the halogen atom of X, for example, one of a group consisting of a fluorine atom, a chlorine atom, a bromine atom and an iodine atom is shown, and since it is stable, either a fluorine atom or a chlorine atom is preferable.

As the trialkyltin of X, for example, one of the group consisting of trimethyltin, triethyltin and tributyltin is shown, and trimethyltin is preferable because it tends to be a solid.

Examples of the dialkoxyboron of X include dimethoxyboron, diethoxyboron, 4,4,5,5-tetramethyl-1,3-dioxaborolan-2-yl and 5,5-dimethyl-1,3-dioxabolinane. It represents one of the group consisting of -2-yl, and 4,4,5,5-tetramethyl-1,3-dioxaborolan-2-yl is preferable because of its high reactivity.

Examples of the alkyl group having 1 to 30 carbon atoms of X include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group and a dodecyl group. Linear alkyl groups such as groups, tridecyl groups, tetradecyl groups, pentadecyl groups, hexadecyl groups, heptadecyl groups, octadecyl groups, nonadesyl groups, icosyl groups, henicosyl groups, docosyl groups, isopropyl groups, isobutyl groups, isovaleryl groups, isohexyl groups, 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, 4 -Branched alkyl groups such as octyldodecyl group, 4-decyltetradecyl group, 4-decylhexadecyl group, 4-cyclohexylbutyl group, 8-cyclohexyloctyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, 3-decylcyclopentyl Examples thereof include a cyclic alkyl group such as a group and a 4-decylcyclohexyl group, and examples thereof include a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group and a heptadecyl. One of a group consisting of a linear alkyl group having 6 to 24 carbon atoms such as a group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, and a docosyl group is preferable.

As a method for producing a conjugated polymer represented by the formula (1) of the present invention, any production method can be used as long as the conjugated polymer can be produced.

Examples of the method for producing the conjugated polymer include a method of cross-coupling reaction using compounds represented by the following formulas (2) and (3).
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 formula (1). And e have the same meaning. Z ¹ to Z ⁴ independently represent a halogen atom, trifluoromethanesulfonyloxy, methanethrophonyloxy, toluenesulfoniloxy, trialkyltin, triaryltin, and dialkoxyboron. , Dihydroxyboron, zinc halide, dimethylfluorosilicon, difluoromethylsilicon, triethoxysilicon, trimethoxysilicon, or magnesium halide. However, ^two of ^Z1 to Z4 are halogen atoms and trifluoromethanesulfos. It is selected from the group consisting of nyloxy, methanethrophonyloxy, and toluenesulfonyloxy, and the remaining two are trialkyltin, triaryltin, dialkoxyboron, dihydroxyboron, zinc halide, dimethylfluorosilicon, and difluoromethyl. It is selected from the group consisting of silicon, triethoxysilicon, trimethoxysilicon, and magnesium halide.)

Since the coupling reaction is an aryl-aryl coupling reaction and has a high yield, it is a group consisting of a still coupling reaction, a Suzuki coupling reaction, a Negishi coupling reaction, a Kumada coupling reaction, and a Hiyama coupling reaction. At least one of the above is preferable, and at least one of a still coupling reaction and a Suzuki coupling reaction is more preferable.

Z ¹ to Z ⁴ in the formulas (2) and (3) independently represent a halogen atom, trifluoromethanesulfonyloxy, methanethrophonyloxy, toluenesulfonyloxy, trialkyltin, triaryltin, and dialkoxy. Indicates boron, dihydroxyboron, zinc halide, dimethylfluorosilicon, difluoromethylsilicon, triethoxysilicon, trimethoxysilicon, or magnesium halide.

The halogen atom represents one of a group consisting of a bromine atom, an iodine atom, a chlorine atom and a fluorine atom, and because of its high reactivity, either a bromine atom or an iodine atom is preferable.

The alkyl group of the trialkyltin represents an alkyl group having 1 to 10 carbon atoms, and examples of the trialkyltin include trimethyltin, triethyltin, tripropyltin, tributyltin, trihexyltin, and tricyclohexyltin. At least one of trimethyltin and tributyltin is preferable because of its availability.

The aryl group of the triaryl tin represents an aryl group having 6 to 10 carbon atoms, and examples of the triaryl tin include triphenyl tin, tri (o-tolyl) tin, tri (m-tolyl) tin, and tri (p). -Trill) tin, trinaphthyl tin can be mentioned.

The alkoxy group of the dialkoxyboron represents an alkoxy group having 1 to 10 carbon atoms, and examples of the dialkoxyboron include dimethoxyboron, diethoxyboron, dipropyroxyboron, diisopropyroxyboron, dibutoxyboron, and dihex. Indicates siloxyboron. The two alkoxy groups can be bonded to each other to form a ring, and for example, 1,3,2-dioxaborolan-2-yl group, 1,3,2-dioxabolinan-2-yl group and the like can be formed. Can be mentioned. As the dialkoxyboron, due to its high reactivity, 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl group, 1,3,2-dioxabolinan-2-yl group, 5,5-Dimethyl-1,3,2-dioxabolinan-2-yl group and the like are preferable.

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

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

Of Z ¹ to Z ⁴ , two are selected from the group consisting of halogen atoms, trifluoromethanesulfonyloxy, methanethrophonyloxy, and toluenesulfoniloxy, and the other two are trialkyltin, triaryltin, and so on. It is selected from the group consisting of dialkoxyboron, dihydroxyboron, zinc halide, dimethylfluorosilicon, difluoromethylsilicon, triethoxysilicon, trimethoxysilicon, or magnesium halide. For example, because of its high reactivity, Z ¹ and Z ² are trialkyltin, triaryltin, dialkoxyboron, dihydroxyboron, zinc halide, dimethylfluorosilicon, difluoromethylsilicon, triethoxysilicon, trimethoxysilicon, Selected from the group consisting of magnesium halides, Z ³ and Z ⁴ are selected from the group consisting of halogen atoms, trifluoromethanesulfonyloxy, methanethrophoniroxy, toluenesulfoniloxy, or Z ¹ and Z ² . Is selected from the group consisting of halogen atom, trifluoromethanesulfonyloxy, methanethrophonyloxy, and toluenesulfonyloxy, and Z3 and Z4 ^are trialkyltin, ^triaryltin , dialkoxyboron, dihydroxyboron, halogen. It is preferably selected from the group consisting of zinc oxide, dimethylfluorosilicon, difluoromethylsilicon, triethoxysilicon, trimethoxysilicon, and magnesium halide.

At least a 0-valent palladium compound or a divalent palladium compound is used in the still coupling reaction, Suzuki coupling reaction, Negishi coupling reaction, Kumada coupling reaction, and Hiyama coupling reaction, which are methods for producing the conjugated polymer of the formula (1). Either catalyst is used. Examples of the zero-valent palladium compound include tris (dibenzylideneacetone) dipalladium, bis (dibenzylideneacetone) palladium, tetrakis (triphenylphosphine) palladium, and bis {tri (tert-butyl) phosphine} palladium. Examples of the divalent palladium compound include dichlorobis (triphenylphosphine) palladium, {1,2-bis (diphenylphosphino) ethane} palladium dichloride, {1,3-bis (diphenylphosphino) propane} palladium dichloride, and the like. {1,1'-Bis (diphenylphosphino) ferrocene} Palladium dichloride, bis (acetohydrate) palladium dichloride, bis (ethylenediamine) palladium dichloride, palladium acetate can be mentioned. Further, the palladium compound includes tri (o-tolyl) phosphine, triphenylphosphine, tri (tert-butyl) phosphine, tri (tert-butyl) phosphonium tetrafluoroborate, tri (tert-butyl) phosphine, and tri (tert-butyl). ) At least one phosphine in the group consisting of phosphonium tetraphenylborate can also be added.

