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

Abstract

To provide: a conjugated polymer having an oligoheteroacene comprising a thienothiophene skeleton as a repeating unit; an organic thin film comprising the conjugated polymer; and a transistor element comprising the organic thin film.SOLUTION: A conjugated polymer comprises a structural unit represented by the general formula (1) in the figure and a structural unit represented by the general formula (2) in the figure. The conjugated polymer is formed into an organic thin film to be included in a transistor element so as to exhibit excellent transistor performance.SELECTED DRAWING: None

Description

[Technical Field]

[0001] 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. [Background technology]

[0002] Conjugated compounds are well known as organic semiconductors used in organic thin-film solar cells, organic thin-film transistors, organic electroluminescence (EL), etc. Conjugated compounds have properties not found in inorganic compounds, such as energy saving, low cost, solubility in organic solvents, light weight, and flexibility, and can also be used as coating materials applied to printed electronics (Patent Document 1).

[0003] 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 application to organic thin-film transistors. Among them, oligoheteroacenes having a thienothiophene skeleton tend to exhibit high carrier mobility. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-59668 [Non-patent literature]

[0005] [Non-Patent Document 1] Polymer Journal, Vol. 49, pp. 23-30, 2017 [Non-patent document 2] Chemical Reviews, Vol. 115, pp. 3036-3140, 2015 [Non-patent document 3] Tetrahedron Letters, Volume 55, Pages 5663-5666, 2014 Summary of the Invention [Problem to be solved by the invention]

[0006] 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. [Means for solving the problem]

[0007] In order to solve the above problems, the present 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 such structural units 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 such structural units, such as solubility and heat resistance, or their carrier mobility. Furthermore, the present inventors also discovered that organic thin films can be easily formed using a film-forming composition containing such conjugated polymers, and that organic thin-film transistor devices fabricated using such organic thin films operate stably, leading to the completion of the present invention.

