JP7788883B2 - Conjugated polymer, film-forming composition, organic thin film, organic semiconductor device, and method for producing conjugated polymer - Google Patents

Description

The present invention relates to a conjugated polymer containing, as a structural unit, an oligoheteroacene having a chalcogenochalcogenophene skeleton, a method for producing the same, a film-forming composition, an organic thin film, and an organic semiconductor device.

Conjugated compounds are well known as organic semiconductors used in organic thin-film solar cells, organic thin-film transistors, organic electroluminescence (EL), and other applications. Conjugated compounds have characteristics not found in inorganic compounds, such as energy conservation, low cost, organic solvent solubility, light weight, and flexibility, and can also be used as coating materials for printed electronics (Patent Document 1).

Conjugated compounds such as oligoacenes, such as pentacene, disclosed in Non-Patent Document 1, and oligoacenes having a thiophene skeleton, a thienothiophene skeleton, or the like (hereinafter referred to as oligoheteroacenes), disclosed in Non-Patent Document 2, are being studied for their application to organic thin-film transistors. Among these, oligoheteroacenes having a thienothiophene skeleton tend to exhibit high carrier mobility.

Japanese Patent Application Laid-Open No. 2017-59668

Polymer Journal, Vol. 49, pp. 23-30, 2017 Chemical Reviews, Vol. 115, pp. 3036-3140, 2015 Tetrahedron Letters, Vol. 55, pp. 5663-5666, 2014

However, oligoheteroacenes have been shown to have problems such as low solubility and low stability in the atmosphere (Non-Patent Document 3), which has led to the need for the development of new conjugated compounds.
In order to solve the above problems, the present invention aims to provide a new conjugated polymer that has high carrier mobility, high heat resistance, high atmospheric stability, and high solubility, a method for producing the polymer, a film-forming composition containing the polymer, an organic thin film containing the polymer, and a semiconductor device and an organic thin film transistor device each containing the polymer.

To solve the above problems, the inventors conducted extensive research and discovered that conjugated polymers containing a 5,5,10,10-tetraalkyl-5,10-dihydrochalcogeno[2",3":4",5']chalcogeno[2',3':4,5]pentaleno[1,2-b]chalcogeno[2,3-d]chalcogenophene skeleton as a structural unit exhibit high solubility, high heat resistance, high atmospheric stability, and excellent film-forming properties. Conjugated polymers containing this structural unit are novel, and no method for producing them has been reported. Furthermore, there have been no reports on the physical properties of conjugated polymers containing this structural unit, such as solubility and heat resistance, or their carrier mobility. Furthermore, the inventors also discovered that organic thin films can be easily formed using a film-forming composition containing this conjugated polymer, and that organic thin-film transistor devices fabricated using this organic thin film operate stably, leading to the completion of the present invention.

That is, the present invention comprises the following gist.
[Summary 1]
A structural unit represented by the following general formula (1),

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may be combined together to form a ring with the carbon atom to which they are bonded. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may be combined together to form a ring with the carbon atom to which they are bonded. ^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom.)
A conjugated polymer comprising a structural unit represented by the following general formula (2):

(wherein ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms).
Regarding the aspect 1, the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) may be alternately arranged.
In Summary 1, ^R1 and ^R2 are each independently an alkyl group having 1 to 34 carbon atoms, and ^R1 and ^R2 may be joined together to form a ring with the carbon atom to which they are attached; ^R3 and ^R4 are each independently an alkyl group having 1 to 34 carbon atoms, and ^R3 and ^R4 may be joined together to form a ring with the carbon atom to which they are attached; ^R5 and ^R6 are each independently a hydrogen atom, an alkyl group having 1 to 34 carbon atoms, or a fluorine atom; and ^J1 , ^J2 , ^J3 , and ^J4 may each independently be an oxygen atom, a sulfur atom, or a selenium atom.
Regarding Aspect 1, R ⁵ and R ⁶ may be hydrogen atoms, and J ¹ , J ² , J ³ and J ⁴ may be sulfur atoms.
In the above aspect 1, X ¹ may be a divalent heteroaromatic ring linking group selected from the group consisting of general formulae (4) to (8) described later.
In Summary 1, A ¹ , A ² , A ³ , A ⁴ and A ⁵ each independently represent an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom which may be substituted with an alkyl group having 6 to 50 carbon atoms; R ⁷ is a group selected from the group consisting of an alkoxy group having 6 to 50 carbon atoms, a fluorine atom or a hydrogen atom; R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an alkyl group having 6 to 50 carbon atoms or a hydrogen atom; and R ¹² and R ¹³ each independently represent an alkyl group having 6 to 50 carbon atoms.
In Summary 1, ^A1 and ^A2 are sulfur atoms, ^A3 is an oxygen atom or a nitrogen atom which may be substituted with an alkyl group having 6 to 34 carbon atoms, ^A4 is an oxygen atom, a sulfur atom, or a selenium atom, ^A5 is an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom which may be substituted with an alkyl group having 6 to 34 carbon atoms, ^R7 is a group selected from the group consisting of an alkoxy group having 6 to 34 carbon atoms, a fluorine atom, or a hydrogen atom, ^R8 , ^R9 , ^R10 , and ^R11 are each independently an alkyl group having 6 to 34 carbon atoms or a hydrogen atom, and ^R12 and ^R13 may each independently be an alkyl group having 6 to 34 carbon atoms.
[Summary 2]
A monomer represented by the following general formula (mono-hal):

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may be combined together to form a ring with the carbon atom to which they are bonded. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may be combined together to form a ring with the carbon atom to which they are bonded. ^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-hal and M2 ^-hal each independently represent a halogen atom.)
A monomer represented by the following general formula (mono-X ¹ -B) is reacted in the presence of a transition metal catalyst:

(In the formula, ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms. ^M3-B and M4 ^-B each independently represent a boron-containing group.)
A structural unit represented by the following general formula (1),

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ and J ⁴ have the same meanings as defined above.)
and a structural unit represented by the following general formula (2):

(In the formula, ^X1 has the same meaning as above.)
[Summary 3]
A monomer represented by the following general formula (mono-hal):

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may be combined together to form a ring with the carbon atom to which they are bonded. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may be combined together to form a ring with the carbon atom to which they are bonded. ^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-hal and M2 ^-hal each independently represent a halogen atom.)
A monomer represented by the following general formula (mono-X ¹ -Sn) is reacted in the presence of a transition metal catalyst:

(In the formula, ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms. ^M3-Sn and M4 ^-Sn each independently represent a tin-containing group.)
A structural unit represented by the following general formula (1),

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ and J ⁴ have the same meanings as defined above.)
and a structural unit represented by the following general formula (2):

(In the formula, ^X1 has the same meaning as above.)
[Summary 4]
A monomer represented by the following general formula (mono-B):

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may be combined together to form a ring with the carbon atom to which they are bonded. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may be combined together to form a ring with the carbon atom to which they are bonded. ^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-B and M2 ^-B each independently represent a boron-containing group.)
A monomer represented by the following general formula (mono-X ¹ -hal) is reacted in the presence of a transition metal catalyst:

(In the formula, ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms; ^M3-hal and M4 ^-hal each independently represent a halogen atom.)
A structural unit represented by the following general formula (1),

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ and J ⁴ have the same meanings as defined above.)
and a structural unit represented by the following general formula (2):

(In the formula, ^X1 has the same meaning as above.)
[Summary 5]
A monomer represented by the following general formula (mono-Sn):

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may be combined together to form a ring with the carbon atom to which they are bonded. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may be combined together to form a ring with the carbon atom to which they are bonded. ^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-Sn and M2 ^-Sn each independently represent a tin-containing group.)
A monomer represented by the following general formula (mono-X ¹ -hal) is reacted in the presence of a transition metal catalyst:

(In the formula, ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms; ^M3-hal and M4 ^-hal each independently represent a halogen atom.)
A structural unit represented by the following general formula (1),

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ and J ⁴ have the same meanings as defined above.)
and a structural unit represented by the following general formula (2):

(In the formula, ^X1 has the same meaning as above.)
[Summary 6]
A film-forming composition comprising the conjugated polymer according to aspect 1.
[Summary 7]
10. An organic thin film comprising the conjugated polymer according to claim 1.
[Abstract 8]
10. An organic semiconductor device comprising the conjugated polymer according to claim 1.
[Abstract 9]
10. An organic transistor device comprising the conjugated polymer according to claim 1.

The conjugated polymer of the present invention is an organic semiconductor that combines high carrier mobility, high heat resistance, high atmospheric stability, and high solubility, and can efficiently drive organic thin-film transistor elements that use this as the active layer.

1A and 1B are diagrams showing the cross-sectional structure of an organic thin film transistor element.

The following describes in detail the embodiments of the present invention. However, the present invention is not limited to these, and various modifications are possible within the scope described. The technical scope of the present invention also includes embodiments obtained by appropriately combining the technical means disclosed in different embodiments. In this specification, unless otherwise specified, "A to B" representing a numerical range means "greater than or equal to A and less than or equal to B."

[Conjugated polymers]
A conjugated polymer according to one embodiment of the present invention (sometimes referred to herein as the "conjugated polymer of the present embodiment") is composed of a structural unit represented by general formula (1) and a structural unit represented by general formula (2).

(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may be combined together to form a ring with the carbon atom to which they are bonded. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may be combined together to form a ring with the carbon atom to which they are bonded. ^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom.)

(wherein ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms).

(Structural unit represented by general formula (1))
R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R The alkyl group having 1 to 50 carbon atoms, represented by ^6, may be linear, branched, or cyclic, and examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, icosyl, henicosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, hentriacontyl, dodoriacontyl, tritriacontyl, tetratriacontyl, pentatriacontyl, hexatriacontyl, tetracontyl, and hentetracosyl. Examples of such alkyl groups include linear alkyl groups such as ethyl, dotetracontyl, tritetracontyl, tetratetracontyl, and pentacontyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, 3,7-dimethyloctyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldodecyl, 2-decyltetradecyl, 2-dodecyltetradecyl, 2-dodecylhexadecyl, 2-tetradecylhexadecyl, 3-decylpentadecyl, 3-dodecylheptadecyl, 3-tetradecylnonacosyl, 4-decylhexadecyl, 4-dodecyloctadecyl, and 4-tetradecylicosyl; and cyclic alkyl groups such as cyclopentyl and cyclohexyl.

The alkyl group represented by R ¹ , R ² , R ³ and R ⁴ is preferably an alkyl group having 6 to 50 carbon atoms, more preferably an alkyl group having 1 to 34 carbon atoms, still more preferably an alkyl group having 6 to 34 carbon atoms, in terms of increasing the solubility of the conjugated polymer of this embodiment, and is preferably 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, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, a hentriacontyl group, a dodoriacontyl group, a tritriacontyl group, or a tetratriacontyl group. More preferred are a pentatriacontyl group, a hexatriacontyl group, a tetracontyl group, a hentetracontyl group, a dotetracontyl group, a tritetracontyl group, a tetratetracontyl group, a pentacontyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-hexyloctyl group, a 2-hexyldecyl group, a 2-octyldodecyl group, a 2-decyltetradecyl group, a 2-dodecyltetradecyl group, a 2-dodecylhexadecyl group, a 2-tetradecylhexadecyl group, a 3-decylpentadecyl group, a 3-dodecylheptadecyl group, a 3-tetradecylnonacosyl group, a 4-decylhexadecyl group, a 4-dodecyloctadecyl group, or a 4-tetradecylicosyl group, and a hexyl group or a decyl group is particularly preferred.

^R1 and ^R2 may combine together to form a ring with the carbon atoms to which they are bonded. Examples of such a ring include a cyclopropane-1,1-diyl group, a cyclobutane-1,1-diyl group, a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, a cycloheptane-1,1-diyl group, a cyclooctane-1,1-diyl group, an indene-1,1-diyl group, or a fluorene-9,9-diyl group. In terms of increasing the solubility of the conjugated polymer of this embodiment, the ring is preferably a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, an indene-1,1-diyl group, or a fluorene-9,9-diyl group, and more preferably a cyclohexane-1,1-diyl group or a fluorene-9,9-diyl group. ^R3 and ^R4 may combine together to form a ring with the carbon atoms to which they are bonded. Examples of the ring include a cyclopropane-1,1-diyl group, a cyclobutane-1,1-diyl group, a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, a cycloheptane-1,1-diyl group, a cyclooctane-1,1-diyl group, an indene-1,1-diyl group, or a fluorene-9,9-diyl group. In terms of increasing the solubility of the conjugated polymer of this embodiment, the ring is preferably a cyclopentane-1,1-diyl group, a cyclohexane-1,1-diyl group, an indene-1,1-diyl group, or a fluorene-9,9-diyl group, and more preferably a cyclohexane-1,1-diyl group or a fluorene-9,9-diyl group.

^R5 and ^R6 are preferably a hydrogen atom, a fluorine atom, or an alkyl group having 6 to 50 carbon atoms, more preferably a hydrogen atom, a fluorine atom, or an alkyl group having 6 to 34 carbon atoms, in that the carrier mobility of the conjugated polymer of this embodiment is increased, and are preferably a hydrogen atom, a fluorine atom, 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, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, a hentriacontyl group, a dodoriacontyl group, or a tritriacontyl group. More preferred are a tetratriacontyl group, a pentatriacontyl group, a hexatriacontyl group, a tetracontyl group, a hentetracontyl group, a dotetracontyl group, a tritetracontyl group, a tetratetracontyl group, a pentacontyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-hexyloctyl group, a 2-hexyldecyl group, a 2-octyldodecyl group, a 2-decyltetradecyl group, a 2-dodecyltetradecyl group, a 2-dodecylhexadecyl group, a 2-tetradecylhexadecyl group, a 3-decylpentadecyl group, a 3-dodecylheptadecyl group, a 3-tetradecylnonacosyl group, a 4-decylhexadecyl group, a 4-dodecyloctadecyl group, or a 4-tetradecylicosyl group. Among these, it is particularly preferable that ^R5 and ^R6 are hydrogen atoms or fluorine atoms, since this will further increase the carrier mobility of the conjugated polymer of this embodiment.

As the chalcogen atoms represented by J ¹ , J ² , J ³ and J ⁴ , an oxygen atom, a sulfur atom and a selenium atom are preferred, an oxygen atom and a sulfur atom are more preferred, and a sulfur atom is even more preferred, in terms of increasing the solubility of the conjugated polymer of this embodiment.

Specific examples of structural units represented by general formula (1) include structural units represented by the following formulas (1-1) to (1-20), which have high film-forming properties and carrier mobility.

In the formulas (1-1) to (1-20), the alkyl group represented by C _n H _(2n+1) is a linear alkyl group having n carbon atoms. In terms of improving the film formability and carrier mobility of the conjugated polymer of this embodiment, the constitutional unit represented by general formula (1) is preferably any of the constitutional units represented by formulas (1-6) to (1-20), more preferably any of the constitutional units represented by formulas (1-6) to (1-16), and even more preferably a constitutional unit represented by formula (1-10).