Further, a nickel compound can be used as a catalyst. The nickel compounds include dichlorobis (triphenylphosphine) nickel, bis (1,5-cyclooctadienyl) nickel, {1,2-bis (diphenylphosphino) ethane} nickel dichloride, {1,3-bis (diphenyl). Phosphino) propane} nickel dichloride can be mentioned.

A copper compound may be added to the paradim compound and the nickel compound. Examples of the copper compound include monovalent copper such as copper iodide (I), copper (I) chloride, copper bromide (I) and copper (I) acetate; copper (II) chloride and copper bromide (II). ), Copper iodide (II), copper acetate (II), divalent copper such as acetylacetonate copper (II), etc., among which monovalent copper is preferable, and copper iodide (I) is further used. 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 hydrogencarbonate, potassium hydrogencarbonate, potassium hydroxide, and sodium hydroxide; triethylamine, trimethylamine, and tributylamine. , Ethylenediamine, N, N, N', N'-tetramethylethylenediamine, diisopropylamine, pyridine, 1,4-diazabicyclo [2.2.2] octane, sodium tert-butoxide, at least one organic base in the group. Can be mentioned as a suitable one.

In the aryl-aryl coupling reaction, fluoride may be added to promote the reaction. As the fluoride, for example, tetrabutylammonium fluoride, potassium fluoride, fuccanatrim, cesium fluoride, lithium fluoride and the like can be mentioned as suitable ones.

Further, in the aryl-aryl coupling reaction, a phase transfer catalyst may be added to promote the reaction. As the phase transfer catalyst, for example, trioctylmethylammonium chloride, didodecyldimethylammonium chloride, benzyldimethylhexadecylammonium chloride hydrate and the like can be mentioned as suitable catalysts.

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

The amount of the palladium catalyst and the nickel catalyst used is in the range of 0.1 to 20 mol%, preferably 0.5 to 10 mol%, based on the compound of the 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 used is in the range of 0.5 to 30 mol% with respect to the compound of the formula (2), preferably in the range of 1 to 20 mol%.

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 the formula (2).

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

The temperature at the time of 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.

Further, the produced conjugated polymer of the 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 formula (2), for example, when Z ¹ and Z ² are trimethyl tin, b is 1, B is the above formula (B-1), and R is a heptadecyl group (B). -1-SnMe ₃ ) can be produced by the method according to the following steps A1 to E1.

(Step A1); 2-bromo-4-chlorophenyl-1-zinc chloride derived from 2-bromo-4-chloro-1-iodobenzene and 1-bromo-4-chloro-2 in the presence of a palladium catalyst. -A step of producing 2,2'-dibromo-4,5'-dichlorobiphenyl from iodobenzene.
(Step B1); 2,2'-dibromo-4,5'-dichlorobiphenyl obtained by step A1 is converted into a dilithium compound with butyl lithium and intramolecularly cyclized with copper (II) chloride to form 2,6-. The process of producing dichlorobiphenylene.
(Step C1); 3- (1-ethoxy-1-) derived from 3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] thiophene in the presence of a palladium catalyst. Heptadecyl octadecyl) -5-trimethylsilylthioeno [3,2-b] thiophene-2-ylzinc chloride and 2,6-bis {3- (1-ethoxy) from 2,6-dichlorobiphenylene obtained by the B1 step. -1-Heptadecyl octadecyl) -5-trimethylsilylthioeno [3,2-b] thiophene-2-yl} A step of producing biphenylene.
(Step D1); 2,6-bis {3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] thiophene-2-yl} biphenylene obtained by step C1 A step of treating with boron tribromide to produce (B-1-H).
(Step E1); A step of converting (B-1-H) obtained by the D1 step into a dilithium compound with butyllithium and reacting with trimethyltin chloride to produce (B-1-SnMe ₃ ).

Details of each process of A1 to E1 are shown below.

The A1 step consists of 2-bromo-4-chlorophenyl-1-zinc chloride derived from 2-bromo-4-chloro-1-iodobenzene and 1-bromo-4-chloro-2 in the presence of a palladium catalyst. -A step of producing 2,2'-dibromo-4,5'-dichlorobiphenyl from cross-coupling of iodobenzene.

2-bromo-4-chlorophenyl-1-zinc chloride uses an organic metal reagent such as ethylmagnesium chloride or isopropylmagnesium bromide to replace iodine in 2-bromo-4-chloro-1-iodobenzene with magnesium halide. After that (preparation of 2-bromo-4-chlorophenyl-1-magnesium halide), it can be prepared by exchanging metal with zinc chloride. It is also possible to use magnesium metal instead of the organometallic reagent.

As a condition for preparing 2-bromo-4-chlorophenyl-1-magnesium halide, for example, it can be carried out in a solvent such as THF or diethyl ether within a temperature range of −80 ° C. to 20 ° C. 2-Bromo-4-chlorophenyl-1-zinc chloride can be prepared by reacting zinc chloride with a solution of the magnesium salt (2-bromo-4-chlorophenyl-1-magnesium halide). Zinc chloride may be used as it is, or may be a THF or diethyl ether solution. The temperature of the reaction 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 the A1 step include tetrakis (triphenylphosphine) palladium and dichlorobis (triphenylphosphine) palladium, and the reaction temperature may be in the range of 20 ° C to 80 ° C.

The B1 step is carried out by converting the 2,2'-dibromo-4,5'-dichlorobiphenyl obtained by the A1 step into a dilithium compound with 2 equivalents or more of butyl lithium and intramolecularly cyclizing it with copper (II) chloride. This is a process for producing 2,6-dichlorobiphenylene.

As a condition for preparing the dilithium salt, for example, 2 to 4 equivalents of butyllithium or tert-butyllithium may be used in a solvent such as THF or diethyl ether in a temperature range of -80 ° C to 20 ° C. can.

Copper (II) chloride is used in an amount of 1 to 3 equivalents with respect to the dilithium compound, and the intramolecular cyclization reaction can be carried out in the temperature range of −80 ° C. to 30 ° C. Copper bromide (II) can also be used instead of copper (II) chloride.

In the C1 step, 2,6-dichlorobiphenylene obtained in the B1 step is subjected to 3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-] in the presence of a palladium catalyst or a nickel catalyst. b] This is a step of coupling reaction with 3- (1-ethoxy-1-heptadecyl octadecyl) -5-trimethylsilylthioeno [3,2-b] thiophene-2-ylzinc chloride derived from thiophene.

Examples of the palladium catalyst in the C1 step include tetrakis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) palladium, bis {tri (tert-butyl) phosphine} palladium, tris (dibenzilidenacetone) dipalladium, {1, 1'-bis (diphenylphosphine) ferrocene} palladium dichloride and the like can be mentioned, and the palladium compound includes tri (o-tolyl) phosphine, triphenylphosphine, tri (tert-butyl) phosphine, and dicyclohexyl (2'). , 4', 6'-triisopropyl- [1,1'-biphenyl] -2-yl) phosphine, 2- (dicyclohexylphosphine) -2'-(dimethylamino) biphenyl at least one of the phosphines in the group. Can also be added.

The coupling reaction can be carried out in a solvent such as THF, diethyl ether or toluene in a temperature range of 20 ° C to 100 ° C.