[0008] That is, the present invention comprises the following gist. [Abstract 1] A structural unit represented by the following general formula (1), [ka] (In the formula, R 1 and R 2 R each independently represents an alkyl group having 1 to 50 carbon atoms. 1 and R 2 and may be taken together to form a ring together with the carbon atoms to which they are attached. 3 and R 4 R each independently represents an alkyl group having 1 to 50 carbon atoms. 3 and R 4 and may be taken together to form a ring together with the carbon atoms to which they are attached. 5 and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. 1 , J 2 , J 3 and J 4 each independently represents a chalcogen atom. A conjugated polymer comprising a structural unit represented by the following general formula (2): [ka] (In the formula, X 1 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 first aspect, the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) may be alternately arranged. Regarding Abstract 1, R 1 and R 2 are each independently an alkyl group having 1 to 34 carbon atoms, and R 1 and R 2 may be taken together to form a ring with the carbon atoms to which they are attached, and R 3 and R 4 are each independently an alkyl group having 1 to 34 carbon atoms, and R 3 and R 4 may be taken together to form a ring with the carbon atoms to which they are attached, and R 5 and R 6 are each independently a hydrogen atom, an alkyl group having 1 to 34 carbon atoms, or a fluorine atom, and J1 , J 2 , J 3 and J 4 may each independently be an oxygen atom, a sulfur atom, or a selenium atom. Regarding Abstract 1, R 5 and R 6 is a hydrogen atom, and J 1 , J 2 , J 3 and J 4 may be a sulfur atom. Regarding Abstract 1, X 1 may be a divalent heteroaromatic ring linking group selected from the group consisting of general formulae (4) to (8) described below. Regarding Summary 1, A 1 , A 2 , A 3 , A 4 and A 5 are each independently 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, and 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, and R 8 , R 9 , R 10 and R 11 are each independently an alkyl group having 6 to 50 carbon atoms or a hydrogen atom, and R 12 and R 13 may each independently be an alkyl group having 6 to 50 carbon atoms. Regarding Summary 1, A 1 and A 2 is a sulfur atom, and A 3 is an oxygen atom or a nitrogen atom which may be substituted with an alkyl group having 6 to 34 carbon atoms, and A 4 is an oxygen atom, a sulfur atom, or a selenium atom, and A 5 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, and 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, and R 8 , R 9 , R 10 and R 11are each independently an alkyl group having 6 to 34 carbon atoms or a hydrogen atom, and R 12 and R 13 may each independently be an alkyl group having 6 to 34 carbon atoms. [Abstract 2] A monomer represented by the following general formula (mono-hal): [ka] (In the formula, R 1 and R 2 R each independently represents an alkyl group having 1 to 50 carbon atoms. 1 and R 2 and may be taken together to form a ring together with the carbon atoms to which they are attached. 3 and R 4 R each independently represents an alkyl group having 1 to 50 carbon atoms. 3 and R 4 and may be taken together to form a ring together with the carbon atoms to which they are attached. 5 and R 6 Each of J independently represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. 1 , J 2 , J 3 and J 4 Each independently represents a chalcogen atom. M 1-hal and M 2-hal each independently represents a halogen atom. In the presence of a transition metal catalyst, 1 -B) reacting a monomer represented by the formula [ka] (In the formula, X 1 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. M 3-B and M 4-B each independently represents a boron-containing group. A structural unit represented by the following general formula (1), [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , J 1 , J 2 , J 3 and J 4 represents the same meaning as above.) A method for producing a conjugated polymer comprising a structural unit represented by the following general formula (2): [ka] (In the formula, X 1 represents the same meaning as above.) [Abstract 3] A monomer represented by the following general formula (mono-hal): [ka] (In the formula, R 1 and R 2 R each independently represents an alkyl group having 1 to 50 carbon atoms. 1 and R 2 and may be taken together to form a ring together with the carbon atoms to which they are attached. 3 and R 4 R each independently represents an alkyl group having 1 to 50 carbon atoms. 3 and R 4 and may be taken together to form a ring together with the carbon atoms to which they are attached. 5 and R 6 Each of J independently represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. 1 , J 2 , J 3 and J 4 Each independently represents a chalcogen atom. M 1-hal and M 2-hal each independently represents a halogen atom. In the presence of a transition metal catalyst, 1 -Sn) [ka] (In the formula, X 1 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. M 3-Sn and M 4-Sn each independently represents a tin-containing group. A structural unit represented by the following general formula (1), [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , J 1 , J 2 , J 3 and J 4 represents the same meaning as above.) A method for producing a conjugated polymer comprising a structural unit represented by the following general formula (2): [ka] (In the formula, X 1 represents the same meaning as above.) [Abstract 4] A monomer represented by the following general formula (mono-B): [ka] (In the formula, R 1 and R 2 R each independently represents an alkyl group having 1 to 50 carbon atoms. 1 and R 2 and may be taken together to form a ring together with the carbon atoms to which they are attached. 3 and R 4 R each independently represents an alkyl group having 1 to 50 carbon atoms. 3 and R 4and may be taken together to form a ring together with the carbon atoms to which they are attached. 5 and R 6 Each of J independently represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. 1 , J 2 , J 3 and J 4 Each independently represents a chalcogen atom. M 1-B and M 2-B each independently represents a boron-containing group. In the presence of a transition metal catalyst, 1 -hal), [ka] (In the formula, X 1 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. M 3-hal and M 4-hal each independently represents a halogen atom. A structural unit represented by the following general formula (1), [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , J 1 , J 2 , J 3 and J 4 represents the same meaning as above.) A method for producing a conjugated polymer comprising a structural unit represented by the following general formula (2): [ka] (In the formula, X 1 represents the same meaning as above.) [Abstract 5] A monomer represented by the following general formula (mono-Sn): [ka] (In the formula, R 1 and R 2 R each independently represents an alkyl group having 1 to 50 carbon atoms. 1 and R 2 and may be taken together to form a ring together with the carbon atoms to which they are attached. 3 and R 4 R each independently represents an alkyl group having 1 to 50 carbon atoms. 3 and R 4 and may be taken together to form a ring together with the carbon atoms to which they are attached. 5 and R 6 Each of J independently represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. 1 , J 2 , J 3 and J 4 Each independently represents a chalcogen atom. M 1-Sn and M 2-Sn each independently represents a tin-containing group. In the presence of a transition metal catalyst, 1 -hal), [ka] (In the formula, X 1 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. M 3-hal and M 4-hal each independently represents a halogen atom. A structural unit represented by the following general formula (1), [ka] (In the formula, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , J 1 , J2 , J 3 and J 4 represents the same meaning as above.) A method for producing a conjugated polymer comprising a structural unit represented by the following general formula (2): [ka] (In the formula, X 1 represents the same meaning as above.) [Abstract 6] A film-forming composition comprising the conjugated polymer according to aspect 1. [Abstract 7] An organic thin film comprising the conjugated polymer according to Abstract 1. [Abstract 8] An organic semiconductor device comprising the conjugated polymer according to aspect 1. [Abstract 9] An organic transistor device comprising the conjugated polymer according to aspect 1. [Effects of the Invention]