(Structural unit represented by general formula (2))
Examples of ^X1 include divalent heteroaromatic ring linking groups which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms. Specific preferred examples of the divalent heteroaromatic ring linking groups include divalent heteroaromatic ring linking groups selected from the group consisting of the following general formulae (4) to (8):

(In the formula, A ¹ represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. R ⁷ represents one group selected from the group consisting of an alkyl group having 1 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, a fluorine atom, and a hydrogen atom. Multiple R ^7s may be the same or different. R ⁸ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple R ^8s may be the same or different. p ¹ and q ¹ each independently represent 0 or 1.)

(In the formula, ^A2 represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. ^A3 represents a chalcogen atom. ^R9 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple ^R9s may be the same or different. ^p2 and ^q2 each independently represent 0 or 1.)

(In the formula, ^A4 and ^A5 each independently represent a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. ^R10 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple ^R10s may be the same or different. ^R11 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple ^R11s may be the same or different. ^p3 and ^q3 each independently represent 0 or 1.)

(In the formula, R ¹² represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple R ¹² may be the same or different. ^{p 4} and q ⁴ each independently represent 0 or 1.)

(In the formula, R ¹³ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple R ^13s may be the same or different. p ⁵ and q ⁵ each independently represent 0 or 1.)

Examples of the alkyl group having 1 to 50 carbon atoms represented by ^R7 include the alkyl groups exemplified in the description of ^R1 to ^R6. However, in terms of increasing the solubility of the conjugated polymer of this embodiment, an alkyl group having 6 to 50 carbon atoms is preferred, and an alkyl group having 6 to 34 carbon atoms is more preferred, 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, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, a hentriacontyl group, a dodoriacontyl group, a tritriacontyl group, a tetratriacontyl group, a tetratriacontyl group, a hexyl group, a hexyl group, a hexyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, a tritriacontyl group, a tetratriacontyl group, a hexyl group, a hexyl group, a hexyl group, a hexacos ... More preferred are a contyl group, a pentatriacontyl group, a hexatriacontyl group, a tetracontyl group, a hentetracontyl group, a dotetracontyl group, a tritetracontyl group, a tetratetracontyl group, a pentacontyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-hexyloctyl group, a 2-hexyldecyl group, a 2-octyldodecyl group, a 2-decyltetradecyl group, a 2-dodecyltetradecyl group, a 2-dodecylhexadecyl group, a 2-tetradecylhexadecyl group, a 3-decylpentadecyl group, a 3-dodecylheptadecyl group, a 3-tetradecylnonacosyl group, a 4-decylhexadecyl group, a 4-dodecyloctadecyl group, or a 4-tetradecylicosyl group.

The alkoxy group having 1 to 50 carbon atoms represented by ^R7 may be linear, branched, or cyclic, and examples thereof 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, a nonyloxy group, a decyloxy group, an undecyloxy group, a dodecyloxy group, a tridecyloxy group, a tetradecyloxy group, a pentadecyloxy group, a hexadecyloxy group, a heptadecyloxy group, an octadecyloxy group, a nonadecyloxy group, an icosyloxy group, a henicosyloxy group, a docosyloxy group, a tricosyloxy group, a tetracosyloxy group, a pentacosyloxy group, a hexacosyloxy group, a heptacosyloxy group, an octacosyloxy group, a nonacosyloxy group, a triacontyloxy group, a hentriacontyloxy group, a dodecyloxy group, a triacont ... Examples of alkoxy groups include linear alkoxy groups such as a silyl group, a tritriacontyloxy group, a tetratriacontyloxy group, a pentatriacontyloxy group, a hexatriacontyloxy group, a tetracontyloxy group, a hentetracontyloxy group, a dotetracontyloxy group, a tritetracontyloxy group, a tetratetracontyloxy group, and a pentacontyloxy group; branched alkoxy groups such as an isopropoxy group, a 1-(2-methylpropyl)oxy group, a 2-butyloxy group, a tert-butoxy group, a 2-ethylhexyloxy group, a 3,7-dimethyloctyloxy group, a 2-decyltetradecyloxy group, a 2-dodecyltetradecyloxy group, a 2-dodecylhexadecyloxy group, and a 2-tetradecylhexadecyloxy group; and cyclic alkoxy groups such as a cyclopentyloxy group and a cyclohexyloxy group.

As the alkoxy group having 1 to 50 carbon atoms represented by ^R7 , an alkoxy group having 6 to 50 carbon atoms is preferable, and an alkoxy group having 6 to 34 carbon atoms is more preferable, from the viewpoint of increasing the solubility of the conjugated polymer of this embodiment, and a butyloxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonyloxy group, a decyloxy group, a dodecyloxy group, a 2-decyltetradecyloxy group, a 2-dodecyltetradecyloxy group, a 2-dodecylhexadecyloxy group, or a 2-tetradecylhexadecyloxy group is even more preferable, and a hexyloxy group, an octyloxy group, a 2-decyltetradecyloxy group, or a 2-dodecyltetradecyloxy group is particularly preferable.

^R7 is preferably a hydrogen atom, a fluorine atom, or an alkoxy group having 4 to 50 carbon atoms, more preferably a hydrogen atom or a fluorine atom, and particularly preferably a hydrogen atom, in that the carrier mobility of the conjugated polymer of this embodiment is increased.

The alkyl group having 1 to 50 carbon atoms represented by R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ includes R ¹ to R Examples of alkyl groups include the alkyl groups exemplified in the description of ^{No. 6} , but in terms of increasing the solubility of the conjugated polymer of this embodiment, an alkyl group having 6 to 50 carbon atoms is preferred, and an alkyl group having 6 to 34 carbon atoms is more preferred, 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, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, a hentriacontyl group, a dodoriacontyl group, a tritriacontyl group, and a tetratriacontyl group. More preferred are a contyl group, a pentatriacontyl group, a hexatriacontyl group, a tetracontyl group, a hentetracontyl group, a dotetracontyl group, a tritetracontyl group, a tetratetracontyl group, a pentacontyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-hexyloctyl group, a 2-hexyldecyl group, a 2-octyldodecyl group, a 2-decyltetradecyl group, a 2-dodecyltetradecyl group, a 2-dodecylhexadecyl group, a 2-tetradecylhexadecyl group, a 3-decylpentadecyl group, a 3-dodecylheptadecyl group, a 3-tetradecylnonacosyl group, a 4-decylhexadecyl group, a 4-dodecyloctadecyl group, or a 4-tetradecylicosyl group.

R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are preferably a hydrogen atom or an alkyl group having 6 to 50 carbon atoms, more preferably a hydrogen atom, in that the carrier mobility of the conjugated polymer of this embodiment is increased.

The chalcogen atoms represented by A ¹ , A ² , A ³ , A ⁴ and A ⁵ are preferably oxygen atoms, sulfur atoms, selenium atoms or tellurium atoms, more preferably oxygen atoms or sulfur atoms, and even more preferably sulfur atoms.

In the nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms, represented by A ¹ , A ² , A ⁴ and A ⁵ , the alkyl group having 1 to 50 carbon atoms may be any of linear, branched and cyclic, and examples thereof 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, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, an octadecyl group, a nonadecyl group, an icosyl group, a henicosyl group, a docosyl group, a tricosyl group, a tetracosyl group, a pentacosyl group, a hexacosyl group, a heptacosyl group, an octacosyl group, a nonacosyl group, a triacontyl group, a hentriacontyl group, a dodoli group, a cyclohexyl ... Examples include straight-chain alkyl groups such as an acontyl group, a tritriacontyl group, a tetratriacontyl group, a pentatriacontyl group, a hexatriacontyl group, a tetracontyl group, a hentetracontyl group, a dotetracontyl group, a tritetracontyl group, a tetratetracontyl group, and a pentacontyl group; branched alkyl groups such as an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-hexyldecyl group, a 2-decyltetradecyl group, a 2-dodecyltetradecyl group, a 2-dodecylhexadecyl group, and a 2-tetradecylhexadecyl group; and cyclic alkyl groups such as a cyclopentyl group and a cyclohexyl group. In terms of improving the film-forming properties and solubility of the conjugated polymer of this embodiment, a hexyl group, an octyl group, a dodecyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-hexyldecyl group, a 2-decyltetradecyl group, a 2-dodecyltetradecyl group, a 2-dodecylhexadecyl group, or a 2-tetradecylhexadecyl group is preferred, a hexyl group, an octyl group, a dodecyl group, a 2-ethylhexyl group, or a 3,7-dimethyloctyl group is more preferred, an octyl group, a dodecyl group, or a 2-ethylhexyl group is even more preferred, and an octyl group is particularly preferred.

A ¹ , A ² , A ⁴ and A ⁵ are preferably a sulfur atom, an oxygen atom or a nitrogen atom which may be substituted with an alkyl group having 6 to 34 carbon atoms, more preferably a sulfur atom or an oxygen atom, and even more preferably a sulfur atom, in that the film-forming property and carrier mobility of the conjugated polymer of this embodiment are improved.

^A3 is preferably a sulfur atom, an oxygen atom, or a selenium atom, more preferably a sulfur atom or an oxygen atom, and even more preferably a sulfur atom, in that the film-forming property and carrier mobility of the conjugated polymer of this embodiment are improved.

p ¹ , p ² and p ³ are preferably 0 or 1, and more preferably 0, in that the film-forming properties and carrier mobility of the conjugated polymer of this embodiment are improved.

^p4 and ^p5 are preferably 0 or 1, and more preferably 1, in that the film-forming properties and carrier mobility of the conjugated polymer of this embodiment are improved.

q ¹ , q ² and q ³ are preferably 0 or 1, and more preferably 0, in that the film-forming properties and carrier mobility of the conjugated polymer of this embodiment are improved.

^q4 and ^q5 are preferably 0 or 1, and more preferably 1, in that the film-forming properties and carrier mobility of the conjugated polymer of this embodiment are improved.

More specifically, examples of structural units represented by general formula (2) include formulas (11-1) to (11-261), which increase the solubility of the conjugated polymer of this embodiment.

In the formulas (11-1) to (11-261), the alkyl group represented by C _n H _(2n+1) is a linear alkyl group having n carbon atoms.

As the structural unit represented by general formula (2), any of the structural units represented by formulas (11-1) to (11-26), (11-43) to (11-98), (11-112) to (11-137), (11-221) to (11-228), or (11-256) to (11-261) is preferred, in that the film-forming properties and carrier mobility of the conjugated polymer of this embodiment are improved, and formula (11-1), Any structural unit represented by formula (11-2), formula (11-26), formula (11-73), formula (11-74), formula (11-98), formula (11-112), formula (11-113), formula (11-137), formula (11-222), formula (11-223), formula (11-256), formula (11-257), formula (11-258), formula (11-259), formula (11-260), or formula (11-261) is more preferred.

The conjugated polymer of this embodiment is not particularly limited in the order of the structural units as long as it contains a structural unit represented by general formula (1) and a structural unit represented by general formula (2), and examples thereof include alternating, random, gradient, etc. In terms of improving the film-forming property and mobility of the conjugated polymer of this embodiment, a conjugated polymer having a structure in which the structural unit represented by general formula (1) and the structural unit represented by general formula (2) are alternately repeated is preferred, and this structure can be represented by general formula (3).

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , and X ¹ have the same meanings as defined above.)

Specific examples of structural units represented by general formula (3) include structural units represented by formulas (3-1) to (3-680), which have high film-forming properties and carrier mobility.

In the formulas (3-1) to (3-680), the alkyl group represented by C _n H _(2n+1) is a linear alkyl group having n carbon atoms. In order to improve the film formability and carrier mobility of the conjugated polymer of this embodiment, the structural unit represented by general formula (3) is preferably one of the structural units represented by formulas (3-6) to (3-20), formulas (3-26) to (3-40), formulas (3-46) to (3-60), formulas (3-66) to (3-80), formulas (3-86) to (3-100), formulas (3-106) to (3-120), and formulas (3-126) to (3 -140), formula (3-146) to formula (3-160), formula (3-166) to formula (3-180), formula (3-186) to formula (3-200), formula (3-206) to formula (3-220), formula ( 3-226) ~ formula (3-240), formula (3-246) ~ formula (3-260), formula (3-266) ~ formula (3-280), formula (3-286) ~ formula (3-300), formula (3-306) ~ formula ( 3-320), formula (3-326) to formula (3-340), formula (3-346) to formula (3-360), formula (3-366) to formula (3-380), formula (3-386) to formula (3-400), formula (3-406) to formula (3-420), formula (3-426) to formula (3-440), formula (3-446) to formula (3-480), formula (3-486) to formula (3-500), formula (3-506) to Any of the formulas represented by formula (3-520), formula (3-526) to formula (3-540), formula (3-546) to formula (3-560), formula (3-566) to formula (3-580), formula (3-586) to formula (3-600), formula (3-606) to formula (3-620), formula (3-626) to formula (3-640), formula (3-646) to formula (3-660), and formula (3-666) to formula (3-680) The structural units of formula (3-6) to formula (3-16), formula (3-26) to formula (3-36), formula (3-46) to formula (3-56), formula (3-66) to formula (3-76), formula (3-86) to formula (3-96), formula (3-106) to formula (3-116), formula (3-126) to formula (3-136), formula (3-146) to formula (3-156), formula (3-166) to formula (3-1 76), formula (3-186) to formula (3-296), formula (3-206) to formula (3-216), formula (3-226) to formula (3-236), formula (3-246) to formula (3-256), formula (3- 266) ~ Formula (3-276), Formula (3-286) ~ Formula (3-296), Formula (3-306) ~ Formula (3-316), Formula (3-326) ~ Formula (3-336), Formula (3-346) ~ Formula (3- 356), formula (3-366) to formula (3-376), formula (3-386) to formula (3-396), formula (3-406) to formula (3-416), formula (3-426) to formula (3-436), formula (3 -446) to formula (3-476), formula (3-486) to formula (3-496), formula (3-506) to formula (3-516), formula (3-526) to formula (3-536), formula (3-546) to formula ( 3-556), any structural unit represented by formula (3-566) to formula (3-576), formula (3-586) to formula (3-596), formula (3-606) to formula (3-616), formula (3-626) to formula (3-636) is more preferred, and structural units represented by formula (3-10), formula (3-6), formula (3-646), formula (3-650), and formula (3-666) are even more preferred.

The conjugated polymer of this embodiment may contain structural units other than the structural units represented by general formula (1) and the structural units represented by general formula (2), as long as the effects of the present invention are not impaired. The total content of the structural units represented by general formula (1) and the structural units represented by general formula (2) in the conjugated polymer of this embodiment is preferably 90% by mass or more, and more preferably 95% by mass or more.

The terminal structure of the conjugated polymer of this embodiment is not particularly limited, but examples include boron-containing groups such as hydrogen atoms, boronic acids, and boronic acid esters; tin-containing groups such as trimethylstannyl and tributylstannyl; halogen atoms such as chlorine atoms, bromine atoms, and iodine atoms; and aromatic groups such as phenyl and thienyl groups. The structures of both terminals may be the same or different.

The weight-average molecular weight (Mw) of the conjugated polymer of this embodiment is preferably 3,000 to 10,000,000, more preferably 3,000 to 1,000,000, and even more preferably 3,000 to 500,000.