The coupling reaction can also be catalyzed by a nickel compound. The nickel compounds include dichlorobis (triphenylphosphine) nickel, bis (1,5-cyclooctadienyl) nickel, {1,2-bis (diphenylphosphino) ethane} nickel dichloride, {1,3-bis (diphenyl). At least one of the group consisting of phosphino) propane} nickel dichloride can be mentioned.

The reactant of the reaction, 3- (1-ethoxy-1-heptadecyl octadecyl) -5-trimethylsilylthioeno [3,2-b] thiophen-2-ylzinc chloride, is, for example, 3- (1-ethoxy-). 1-Heptadecyl octadecyl) -5-trimethylsilylthioeno [3,2-b] Thiophene can be prepared by lithiating with butyllithium in THF or diethyl ether and then exchanging metal with zinc chloride.

Further, the 3- (1-ethoxy-1-heptadecyl octadecyl) -5-trimethylsilyl thieno [3,2-b] thiophen-2-ylzinc chloride is 3- (1-ethoxy-1-heptadecyl octadecyl) thieno. [3,2-b] Thiophene-2-ylmagnesium chloride or 3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] Thiophene-2-ylmagnesium bromide Can be used.

In the D1 step, 2,6-bis {3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] thiophene-2-yl} biphenylene obtained by the C1 step was used. This is a step of producing (B-1-H) by intramolecular cyclization with boron tribromide.

Boron tribromide is 1-8 with respect to 2,6-bis {3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] thiophen-2-yl} biphenylene. The equivalent amount can be used and carried out in a solvent such as dichloromethane, tetrachloroethane, chlorobenzene, dichlorobenzene and the like in a temperature range of −80 ° C. to 40 ° C.

In the E1 step, (B-1-H) obtained by the D1 step is converted into a dilithium compound with 2 equivalents or more of butyllithium and then reacted with trimethyltin chloride to produce (B-1-SnMe ₃ ). It is a process.

As a condition for preparing the dilithium salt, for example, 2 to 6 equivalents of butyllithium can be used, and the dilithium salt can be prepared in a temperature range of −80 ° C. to 35 ° C. in a solvent such as THF or diethyl ether.

Instead of butyllithium, sec-butyllithium, tert-butyllithium, butyllithium / tetramethylethylenediamine, butyllithium / diisopropylamine, butyllithium / 2,2,6,6, -tetramethylpiperidine and the like can be used. ..

The reaction with trimethyltin chloride can be carried out in the temperature range of −80 ° C. to 35 ° C. using 2 to 6 equivalents of trimethyltin chloride.

A specific production method (B-1-SnMe ₃ ), which is preferable because the number of reaction steps is small, is shown in the following reaction scheme.

The compound of the formula (2) produced above can be purified by solvent washing, solvent reprecipitation or recrystallization, and the purity can be improved by increasing the number of recrystallizations. The number of recrystallizations is preferably 2 to 5 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 solvent washing, reprecipitation or recrystallization include hexane, heptane, octane, toluene, xylene, chloroform, chlorobenzene, dichlorobenzene, ethanol, methanol and the like, and a mixture thereof in any proportion. May be.

In the recrystallization method, a solution of the compound of the formula (2) is prepared by heating (the concentration of the solution at that time is preferably in the range of 0.01 to 10.0% by weight in order to efficiently remove impurities, and is 0. A range of 0.05 to 5.0% by weight is more preferable.) The solution is cooled to precipitate and isolate crystals of the compound of the formula (2), but the final cooling temperature at the time of isolation is In order to improve the purity and recovery rate, it is preferably in the range of −20 ° C. to 40 ° C. When measuring the purity, it can be analyzed by liquid chromatography.

The compound represented by the above formula (3) can be synthesized by a known production method. Alternatively, a commercially available product can be used as it is.

The solution for forming an organic semiconductor layer, which is one aspect of the present invention, will be described in detail below.

The conjugate polymer of the present invention can be dissolved in an appropriate solvent to prepare a solution for forming an organic semiconductor layer containing the conjugate polymer. As the solvent, any solvent may be used as long as it can dissolve the conjugated polymer represented by the formula (1), and the drying speed of the solvent is suitable when forming the organic semiconductor layer. Therefore, an organic solvent having a boiling point of 100 ° C. or higher at normal pressure is preferable.

The solvent that can be used in the present invention is not particularly limited, and for example, fragrances such as toluene, mesitylene, o-xylene, isopropylbenzene, pentylbenzene, cyclohexylbenzene, 1,2,4-trimethylbenzene, tetraline, and indan. Group hydrocarbons; anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole, ethylphenyl ether, butylphenyl ether, 1,2- Aromatic ethers such as methylenedioxybenzene and 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 methylpropyl 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 monomethyl ether acetate , Glycols such as 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, 3-methoxy Benzene acetate, tetrahydrofurfuryl acetate, tetrahydrof Esters such as rufuryl propionate and γ-butyrolactone; at least one of the group consisting of cyclic ethers such as THF and 2-methoxymethyl tetrahydrofuran can be mentioned, and among them, since they have an appropriate drying rate. , Preferably toluene, o-xylene, mesitylene, 1,2,4-trimethylbenzene, tetraline, indan, octane, nonane, decane, anisole, 2-methylanisole, 3-methylanisole, 2,3-dimethylanisole, 3 , 4-dimethylanisole, 2,6-dimethylanisole, ethylphenyl 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, tetraline, indan, octane, nonan, decane, anisole, 2-methylanisole. , 3-Methylanisole, 2,3-dimethylanisole, 3,4-dimethylanisole, 2,6-dimethylanisole, at least one of the group.

As the solvent used in the present invention, one kind of solvent can be used alone, or two or more kinds of solvents having different properties such as boiling point, polarity, and solubility parameter can be mixed and used.

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

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

In the present invention, when the concentration of the conjugated polymer represented by the formula (1) in the solution for forming the organic semiconductor layer of the present invention is in the range of 0.1 to 10.0% by weight, the handling becomes easy and the organic semiconductor layer is formed. It will be more efficient in forming. Further, when the viscosity of the solution for forming an organic semiconductor layer is in the range of 0.3 to 20 mPa · s, more suitable coatability is exhibited.

Since the conjugated polymer itself has appropriate cohesiveness, the solution can be prepared at a relatively low temperature, and since it has oxidation resistance, it can be suitably applied to the production of an organic thin film by a coating method. .. That is, since it is not necessary to remove air from the atmosphere, the coating process can be simplified. Further, the solution may be, for example, 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-co-norbornen), polyphenylene ether, polycarbonate, polycarbazole, polytriarylamine, poly (9,9-dioctylfluorene-co-dimethyltriaryl) Amin), poly (N-vinylcarbazole), polymethyl methacrylate, poly (styrene-methyl methacrylate), ethyl polymethacrylate, propylpolymethacrylate, isopropyl polymethacrylate, butyl polymethacrylate, polymethacrylate Examples thereof include phenyl, methyl polyacrylate, ethyl polyacrylate, propyl polyacrylate, etc., preferably composed of polystyrene, poly (α-methylstyrene), poly (ethylene-co-norbornene), polymethylmethacrylate and the like. At least one polymer in the group can also be present as a binder. The concentration of these polymer binders is preferably 0.001 to 10.0% by weight because of the appropriate viscosity of the solution.

The glass transition temperature (Tg) of the polymer binder is preferably 105 ° C. or higher, more preferably 120 ° C. or higher, and even more preferably 130 ° C. or higher, because it is more suitable for dealing with the process temperature during manufacturing of electronic devices. Is particularly preferable.