[0009] The conjugated polymer of the present invention is an organic semiconductor that has high carrier mobility, high heat resistance, high atmospheric stability, and high solubility, and can efficiently drive an organic thin film transistor device that uses this as an active layer. [Brief explanation of the drawings]

[0010] [Figure 1] 1A and 1B are diagrams illustrating the cross-sectional structure of an organic thin film transistor element. DETAILED DESCRIPTION OF THE INVENTION

[0011] Hereinafter, embodiments of the present invention will be described in detail. However, the present invention is not limited to these, and various modifications are possible within the scope of the description. Embodiments obtained by appropriately combining the technical means disclosed in different embodiments are also included in the technical scope of the present invention. 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."

[0012] [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).

[0013] [ka] (In the formula, R 1 and R 2 R each independently represents an alkyl group having 1 to 50 carbon atoms. 1 and R 2 and may be taken together to form a ring together with the carbon atoms to which they are attached. 3 and R 4 R each independently represents an alkyl group having 1 to 50 carbon atoms. 3 and R 4 and may be taken together to form a ring together with the carbon atoms to which they are attached. 5 and R 6 each independently represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. 1 , J 2 , J 3 and J 4 each independently represents a chalcogen atom.

[0014] [ka] (In the formula, X 1 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.

[0015] (Structural unit represented by general formula (1)) R 1 , R 2 , R 3 , R 4 , R 5 and R 6The alkyl group having 1 to 50 carbon atoms represented by the formula (I) 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 hentetracontyl. Examples of the alkyl group include linear alkyl groups such as a 2-ethylhexyl 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, and a 4-tetradecylicocosyl group; and cyclic alkyl groups such as a cyclopentyl group and a cyclohexyl group.

[0016] R 1 , R 2 , R 3 and R 4As the alkyl group represented by the formula (I), an alkyl group having 6 to 50 carbon atoms is preferred in terms of increasing the solubility of the conjugated polymer of this embodiment, an alkyl group having 1 to 34 carbon atoms is more preferred, an alkyl group having 6 to 34 carbon atoms is even more preferred, and an alkyl group having 6 to 34 carbon atoms is particularly 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. , pentatriacontyl group, hexatriacontyl group, tetracontyl group, hentetracontyl group, dotetracontyl group, tritetracontyl group, tetratetracontyl group, pentacontyl group, 2-ethylhexyl group, 3,7-dimethyloctyl group, 2-hexyloctyl group, 2-hexyldecyl group, 2-octyldodecyl group, 2-decyltetradecyl group, 2-dodecyltetradecyl group, 2-dodecylhexadecyl group, 2-tetradecylhexadecyl group, 3-decylpentadecyl group, 3-dodecylheptadecyl group, 3-tetradecylnonacosyl group, 4-decylhexadecyl group, 4-dodecyloctadecyl group, or 4-tetradecylicosyl group is even more preferred, and a hexyl group or a decyl group is especially preferred.

[0017] R 1 and R 2may combine with the carbon atom to which they are bonded to form a ring. Examples of such rings 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. R 3 and R 4 may combine with the carbon atom to which they are bonded to form a ring. Examples of such rings 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.

[0018] R 5 and R 6is 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 high, and is 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, and a 4-tetradecylicosyl group. 5 and R 6 is particularly preferably a hydrogen atom or a fluorine atom.

[0019] J 1 , J 2 , J 3 and J 4 As the chalcogen atom represented by the formula (I), an oxygen atom, a sulfur atom, or a selenium atom is preferred, an oxygen atom or a sulfur atom is more preferred, and a sulfur atom is even more preferred, in that the solubility of the conjugated polymer of this embodiment is increased.

[0020] As the constitutional unit represented by general formula (1), specific examples include structural units represented by the following formulae (1-1) to (1-20), which have high film formability and carrier mobility.

[0021] [ka]

[0022] [ka]

[0023] [ka]

[0024] [ka]

[0025] [ka]

[0026] [ka]

[0027] [ka]

[0028] [ka]

[0029] [ka]

[0030] [ka]

[0031] In the formulas (1-1) to (1-20), C n H (2n+1) The alkyl group represented by 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).

[0032] (Structural unit represented by general formula (2)) X 1 Examples of the heteroaromatic ring linking group include 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. Specific preferred examples of the divalent heteroaromatic ring linking group include divalent heteroaromatic ring linking groups selected from the group consisting of the following general formulae (4) to (8).