The molecular weight distribution (PDI) of the conjugated polymer of this embodiment is preferably 1.05 to 20.0, more preferably 1.2 to 10.0, even more preferably 1.4 to 9.0, and particularly preferably 1.4 to 7.0.

In the conjugated polymer of this embodiment, the molar ratio of the structural units represented by general formula (1) to the structural units represented by general formula (2) (structural units represented by general formula (1):structural units represented by general formula (2)) is not particularly limited, but is preferably in the range of 10:1 to 1:10, more preferably in the range of 5:1 to 1:5, more preferably in the range of 2:1 to 1:2, even more preferably in the range of 1.2:1 to 1:1.2, and particularly preferably 1:1.

[Method for producing conjugated polymers]
Next, a method for producing the conjugated polymer of this embodiment (hereinafter referred to as the "production method of this embodiment") will be described. The method for producing the conjugated polymer of this embodiment is as shown in the following production steps (A) to (D).

<Manufacturing process (A)>
The production process (A) is a method for producing the conjugated polymer of this embodiment by coupling a compound (monomer) represented by the general formula (mono-hal) with a compound (monomer) represented by the general formula (mono-X ¹ -B) in the presence of a transition metal catalyst.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , and X ¹ are as defined above. ^{M 1-hal} and M ^2-hal each independently represent a halogen atom. ^{M 3-B} and M ^4-B each independently represent a boron-containing group.)

As the halogen atom represented by M ^1-hal and M ^2-hal , a chlorine atom, a bromine atom, or an iodine atom is preferable, a bromine atom or an iodine atom is more preferable, and a bromine atom is even more preferable, in terms of improving the production efficiency of the conjugated polymer of this embodiment.

As the boron-containing group represented by M ^3-B and M ^4-B , in terms of improving the production efficiency of the conjugated polymer of this embodiment, boronic acid, boronic acid ester, borate salt, or the like is preferred, any of the groups represented by the following formulas (12-1) to (12-6) is more preferred, a group represented by formula (12-1), formula (12-3), formula (12-5) or formula (12-6) is even more preferred, formula (12-1) or formula (12-3) is still more preferred, and formula (12-3) is particularly preferred.

Examples of compounds represented by the general formula (mono-hal) include the following general formulas (mono-hal-1) to (mono-hal-60):

In terms of improving the film-forming properties and carrier mobility of the conjugated polymer of this embodiment, the compound represented by general formula (mono-hal) is preferably any of the compounds represented by formulas (mono-hal-1) to (mono-hal-48), more preferably any of the compounds represented by formulas (mono-hal-1) to (mono-hal-35), and more preferably any of formulas (mono-hal-1), (mono-hal-2), (mono-hal-4), (mono-hal-5), (mono-hal-7), (mono-hal-8), (mono-hal-10), (mono-hal-11), (mono-hal-13), and (mono-hal-14). Compounds represented by formula (mono-hal-14), formula (mono-hal-16), formula (mono-hal-17), formula (mono-hal-19), formula (mono-hal-20), formula (mono-hal-22), formula (mono-hal-23), formula (mono-hal-25), formula (mono-hal-26), formula (mono-hal-28), formula (mono-hal-29), formula (mono-hal-31), formula (mono-hal-32), formula (mono-hal-34) or formula (mono-hal-35) are more preferred, and compounds represented by formula (mono-hal-28) or formula (mono-hal-29) are especially preferred.

Production step (A) must be carried out in the presence of a transition metal catalyst. Examples of transition metal catalysts that can be used include palladium catalysts, nickel catalysts, and platinum catalysts. These transition metal catalysts can be "metals," "supported metals," "metal salts such as metal chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, or oxides," or "complex compounds such as olefin complexes, phosphine complexes, amide complexes, amine complexes, carbene complexes, and acetylacetonato complexes." Furthermore, these metals, supported metals, metal salts, and complex compounds can also be used in combination with tertiary phosphorus compounds or carbene compounds. In terms of high yield, palladium catalysts or nickel catalysts are preferred as the transition metal catalyst, with palladium catalysts being more preferred.

Palladium catalysts are not particularly limited, but examples include palladium metal such as palladium black and palladium sponge. Other examples of palladium catalysts include supported palladium metal such as palladium on alumina, palladium on carbon, palladium on silica, and palladium on Y-type zeolite. Further, metal salts such as palladium chloride, palladium bromide, palladium iodide, palladium acetate, palladium trifluoroacetate, and palladium nitrate, π-allylpalladium chloride dimer, palladium acetylacetonate, dichlorobis(acetonitrile)palladium, dichlorobis(benzonitrile)palladium, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, dichlorodiamminepalladium, dichlorobis(triphenylphosphine)palladium, dichlorobis(tricyclohexylphosphine)palladium, tetrakis(triphenylphosphine)palladium, dichloro[1,2-bis(diphenylphosphino)ethane]palladium, dichloro[1,3-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphine)palladium], dichloro[1,4-bis(diphenylphosphine)palladium], dichloro[1,5-bis(diphenylphosphino)ethane]palladium, dichloro[1,6-bis(diphenylphosphino)propane]palladium, dichloro[1,7-bis(diphenylphosphino)propane]palladium, dichloro[1,8-bis(diphenylphosphino)propane]palladium, dichloro[1,9-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis(diphenylphosphino)propane]palladium, dichloro[1,5-bis(diphenylphosphino)propane]palladium, dichloro[1,6-bis(diphenylphosphino)propane]palladium, dichloro[1,8-bis(diphenylphosphino)propane]palladium, dichloro[1,9-bis(diphenylphosphino)propane]palladium, dichloro[1,4-bis( Examples of palladium catalysts include [1,1'-bis(diphenylphosphino)butane]palladium and dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium, bis(tri-tert-butylphosphine)palladium, bis(tricyclohexylphosphine)palladium, [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride (Pd-PEPPSI-IPent), [1,3-bis(2,6-di-3-pentylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(II) dichloride (Pd-PEPPSI-IPr), and [1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene](3-chloropyridyl)palladium(II) dichloride (Pd-PEPPSI-SIPr).

In terms of good yield, it is preferable to use, as the palladium catalyst, palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ), or bis(tri-tert-butylphosphine)palladium.

The nickel catalyst is not particularly limited, but specific examples include nickel(II) chloride, bis(triphenylphosphine)nickel(II) dichloride, bis(2,4-pentanedionato)nickel(II) hydrate, bis(1,5-cyclooctadiene)nickel(0), dichloro(1,1'-bis(diphenylphosphino)ethane)nickel, dichloro(1,1'-bis(diphenylphosphino)propane)nickel, and [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]triphenylphosphinenickel(II) dichloride.

These palladium or nickel catalysts may be used alone or in combination with a tertiary phosphorus compound or a carbene compound. Examples of tertiary phosphorus compounds that can be used include triphenylphosphine, trimethylphosphine, triethylphosphine, tributylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, tri(o-tolyl)phosphine, trioctylphosphine, 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, 2-(di-tert-butylphosphino)biphenyl, 2-(dicyclohexylphosphino)biphenyl, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, and 1,5-bis(diphenylphosphino)butane. ,1'-bis(diphenylphosphino)ferrocene, tert-butyldiphenylphosphine, 2-(diphenylphosphino)-2'-(N,N-dimethylamino)biphenyl, bis(diphenylphosphino)methane, 1,4-bis(diphenylphosphino)butane, tri(2-furyl)phosphine, tris(2,5-xylyl)phosphine, (R)-(+)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, (S)-(-)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, and (±)-2,2'-bis(diphenylphosphino)-1,1'-binaphthyl can be exemplified. Examples of carbene compounds that can be used include 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, 1,3-bis(2,6-diisopropylphenyl)imidazolidine-2-ylidene, 1,3-di-tert-butylimidazol-2-ylidene, and 1,3-dimesitylimidazol-2-ylidene.

In terms of good yield, it is preferable to use triphenylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, or tri(o-tolyl)phosphine as the tertiary phosphorus compound.

The molar ratio of the tertiary phosphorus compound to the transition metal catalyst (tertiary phosphorus compound:transition metal catalyst) is preferably in the range of 1:10 to 10:1, and from the standpoint of good yield, a range of 1:5 to 5:1 is even more preferable.

When used in combination with a tertiary phosphorus compound or a carbene compound, a palladium catalyst having triphenylphosphine or tri(o-tolyl)phosphine as a ligand is preferred as it provides good yields.

There are no particular restrictions on the amount of transition metal catalyst used, but in terms of good yield, an amount of 0.001 to 50 mol percent relative to the compound represented by the general formula (mono-hal) is preferred, and 0.001 to 20 mol percent is even more preferred.

A promoter can also be used in production step (A). There are no particular limitations on the promoter, but specific examples include monovalent or divalent copper salts such as copper fluoride, copper chloride, copper bromide, copper iodide, and copper oxide. Monovalent copper iodide is preferred due to its high yield.

There are no particular restrictions on the amount of co-catalyst used, but in terms of good yield, an amount of 0.001 to 50 mol percent relative to the compound represented by the general formula (mono-hal) is preferred, and 0.001 to 20 mol percent is even more preferred.

Production step (A) can be carried out in a solvent. There are no particular restrictions on the solvent that can be used as long as it does not inhibit the reaction, and examples include aliphatic hydrocarbon solvents such as hexane, heptane, decane, and tridecane; ether solvents such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; carbonate ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ester solvents such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone; N,N-dimethylformamide (DMF), dimethylacetamide (DMAc), and N-methylpyrrolidone (N urea solvents such as N,N,N',N'-tetramethylurea (TMU) and N,N'-dimethylpropyleneurea (DMPU); sulfoxide solvents such as dimethyl sulfoxide (DMSO); alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol; halogenated solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and orthodichlorobenzene; fluorinated solvents such as bis(2,2,2-trifluoroethyl)=N,N-diisopropylphosphoramidate (PF-37) and phosphoric acid=tris(2,2,2-trifluoroethyl) (TFEP); nitromethane; water; and the like, and these may be mixed and used in any ratio. Among these, in terms of good yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, fluorinated solvents, mixed solvents of aromatic hydrocarbon solvents and water, mixed solvents of halogenated solvents and water, mixed solvents of ether solvents and water, mixed solvents of aromatic hydrocarbon solvents and sulfoxide solvents, mixed solvents of halogenated solvents and sulfoxide solvents, ether solvents and sulfoxide solvents, mixed solvents of aromatic hydrocarbon solvents and fluorinated solvents, mixed solvents of halogenated solvents and fluorinated solvents, and mixed solvents of ether solvents and fluorinated solvents are preferred, and aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, fluorinated solvents, mixed solvents of halogenated solvents and fluorinated solvents are preferred. More preferred are halogen solvents, ether solvents, mixed solvents of aromatic hydrocarbon solvents and water, mixed solvents of halogen solvents and water, mixed solvents of ether solvents and water, mixed solvents of aromatic hydrocarbon solvents and sulfoxide solvents, mixed solvents of halogen solvents and sulfoxide solvents, mixed solvents of ether solvents and sulfoxide solvents, mixed solvents of aromatic hydrocarbon solvents and fluorine solvents, mixed solvents of halogen solvents and fluorine solvents, and mixed solvents of ether solvents and fluorine solvents, and even more preferred are tetralin, toluene, monochlorobenzene, orthodichlorobenzene, THF, mixed solvents of toluene and water, and mixed solvents of tetralin and water.

There are no particular restrictions on the amount of solvent used, but it is preferable that it be in the range of 0.001 to 100 mL/mg relative to the weight of the compound represented by the general formula (mono-hal).

Production step (A) can also be carried out with the addition of a phase transfer catalyst. Usable phase transfer catalysts include ethyltrimethylammonium iodide, didodecyldimethylammonium chloride, dimethyldioctadecylammonium iodide, dimethyldioctylammonium bromide, didecyldimethylammonium bromide, dimethyldimyristylammonium bromide, dihexadecyldimethylammonium bromide, diallyldimethylammonium chloride, dimethyldioctadecylammonium chloride, didodecyldimethylammonium bromide, 4-dimethylamino-1-neopentylpyridinium chloride, dodecyltrimethylammonium bromide, decyltrimethylammonium bromide, 1,1-dimethyl-4-phenylpiperazinium iodide, decamethonium iodide, and decamethonium bromide. Benzyltrimethylammonium chloride, decyltrimethylammonium chloride, ethylhexadecyldimethylammonium bromide, (3-chloro-2-hydroxypropyl)trimethylammonium chloride, carbachol, choline chloride, chlorocholine chloride, bis(2-hydroxyethyl)dimethylammonium chloride, benzyldodecyldimethylammonium bromide, benzyltrimethylammonium bromide, benzyldodecyldimethylammonium chloride dihydrate, benzyltrimethylammonium dichloroiodate, benzyltributylammonium chloride, benzyltributylammonium bromide, bromocholine bromide, benzyltrimethylammonium chloride, benzyltriethylammonium iodide, benzyltrimethylammonium chloride, Dimethyltriethylammonium hydroxide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, benzyldimethylphenylammonium chloride, benzalkonium chloride, benzoylthiocholine iodide, benzyldimethylhexadecylammonium chloride hydrate, benzoylcholine iodide, benzoylcholine chloride, benzoylcholine bromide, zephiran chloride hydrate, tetrabutylammonium p-toluenesulfonate, tetrabutylammonium nitrate, tetrahexylammonium hydrogen sulfate, tetraethylammonium nitrate, tributylammonium chloride, trimethylpropylammonium bromide, trimethylnonylammonium bromide, tetrabutylammonium acetate , tetrabutylammonium tetrafluoroborate, trimethyl[2-[(trimethylsilyl)methyl]benzyl]ammonium iodide, triethylammonium tetrafluoroborate, tris(2-hydroxyethyl)methylammonium hydroxide, tetrapropylammonium chloride, tetraethylammonium trifluoromethanesulfonate, tetra-n-octylammonium bromide, tetraheptylammonium bromide, tetrahexylammonium bromide, tetrabutylammonium triflate, tetrabutylammonium tetraphenylborate, tetrapentylammonium chloride, tetrapentylammonium bromide, tetramethylammonium acetate, tetraheptylammonium iodide, methyltri -n-octylammonium chloride, tetramethylammonium hexafluorophosphate, tetrabutylammonium bifluoride, tetrabutylammonium tribromide, tetrabutylammonium hexafluorophosphate, tetrabutylammonium thiocyanate, tetrabutylammonium triiodide, tetramethylammonium sulfate, tetra-n-octylammonium iodide, tetra(decyl)ammonium bromide, tetramethylammonium acetate, tetrahexylammonium iodide, tetraethylammonium tetrafluoroborate, tetraethylammonium p-toluenesulfonate, trimethyltetradecylammonium chloride, tetrabutylammonium tetrafluoroborate, tetradecylammonium iodide Tetramethylammonium bromide, tetramethylammonium tetrafluoroborate, tetrabutylammonium perchlorate, tetrabutylammonium hydrogen sulfate, trioctylmethylammonium chloride (Aliquat 336), tetrapropylammonium bromide, tetrapropylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium iodide, tetraethylammonium bromide, tetraethylammonium chloride, tetraethylammonium iodide, tetramethylammonium bromide, tetramethylammonium chloride, tetramethylammonium iodide, (ferrocenylmethyl)trimethylammonium bromide, (ferrocenylmethyl)dodecyl, hexadecyltrimethylammonium bromide ammonium salts such as tetrabutylammonium bromide, hexadecyltrimethylammonium chloride, hexyltrimethylammonium bromide, triethylammonium chloride, methyltri-n-octylammonium hydrogen sulfate, trimethyl-n-octylammonium bromide, trimethyl-n-octylammonium chloride, trimethylphenylammonium bromide, trimethylphenylammonium chloride, trimethylphenylammonium tribromide, octadecyltrimethylammonium bromide, tetrabutylammonium bromide, tetrabutylphosphonium tetraphenylborate, tetrabutylphosphonium hexafluorophosphate, tetrabutylphosphonium tetrafluoroborate, tetraethylphosphonium tetrafluoroborate, tetramethylammonium bromide ... Examples of phosphonium salts include tetraethylphosphonium hexafluorophosphate, tetra-n-octylphosphonium bromide, tetrabutylphosphonium chloride, tetraethylphosphonium bromide, tetraphenylphosphonium chloride, tetrabutylphosphonium bromide, tetrakis(hydroxymethyl)phosphonium sulfate, tetraphenylphosphonium bromide, tetrakis(hydroxymethyl)phosphonium chloride, tributyl-n-octylphosphonium bromide, hexadecyltributylphosphonium bromide, tributyldodecylphosphonium bromide, (2-carboxyethyl)triphenylphosphonium bromide, and tributyl(cyanomethyl)phosphonium chloride, and these may be mixed in any ratio. Of these, ammonium salts are preferred due to their good reaction yield, and Aliquat 336 is more preferred.