Further, the molecular weight of the polymer is preferably 5,000 to 1,000,000, more preferably 10,000 to 500,000 because it is suitable for obtaining an organic thin film transistor having a higher carrier mobility. 20,000 to 100,000 are particularly preferable. In the present invention, the molecular weight of the polymer refers to the polystyrene-equivalent weight average molecular weight (Mw).

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

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

Specific examples of the polymer that can be used as the polymer binder in the present invention include, for example, polar cyclic polyolefins, polysulfones, acrylonitrile-styrene copolymers, and methylmethacrylate-styrene, in addition to the polymers mentioned above. Polymers and the like can be mentioned.

More specifically, the polar cyclic polyolefins are more preferably a polymer represented by the following formula (4).

(Here, R ⁴ to R ⁶ are independently hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and alkyloxycarbonyl group having 2 to 20 carbon atoms. , Aryloxycarbonyl group with 7 to 20 carbon atoms, cyano group, nitro group, alkoxy group with 1 to 20 carbon atoms, aryloxy group with 6 to 20 carbon atoms, hydroxyl group, amino group, or 1 to 20 carbon atoms. An alkylamino group is shown, where X2 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, an alkoxy group having 1 to 20 carbon atoms, and the like. Indicates 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 indicates an integer of 20 to 5,000, and q and r are independently 0. Indicates an integer of ~ 2. A bond consisting of a solid line and a dotted line indicates a single bond or a double bond.)

R ⁴ to R ⁶ in the formula (4) are independently hydrogen atom, halogen atom, alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 20 carbon atoms, and alkyloxycarbonyl having 2 to 20 carbon atoms. Group, aryloxycarbonyl group with 7 to 20 carbon atoms, cyano group, nitro group, alkoxy group with 1 to 20 carbon atoms, aryloxy group with 6 to 20 carbon atoms, hydroxyl group, amino group, or 1 to 20 carbon atoms Alkoxyamino group of the above, and because of its high heat resistance, at least one of the group consisting of a hydrogen atom and an alkyl group having 1 to 20 carbon atoms is preferable. ^R4 to R6 may be the ^same or different.

Examples of the alkyl group having ¹ to 20 carbon atoms in ^R4 to R6 include a linear or branched alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, an isobutyl group, a sec-butyl group and a pentyl group. Be done. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a p-tolyl group, a p- (hexyl) phenyl group, a p- (octyl) phenyl group, a p- (2-ethylhexyl) phenyl group and the like. Examples of the alkyloxycarbonyl group having 2 to 20 carbon atoms include a methyloxycarbonyl group, an ethyloxycarbonyl group, a propyloxycarbonyl group and the like. Examples of the aryloxycarbonyl group having 7 to 20 carbon atoms include a phenoxycarbonyl group and a 4-methylphenoxycarbonyl group. Examples of the alkoxy group having 1 to 20 carbon atoms include a methoxy group, an ethoxy group, a propoxy group and the like. Examples of the aryloxy group having 6 to 20 carbon atoms include a 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 them, the substituent ^R4 is preferably a methyl group, an ethyl group or an n ^- propyl group, and the substituents R5 and ^R6 are preferably hydrogen atoms because of the high heat resistance.

X ² in the formula (4) 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, an alkoxy group having 1 to 20 carbon atoms, and carbon. It indicates an aryloxy group having a number of 6 to 20, 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 X ² include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, a cyclohexyloxycarbonyl group, and the like, and have 7 carbon atoms. Examples of the aryloxycarbonyl group to 20 include a phenoxycarbonyl group, a 4-methylphenoxycarbonyl group, a 2,4-dimethylphenoxycarbonyl group, a 4-ethylphenoxycarbonyl group and the like. 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 a 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. It is preferably an alkyloxycarbonyl group having 2 to 20 carbon atoms because of its high solubility and high heat resistance.

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

A bond consisting of a solid line and a dotted line indicates a single bond or a double bond, and is preferably a single bond because of 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, at least one of the group consisting of the polysulfones shown in the following polysulfones 1 to 5 can be mentioned.

(Here, the substituents R ⁷ to R ¹⁰ independently indicate an alkyl group having 1 to 20 carbon atoms, and s indicates an integer of 10 to 20,000. R ⁷ to R ¹⁰ are the same. It may or may not be different.)

The alkyl groups having 1 to 20 carbon atoms in the substituents R ⁷ to R ¹⁰ include, 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 and an octyl group. Examples thereof include a linear or branched alkyl group such as a nonyl group, a decyl group, a dodecyl group, a tetradecyl group, an octadecyl group, a 2-ethylhexyl group, a 3-ethylheptyl group, a 3-ethyldecyl group and a 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 the polymer binder in the present invention is a copolymer having an arbitrary ratio of acrylonitrile and styrene, exhibits good electrical properties, and changes in the threshold voltage when bias stress is applied. The weight ratio of acrylonitrile to styrene is preferably 10:90 to 50:50, and more preferably 20:80 to 40:60, because reliability is improved, such as becoming smaller.

The methylmethacrylate-styrene copolymer used as the polymer binder in the present invention is a copolymer having an arbitrary ratio of methylmethacrylate and styrene, exhibits good electrical characteristics, and changes in the threshold voltage when bias stress is applied. The molar ratio of methyl methacrylate to styrene is preferably 1:99 to 90:10, and more preferably 1:99 to 70:30, because reliability is improved such that the polymer becomes smaller.

As the polymer used as the polymer binder in the present invention, a polymer whose surface energy is adjusted by a surface treatment agent can be used. As the surface treatment agent, a silane coupling agent can be used, and specific examples thereof include 1,1,1,3,3,3-hexamethyldisilazane, phenyltrimethoxysilane, and octyltrichlorosilane. Examples thereof include β-phenyltilt trichlorosilane and β-phenetilt trimethoxysilane. The polymer binder used in the present invention can be used alone or as a mixture of two or more kinds of polymers. Furthermore, it is also possible to use a mixture of polymers having different molecular weights.

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

Hereinafter, an organic semiconductor layer using a solution for forming an organic semiconductor layer, which is one aspect of the present invention, will be described in detail.

The coating method for forming the organic semiconductor layer using the solution for forming the organic semiconductor layer of the present invention is not particularly limited as long as it is a method capable of forming the organic semiconductor layer, and is, for example, spin coat, drop cast, or dip. Simple coating methods such as coats and cast coats; printing methods such as dispensers, inkjets, slit coats, slot die coats, blade coats, flexo printing, screen printing, gravure printing, offset printing, etc. Since it can be used as a semiconductor layer, spin coat, drop cast, inkjet, and slot die coat are preferable.

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

When the solvent is dried and removed from the coated organic semiconductor layer, the drying conditions are not particularly limited, and for example, the solvent can be dried and removed under normal pressure or reduced pressure.

The temperature for drying and removing the organic solvent from the coated organic semiconductor layer is not particularly limited, but the organic solvent can be efficiently dried and removed from the coated organic semiconductor layer, and the organic semiconductor layer can be formed. The temperature range of 10 to 150 ° C. is preferable, and the temperature range of 10 to 140 ° C. is more preferable in consideration of the heat resistance of the plastic substrate.

When the organic solvent is dry-removed from the coated organic semiconductor layer, the vaporization rate of the organic solvent to be removed can be adjusted to promote the growth of the orientation of the conjugate polymer represented by the formula (1).

The film thickness of the organic semiconductor layer formed by the solution for forming an organic semiconductor layer of the present invention is not limited, and good carrier transfer can be obtained. Therefore, the range is preferably 1 nm to 1 μm, and the range is 10 nm to 300 nm. Is more preferable.