[0033] [ka] (In the formula, A 1 R represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. 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. 7 may be the same or different. 8 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. 8 may be the same or different. 1 and q 1 each independently represents 0 or 1.

[0034] [ka] (In the formula, A 2 represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. 3 represents a chalcogen atom. 9 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. 9 may be the same or different. 2 and q 2 each independently represents 0 or 1.

[0035] [ka] (In the formula, A 4 and A 5 R each independently represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. 10 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. 10 may be the same or different. 11 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. 11 may be the same or different. 3 and q 3 each independently represents 0 or 1.

[0036] [ka] (In the formula, R 12 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. 12 may be the same or different. 4 and q 4 each independently represents 0 or 1.

[0037] [ka] (In the formula, R 13 represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. 13may be the same or different. 5 and q 5 each independently represents 0 or 1.

[0038] R 7 Examples of the alkyl group having 1 to 50 carbon atoms represented by R 1 ~R 6 Examples of alkyl groups include those exemplified in the explanation of (1), 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, 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.

[0039] R 7The alkoxy group having 1 to 50 carbon atoms represented by the formula (I) may be linear, branched or cyclic, and includes methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexadecyloxy, heptadecyloxy, octadecyloxy, nonadecyloxy, icosyloxy, henicosyloxy, docosyloxy, tricosyloxy, tetracosyloxy, pentacosyloxy, hexacosyloxy, heptacosyloxy, octacosyloxy, nonacosyloxy, triacontyloxy, hentriacontyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentadecyloxy, hexacosyloxy, heptacosyloxy, octadecyloxy, nonacosyloxy, triacontyloxy, hentriacontyloxy, dodecyloxy, tridecyloxy, tetradecyloxy, pentacos ... triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, triacontyloxy, tria 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.

[0040] R 7As the alkoxy group having 1 to 50 carbon atoms represented by the formula (I), an alkoxy group having 6 to 50 carbon atoms is preferred, and an alkoxy group having 6 to 34 carbon atoms is more preferred, 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 preferred, and a hexyloxy group, an octyloxy group, a 2-decyltetradecyloxy group, or a 2-dodecyltetradecyloxy group is particularly preferred.

[0041] R 7 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.

[0042] R 8 , R 9 , R 10 , R 11 , R 12 and R 13 Examples of the alkyl group having 1 to 50 carbon atoms represented by R 1 ~R 6Examples of alkyl groups include those exemplified in the explanation of (1), 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, 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.

[0043] R 8 , R 9 , R 10 , R 11 , R 12 and R 13 is 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.

[0044] A 1 , A 2 , A 3 , A 4 and A 5 The chalcogen atom represented by the formula (I) is preferably an oxygen atom, a sulfur atom, a selenium atom or a tellurium atom, more preferably an oxygen atom or a sulfur atom, and even more preferably a sulfur atom.

[0045] A 1 , A 2 , A 4 and A 5 In the nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms, 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 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.

[0046] A 1 , A 2 , A4 and A 5 As the substituent, a sulfur atom, an oxygen atom, or a nitrogen atom which may be substituted with an alkyl group having 6 to 34 carbon atoms is preferred, from the viewpoint of improving the film formability and carrier mobility of the conjugated polymer of this embodiment, a sulfur atom or an oxygen atom is more preferred, and a sulfur atom is even more preferred.

[0047] A 3 As the atom, a sulfur atom, an oxygen atom, or a selenium atom is preferable, a sulfur atom or an oxygen atom is more preferable, and a sulfur atom is even more preferable, in terms of improving the film formability and carrier mobility of the conjugated polymer of this embodiment.

[0048] p 1 , p 2 and p 3 As the number, 0 or 1 is preferable, and 0 is more preferable, since the film-forming property and carrier mobility of the conjugated polymer of this embodiment are improved.

[0049] p 4 and p 5 As the number, 0 or 1 is preferable, and 1 is more preferable, since the film-forming property and carrier mobility of the conjugated polymer of this embodiment are improved.

[0050] q 1 , q 2 and q 3 As the number, 0 or 1 is preferable, and 0 is more preferable, since the film-forming property and carrier mobility of the conjugated polymer of this embodiment are improved.

[0051] q 4 and q 5 As the number, 0 or 1 is preferable, and 1 is more preferable, since the film-forming property and carrier mobility of the conjugated polymer of this embodiment are improved.