Production step (A) can be carried out in the presence of a base. Examples of bases that can be used include metal alkoxides such as sodium butoxide and potassium butoxide; metal alkyls such as butyllithium; metal amides such as lithium hexamethyldisilazide, lithium diisopropylamide, 2,2,6,6-tetramethylpiperidinyllithium, and 2,2,6,6-tetramethylpiperidinylmagnesium chloride lithium chloride complex; lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, and carbon dioxide. Examples of suitable bases include inorganic bases such as potassium carbonate and cesium carbonate; and organic bases such as triethylamine, diisopropylethylamine, pyridine, lutidine, diazabicycloundecene (DBU), 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD), 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene (MTBD), and 1,4-diazabicyclo[2.2.2]octane (DABCO). These bases may be mixed in any ratio. Of these, inorganic salts are preferred due to their good reaction yield, and sodium carbonate or potassium carbonate is more preferred.

Production step (A) can be carried out at a temperature appropriately selected from the range of 0°C to 240°C. From the perspective of achieving a good yield, it is preferably carried out at a temperature appropriately selected from the range of 70°C to 220°C, and more preferably at a temperature appropriately selected from the range of 100°C to 200°C.

Production step (A) can also be carried out using a microwave reactor.

Preparation step (A) is preferably carried out in an inert gas atmosphere such as argon gas or nitrogen gas, or in a vacuum.

The reaction time varies depending on the compound used (a compound represented by the general formula (mono-hal) or the general formula (mono-X ¹ -B)), the solvent, and the reaction temperature, but is usually preferably 0.1 to 100 hours, more preferably 1 to 78 hours.

The conjugated polymer of this embodiment can be obtained by carrying out conventional treatments after completion of production step (A). If necessary, it may be purified using any of the commonly used methods used by those skilled in the art for purifying polymer compounds, such as washing, precipitation, filtration, dialysis, column chromatography, preparative HPLC, or Soxhlet extraction.

For the purpose of improving mobility or solubility, an organoboron compound or an organotin compound can be added during or after the reaction to produce a conjugated polymer of this embodiment in which a functional group such as a thienyl group or a phenyl group is introduced at the end. The functional group may be introduced by combining known methods, for example, according to the method disclosed in Macromolecules, Vol. 48, pp. 6994-7006, 2015.

The compound represented by the general formula (mono-hal) used in production step (A) may be obtained by any method, but can be produced by referring to methods described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 19254-19259, 2012, Journal of the American Chemical Society, Vol. 143, pp. 4281-4289, 2021, etc.). Commercially available products may also be used.

The compound represented by the general formula (mono-X ¹ -B) used in the production step (A) may be obtained by any method, and may be produced by referring to, for example, a method described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 3498-3507, 2012, etc.). Alternatively, a commercially available product may be used.

<Manufacturing process (B)>
The production process (B) is a method for producing the conjugated polymer of this embodiment by coupling a compound (monomer) represented by the general formula (mono-hal) with a compound (monomer) represented by the general formula (mono-X ¹ -Sn) in the presence of a transition metal catalyst.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , X ¹ , M ^1-hal and M ^2-hal are as defined above. ^{M 3-Sn} and M ^4-Sn each independently represent a tin-containing group.)

Examples of the tin-containing groups represented by M ^3-Sn and M ^4-Sn include a trialkylstannyl group, a dialkylarylstannyl group, an alkyldiarylstannyl group, a triarylstannyl group, etc. In terms of improving the production efficiency of the conjugated polymer of this embodiment, a trialkylstannyl group or a triarylstannyl group is preferred, any of the groups represented by formulas (13-1) to (13-5) is more preferred, and a group represented by formula (13-1) is even more preferred.

Production step (B) must be carried out in the presence of a transition metal catalyst. Examples of transition metal catalysts that can be used include palladium catalysts, nickel catalysts, and platinum catalysts. These transition metal catalysts can be "metals," "supported metals," "metal salts such as metal chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, or oxides," or "complex compounds such as olefin complexes, phosphine complexes, amide complexes, amine complexes, carbene complexes, and acetylacetonate complexes." Furthermore, these metals, supported metals, metal salts, and complex compounds can also be used in combination with tertiary phosphorus compounds or carbene compounds. In terms of high yield, palladium catalysts or nickel catalysts are preferred as the transition metal catalyst, with palladium catalysts being more preferred.

The palladium catalyst is not particularly limited, but examples include the palladium catalysts exemplified in the description of production process (A).

In terms of good yield, it is preferable to use, as the palladium catalyst, palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ), or bis(tri-tert-butylphosphine)palladium.

The nickel catalyst is not particularly limited, but examples include the nickel catalysts exemplified in the description of production process (A).

These palladium or nickel catalysts may be used alone or in combination with a tertiary phosphorus compound or a carbene compound. Examples of tertiary phosphorus compounds or carbene compounds that can be used include the tertiary phosphorus compounds or carbene compounds exemplified in the description of production step (A).

In terms of good yield, it is preferable to use triphenylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, or tri(o-tolyl)phosphine as the tertiary phosphorus compound.

The molar ratio of the tertiary phosphorus compound to the transition metal catalyst (tertiary phosphorus compound:transition metal catalyst) is preferably in the range of 1:10 to 10:1, and from the standpoint of good yield, a range of 1:5 to 5:1 is even more preferable.

When used in combination with a tertiary phosphorus compound or a carbene compound, a palladium catalyst having triphenylphosphine or tri(o-tolyl)phosphine as a ligand is preferred as it provides good yields.

There are no particular restrictions on the amount of transition metal catalyst used, but in terms of good yield, it is preferably 0.001 to 50 mole percent, and more preferably 0.001 to 20 mole percent, relative to the compound represented by the general formula (mono-hal).

A promoter can also be used in production step (B). There are no particular limitations on the promoter, but specific examples include monovalent or divalent copper salts such as copper fluoride, copper chloride, copper bromide, copper iodide, and copper oxide. Monovalent copper iodide is preferred due to its good yield.

There are no particular restrictions on the amount of co-catalyst used, but in terms of good yield, it is preferably 0.001 to 50 mol percent, and more preferably 0.001 to 20 mol percent, relative to the compound represented by the general formula (mono-hal).

Production step (B) can be carried out in a solvent. There are no particular restrictions on the solvent that can be used as long as it does not inhibit the reaction, and examples include the solvents exemplified in the description of production step (A). From the perspective of good yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, fluorinated solvents, mixed solvents of aromatic hydrocarbon solvents and water, mixed solvents of halogenated solvents and water, mixed solvents of ether solvents and water, mixed solvents of aromatic hydrocarbon solvents and sulfoxide solvents, mixed solvents of halogenated solvents and sulfoxide solvents, mixed solvents of ether solvents and sulfoxide solvents, mixed solvents of aromatic hydrocarbon solvents and fluorinated solvents, mixed solvents of halogenated solvents and fluorinated solvents, and mixed solvents of ether solvents and fluorinated solvents are preferred. Aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, mixed solvents of aromatic hydrocarbon solvents and fluorinated solvents, mixed solvents of halogenated solvents and fluorinated solvents, and mixed solvents of ether solvents and fluorinated solvents are more preferred. Tetralin, toluene, monochlorobenzene, orthodichlorobenzene, and THF are even more preferred.

There are no particular restrictions on the amount of solvent used, but it is preferable that it be in the range of 0.001 to 100 mL/mg relative to the weight of the compound represented by the general formula (mono-hal).

Production step (B) can be carried out in the presence of a base. Examples of bases that can be used include the bases exemplified in the description of production step (A). Inorganic salts are preferred because they provide a good reaction yield, and sodium carbonate or potassium carbonate is more preferred.

Production step (B) can be carried out at a temperature appropriately selected from the range of 0°C to 240°C. From the perspective of achieving a good yield, it is preferably carried out at a temperature appropriately selected from the range of 70°C to 220°C, and more preferably at a temperature appropriately selected from the range of 100°C to 200°C.

Production step (B) can also be carried out using a microwave reactor.

Preparation step (B) is preferably carried out in an inert gas atmosphere such as argon gas or nitrogen gas, or in the open air.

The reaction time varies depending on the compound used (compound represented by general formula (mono-hal) or general formula (mono-X ¹ -Sn)), solvent and reaction temperature, but is preferably 0.1 to 100 hours, more preferably 1 to 78 hours.

The conjugated polymer of this embodiment can be obtained by carrying out conventional treatments after completion of production step (B). If necessary, it may be purified using any of the commonly used methods used by those skilled in the art for purifying polymer compounds, such as washing, precipitation, filtration, dialysis, column chromatography, preparative HPLC, or Soxhlet extraction.

For the purpose of improving mobility or solubility, an organoboron compound or an organotin compound can be added during or after the reaction to produce a conjugated polymer of this embodiment in which a functional group such as a thienyl group or a phenyl group is introduced at the end. The functional group may be introduced by combining known methods, for example, according to the method disclosed in Macromolecules, Vol. 48, pp. 6994-7006, 2015.

The compound represented by general formula (mono-hal) used in production step (B) may be obtained by any method, but can be produced by reference to methods described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 19254-19259, 2012, Journal of the American Chemical Society, Vol. 143, pp. 4281-4289, 2021, etc.). Commercially available products may also be used.

The compound represented by the general formula (mono-X ¹ -Sn) used in the production step (B) may be obtained by any method, and may be produced by referring to, for example, a method described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 3498-3507, 2012, etc.). Alternatively, a commercially available product may be used.

<Manufacturing process (C)>
The production process (C) is a method for producing the conjugated polymer of this embodiment by coupling a compound (monomer) represented by the general formula (mono-B) with a compound (monomer) represented by the general formula (mono-X ¹ -hal) in the presence of a transition metal catalyst.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , and X ¹ are as defined above. ^{M 1-B} and M ^2-B each independently represent a boron-containing group. ^{M 3-hal} and M ^4-hal each independently represent a halogen atom.)

As the boron-containing group represented by M ^1-B and M ^2-B , in terms of improving the production efficiency of the conjugated polymer of this embodiment, boronic acid, boronic acid ester, borate salt, or the like is preferred, any of the groups represented by formulas (12-1) to (12-6) is more preferred, a group represented by formula (12-1), formula (12-3), formula (12-5) or formula (12-6) is even more preferred, formula (12-1) or formula (12-3) is still more preferred, and formula (12-3) is particularly preferred.

As the halogen atom represented by M ^3-hal and M ^4-hal , a chlorine atom, a bromine atom, or an iodine atom is preferable, a bromine atom or an iodine atom is more preferable, and a bromine atom is even more preferable, in terms of improving the production efficiency of the conjugated polymer of this embodiment.

Examples of compounds represented by general formula (mono-B) include compounds represented by the following general formulas (mono-B-1) to (mono-B-60).

In terms of improving the film-forming properties and carrier mobility of the conjugated polymer of this embodiment, the compound represented by general formula (mono-B) is preferably any of the compounds represented by formulas (mono-B-1) to (mono-B-48), more preferably any of the compounds represented by formulas (mono-B-1) to (mono-B-35), and more preferably any of formulas (mono-B-1), (mono-B-2), (mono-B-4), (mono-B-5), (mono-B-7), (mono-B-8), (mono-B-10), (mono-B-11), (mono-B-13), and (mono-B-14). Compounds represented by formula (mono-B-14), formula (mono-B-16), formula (mono-B-17), formula (mono-B-19), formula (mono-B-20), formula (mono-B-22), formula (mono-B-23), formula (mono-B-25), formula (mono-B-26), formula (mono-B-28), formula (mono-B-29), formula (mono-B-31), formula (mono-B-32), formula (mono-B-34) or formula (mono-B-35) are more preferred, and compounds represented by formula (mono-B-28) or formula (mono-B-29) are particularly preferred.

Production step (C) must be carried out in the presence of a transition metal catalyst. Examples of transition metal catalysts that can be used include palladium catalysts, nickel catalysts, and platinum catalysts. These transition metal catalysts can be "metals," "supported metals," "metal salts such as metal chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, or oxides," or "complex compounds such as olefin complexes, phosphine complexes, amide complexes, amine complexes, carbene complexes, or acetylacetonate complexes." Furthermore, these metals, supported metals, metal salts, and complex compounds can also be used in combination with tertiary phosphorus compounds or carbene compounds. In terms of high yield, palladium or nickel catalysts are preferred as the transition metal catalyst, with palladium catalysts being more preferred.

The palladium catalyst is not particularly limited, but examples include the palladium catalysts exemplified in the description of production process (A).

In terms of good yield, it is preferable to use, as the palladium catalyst, palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ), or bis(tri-tert-butylphosphine)palladium.

The nickel catalyst is not particularly limited, but examples include the nickel catalysts exemplified in the description of production process (A).

These palladium or nickel catalysts may be used alone or in combination with a tertiary phosphorus compound or a carbene compound. Examples of tertiary phosphorus compounds or carbene compounds that can be used include the tertiary phosphorus compounds or carbene compounds exemplified in the description of production step (A).

In terms of good yield, it is preferable to use triphenylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, or tri(o-tolyl)phosphine as the tertiary phosphorus compound.

The molar ratio of the tertiary phosphorus compound to the transition metal catalyst (tertiary phosphorus compound:transition metal catalyst) is preferably in the range of 1:10 to 10:1, and from the standpoint of good yield, a range of 1:5 to 5:1 is even more preferable.