Further, the obtained organic semiconductor layer can be annealed at 40 to 200 ° C. after forming the organic semiconductor layer, but the temperature range of 40 to 140 ° C. is preferable in consideration of the heat resistance of the plastic substrate. 40 to 130 ° C. is more preferable.

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

Hereinafter, an organic thin film transistor including an organic semiconductor layer, which is one aspect of the present invention, will be described in detail.

The organic thin film can be obtained by laminating an organic semiconductor layer provided with a source electrode and a drain electrode on a substrate via an insulating layer, and is used for forming the organic semiconductor layer of the present invention on the organic semiconductor layer. By using an organic semiconductor layer formed by a solution, it is possible to obtain an organic thin film exhibiting excellent semiconductor and electrical characteristics.

FIG. 1 shows a structure of a general organic thin film transistor based on the cross-sectional shape. 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 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, which are formed from the organic semiconductor layer forming solution of the present invention. The organic semiconductor layer to be formed can be applied to any organic thin film transistor.

The substrate according to the present invention is not particularly limited, and for example, polyethylene terephthalate, polyethylene naphthalate, polymethylmethacrylate, polymethylacrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, fluorinated cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, etc. 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, high-doped silicon , Inorganic material substrates such as silicon oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide; metal substrates such as gold, copper, chromium, titanium and aluminum can be mentioned. When high-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 is, for example, aluminum, gold, silver, copper, high-doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, graphene, carbon nanotubes and the like. Inorganic materials; organic materials such as doped conductive polymers (eg PEDOT-PSS) can be mentioned.

Further, the above-mentioned inorganic material can be used without any problem as a metal nanoparticle ink. In this case, the solvent is a polar solvent such as water, methanol, ethanol, 2-propanol, 1-butanol, 2-butanol, etc. for appropriate dispersibility; carbon number of hexane, heptane, octane, decane, dodecane, tetradecane, etc. 6-14 aliphatic hydrocarbon solvents; toluene, xylene, mesitylene, ethylbenzene, pentylbenzene, hexylbenzene, octylbenzene, cyclohexylbenzene, tetraline, indan, anisole, 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, It is preferably 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 annealing treatment in a temperature range of 80 ° C. to 200 ° C. in order to improve conductivity.

The gate insulating layer according to the present invention is not particularly limited, and is, for example, silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide, and titanium. Inorganic materials such as barium acid acid, bismuth titanate; polymethylmethacrylate, polymethylacrylate, polyimide, polycarbonate polyamic acid, polyvinylphenol, polyvinyl alcohol, poly (diisopropylfumarate), poly (diethylfumarate), polyethylene terephthalate, polyethylene na Phtalate, ethyl polysilicate, methyl polysilicate, ethyl polycrotonate, polyethersulfone, polypropylene-co-1-butene, polyisobutylene, polypropylene, polycyclopentane, polycyclohexane, polycyclohexane-ethylene copolymer, Polyfluorinated cyclopentane, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene copolymer, BCB resin (trade name: cycloten, manufactured by Dow Chemical Co., Ltd.), Cytop (trademark), Polyimide (trademark), parylene C, etc. The polymer insulating material of Parylene (trademark) of the above can be mentioned, and since the production method is simple, the polymer insulating material (polymer gate insulating layer) to which the coating method can be applied is preferable.

The polymer gate insulating layer can also be used after photocrosslinking.

The solvent used for dissolving the polymer material is not particularly limited, and is, for example, an aliphatic hydrocarbon solvent having 6 to 14 carbon atoms such as hexane, heptane, octane, decane, dodecane, and tetradecane; mesitylene, p-simene, and pentyl. Aromatic hydrocarbon solvents with 9 to 20 carbon atoms such as benzene and cyclohexylbenzene; ether solvents such as THF, 1,2-dimethoxyethane and dioxane; ethanol, isopropyl alcohol, 1-butanol, 2-butanol, 2-ethyl Alcohol-based solvents such as hexanol and tetrahydrofurfuryl alcohol; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, diisopropyl ketone and acetophenone; ethyl acetate, γ-butyrolactone, cyclohexanol acetate, 3-methoxybutyl acetate, tetrahydrofurfuryl acetate , Tetrahydroflufuryl propionate and other ester solvents; DMF, NMP and other amide solvents; 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-hexanediol diacetate, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate , Glycol-based solvent such as diethylene glycol monobutyl ether acetate; fluorinated solvent such as perfluorohexane, perfluorooctane, 2- (pentafluoroethyl) hexane, 3- (pentafluoroethyl) heptane and the like.

The concentration of the polymer insulating material is, for example, 0.1 to 10.0% by weight at a temperature of 20 to 40 ° C. The film thickness of the insulating layer obtained at the concentration is not limited, and is preferably 100 nm to 1 μm, more preferably 150 nm to 900 nm from the viewpoint of insulation resistance.

The surface of these gate insulating layers is, for example, octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenetyltrichlorosilane, β-phenetyltrimethoxysilane, phenyltri. Silanes such as chlorosilane and phenyltrimethoxysilane; phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid and octylphosphonic acid; and silylamines such as hexamethyldisilazane can also be used. Generally, by surface-treating the gate insulating layer, it is preferable to improve the carrier mobility, the current on / off ratio, and the threshold voltage in order to increase the crystal grain size and the molecular orientation of the organic semiconductor material. The result is obtained.

The material of the source electrode and the 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, and the material may be the same as or different from that of the gate electrode, and different materials may be used. May be laminated. In addition, surface treatment can be applied to these electrode materials in order to increase the efficiency of carrier injection. Examples of the surface treatment agent used for the surface treatment include benzenethiol, pentafluorobenzenethiol, 4-fluorobenzenethiol, 4-methoxybenzenethiol and the like.

The organic thin film transistor of the present invention preferably has a carrier mobility of 0.10 cm ² / V · sec or more because of its high operability. Further, due to the high switch characteristics, the current on / off ratio is preferably 1.0 × ¹⁰⁵ or more.

The conjugated polymer of the present invention is used for organic semiconductor layers of organic thin films such as electronic papers, organic EL displays, liquid crystal displays, IC tags (RFID tags), pressure sensors, biosensors, etc .; organic thin film solar cells, thermoelectric conversion elements, etc. It can be used for semiconductor layer applications; organic EL display materials; organic semiconductor laser materials; photonic crystal materials; semiconductor materials for image pickup devices and the like.

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

¹ H NMR spectrum, gas chromatography-mass spectrum (GCMS), and liquid chromatography-mass spectrum (LCMS) analysis were used to identify the product.

< ^{1 1} H NMR spectrum analysis>
Equipment; manufactured by JEOL Ltd. (trade name) Delta V5 (400MHz)
Measurement temperature; 23 ° C (when no temperature is specified)
<Gas Chromatography-Mass Spectrum Analysis>
Equipment; manufactured by Shimadzu Corporation, (trade name) QP-2010 Ultra
Column: Made by Agilent, (trade name) DB-1, 30m.
MS ionization; electron impact (EI) method (70 electron volt)
<Directly introduced mass spectrum analysis>
Equipment; manufactured by Shimadzu Corporation, (trade name) QP-2010 Ultra
MS ionization; electron impact (EI) method (70 electron volt)
<Liquid Chromatography-Mass Spectrum (LCMS) Analysis>
Equipment; Bruker Daltonics, (trade name) microTOF focus
MS ionization; Atmospheric chemical ionization (APCI) method LC conditions; Conditions described in the following items of liquid chromatography analysis.