[0052] As the structural unit represented by the general formula (2), more specific examples include formulae (11-1) to (11-261), which increase the solubility of the conjugated polymer of this embodiment.

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[0149] In the formulas (11-1) to (11-261), C n H (2n+1) The alkyl group indicated by is a straight-chain alkyl group having n carbon atoms.

[0150] 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 property and carrier mobility of the conjugated polymer of this embodiment are improved, and the structural unit represented by 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.

[0151] 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 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). [ka] (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 represents the same meaning as above.)

[0152] As the structural unit represented by the general formula (3), specific examples include structural units represented by the formulae (3-1) to (3-680), which have high film formability and carrier mobility.

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[0493] In the formulas (3-1) to (3-680), 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 a structural unit represented by formula (3-6) to formula (3-20), formula (3-26) to formula (3-40), formula (3-46) to formula (3-60), formula (3-66) to formula (3-80), formula (3-86) to formula (3-100), formula (3-106) to formula (3-120), formula (3-126) to formula (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) ~ formula (3-340), formula (3-346) ~ formula (3-360) , formula (3-366) ~ formula (3-380), formula (3-386) ~ formula (3-400), formula (3-406) ~ formula (3-420), formula (3-4 26) ~ Formula (3-440), Formula (3-446) ~ Formula (3-480), Formula (3-486) ​​~ Formula (3-500), Formula (3-506) ~ Formula (3 (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) are preferred, and any structural unit represented by 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) are also preferred. Formula (3-96), Formula (3-106) ~ Formula (3-116), Formula (3-126) ~ Formula (3-136), Formula (3-146) ~ Formula (3-156) ), formula (3-166) ~ formula (3-176), formula (3-186) ~ formula (3-296), formula (3-206) ~ formula (3-216), formula (3-2) 26) ~ Formula (3-236), Formula (3-246) ~ 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) ~ Formula (3-376), Formula (3-386) ~ Formula (3-396), Formula (3-406) ~ Formula (3-416), Formula (3-426) ~ Formula (3-436), Formula (3-446) ) ~ formula (3-476), formula (3-486) ​​~ formula (3-496), formula (3-506) ~ formula (3-516), formula (3-526) ~ formula (3-536), formula (3-546) ~ formula (3-5) More preferred are structural units represented by formula (3-56), formula (3-566) to formula (3-576), formula (3-586) to formula (3-596), formula (3-606) to formula (3-616), and formula (3-626) to formula (3-636), and even more preferred are structural units represented by formula (3-10), formula (3-6), formula (3-646), formula (3-650), and formula (3-666).

[0494] The conjugated polymer of this embodiment may contain structural units other than the structural unit represented by general formula (1) and the structural unit represented by general formula (2), as long as the effects of the present invention are not impaired. The total content of the structural unit represented by general formula (1) and the structural unit 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.

[0495] The terminal structure of the conjugated polymer of this embodiment is not particularly limited, and examples thereof 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 groups and thienyl groups. The structures of both terminals may be the same or different.

[0496] 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.

[0497] 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.

[0498] In the conjugated polymer of this embodiment, the molar ratio of the structural unit represented by general formula (1) to the structural unit represented by general formula (2) (structural unit represented by general formula (1):structural unit 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.

[0499] [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).

[0500] <Manufacturing process (A)> In the production process (A), a compound (monomer) represented by the general formula (mono-hal) is reacted with a compound (mono-X) represented by the general formula (mono-X) in the presence of a transition metal catalyst. 1 -B) to produce the conjugated polymer of this embodiment.

[0501] [ka]

[0502] (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 has the same meaning as above. M 1-hal and M 2-hal Each independently represents a halogen atom. 3-B and M 4-B each independently represents a boron-containing group.

[0503] M 1-hal and M 2-hal As the halogen atom represented by the formula (I), a chlorine atom, a bromine atom, or an iodine atom is preferred, a bromine atom or an iodine atom is more preferred, and a bromine atom is even more preferred, in terms of improving the production efficiency of the conjugated polymer of this embodiment.

[0504] M 3-B and M 4-B As the boron-containing group represented by the formula (12-1), from the viewpoint 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.

[0505] [ka]

[0506] Examples of compounds represented by the general formula (mono-hal) include the following general formulae (mono-hal-1) to (mono-hal-60).