When used in combination with a tertiary phosphorus compound or a carbene compound, a palladium catalyst having triphenylphosphine or tri(o-tolyl)phosphine as a ligand is preferred as it provides good yields.

There are no particular restrictions on the amount of transition metal catalyst used, but in terms of good yield, it is preferably 0.001 to 50 mol percent, and more preferably 0.001 to 20 mol percent, relative to the compound represented by general formula (mono-B).

A promoter can also be used in production step (C). There are no particular limitations on the promoter, but specific examples include monovalent or divalent copper salts such as copper fluoride, copper chloride, copper bromide, copper iodide, and copper oxide. Monovalent copper iodide is preferred due to its good yield.

There are no particular restrictions on the amount of co-catalyst used, but in terms of good yield, it is preferably 0.001 to 50 mol percent, and more preferably 0.001 to 20 mol percent, relative to the compound represented by general formula (mono-B).

Production step (C) can be carried out in a solvent. There are no particular restrictions on the solvents that can be used as long as they do not inhibit the reaction, and examples include the solvents exemplified in the description of production step (A). In terms of good yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, fluorinated solvents, mixed solvents of aromatic hydrocarbon solvents and water, mixed solvents of halogenated solvents and water, mixed solvents of ether solvents and water, mixed solvents of aromatic hydrocarbon solvents and sulfoxide solvents, mixed solvents of halogenated solvents and sulfoxide solvents, mixed solvents of ether solvents and sulfoxide solvents, mixed solvents of aromatic hydrocarbon solvents and fluorinated solvents, mixed solvents of halogenated solvents and fluorinated solvents, and mixed solvents of ether solvents and fluorinated solvents are preferred. Also preferred are aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, Ether solvents, mixed solvents of aromatic hydrocarbon solvents and water, mixed solvents of halogenated solvents and water, mixed solvents of ether solvents and water, mixed solvents of aromatic hydrocarbon solvents and sulfoxide solvents, mixed solvents of halogenated solvents and sulfoxide solvents, ether solvents and sulfoxide solvents, mixed solvents of aromatic hydrocarbon solvents and fluorinated solvents, mixed solvents of halogenated solvents and fluorinated solvents, and mixed solvents of ether solvents and fluorinated solvents are more preferred, and tetralin, toluene, monochlorobenzene, orthodichlorobenzene, THF, mixed solvents of toluene and water, mixed solvents of tetralin and water, and mixed solvents of tetralin and DMSO are even more preferred.

There are no particular restrictions on the amount of solvent used, but it is preferably in the range of 0.001 to 100 mL/mg relative to the weight of the compound represented by general formula (mono-B).

Production step (C) can also be carried out with the addition of a phase transfer catalyst. Examples of phase transfer catalysts that can be used include those exemplified in the description of production step (A). Ammonium salts are preferred, with Aliquat 336 being more preferred, due to their high reaction yield.

Production step (C) can be carried out in the presence of a base. Examples of bases that can be used include the bases exemplified in the description of production step (A). Inorganic salts are preferred because they provide a good reaction yield, and sodium carbonate or potassium carbonate is more preferred.

Production step (C) can be carried out at a temperature appropriately selected from the range of 0°C to 240°C. From the perspective of achieving a good yield, it is preferably carried out at a temperature appropriately selected from the range of 70°C to 220°C, and more preferably at a temperature appropriately selected from the range of 100°C to 200°C.

Production step (C) can also be carried out using a microwave reactor.

Preparation step (C) is preferably carried out in an inert gas atmosphere such as argon gas or nitrogen gas, or in a vacuum.

The reaction time varies depending on the compound used (compound represented by general formula (mono-B) or general formula (mono-X ¹ -hal)), solvent and reaction temperature, but is usually preferably 0.1 to 100 hours, more preferably 1 to 78 hours.

The conjugated polymer of this embodiment can be obtained by carrying out conventional treatments after completion of production step (C). If necessary, it may be purified using any of the commonly used methods used by those skilled in the art for purifying polymer compounds, such as washing, precipitation, filtration, dialysis, column chromatography, preparative HPLC, or Soxhlet extraction.

For the purpose of improving mobility or solubility, an organoboron compound or an organotin compound can be added during or after the reaction to produce a conjugated polymer of this embodiment in which a functional group such as a thienyl group or a phenyl group is introduced at the end. The functional group may be introduced by combining known methods, for example, according to the method disclosed in Macromolecules, Vol. 48, pp. 6994-7006, 2015.

The compound represented by general formula (mono-B) used in production step (C) may be obtained by any method, but can be produced by referring to methods described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 19254-19259, 2012, Journal of the American Chemical Society, Vol. 143, pp. 4281-4289, 2021, etc.). Commercially available products may also be used.

The compound represented by the general formula (mono-X ¹ -hal) used in the production step (C) may be obtained by any method, and may be produced by referring to, for example, a method described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 3498-3507, 2012, etc.). Alternatively, a commercially available product may be used.

<Manufacturing process (D)>
The production process (D) is a method for producing the conjugated polymer of this embodiment by coupling a compound (monomer) represented by the general formula (mono-Sn) with a compound (monomer) represented by the general formula (mono-X ¹ -hal) in the presence of a transition metal catalyst.

(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ , X ¹ , M ^3-hal and M ^4-hal are as defined above. ^{M 1-Sn} and M ^2-Sn each independently represent a tin-containing group.)

Examples of the tin-containing groups represented by M ^1-Sn and M ^2-Sn include a trialkylstannyl group, a dialkylarylstannyl group, an alkyldiarylstannyl group, a triaryltin group, etc. In terms of improving the production efficiency of the conjugated polymer of this embodiment, a trialkylstannyl group or a triarylstannyl group is preferred, any of the groups represented by formulas (13-1) to (13-5) is more preferred, and a group represented by formula (13-1) is even more preferred.

Examples of compounds represented by the general formula (mono-Sn) include compounds represented by the following general formulas (mono-Sn-1) to (mono-Sn-60):

Production step (D) must be carried out in the presence of a transition metal catalyst. Examples of transition metal catalysts that can be used include palladium catalysts, nickel catalysts, and platinum catalysts. These transition metal catalysts can be "metals," "supported metals," "metal salts such as metal chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, or oxides," or "complex compounds such as olefin complexes, phosphine complexes, amide complexes, amine complexes, carbene complexes, or acetylacetonate complexes." Furthermore, these metals, supported metals, metal salts, and complex compounds can also be used in combination with tertiary phosphorus compounds or carbene compounds. From the perspective of good yield, palladium catalysts or nickel catalysts are preferred as the transition metal catalyst, with palladium catalysts being more preferred.

The palladium catalyst is not particularly limited, but examples include the palladium catalysts exemplified in the description of production process (A).

In terms of good yield, it is preferable to use, as the palladium catalyst, palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium (Pd(PPh ₃ ) ₄ ), or bis(tri-tert-butylphosphine)palladium.

The nickel catalyst is not particularly limited, but examples include the palladium catalyst exemplified in the description of production process (A).

These palladium or nickel catalysts may be used alone or in combination with a tertiary phosphorus compound or a carbene compound. Examples of tertiary phosphorus compounds or carbene compounds that can be used include the tertiary phosphorus compounds or carbene compounds exemplified in the description of production process (A).

In terms of good yield, it is preferable to use triphenylphosphine, tri(tert-butyl)phosphine, tricyclohexylphosphine, or tri(o-tolyl)phosphine as the tertiary phosphorus compound.

The molar ratio of the tertiary phosphorus compound to the transition metal catalyst (tertiary phosphorus compound:transition metal catalyst) is preferably in the range of 1:10 to 10:1, and from the standpoint of good yield, a range of 1:5 to 5:1 is even more preferable.

When used in combination with a tertiary phosphorus compound or a carbene compound, a palladium catalyst having triphenylphosphine or tri(o-tolyl)phosphine as a ligand is preferred as it provides good yields.

There are no particular restrictions on the amount of transition metal catalyst used, but in terms of good yield, it is preferably 0.001 to 50 mole percent, and more preferably 0.001 to 20 mole percent, relative to the compound represented by the general formula (mono-Sn).

A promoter can also be used in production step (D). There are no particular limitations on the promoter, but specific examples include monovalent or divalent copper salts such as copper fluoride, copper chloride, copper bromide, copper iodide, and copper oxide. Monovalent copper iodide is preferred due to its good yield.

There are no particular restrictions on the amount of co-catalyst used, but in terms of good yield, it is preferably 0.001 to 50 mol percent, and more preferably 0.001 to 20 mol percent, relative to the compound represented by the general formula (mono-Sn).

Production step (D) can be carried out in a solvent. There are no particular limitations on the solvent that can be used as long as it does not inhibit the reaction, and examples include the solvents exemplified in the description of production step (A). From the perspective of good yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, fluorinated solvents, mixed solvents of aromatic hydrocarbon solvents and water, mixed solvents of halogenated solvents and water, mixed solvents of ether solvents and water, mixed solvents of aromatic hydrocarbon solvents and sulfoxide solvents, mixed solvents of halogenated solvents and sulfoxide solvents, mixed solvents of ether solvents and sulfoxide solvents, mixed solvents of aromatic hydrocarbon solvents and fluorinated solvents, mixed solvents of halogenated solvents and fluorinated solvents, and mixed solvents of ether solvents and fluorinated solvents are preferred. Aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, and mixed solvents of ether solvents and fluorinated solvents are more preferred. Tetralin, toluene, monochlorobenzene, orthodichlorobenzene, and THF are even more preferred.

There are no particular restrictions on the amount of solvent used, but it is preferable that it be in the range of 0.001 to 100 mL/mg relative to the weight of the compound represented by the general formula (mono-Sn).

Production step (D) can be carried out at a temperature appropriately selected from the range of 0°C to 240°C. From the perspective of achieving a good yield, it is preferably carried out at a temperature appropriately selected from the range of 70°C to 220°C, and more preferably at a temperature appropriately selected from the range of 100°C to 200°C.

Production step (D) can also be carried out using a microwave reactor.

Preparation step (D) is preferably carried out in an inert gas atmosphere such as argon gas or nitrogen gas, or in a vacuum.

The reaction time varies depending on the compound used (a compound represented by the general formula (mono-Sn) or the general formula (mono-X ¹ -hal)), the solvent, and the reaction temperature, but is usually preferably 0.1 to 100 hours, more preferably 1 to 78 hours.

The conjugated polymer of this embodiment can be obtained by carrying out conventional treatments after completion of production step (D). If necessary, it may be purified using any of the commonly used methods used by those skilled in the art for purifying polymer compounds, such as washing, precipitation, filtration, dialysis, column chromatography, preparative HPLC, or Soxhlet extraction.

For the purpose of improving mobility or solubility, an organoboron compound or an organotin compound can be added during or after the reaction to produce a conjugated polymer of this embodiment in which a functional group such as a thienyl group or a phenyl group is introduced at the end. The functional group may be introduced by combining known methods, for example, according to the method disclosed in Macromolecules, Vol. 48, pp. 6994-7006, 2015.

The compound represented by the general formula (mono-Sn) used in the production step (D) may be obtained by any method, but may be obtained by, for example, the method described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 19254-19259, 2012, or Journal of the American Chemical Society,
Society, Vol. 143, pp. 4281-4289, 2021. etc.) Commercially available products may also be used.

The compound represented by the general formula (mono-X ¹ -hal) used in the production step (D) may be obtained by any method, and may be produced by referring to, for example, a method described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 3498-3507, 2012, etc.). Alternatively, a commercially available product may be used.

[Film-forming composition]
Next, a method for producing a film-forming composition containing the conjugated polymer of this embodiment (hereinafter referred to as the "film-forming composition of this embodiment") will be described.

The film-forming composition of this embodiment is a film-forming composition containing the conjugated polymer of this embodiment and a solvent, obtained by dissolving or dispersing the conjugated polymer of this embodiment in a solvent.

The solvent is not particularly limited as long as it can dissolve or disperse the conjugated polymer of this embodiment in the solvent. Examples of suitable solvents include ether solvents such as diisopropyl ether, dibutyl ether, cyclopentyl methyl ether (CPME), tetrahydrofuran (THF), 2-methyltetrahydrofuran, 1,4-dioxane, and dimethoxyethane; aromatic hydrocarbon solvents such as benzene, toluene, xylene, mesitylene, and tetralin; carbonate ester solvents such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, ethyl methyl carbonate, and 4-fluoroethylene carbonate; ester solvents such as ethyl acetate, butyl acetate, methyl propionate, ethyl propionate, methyl butyrate, and γ-lactone; N,N-dimethylformamide (DMF), N, Examples of solvents include amide solvents such as N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP); urea solvents such as N,N,N',N'-tetramethylurea (TMU) and N,N'-dimethylpropyleneurea (DMPU); sulfoxide solvents such as dimethyl sulfoxide (DMSO); alcohol solvents such as methanol, ethanol, 2-propanol, butanol, octanol, benzyl alcohol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, and 2,2,2-trifluoroethanol; halogen solvents such as chloroform, dichloromethane, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, and orthodichlorobenzene (o-DCB); nitromethane; water; and the like, and these may be mixed and used in any ratio. Of these, aromatic hydrocarbons and halogenated solvents are preferred because they have high boiling points and volatility, with toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3,4-dimethylanisole, chlorobenzene, and o-DCB being more preferred.

There are no particular restrictions on the amount of solvent used, and it is more preferable to add the solvent so that the concentration of the conjugated polymer of this embodiment is 0.001 to 95 weight percent, or a concentration appropriately selected from 0.01 to 30 weight percent.

The conjugated polymer of this embodiment can be dissolved or dispersed in a solvent using methods well known to those skilled in the art, such as stirring, shaking, or ball milling. Heating may also be used during this process.

The film-forming composition of this embodiment may contain a binder to improve film-forming properties. Examples of such binders include polymers such as polystyrene, poly-α-methylstyrene, polyvinylnaphthalene, poly(ethylene-co-norbornene), polymethyl methacrylate, polytriarylamine, and poly(9,9-dioctylfluorene-co-dimethyltriphenylamine). There are no particular restrictions on the concentration of the binder, but a concentration of 0.1 to 10.0 weight percent is preferred in terms of good coatability.

[Organic thin film]
Next, an organic thin film containing the conjugated polymer of this embodiment (hereinafter referred to as the "organic thin film of this embodiment"), more specifically, a method for forming an organic thin film using the film-forming composition, will be described.

The method for forming the organic thin film of this embodiment using the film-forming composition of this embodiment is not particularly limited, and examples include simple coating methods such as spin coating, drop casting, dip coating, and cast coating; and printing methods such as dispenser, inkjet, slit coating, blade coating, flexographic printing, screen printing, gravure printing, and offset printing. Among these, spin coating, drop casting, and inkjet are preferred because they allow for efficient film formation.

There are no particular limitations on the film thickness of the organic thin film of this embodiment, but a thickness of 1 nm to 1000 nm is preferred, and 10 nm to 500 nm is more preferred, in terms of increasing carrier mobility.