Thin layer chromatography, gas chromatography (GC), and liquid chromatography (LC) analysis were used to confirm the progress of the reaction. The purity of the biphenylene derivative was also measured using liquid chromatography analysis.

<Thin layer chromatography analysis>
Merck's thin layer chromatography PLC silica gel 60F254 0.5 mm was used, and hexane and / and toluene, ethyl acetate and toluene were used as the developing solvent.
<Gas chromatography analysis>
Equipment; manufactured by Shimadzu Corporation, (trade name) GC2014
Column; manufactured by RESTEK, (trade name) Rxi-1HT, 30 m
<Liquid chromatography analysis>
Equipment; manufactured by Tosoh (controller: PX-8020, pump; CCPM-II, degasser; SD-8022)
Column; manufactured by Tosoh, (trade name) ODS-100V, 5 μm, 4.6 mm x 250 mm
Column temperature; 33 ° C
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 was used for the molecular weight measurement of the conjugated polymer.

<High temperature GPC analysis>
Equipment; Tosoh HLC-8321GPC / HT
Column; TSK gel GMHHR-H (20) HT manufactured by Tosoh, 7.8 mm × 300 mm, 3 columns temperature; 140 ° C.
Eluent; 1,2,4-trichlorobenzene flow rate; 1.0 ml / min Detector; RI

DSC (Differential Scanning Calorimetry) was used to measure the melting point of the conjugated polymer.

<DSC measurement>
Equipment: SII Nanotechnology, Inc., model: DSC6220
Elevating temperature rate; 10 ° C / min
Scanning range; -10 ° C to 300 ° C

Synthesis Example 1 (Synthesis of 2,2'-dibromo-4,5'-dichlorobiphenyl) (A1 step)
Under a nitrogen atmosphere, 1.29 g (4.06 mmol) of 2-bromo-4-chloro-1-iodobenzene (Tokyo Chemical Industry) and 11 ml of THF (dehydration grade) were added to a 50 ml Schlenk reaction vessel. This solution was cooled to 0 ° C., and 2.1 ml (4.2 mmol) of a THF solution of ethyl magnesium chloride (Sigma-Aldrich, 2.0 M) was added dropwise. The mixture was aged at 0 ° C. for 15 minutes to prepare 2-bromo-4-chlorophenyl-1-magnesium chloride.
On the other hand, 724 mg (5.31 mmol) of zinc chloride (Wako Pure Chemical Industries, Ltd.) and 6 ml of THF (dehydration grade) were added to a 100 ml Schlenk reaction vessel under a nitrogen atmosphere, and the mixture was cooled to 0 ° C. The previously prepared 2-bromo-4-chlorophenyl-1-magnesium chloride solution was added dropwise to the obtained white microslurry solution using a Teflon (registered trademark) cannula, and 1 ml of THF (dehydration grade) was used. The 50 ml Schlenk reaction vessel and Teflon® canula were added while washing. The obtained mixture was stirred while gradually raising the temperature to room temperature. To the generated 2-bromo-4-chlorophenyl-1-zinc chloride slurry solution, 1.00 g (3.14 mmol) of 1-bromo-4-chloro-2-iodobenzene (Combi-Blocks) and tetrakis (tri) as a catalyst. Palladium (phenylphosphine) palladium (Tokyo Chemical Industry) 29.0 mg (0.0251 mmol, 0.80 mol% based on 1-bromo-4-chloro-2-iodobenzene) was added. After carrying out the reaction at 50 ° C. for 8 hours, the container was cooled with water and 1M hydrochloric acid was added to stop the reaction. Toluene and saline were added, the organic phase was split, the organic phase was washed with saline and dried over anhydrous sodium sulfate. The residue was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (solvent: hexane). 1.10 g of 2,2'-dibromo-4,5'-dichlorobiphenyl was obtained (yield 92%).
MS m / z: 382 (M ^{+ + 2} , 57%), 380 (M ⁺ , 100%), 378 (M ⁺ -2, 54).
^{1 1} H NMR (CDCl ₃ ): δ = 7.69 (d, J = 2.2 Hz, 1H), 7.59 (d, J = 8.6 Hz, 1H), 7.37 (dd, J = 8. 2Hz, 2.2Hz, 1H), 7.25 (dd, J = 8.2Hz, 2.4Hz, 1H), 7.21 (d, J = 2.6Hz, 1H), 7.16 (d, J) = 8.2Hz, 1H).

Synthesis Example 2 (Synthesis of 2,6-dichlorobiphenylene) (B1 step)
Under a nitrogen atmosphere, 1.09 g (2.86 mmol) of 2,2'-dibromo-4,5'-dichlorobiphenyl synthesized in Synthesis Example 1 and 38 ml of THF (dehydration grade) were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to −78 ° C., and 3.8 ml (6.0 mmol) of a hexane solution of butyllithium (Tokyo Chemical Industry, 1.6 M) was added dropwise. The mixture was aged at −78 ° C. for 1 hour. To this, 1.15 g (8.55 mmol) of copper (II) chloride (Wako Pure Chemical Industries, Ltd.) was added at −78 ° C. The obtained mixture was stirred while gradually raising the temperature to room temperature. After adding 3M hydrochloric acid to the reaction mixture, toluene was added and the phase was separated. The organic phase was washed with 3M hydrochloric acid and brine and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure, and the obtained residue was purified by silica gel column chromatography (solvent; hexane). 411 mg of a pale yellow solid of 2,6-dichlorobiphenylene was obtained (yield 65%).
MS m / z: 220 (M ⁺ , 100%).
^{1 1} H NMR (CDCl ₃ ): δ = 6.76 (dd, J = 7.4Hz, 1.8Hz, 2H), 6.64 (d, J = 1.8, 2H), 6.57 (dd, dd, J = 7.3, 2H).

Synthesis Example 3 (Synthesis of 3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] thiophene)
Under a nitrogen atmosphere, 2.24 g (7.52 mmol) of 3,6-dibromothieno [3,2-b] thiophene (Fuji Film Wako Pure Chemical Industries, Ltd.) and 37 ml of diethyl ether (dehydration grade) were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to −78 ° C., and 4.6 ml (7.4 mmol) of a hexane solution of butyllithium (Tokyo Chemical Industry, 1.6 M) was added dropwise. The mixture was aged at −78 ° C. for 30 minutes. To this, 1.0 ml of methanol was added at −78 ° C. to quench the reaction. The obtained mixture was heated to room temperature, water was added, and toluene was extracted. The organic phase was washed with water and dried over anhydrous sodium sulfate. The organic phase was concentrated under reduced pressure to give 1.65 g of oil. From GC analysis, the purity of 3-bromothieno [3,2-b] thiophene was 90%.
^{1 1} H NMR (CDCl ₃ ): δ = 7.44 (dd, J = 5.1Hz, 1.7Hz, 1H), 7.30 (d, J = 5.4Hz, 1H), 7.28 (d, J = 1.7Hz, 1H).
Under a nitrogen atmosphere, 1.83 g (8.35 mmol) of 3-bromothieno [3,2-b] thiophene synthesized above and 26 ml of diethyl ether (dehydration grade) were added to a 200 ml Schlenk reaction vessel. The mixture was cooled to −78 ° C., and 5.2 ml (8.3 mmol) of a hexane solution of butyllithium (Tokyo Chemical Industry, 1.6 M) was added dropwise. After aging this mixture at −78 ° C. for 2 hours, 4.13 g (8.14 mmol) of 18-pentatria contanone (Tokyo Chemical Industry) was added at −78 ° C. After gradually raising the temperature to room temperature, water was added and quenched. It was acidified with 3M hydrochloric acid and extracted with toluene. 1.0 ml of methanol was added and the reaction was quenched. The obtained mixture was heated to room temperature, water was added, and toluene was extracted. The organic phase was washed with water and concentrated under reduced pressure to obtain 4.75 g of a reddish brown solid.
Under a plain atmosphere, 4.75 g of concentrate, 20 ml of ethanol, 7 ml of hexane and 0.70 ml of sulfuric acid were added to a 200 ml Schlenk reaction vessel. The mixture was stirred at room temperature for 4 days, water was added and quenched. Toluene was extracted, the organic phase was washed with water, and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent: hexane → hexane / toluene = 10/1), and 3- (1-ethoxy-1-heptadecyloctadecyl) thieno [3,2-b] thiophene oil. 1.15 g was obtained.
Under a nitrogen atmosphere, 351 mg (0.520 mmol) of 3- (1-ethoxy-1-heptadecyloctadecyl) thieno [3,2-b] thiophene and 15 ml of diTHF (dehydration grade) were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to −55 ° C., and 0.46 ml (0.74 mmol) of a hexane solution of butyllithium (Tokyo Chemical Industry, 1.6 M) was added dropwise. The mixture was aged at −57 ° C. to −45 ° C. for 1.5 hours, and then 84 mg (0.77 mmol) of trimethylsilyl chloride (Fuji Film Wako Pure Chemical Industries, Ltd.) was added at −45 ° C. The obtained mixture was gradually heated to room temperature, water was added, and hexane was extracted. The organic phase was washed with water and dried over anhydrous sodium sulfate. After concentration under reduced pressure, 343 mg of yellow oil of 3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] thiophene was obtained.
^{1 1} H NMR (CDCl ₃ ): δ = 7.31 (s, 1H), 7.05 (s, 1H), 3.17 (q, J = 6.9Hz, 2H), 1.91 (m, 4H) ), 1.19 (m, 63H), 0.88 (t, J = 6.7Hz, 6H), 0.36 (s, 9H).

Synthesis Example 4 (Synthesis of 2,6-bis {3- (1-ethoxy-1-heptadecyl octadecyl) -5-trimethylsilylthioeno [3,2-b] thiophen-2-yl} biphenylene) (Step C1)
3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] thiophene 797 mg (1.06 mmol) and THF synthesized in Synthesis Example 3 in a 100 ml Schlenk reaction vessel under a nitrogen atmosphere. 20 ml (dehydrated grade) was added. This solution was cooled to −55 ° C., and 0.92 ml (1.5 mmol) of a hexane solution of butyllithium (Tokyo Chemical Industry, 1.6 M) was added dropwise. The mixture was stirred at −55 ° C. to −45 ° C. for 50 minutes to prepare 3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] thiophen-2-yllithium. ..
On the other hand, under a nitrogen atmosphere, 272 mg (1.99 mmol) of zinc chloride (Wako Pure Chemical Industries, Ltd.) and 6 ml of THF (dehydration grade) were added to a 100 ml Schlenk reaction vessel, and the mixture was cooled to −45 ° C. In the obtained white microslurry solution, a previously prepared 3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] thiophen-2-yllithium solution was added to Teflon (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilyltieno [3,2-b]. The solution was added dropwise using a cannula (registered trademark), and a 100 ml Schlenk reaction vessel and a Teflon (registered trademark) canula were added while washing with 2 ml of THF (dehydration grade). The resulting mixture was stirred with a gradual warming to room temperature and a slurry of 3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] thiophen-2-ylzinc chloride. The liquid was prepared. Here, 60.0 mg (0.271 mmol) of 2,6-dichlorobiphenylene synthesized in Synthesis Example 2, 6.7 mg (0.0146 mmol, 2,6 as Pd) of tris (dibenzylideneacetone) dipalladium (Tokyo Chemical Industry) -5.4 mol% relative to dichlorobiphenylene), dicyclohexyl (2', 4', 6'-triisopropyl- [1,1'-biphenyl] -2-yl) phosphine (Tokyo Chemical Industry) 14.1 mg (0) .0295 mmol) and 2.5 ml of THF (dehydrated grade) were added and the reaction was carried out at 65 ° C. for 48 hours. The reaction was stopped by cooling the container with water and adding water. Toluene and saline were added, the organic phase was separated, the organic phase was washed with water and dried over anhydrous sodium sulfate. Concentrate under reduced pressure, and the obtained residue is purified by silica gel column chromatography (solvent: hexane → hexane / toluene = 20/1), 2,6-bis {3- (1-ethoxy-1-heptadecyl octadecyl)-. 91.5 mg of a yellow solid of 5-trimethylsilylthioeno [3,2-b] thiophen-2-yl} biphenylene was obtained (yield 21%).
^{1 1} H NMR (CDCl ₃ ): δ = 7.25 (s, 2H), 6.79 (d, J = 8.1Hz, 2H), 6.69 (s, 2H), 6.63 (d, J) = 7.2Hz, 2H), 3.30 (q, J = 6.9Hz, 4H), 1.90 to 1.78 (m, 4H), 1.77 to 1.67 (m, 4H), 1 .24 (m, 132H), 0.88 (t, J = 6.6Hz, 6H), 0.36 (s, 18H).

Example 1 (Synthesis of B-1-H) (Step D1)
2,6-Bis {3- (1-ethoxy-1-heptadecyloctadecyl) -5-trimethylsilylthioeno [3,2-b] thiophene-2 synthesized in Synthesis Example 4 in a 100 ml Schlenk reaction vessel under a nitrogen atmosphere. -Il} Biphenylene 91.5 mg (0.0556 mmol) and dichloromethane (dehydrated grade) 4 ml were added. After cooling this mixture to −78 ° C., 0.42 ml (0.42 mmol) of a dichloromethane solution of boron tribromide (Tokyo Chemical Industry, 1.0 M) was added dropwise. The resulting mixture was heated to −20 ° C., water was added for quenching, and the mixture was extracted with hexane. The organic phase was washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was purified by silica gel column chromatography (solvent; hexane) to obtain 63.6 mg of a yellow solid of B-1-H (yield 81%).
^{1 1} H NMR (CDCl ₃ ): δ = 7.30 (s, 4H), 6.71 (s, 2H), 6.65 (s, 2H), 2.01 (m, 4H), 1.88 ( m, 4H), 1.24 (m, 120H), 0.87 (t, J = 6.8Hz, 12H).

Example 2 (Synthesis of B-1-SnMe3) (Step E1)
Under a nitrogen atmosphere, 51.7 mg (0.0367 mmol) of B-1-H synthesized in Example 1 and 4 ml of THF (dehydration grade) were added to a 100 ml Schlenk reaction vessel. The mixture was cooled to −78 ° C., and 0.20 ml (0.32 mmol) of a hexane solution of butyllithium (Tokyo Chemical Industry, 1.6 M) was added dropwise. This dilithiation reaction was aged at −78 ° C. for 15 minutes and at room temperature for 20 minutes. The dilithiation reaction product was cooled to −78 ° C. again, and 62.0 mg (0.311 mol) of trimethyltin chloride (Tokyo Chemical Industry) was added. The obtained mixture was heated to room temperature, water and hexane were added, and the phase was separated. The organic phase was washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The obtained residue was washed with 1 ml of ethanol. The residue was vacuum dried to give 62.8 mg of red oil of B-1- _SnMe3 (yield 98%).
^{1 1} H NMR (CDCl ₃ ): δ = 7.33 (s, 2H), 6.70 (s, 2H), 6.63 (s, 2H), 2.00 (m, 4H), 1.87 ( m, 4H), 1.22 (m, 120H), 0.87 (t, J = 6.7Hz, 12H), 0.43 (s, 18H).