The organic thin film of this embodiment can be obtained by drying the solvent after film formation. If necessary, annealing may be performed at a temperature appropriately selected from the range of 40 to 400°C.

[Organic semiconductor element]
Examples of organic semiconductor elements containing the conjugated polymer of this embodiment include organic transistor elements, organic thermoelectric conversion elements, organic photoelectric conversion elements, and organic imaging elements. Of these, organic transistor elements and organic photoelectric conversion elements are preferred, and organic transistor elements are more preferred.

This section describes a method for fabricating an organic thin-film transistor element containing the conjugated polymer of this embodiment (hereinafter referred to as the "organic thin-film transistor element of this embodiment"), particularly an organic thin-film transistor element containing a conjugated polymer in the active layer.

The organic thin-film transistor element of this embodiment is obtained by depositing the organic thin film of this embodiment as an insulating layer and an active layer on a substrate, and then attaching a source electrode, a drain electrode, and a gate electrode to this.

Figure 1 shows the structure of an element included in the organic thin-film transistor element of this embodiment. Here, 1001 is a bottom gate-top contact type, 1002 is a bottom gate-bottom contact type, 1003 is a top gate-top contact type, and 1004 is a top gate-bottom contact type transistor element. 1 is the active layer (organic semiconductor layer), 2 is the substrate, 3 is the gate electrode, 4 is the gate insulating layer, 5 is the source electrode, and 6 is the drain electrode.

Examples of substrates include plastic substrates such as polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefin, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, and cellulose triacetate; inorganic substrates such as glass, quartz, aluminum oxide, silicon, highly doped silicon, silicon oxide, tantalum dioxide, tantalum pentoxide, and indium tin oxide; and metal substrates such as gold, copper, chromium, titanium, and aluminum. Among these, glass, silicon, and highly doped silicon are preferred due to their excellent transistor performance, with glass being more preferred.

Examples of gate electrodes include inorganic electrodes such as aluminum, gold, silver, copper, highly doped silicon, tin oxide, indium oxide, indium tin oxide, chromium, titanium, tantalum, chromium, graphene, and carbon nanotubes, as well as organic electrodes such as doped conductive polymers (PEDOT-PSS). Of these, inorganic electrodes are preferred due to their good conductivity, and gold is more preferred.

Examples of insulating layers include inorganic insulating layers such as silicon oxide, silicon nitride, aluminum oxide, aluminum nitride, titanium oxide, tantalum dioxide, tantalum pentoxide, indium tin oxide, tin oxide, vanadium oxide, barium titanate, and bismuth titanate; and organic insulating layers such as polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polymethyl acrylate, polyethylene, polypropylene, polystyrene, cyclic polyolefins, polyimide, polycarbonate, polyvinylphenol, polyvinyl alcohol, poly(diisopropyl fumarate), poly(diethyl fumarate), poly(diisopropyl maleate), polyethersulfone, polyphenylene sulfide, cellulose triacetate, polycyclopentane, polycyclohexane-ethylene copolymer, polyfluorinated cyclopentane, Cytop, polyfluorinated cyclohexane, polyfluorinated cyclohexane-ethylene copolymer, Parylene N, Parylene C, Parylene D, Parylene HT, and Parylene C-UVF. Of these, organic insulating layers are preferred due to their excellent insulating properties, and parylene C is more preferred. The surfaces of these insulating layers may also be modified with, for example, silanes such as octadecyltrichlorosilane, decyltrichlorosilane, decyltrimethoxysilane, octyltrichlorosilane, octadecyltrimethoxysilane, β-phenethyltrichlorosilane, β-phenethyltrimethoxysilane, phenyltrichlorosilane, and phenyltrimethoxysilane; phosphonic acids such as octadecylphosphonic acid, decylphosphonic acid, and octylphosphonic acid; and amines such as hexamethyldisilazane. Of these, modification with octadecyltrichlorosilane, octyltrichlorosilane, β-phenethyltrichlorosilane, octadecylphosphonic acid, octylphosphonic acid, or hexamethyldisilazane is preferred due to the improved carrier mobility and current on/off ratio and lower threshold voltage of the organic thin-film transistor element of this embodiment.

Examples of the source electrode and drain electrode include the same electrodes as those exemplified for the gate electrode. Of these, inorganic electrodes are preferred due to their good conductivity, and gold is more preferred. Furthermore, to improve carrier injection efficiency, these electrodes can be surface-treated using a surface treatment material. Examples of such surface treatment materials include benzenethiol and pentafluorobenzenethiol.

The present invention will be explained in more detail below using examples, but the present invention is not limited to the following examples.

The monomers and their precursors used as raw materials in the examples were subjected to structural analysis by ¹ H-NMR measurement. The molecular weight and molecular weight distribution of the conjugated polymers obtained in the examples were estimated by gel permeation chromatography (GPC) measurement. Commercially available reagents were used.

<NMR measurement conditions>
Measurement equipment: Bruker ASCEND ^™ ADVANCE III HD (400 MHz)
Measurement solvent: deuterated chloroform (CDCl ₃ ), deuterated dimethyl sulfoxide (DMSO-d ₆ ), deuterated benzene (C ₆ D ₆ )
Internal standard: tetramethylsilane (TMS)

<GPC measurement conditions>
Measurement equipment: Tosoh Corporation high-speed GPC equipment HLC-8320GPC EcoSEC
Column: TSKgel SuperMultiporeHZ-H, TSKgel SuperHZ2000
Measurement solvent: THF
Measurement temperature: 25℃
Calibration curve: polystyrene standards

<High-temperature GPC measurement conditions>
Measurement equipment: Tosoh Corporation high temperature GPC equipment HLC-8321GPC/HT
Column: TSKgel GMH _HR -H(20)HT
Measurement solvent: 1,2,4-trichlorobenzene (TCB)
Measurement temperature: 140℃
Calibration curve: polystyrene standards

<TGA measurement conditions>
Measurement equipment: SII Corporation EXSTAR6000 TGA/DTA6200
Sample container: aluminum pan Measurement atmosphere: nitrogen Flow rate: 50 mL/min
Temperature increase rate: 10°C/min
T _d3 , T _d5 and T _d10 represent the 3%, 5% and 10% weight loss temperatures, respectively.

<DSC measurement conditions>
Measuring device: SII Corporation EXSTAR6000 DSC6220
Sample container: Aluminum pan Measurement conditions: Nitrogen atmosphere, 10°C/min, 0 to 300°C, results obtained using the third HeatingScan.

<Ionization potential measurement conditions>
Measurement equipment: Riken Keiki Co., Ltd. atmospheric photoelectron spectrometer AC-5
Measurement conditions: Measurement in air, light intensity 3 nW

[Reference example 1]

A hexane solution of n-butyllithium (2.3 mL, 3.56 mmol) was added to a mixture of thieno[3,2-b]thiophene (500 mg, 3.56 mmol) and tetrahydrofuran (35 mL) at 0°C, and the mixture was stirred for 1 hour. Subsequently, triisopropylsilyl chloride (0.83 mL, 756 mg, 3.92 mmol) was added, and the mixture was stirred at room temperature for 2 hours. Water was added to the reaction solution, and the mixture was extracted with hexane. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered. The solvent was then distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give 2-triisopropylsilylthieno[3,2-b]thiophene (924 mg, 88%) as a colorless solid.
¹ H-NMR (CDCl ₃ , 400MHz) δ7.39 (d, J=5.2Hz, 1H), 7.37 (d, J=0.4Hz, 1H), 7.25 (dd, J= 5.2Hz, 0.4Hz, 2H), 1.37 (sep, J=7.6Hz, 3H), 1.13 (d, J=7.6Hz, 18H).

[Reference example 2]

N-Bromosuccinimide (660 mg, 3.71 mmol) was added to a mixture of 2-triisopropylsilylthieno[3,2-b]thiophene (1.00 g, 3.37 mmol) obtained in Reference Example 1 and THF (34 mL), and the mixture was stirred at room temperature for 22.5 hours. Water was added to the resulting mixture, which was then extracted with hexane. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give 2-bromo-5-triisopropylsilylthieno[3,2-b]thiophene (900 mg, 71%) as a colorless solid.
¹ H-NMR (DMSO-d6, 400MHz) δ7.66 (s, 1H), 7.56 (s, 1H), 1.40-1.30 (m, 3H), 1.08 (d, J = 7.6Hz, 18H).

[Reference example 3]

Ethynylmagnesium bromide (100 mL, 50.0 mmol) was added dropwise to a mixture of 11-heneicosanone (12.9 g, 41.7 mmol) and tetrahydrofuran (83 mL) at 0°C, and the mixture was stirred at room temperature for 22.5 hours. Saturated aqueous ammonium chloride solution was added to the resulting mixture, and the mixture was extracted with diethyl ether. The collected organic layer was washed with water and saturated brine, then dried over anhydrous magnesium sulfate and filtered. The solvent was then distilled off under reduced pressure to obtain 11-ethynyl-heneicosan-11-ol (14.0 g) as a pale yellow liquid.

A mixture of 2-bromo-5-triisopropylsilylthieno[3,2-b]thiophene (3.75 g, 10.0 mmol) obtained in Reference Example 2, 11-ethynyl-heneicosan-11-ol (3.70 g), and triethylamine (200 mL) was bubbled with argon for 30 minutes. To this mixture, copper(I) iodide (190 mg, 1.00 mmol) and Pd(PPh ₃ ) ₄ (578 mg, 0.500 mmol) were added under an argon stream, and the mixture was stirred at 100°C for 107 hours. The resulting mixture was cooled to room temperature, and then saturated aqueous ammonium chloride solution was added, followed by extraction with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=4/1→3/1→2/1) to give a pale yellow liquid of 11-(5-triisopropylsilyl-thieno[3,2-b]thiophen-2-ylethynyl)-heneicosan-11-ol (5.05 g, 80%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.31 (d, J=0.8Hz, 1H), 7.28 (d, J=0.4Hz, 1H), 1.77-1.70 (m, 4H), 1.5 6-1.51 (m, 4H), 1.43-1.27 (m, 31H), 1.12 (d, J=7.2Hz, 18H), 0.90-0.86 (m, 6H).

[Reference example 4]

To a mixture of 11-(5-triisopropylsilyl-thieno[3,2-b]thiophen-2-ylethynyl)-heneicosan-11-ol (2.71 g, 4.29 mmol) obtained in Reference Example 3 and dichloromethane (86 mL) was added iodine (1.63 g, 6.44 mmol) at −15° C., and the mixture was stirred at −15° C. for 5 hours. A saturated aqueous solution of sodium thiosulfate was added to the resulting mixture, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give 2-triisopropylsilyl-5,6-diiodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (2.87 g, 77%) as a reddish-brown liquid.
¹ H-NMR (CDCl ₃ , 400MHz) δ7.40 (s, 1H), 1.94-1.86 (m, 2H), 1.68-1.61 (m, 2H), 1.43-1.11 (m, 47H), 0.90-0.84 (m, 10H), 0.61-0.55 (m, 2H).

[Reference example 5]

To a mixture of 2-triisopropylsilyl-5,6-diiodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (551 mg, 0.636 mmol) obtained in Reference Example 4 and tetrahydrofuran (6.4 mL), a hexane solution of n-butyllithium (0.40 mL, 0.636 mmol) was added at −78° C., and the mixture was stirred for 1.5 hours. Thereafter, 11-heneicosanone (237 mg, 0.763 mmol) was added, and the mixture was stirred at room temperature for 2 hours. A saturated aqueous solution of ammonium chloride was added to the resulting mixture, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=10/1→5/1→2/1→1/1) to give a colorless solid, 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-iodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (431 mg, 64%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.36 (s, 1H), 2.39-2.32 (m, 2H), 1.84-1.77 (m, 2H), 1.70-1. 58 (m, 4H), 1.47-1.10 (m, 81H), 0.87-0.84 (m, 14H), 0.57-0.48 (m, 2H).

[Reference example 6]

A mixture of 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-iodo-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (2.04 g, 1.94 mmol) obtained in Reference Example 5, thieno[3,2-b]thiophene-2-boronic acid (714 mg, 3.88 mmol), 1,2-dimethoxyethane (49 mL), and 2 M aqueous potassium carbonate (19 mL, 38 mmol) was bubbled with argon for 30 minutes. To this mixture was added (AMPHOS) ₂ PdCl ₂ (69 mg, 97 μmol) under an argon stream, and the mixture was stirred at 100° C. for 37.5 hours. The resulting mixture was cooled to room temperature, saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The combined organic layers were washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform = 10/1 → 5/1 → 2/1) to give 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (1.06 g, 52%) as a yellow solid.
¹ H-NMR (CDCl ₃ , 400MHz) δ7.41 (s, 1H), 7.38 (d, J=5.2Hz, 1H), 7.27-7.26 (m, 1H), 7.00 (s, 1H), 1.93-1.83 (m, 4H), 1.76-1.69 (m, 2H), 1.64-1.57 (m, 2H), 1.47-1.14 (m, 83H), 0.88-0.84 (m, 12H), 0.72-0.69 (m, 2H).

[Reference example 7]

To a mixture of 2-triisopropylsilyl-5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (1.30 g, 1.22 mmol) obtained in Reference Example 6 and tetrahydrofuran (24 mL) was added a 1 M solution of tetrabutylammonium fluoride in tetrahydrofuran (1.5 mL, 1.5 mmol), and the mixture was stirred at room temperature for 22 hours. Water was added to the resulting mixture, which was then extracted with ethyl acetate. The combined organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=5/1→2/1) to give a yellow solid of 5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (0.995 g, 90%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.39 (d, J=5.2Hz, 1H), 7.31 (s, 2H), 7.27-7.26 (m, 1H), 6.70 (s, 1H), 1.89-1.60 (m, 8H), 1.51-1.13 (m, 60H), 0.88-0.84 (m, 14H), 0.74-0.63 (m, 2H).

[Reference example 8]

To a mixture of 5-(1-decyl-1-hydroxyundecyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (300 mg, 0.330 mmol) obtained in Reference Example 7 and tetrahydrofuran (6.6 mL), N-bromosuccinimide (129 mg, 0.727 mmol) was added at 0°C, and the mixture was stirred at room temperature for 23 hours. A saturated aqueous solution of sodium thiosulfate was added to the resulting mixture, which was then extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=5/1→2/1) to give a yellow solid, 2-bromo-5-(1-decyl-1-hydroxyundecyl)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (268 mg, 76%).
¹ H-NMR (C ₆ D ₆ , 400MHz) δ7.00 (s, 1H), 6.74 (s, 1H), 6.67 (s, 1H), 2.00-1.80 (m, 6H), 1.69-1.47 (m, 8H), 1.33-1.21 (m, 54H), 0.92-0.89 (m, 16H).