Example 3 (Synthesis of conjugated polymer (Compound 1))
Tris (dibenzylideneacetone) dipalladium (Tokyo Chemical Industry) 4.3 mg (0.00939 mmol as Pd), tri-o-tolylphosphine (Tokyo Chemical Industry) 5.8 mg (0) in a 50 ml Schlenk reaction vessel under a nitrogen atmosphere. 0.0190 mmol) and 5 ml of chlorobenzene (dehydrated grade) were added. The solution of this catalyst mixture was stirred at room temperature for 1 hour.
B-1-SnMe ₃ 62.0 mg (0.0357 mmol), 4,7-dibromo-2,1,3-benzothiadiazole synthesized in Example 2 in a 100 ml Schlenk reaction vessel under a nitrogen atmosphere (Tokyo Kasei Kogyo). 10.3 mg (0.0350 mmol), 4 ml of chlorobenzene (dehydrated grade), and 0.75 ml of the above catalyst mixture solution (0.0014 mmol as Pd, 3.9 mol%) were added. The mixture was stirred at 120 ° C. for 48 hours. The obtained reaction mixture was cooled to room temperature and poured into a mixed solution of 35 ml of methanol and 2 ml of hydrochloric acid. The produced slurry liquid was filtered, and the obtained solid was extracted by Soxhlet. Extraction was performed with methanol, hexane and chloroform, and the chloroform extract component was reprecipitated twice from methanol to obtain 41.3 mg of a blue-green solid of Compound 1 (yield 77%).
From GPC, Mw = 36,000, Mn = 19,000, and PDI = 1.9.

Example 4 (Preparation of a solution for forming an organic semiconductor layer)
To a 10 ml sample tube under a nitrogen atmosphere, 10 mg of the conjugate polymer (Compound 1) synthesized in Example 3 and 1240 mg of 1,2-dichlorobenzene (sigma-Aldrich, dehydration grade) were added, and the mixture was heated and dissolved at 50 ° C. and then dissolved. The solution was allowed to cool at room temperature (25 ° C.) to prepare a solution for forming an organic semiconductor layer. The solution state was maintained even after 10 hours at 25 ° C. (concentration of compound 1 was 0.80% by weight), and it was confirmed that the compound was suitable for film formation by spin coating and inkjet.

Example 5 (Preparation of Organic Semiconductor Layer and Organic Thin Film Transistor)
Using the solution for forming an organic semiconductor layer obtained in Example 4, a top gate-bottom contact type (D) p-type organic thin film transistor was produced. Table 1 shows the materials and film forming methods of each component. The film thickness of the thin film of the conjugated polymer (Compound 1) was 37 nm.

The electrical properties of the produced organic thin film transistor are transmitted by scanning the gate voltage (Vg) from +10 to -50V in 0.5V increments with a drain voltage (Vd = -50V) using a semiconductor parameter analyzer (Keithley 4200SCS). The characteristics were evaluated.
As a result, the carrier mobility of holes was 0.26 cm ² / ^V · sec, and the current on / off ratio was 4.0 × 105.

Example 6 (Preparation of Organic Semiconductor Layer and Organic Thin Film Transistor)
In Example 5, the obtained thin film of the conjugated polymer was annealed at 130 ° C. for 15 minutes, and the same operation as in Example 5 was carried out to prepare an organic thin film transistor. From the transfer characteristics of the obtained organic thin film transistor, the hole carrier mobility is 0.38 cm ² / V · sec, the current on / off ratio is 1.7 × ¹⁰⁶ , and the performance is improved by thermal annealing at 130 ° C. It was observed.

Comparative Example 1
(Preparation of solution for forming organic semiconductor layer)
Using poly {2,5-bis (3-tetradecylthiophene-2-yl) thieno [3,2-b] thiophene} (sigma-Aldrich) in a 10 ml sample tube under a nitrogen atmosphere, the same as in Example 4. A solution for forming an organic semiconductor layer was prepared by the above method (0.80% by weight). After 10 hours at 25 ° C., it was in a gel state, which was not suitable for film formation by drop casting and inkjet.
(Manufacturing of organic semiconductor layer and organic thin film transistor)
Using the organic semiconductor layer forming solution in the state of being heated and dissolved at 50 ° C., a poly {2,5-bis (3-tetradecylthienyl-2-) having a film thickness of 41 nm was used in the same manner as in Example 5. ) A thin film of thieno [3,2-b] thiophene} was prepared, and a top gate-bottom contact type p-type organic thin film transistor was prepared.
As a result of evaluating the transmission characteristics of the transistor element, the carrier mobility of holes was 0.068 cm ² / V · sec, and the current ^on / off ratio was 1.0 × 104.

Comparative Example 2
In Comparative Example 1, an organic thin film transistor was produced by performing the same operation as in Comparative Example 1 except that the obtained thin film of the conjugated polymer was annealed at 130 ° C. for 15 minutes. From the transfer characteristics of the obtained organic thin film transistor, the hole carrier mobility was 0.066 cm ² / V · sec and the current ^on / off ratio was 1.0 × 104, and no improvement was observed.

Since the conjugated polymer of the present invention provides high carrier mobility, has excellent solubility, and can be thermally annealed at a mild temperature of 140 ° C. or lower, it can be used as an organic thin film semiconductor device material represented by an organic thin film transistor having a plastic substrate. 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 (6)

A conjugated polymer represented by the following formula (1).

[(Here, A, C, and E are at least 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, respectively. Indicates a divalent linking group containing a ring of. A, C and E may be the same or different, respectively.
B represents a cyclopentabiphenylene structure represented by one of the groups consisting of the following formulas (B-1) to (B-18).
D represents a divalent linking group of a condensed 2 ring to a condensed 7 ring containing at least one of a group consisting of a sulfur atom, an oxygen atom, a selenium atom, or a nitrogen atom in a ring-constituting atom.
b indicates 1 to 3, a, c, d, and e indicate 0 to 3, respectively, and at least one of a, c, d, and e is 1 or more. n represents an integer of 2 or more. )

(Here, R is at least one of a group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryl group having 4 to 30 carbon atoms, respectively. Species are indicated. * Indicates a binding site with other structures.)] The conjugate polymer according to claim 1, wherein D is a linking group represented by one of the groups consisting of the following formulas (D-1) to (D to 71).

(Here, R ³ is at least a group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryl group having 4 to 30 carbon atoms, respectively. 1 type is indicated. * Indicates a binding site with another structure.) A solution for forming an organic semiconductor layer containing the conjugate polymer according to claim 1 or 2. An organic semiconductor layer using the solution for forming an organic semiconductor layer according to claim 3. An organic thin film transistor comprising the organic semiconductor layer according to claim 4. A cyclopentabiphenylene compound represented by one of the groups consisting of the following formulas (B'-1) to (B'-18).

(Here, R is independent of each other and is at least one of a group consisting of a hydrogen atom, a halogen atom, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an aryl group having 4 to 30 carbon atoms. Each of X is independent and represents at least one of a group consisting of a hydrogen atom, a halogen atom, a trialkyltin, a dialkoxyboron, a dihydroxyboron, or an alkyl group having 1 to 30 carbon atoms.)

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