[Reference example 9]

A mixture of 2-bromo-5-(1-decyl-1-hydroxyundecyl)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-didecyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (114 mg, 0.107 mmol) obtained in Reference Example 8 and dichloromethane (4.3 mL) was freeze-degassed. To this mixture, a 1 M solution of tin tetrachloride in dichloromethane (100 μL, 100 μmol) was added under an argon atmosphere, and the mixture was stirred at −15°C for 5 hours. A saturated aqueous solution of sodium bicarbonate was added to the resulting mixture, and the mixture was extracted with hexane. The combined organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered. The solvent was then distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give (mono-hal-28) as a red solid (78 mg, 70%).
¹ H-NMR (C ₆ D ₆ , 400 MHz) δ6.69 (s, 2H), 2.11-2.03 (m, 8H), 1.28-1.08 (m, 62H), 0.91-0.87 (m, 14H).

[Reference example 10]

To a mixture of (mono-hal-28) (200 mg, 0.191 mmol) obtained in Reference Example 9 and tetrahydrofuran (3.8 mL), a hexane solution of n-butyllithium (0.27 mL, 0.420 mmol) was added at 0°C and stirred for 3 hours. Then, trimethyltin chloride (91.3 mg, 0.458 mmol) was added, and the mixture was stirred at room temperature for 22 hours. Water was added to the reaction solution, and the mixture was extracted with hexane. The collected organic layer was washed with water and saturated brine, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by reprecipitation (acetone) to give (mono-Sn-28) as a red solid (131 mg, 56%).
¹ H-NMR (C ₆ D ₆ , 400MHz) δ6.87 (s, 2H), 2.17-2.07 (m, 8H), 1.28-1.23 (m, 4H), 1.07-0.95 (m, 60H), 0.69 (t, J=7.0Hz, 12H), 0.07 (s, 18H).

[Example 1]

A mixture of (mono-hal-28) (100 mg, 95.5 μmol) obtained in Reference Example 9, 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (37.0 mg, 68.3 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.1 mL), and 1 M aqueous sodium carbonate solution (0.64 mL, 0.64 mmol) was bubbled with argon for 30 minutes. To this mixture, Pd ₂ (dba) 3.CHCl ₃ (2.0 mg, 1.9 μmol) and tri(o-tolyl)phosphine (2.3 mg, 7.6 μmol) were added _, and the mixture was stirred at 120° C. for 60 hours. The resulting mixture was cooled to room temperature and then precipitated in a mixed solution of methanol and concentrated hydrochloric acid (150 mL/15 mL), and the precipitated solid was filtered. The resulting solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. The residue on the filter was then dissolved in n-decane. The resulting mixture was concentrated under reduced pressure, and the precipitated solid was filtered by precipitating it in methanol. The resulting solid was washed with methanol and then dried under reduced pressure at 90°C, yielding black solid (3-10) (65.3 mg, 67%).
GPC (THF): Mn=10500g/mol, Mw=17800g/mol, PDI=1.69.
GPC (TCB, 140°C): Mn=8900g/mol, Mw=30300g/mol, PDI=3.4.
T _d3 = 396°C, T _d5 = 403°C, T _d10 = 417°C.
No phase transition point was observed by DSC.

[Example 2]

A mixture of (mono-Sn-28) (100 mg, 82.3 μmol) obtained in Reference Example 10, 4,7-dibromo-2,1,3-benzothiadiazole (24.2 mg, 82.3 μmol), and tetralin (2.5 mL) was bubbled with argon for 30 minutes. To this mixture, Pd ₂ (dba) ₃ ·CHCl ₃ (1.7 mg, 1.6 μmol) and tri(o-tolyl)phosphine (2.0 mg, 6.6 μmol) were added, and the mixture was stirred at 180°C for 2 hours using a microwave reactor. Thereafter, 2-(tributylstannyl)thiophene (0.23 mL, 276 mg, 0.74 mmol) was added to the reaction solution, and the mixture was stirred at 180°C for 10 minutes using a microwave reactor. Further, 2-bromothiophene (0.08 mL, 134 mg, 0.82 mmol) was added, and the mixture was stirred at 180°C for 10 minutes using a microwave reactor. The resulting mixture was cooled to room temperature and then precipitated in a mixed solution of methanol and concentrated hydrochloric acid (150 mL/15 mL), and the precipitated solid was filtered. The resulting solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. The residue on the filter was then dissolved in chloroform. The resulting mixture was concentrated under reduced pressure, and the precipitated solid was precipitated in methanol, and the precipitated solid was filtered. The resulting solid was washed with methanol and then dried under reduced pressure at 90°C, yielding a black solid (3-10) (60 mg, 71%).
GPC (THF): Mn=21000g/mol, Mw=34000g/mol, PDI=1.62.
GPC (TCB, 140°C): Mn=7000g/mol, Mw=21000g/mol, PDI=3.0.
T _d3 = 364°C, T _d5 = 381°C, T _d10 = 397°C.
No phase transition point was observed by DSC.

[Example 3]
A 0.5 wt % o-DCB solution of the conjugated polymer (3-10) synthesized in Example 1 was heated in a glove box under a nitrogen atmosphere to prepare a composition for forming an organic thin film.

After cooling to room temperature, the solution was filtered through a 0.22 μm filter, confirming that the compound remained in solution and was suitable for film formation.

Next, a Parylene C film was formed on a glass substrate as an underlayer using the CVD method. A shadow mask with a channel length of 100 μm and a channel width of 500 μm was then placed on the Parylene C layer, and gold was evaporated under vacuum to form source and drain electrodes. The solution prepared above was spin-coated in a glove box under a nitrogen atmosphere. This was heated to 150°C and held for 15 minutes to create an organic thin film of conjugated polymer (3-10). A Parylene C film was then formed as a gate insulating film using the CVD method, and a silver electrode was then formed by evaporation, resulting in a top-gate-bottom-contact organic thin-film transistor device (the gate electrode was silver, the gate insulating layer was Parylene C, and the source and drain electrodes were gold).

The organic thin-film transistor element was connected to a semiconductor parameter analyzer (Keithley, 4200A-SCS model) in air, and the gate voltage (Vg) was scanned in 1 V increments from +10 to -100 V at a drain voltage (Vd = -100 V) to evaluate the transfer characteristics. The organic thin-film transistor element exhibited p-type characteristics, and the hole carrier mobility was 0.046 cm ² /Vs. Furthermore, after annealing at 150°C for 15 minutes, the hole carrier mobility was 0.043 cm ² /Vs. This confirmed that the carrier mobility did not decrease even after heat treatment.

[Example 4]
The same operation as in Example 3 was repeated, except that the source electrode and drain electrode were surface-treated with pentafluorobenzenethiol. The obtained organic thin-film transistor element exhibited p-type characteristics, and its hole carrier mobility was 0.078 cm ² /Vs. Furthermore, after annealing treatment at 150°C for 15 minutes, the hole carrier mobility was 0.074 cm ² /Vs. This confirmed that the carrier mobility did not decrease even after heat treatment.

[Example 5]
The same procedure as in Example 3 was repeated, except that the conjugated polymer (3-10) synthesized in Example 2 was used. The obtained organic thin-film transistor device exhibited p-type characteristics, and its hole carrier mobility was 0.077 cm ² /Vs. Furthermore, after annealing at 150°C for 15 minutes, the hole carrier mobility was 0.075 cm ² /Vs. This confirmed that the carrier mobility did not decrease even after heat treatment.

[Example 6]
A 0.5 wt % o-DCB solution of the conjugated polymer (3-10) synthesized in Example 1 was heated in a glove box under a nitrogen atmosphere to prepare a composition for forming an organic thin film. Next, a film of parylene C was formed as an underlayer on a glass substrate by CVD, and then the solution prepared above was spin-coated in a glove box under a nitrogen atmosphere. This was heated to 150°C and held for 15 minutes to produce an organic thin film of the conjugated polymer (3-10). The ionization potential of the resulting organic thin film was 5.26 eV, confirming its high atmospheric stability.

[Example 7]
The same procedure as in Example 6 was repeated, except that the conjugated polymer (3-10) synthesized in Example 2 was used. The ionization potential of the obtained organic thin film was 5.15 eV, confirming high atmospheric stability.

[Reference example 11]

Ethynylmagnesium bromide (30.0 mL, 15.0 mmol) was added dropwise to a mixture of 7-tridecanone (2.00 g, 10.0 mmol) and tetrahydrofuran (20 mL) at 0°C, and the mixture was stirred at room temperature for 19 hours. A saturated aqueous solution of ammonium chloride was added to the resulting mixture, and the mixture was extracted with diethyl ether. The collected organic layer was washed with water and saturated brine, then dried over anhydrous magnesium sulfate and filtered. The solvent was then distilled off under reduced pressure to obtain 11-ethynyl-heneicosan-11-ol (1.51 g) as a pale yellow liquid.

A mixture of 2-bromo-5-triisopropylsilylthieno[3,2-b]thiophene (2.30 g, 6.12 mmol) obtained in Reference Example 2, 7-ethynyl-tridecan-7-ol (1.51 g, 6.73 mmol), and triethylamine (123 mL) was bubbled with argon for 30 minutes. To this mixture, copper(I) iodide (116 mg, 612 μmol) and Pd(PPh ₃ ) ₄ (354 mg, 306 μmol) were added under an argon stream, and the mixture was stirred at 100°C for 65 hours. The resulting mixture was cooled to room temperature, and then saturated aqueous ammonium chloride solution was added, followed by extraction with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane → hexane/chloroform = 1/1) to give a yellow liquid of 7-(5-triisopropylsilyl-thieno[2,3-d]thiophen-2-ylethynyl)-tridecan-7-ol (2.80 g, 88%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.31 (s, 1H), 7.28 (s, 1H), 2.03 (s, 1H), 1.76-1.71 (m, 4H), 1.58- 1.51 (m, 4H), 1.40-1.26 (m, 15H), 1.12 (d, J=7.4Hz, 18H), 0.91-0.88 (m, 6H).

[Reference example 12]

To a mixture of 7-(5-triisopropylsilyl-thieno[3,2-b]thiophen-2-ylethynyl)-tridecan-7-ol (2.65 g, 5.11 mmol) obtained in Reference Example 11 and dichloromethane (103 mL) was added iodine (1.94 g, 7.66 mmol) at −15° C., and the mixture was stirred at −15° C. for 5 hours. A saturated aqueous solution of sodium thiosulfate was added to the resulting mixture, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give 2-triisopropylsilyl-5,6-diiodo-7,7-dihexyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (3.21 g, 83%) as a reddish-brown liquid.
¹ H-NMR (CDCl ₃ , 400MHz) δ7.40 (s, 1H), 1.95-1.85 (m, 2H), 1.68-1.61 (m, 2H), 1.43-1.11 (m, 31H), 0.90-0.75 (m, 10H), 0.61-0.52 (m, 2H).

[Reference example 13]

To a mixture of 2-triisopropylsilyl-5,6-diiodo-7,7-dihexyl-7H-cyclopenta[b]thieno[2,3-d]thiophene (3.06 g, 4.06 mmol) obtained in Reference Example 12 and tetrahydrofuran (41 mL), a hexane solution of n-butyllithium (2.60 mL, 4.06 mmol) was added at −78° C., and the mixture was stirred for 1.5 hours. Thereafter, 7-tridecanone (966 mg, 4.87 mmol) was added, and the mixture was stirred at room temperature for 2 hours. A saturated aqueous solution of ammonium chloride was added to the resulting mixture, and the mixture was extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=9/1) to give 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyheptyl)-6-iodo-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (2.04 mg, 61%) as a brown liquid.
¹ H-NMR (CDCl ₃ , 400MHz) δ7.37 (s, 1H), 2.40-2.33 (m, 2H), 2.04 (s, 1H), 1.85-1.77 (m, 2H), 1 70-1.58 (m, 4H), 1.46-1.09 (m, 49H), 0.90-0.75 (m, 14H), 0.52-0.48 (m, 2H).

[Reference example 14]

A mixture of 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyheptyl)-6-iodo-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.57 g, 1.90 mmol) obtained in Reference Example 13, thieno[3,2-b]thiophene-2-boronic acid (699 mg, 3.80 mmol), 1,2-dimethoxyethane (47 mL), and 2 M aqueous potassium carbonate (19 mL, 38 mmol) was bubbled with argon for 30 minutes. To this mixture was added (AMPHOS) ₂ PdCl ₂ (67.3 mg, 95.0 μmol) under an argon stream, and the mixture was stirred at 100° C. for 72 hours. The resulting mixture was cooled to room temperature, saturated aqueous ammonium chloride solution was added, and the mixture was extracted with ethyl acetate. The combined organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered, and the solvent was removed by distillation under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform = 4/1 → 1/1) to give a yellow solid, 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyheptyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.34 g, 84%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.41 (s, 1H), 7.38 (d, J=5.2Hz, 1H), 7.27-7.26 (m, 1H), 7.00 (s, 1H), 2.15 (s, 1H), 1.94-1.84 ( m, 4H), 1.76-1.69 (m, 2H), 1.65-1.58 (m, 2H), 1.48-1.14 (m, 50H), 0.85-0.77 (m, 12H), 0.75-0.68 (m, 3H).

[Reference example 15]

To a mixture of 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyheptyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.42 g, 1.70 mmol) obtained in Reference Example 14 and tetrahydrofuran (34 mL) was added a 1 M solution of tetrabutylammonium fluoride in tetrahydrofuran (2.2 mL, 2.2 mmol), and the mixture was stirred at room temperature for 17 hours. Water was added to the resulting mixture, which was then extracted with ethyl acetate. The combined organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=7/3) to give a yellow-brown liquid of 5-(1-hexyl-1-hydroxyheptyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (0.995 g, 90%).
¹ H-NMR (CDCl ₃ , 400MHz) δ7.39 (d, J=5.2Hz, 1H), 7.31 (s, 2H), 7.27 (d, J=5.2Hz, 1H), 7.00 (s, 1H), 2.14 (s, 1H), 1.92-1.71 (m, 6H), 1.65-1.55 (m, 2H), 1.49-1.44 (m, 2H), 1.33-1.13 (m, 28H), 0.85-0.78 (m, 12H), 0.69-0.66 (m, 2H).

[Reference example 16]

To a mixture of 5-(1-hexyl-1-hydroxyheptyl)-6-thieno[3,2-b]thiophen-2-yl-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (1.02 g, 1.51 mmol) obtained in Reference Example 15 and tetrahydrofuran (31 mL), N-bromosuccinimide (591 mg, 3.32 mmol) was added at 0°C, and the mixture was stirred at room temperature for 15 hours. A saturated aqueous solution of sodium thiosulfate was added to the resulting mixture, which was then extracted with ethyl acetate. The collected organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane/chloroform=85/15→1/1) to obtain a yellow solid, 2-bromo-5-(1-hexyl-1-hydroxyheptyl)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene.
¹ H-NMR (C ₆ D ₆ , 400MHz) δ 7.04 (s, 1H), 6.81 (s, 1H), 6.71 (s, 1H), 2.04-1.83 (m, 6H), 1.72-1.54 (m, 8H), 1.40-1.18 (m, 26H), 0.99-0.88 (m, 12H).

[Reference example 17]

A mixture of 2-bromo-5-(1-hexyl-1-hydroxyheptyl)-6-(5-bromo-thieno[3,2-b]thiophen-2-yl)-7,7-dihexyl-7H-cyclopenta[b]thieno[3,2-b]thiophene (100 mg, 119 μmol) obtained in Reference Example 16 and dichloromethane (4.8 mL) was freeze-degassed. To this mixture, a 1 M solution of tin tetrachloride in dichloromethane (130 μL, 130 μmol) was added under an argon atmosphere, and the mixture was stirred at −15° C. for 1 hour. A saturated aqueous solution of sodium bicarbonate was added to the resulting mixture, and the mixture was extracted with hexane. The collected organic layer was washed with water and saturated brine, then dried over anhydrous magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give (mono-hal-16) as a red solid (85 mg, 87%).
¹ H-NMR (C ₆ D ₆ , 400 MHz) δ6.67 (s, 2H), 2.09-1.98 (m, 8H), 1.28-1.03 (m, 32H), 0.79-0.75 (m, 12H).

[Example 8]

A mixture of (mono-hal-28) (100 mg, 95.5 μmol) obtained in Reference Example 9, 2,5-bis(2-octyldodecyl)-3,6-bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (106 mg, 95.5 μmol), tetrahydrofuran (1.9 mL), and 2 M aqueous potassium carbonate solution (1.0 mL, 2.0 mmol) was bubbled with argon for 30 minutes. To this mixture was added bis(tri-t-butylphosphine)palladium(0) (2.4 mg, 4.8 μmol), and the mixture was stirred at 80° C. for 62 hours. Subsequently, 2-thiopheneboronic acid (110 mg, 860 μmol) was added to the reaction solution and stirred at 80°C for 4 hours. Furthermore, 2-bromothiophene (92 μL, 950 μmol) was added and stirred at 80°C for 4 hours. The resulting mixture was cooled to room temperature and then precipitated in a mixed solution of methanol and concentrated hydrochloric acid (150 mL/15 mL). The precipitated solid was filtered. The resulting solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. The residue on the filter was then dissolved in chloroform. The resulting mixture was concentrated under reduced pressure, and the precipitated solid was filtered by precipitation in methanol. The resulting solid was washed with methanol and then dried under reduced pressure at 90°C to obtain a black solid (3-650) (105 mg, 63%).
GPC (THF): Mn=24400g/mol, Mw=41500g/mol, PDI=1.70.

[Example 9]

A mixture of (mono-hal-16) (100 mg, 121 μmol) obtained in Reference Example 17, 4,7-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2,1,3-benzothiadiazole (47.0 mg, 121 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.9 mL), and 1 M aqueous sodium carbonate solution (0.81 mL, 0.81 mmol) was bubbled with argon for 30 minutes. To this mixture, Pd ₂ (dba) 3.CHCl ₃ (2.5 mg, 2.4 μmol) and tri(o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added _, and the mixture was stirred at 120° C. for 64 hours. The resulting mixture was cooled to room temperature and then precipitated in a mixed solution of methanol and concentrated hydrochloric acid (150 mL/15 mL), and the precipitated solid was filtered. The resulting solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. The residue on the filter was then dissolved in chloroform. The resulting mixture was concentrated under reduced pressure, and the precipitated solid was filtered by precipitating it in methanol. The resulting solid was washed with methanol and then dried under reduced pressure at 90°C to obtain (3-166) as a black solid (47 mg, 49%).
GPC (THF): Mn=5200g/mol, Mw=11800g/mol, PDI=2.27.

[Example 10]

A mixture of (mono-hal-16) (100 mg, 121 μmol) obtained in Reference Example 17, 2,5-bis(2-octyldodecyl)-3,6-bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (135 mg, 121 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.9 mL), and 1 M aqueous sodium carbonate solution (0.81 mL, 0.81 mmol) was subjected to argon bubbling for 30 minutes. To this mixture, Pd ₂ (dba) ₃ ·CHCl ₃ (2.5 mg, 2.4 μmol) and tri(o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added, and the mixture was stirred at 120°C for 66 hours. The resulting mixture was cooled to room temperature and then precipitated in a mixed solution of methanol and concentrated hydrochloric acid (150 mL/15 mL). The precipitated solid was filtered. The resulting solid was subjected to Soxhlet extraction using methanol, acetone, and hexane to remove components soluble in these solvents. The residue on the filter was then dissolved in chloroform. The resulting mixture was concentrated under reduced pressure, and the precipitated solid was filtered by precipitation in methanol. The resulting solid was washed with methanol and then dried under reduced pressure at 90°C to obtain a black solid (3-646) (12 mg, 7%).
GPC (THF): Mn=14800g/mol, Mw=30000g/mol, PDI=2.03.

[Example 11]

A mixture of (mono-hal-16) (100 mg, 121 μmol) obtained in Reference Example 17, 2,5-bis(2-decyltetradecyl)-3,6-bis[5-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)thiophen-2-yl]pyrrolo[3,4-c]pyrrole-1,4(2H,5H)-dione (148 mg, 121 μmol), one drop of tri(n-octylmethyl)ammonium chloride (PTC), toluene (3.9 mL), and 1 M aqueous sodium carbonate solution (0.81 mL, 0.81 mmol) was subjected to argon bubbling for 30 minutes. To this mixture, Pd ₂ (dba) ₃ ·CHCl ₃ (2.5 mg, 2.4 μmol) and tri(o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added, and the mixture was stirred at 120°C for 65 hours. The resulting mixture was cooled to room temperature and then precipitated in a mixed solution of methanol and concentrated hydrochloric acid (150 mL/15 mL). The precipitated solid was filtered. The resulting solid was subjected to Soxhlet extraction using methanol and acetone to remove components soluble in these solvents. The residue on the filter was then dissolved in hexane. The resulting mixture was concentrated under reduced pressure, and the precipitated solid was filtered. The resulting solid was washed with methanol and then dried under reduced pressure at 90°C to obtain (3-666) as a black solid (78 mg, 40%).
GPC (THF): Mn=5500g/mol, Mw=8400g/mol, PDI=1.53

[Comparative Example 1]
The same procedure as in Example 5 was repeated, except that poly2,5-bis(3-tetradecylthiophen-2-yl)thieno-3,2-b-thiophene (Sigma-Aldrich) was used. The ionization potential of the obtained organic thin film was 4.93 eV, and it was confirmed that the film had poor atmospheric stability.

The conjugated polymer provided by this embodiment provides high carrier mobility and has excellent solubility in solvents and heat resistance, and is therefore expected to be used as a semiconductor device material, such as an organic thin-film transistor element or an organic thin-film solar cell.

1 organic semiconductor layer 2 substrate 3 gate electrode 4 gate insulating layer 5 source electrode 6 drain electrode

Claims (17)

A structural unit represented by the following general formula (1),
(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may be combined together to form a ring with the carbon atom to which they are bonded. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may be combined together to form a ring with the carbon atom to which they are bonded. ^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom.)
A conjugated polymer comprising a structural unit represented by the following general formula (2):
(wherein ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms). The conjugated polymer according to claim 1, having structural units represented by the general formula (1) and structural units represented by the general formula (2) alternately. R ¹ and R ² each independently represent an alkyl group having 1 to 34 carbon atoms;
R ¹ and R ² may be joined together to form a ring together with the carbon atoms to which they are attached;
^R3 and ^R4 each independently represent an alkyl group having 1 to 34 carbon atoms;
^R3 and ^R4 may be joined together to form a ring together with the carbon atoms to which they are attached;
^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 34 carbon atoms, or a fluorine atom;
3. The conjugated polymer according to claim 1, wherein ^J1 , ^J2 , ^J3 , and ^J4 each independently represent an oxygen atom, a sulfur atom, or a selenium atom. ^R5 and ^R6 are hydrogen atoms;
4. The conjugated polymer according to claim 1, wherein J ¹ , J ² , J ³ and J ⁴ are sulfur atoms. The conjugated polymer according to any one of claims 1 to 4, wherein X ¹ is a divalent heteroaromatic ring linking group selected from the group consisting of the following general formulas (4) to (8):
(In the formula, A ¹ represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. R ⁷ represents one group selected from the group consisting of an alkyl group having 1 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, a fluorine atom, and a hydrogen atom. Multiple R ^7s may be the same or different. R ⁸ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple R ^8s may be the same or different. p ¹ and q ¹ each independently represent 0 or 1.)
(In the formula, ^A2 represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. ^A3 represents a chalcogen atom. ^R9 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple ^R9s may be the same or different. ^p2 and ^q2 each independently represent 0 or 1.)
(In the formula, ^A4 and ^A5 each independently represent a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. ^R10 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple ^R10s may be the same or different. ^R11 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple ^R11s may be the same or different. ^p3 and ^q3 each independently represent 0 or 1.)
(In the formula, R ¹² represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple R ¹² may be the same or different. ^{p 4} and q ⁴ each independently represent 0 or 1.)
(In the formula, R ¹³ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple R ^13s may be the same or different. p ⁵ and q ⁵ each independently represent 0 or 1.) A ¹ , A ² , A ³ , A ⁴ and A ⁵ each independently represent an oxygen atom, a sulfur atom, a selenium atom or a nitrogen atom which may be substituted with an alkyl group having 6 to 50 carbon atoms;
R ⁷ is a group selected from the group consisting of an alkoxy group having 6 to 50 carbon atoms, a fluorine atom, or a hydrogen atom;
6. The conjugated polymer according to claim 5, wherein R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an alkyl group having 6 to 50 carbon atoms or a hydrogen atom, and R ¹² and R ¹³ each independently represent an alkyl group having 6 to 50 carbon atoms. A ¹ and A ² are sulfur atoms;
^A3 is an oxygen atom or a nitrogen atom optionally substituted with an alkyl group having 6 to 34 carbon atoms,
^A4 is an oxygen atom, a sulfur atom or a selenium atom,
^A5 is an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom which may be substituted with an alkyl group having 6 to 34 carbon atoms;
R ⁷ is a group selected from the group consisting of an alkoxy group having 6 to 34 carbon atoms, a fluorine atom, or a hydrogen atom;
R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ each independently represent an alkyl group having 6 to 34 carbon atoms or a hydrogen atom;
7. The conjugated polymer according to claim 5, wherein R ¹² and R ¹³ each independently represent an alkyl group having 6 to 34 carbon atoms. A monomer represented by the following general formula (mono-hal):
(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may be combined together to form a ring with the carbon atom to which they are bonded. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may be combined together to form a ring with the carbon atom to which they are bonded. ^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-hal and M2 ^-hal each independently represent a halogen atom.)
The method includes reacting a monomer represented by the following general formula (mono-X ¹ -B) in the presence of a transition metal catalyst:
(In the formula, ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms. ^M3-B and M4 ^-B each independently represent a boron-containing group.)
A structural unit represented by the following general formula (1),
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ and J ⁴ have the same meanings as defined above.)
and a structural unit represented by the following general formula (2):
(In the formula, ^X1 has the same meaning as above.) A monomer represented by the following general formula (mono-hal):
(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may be combined together to form a ring with the carbon atom to which they are bonded. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may be combined together to form a ring with the carbon atom to which they are bonded. ^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-hal and M2 ^-hal each independently represent a halogen atom.)
The method comprises reacting a monomer represented by the following general formula (mono-X ¹ -Sn) in the presence of a transition metal catalyst:
(In the formula, ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms. ^M3-Sn and M4 ^-Sn each independently represent a tin-containing group.)
A structural unit represented by the following general formula (1),
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ and J ⁴ have the same meanings as defined above.)
and a structural unit represented by the following general formula (2):
(In the formula, ^X1 has the same meaning as above.) A monomer represented by the following general formula (mono-B):
(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may be combined together to form a ring with the carbon atom to which they are bonded. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may be combined together to form a ring with the carbon atom to which they are bonded. ^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-B and M2 ^-B each independently represent a boron-containing group.)
The method comprises reacting a monomer represented by the following general formula (mono-X ¹ -hal) in the presence of a transition metal catalyst:
(In the formula, ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms; ^M3-hal and M4 ^-hal each independently represent a halogen atom.)
A structural unit represented by the following general formula (1),
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ and J ⁴ have the same meanings as defined above.)
and a structural unit represented by the following general formula (2):
(In the formula, ^X1 has the same meaning as above.) A monomer represented by the following general formula (mono-Sn):
(In the formula, ^R1 and ^R2 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R1 and ^R2 may be combined together to form a ring with the carbon atom to which they are bonded. ^R3 and ^R4 each independently represent an alkyl group having 1 to 50 carbon atoms. ^R3 and ^R4 may be combined together to form a ring with the carbon atom to which they are bonded. ^R5 and ^R6 each independently represent a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. ^J1 , ^J2 , ^J3 , and ^J4 each independently represent a chalcogen atom. ^M1-Sn and M2 ^-Sn each independently represent a tin-containing group.)
The method comprises reacting a monomer represented by the following general formula (mono-X ¹ -hal) in the presence of a transition metal catalyst:
(In the formula, ^X1 represents a divalent heteroaromatic ring linking group which may be substituted with an alkyl group having 1 to 50 carbon atoms or an alkoxy group having 1 to 50 carbon atoms; ^M3-hal and M4 ^-hal each independently represent a halogen atom.)
A structural unit represented by the following general formula (1),
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ and J ⁴ have the same meanings as defined above.)
and a structural unit represented by the following general formula (2):
(In the formula, ^X1 has the same meaning as above.) The method for producing a conjugated polymer according to any one of claims 8 to 11, wherein the conjugated polymer is composed of a structural unit represented by the following general formula (3):
(In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , J ¹ , J ² , J ³ , J ⁴ and X ¹ have the same meanings as defined above.) The method for producing a conjugated polymer according to any one of claims 8 to 12, wherein X ¹ is a divalent heteroaromatic ring linking group selected from the group consisting of the following general formulas (4) to (8):
(In the formula, A ¹ represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. R ⁷ represents one group selected from the group consisting of an alkyl group having 1 to 50 carbon atoms, an alkoxy group having 1 to 50 carbon atoms, a fluorine atom, or a hydrogen atom. Multiple R ^7s may be the same or different. R ⁸ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple R ^8s may be the same or different. p ¹ and q ¹ each independently represent 0 or 1.)
(In the formula, ^A2 represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. ^A3 represents a chalcogen atom. ^R9 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple ^R9s may be the same or different. ^p2 and ^q2 each independently represent an integer of 0 or 1.)
(In the formula, ^A4 and ^A5 each independently represent a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. ^R10 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple ^R10s may be the same or different. ^R11 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple ^R11s may be the same or different. ^p3 and ^q3 each independently represent an integer of 0 or 1.)
(In the formula, R ¹² represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple R ¹² may be the same or different. p ⁴ and q ⁴ each independently represent an integer of 0 or 1.)
(In the formula, R ¹³ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. Multiple R ^13s may be the same or different. p ⁵ and q ⁵ each independently represent an integer of 0 or 1.) A film-forming composition comprising the conjugated polymer described in any one of claims 1 to 7. An organic thin film comprising the conjugated polymer described in any one of claims 1 to 7. An organic semiconductor device comprising the conjugated polymer described in any one of claims 1 to 7. An organic transistor element comprising the conjugated polymer described in any one of claims 1 to 7.