[0507] [ka]

[0508] [ka]

[0509] [ka]

[0510] [ka]

[0511]

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[0512]

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[0513]

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[0514]

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[0515]

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[0516]

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[0517]

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[0518]

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[0519]

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[0520]

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[0521]

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[0522]

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[0523]

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[0524]

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[0525]

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[0526]

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[0527] In terms of increasing the film formability 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 formulae (mono-hal-1) to (mono-hal-48), more preferably any of the compounds represented by formulae (mono-hal-1) to (mono-hal-35), and more preferably any of formulae (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). More preferred are compounds of formula (mono-hal-14), (mono-hal-16), (mono-hal-17), (mono-hal-19), (mono-hal-20), (mono-hal-22), (mono-hal-23), (mono-hal-25), (mono-hal-26), (mono-hal-28), (mono-hal-29), (mono-hal-31), (mono-hal-32), (mono-hal-34) or (mono-hal-35), and especially preferred are compounds of formula (mono-hal-28) or (mono-hal-29).

[0528] 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 chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, or oxides of metals," or "complex compounds such as olefin complexes, phosphine complexes, amide complexes, amine complexes, carbene complexes, or 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. From the viewpoint of high yield, palladium catalysts or nickel catalysts are preferred as the transition metal catalyst, with palladium catalysts being more preferred.

[0529] The palladium catalyst is not particularly limited, but examples thereof include palladium metal such as palladium black and palladium sponge, and also includes palladium metal supported on palladium / alumina, palladium / carbon, palladium / silica, and palladium / Y-type zeolite. Also, 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 ... Examples of palladium catalysts include [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).

[0530] In terms of good yield, it is preferable to use palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), or bis(tri-tert-butylphosphine)palladium as the palladium catalyst.

[0531] The nickel catalyst is not particularly limited, but specific examples include nickel chloride(II), 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.

[0532] These palladium catalysts 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, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,3-bis(diphenylphosphino)butane, 1,4-bis(diphenylphosphino)butane, 1,4-bis(diphenylphosphino)butane, 1,5 ... Examples of the bis(diphenylphosphino) include 1,1'-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. Examples of the carbene compound 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.

[0533] 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.

[0534] 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 more preferably in the range of 1:5 to 5:1 in terms of good yield.

[0535] As the transition metal catalyst 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 in terms of good yield.

[0536] The amount of the transition metal catalyst used is not particularly limited, but in terms of good yield, it is preferably 0.001 to 50 mol % and more preferably 0.001 to 20 mol % relative to the compound represented by the general formula (mono-hal).

[0537] A promoter may be used in the production step (A). The promoter is not particularly limited, 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 because it provides a good yield.

[0538] The amount of the co-catalyst used is not particularly limited, but in terms of good yield, it is preferably 0.001 to 50 mol % and more preferably 0.001 to 20 mol % relative to the compound represented by the general formula (mono-hal).

[0539] The production step (A) can be carried out in a solvent. The solvent that can be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof 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 tris(2,2,2-trifluoroethyl)phosphate (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. A halogen solvent, an ether solvent, a mixed solvent of an aromatic hydrocarbon solvent and water, a mixed solvent of a halogen solvent and water, a mixed solvent of an ether solvent and water, a mixed solvent of an aromatic hydrocarbon solvent and a sulfoxide solvent, a mixed solvent of a halogen solvent and a sulfoxide solvent, a mixed solvent of an ether solvent and a sulfoxide solvent, a mixed solvent of an aromatic hydrocarbon solvent and a fluorine solvent, a mixed solvent of a halogen solvent and a fluorine solvent, or a mixed solvent of an ether solvent and a fluorine solvent is more preferred, and tetralin, toluene, monochlorobenzene, orthodichlorobenzene, THF, a mixed solvent of toluene and water, or a mixed solvent of tetralin and water is even more preferred.

[0540] There is no particular limitation 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 the general formula (mono-hal).

[0541] The production step (A) can also be carried out in the presence 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, decamethonium bromide, decyltrimethylammonium chloride, decyltrimethylammonium chloride, ethylhexadecyldimethylammonium bromide, (3-chloro-2-hydroxypropyl)trimethylammonium chloride, carbachol, choline chloride, chlorocholine chloride, bis(2-hydroxyethyl)dimethylammonium chloride, ammonium chloride, benzyldodecyldimethylammonium bromide, benzyltrimethylammonium bromide, benzyldodecyldimethylammonium chloride dihydrate, benzyltrimethylammonium dichloroiodate, benzyltributylammonium chloride, benzyltributylammonium bromide, bromocholine bromide, benzyltrimethylammonium chloride, benzyltriethylammonium iodide, benzyltriethylammonium 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 hydrogensulfate, 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 phosphate, 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, tetradecyltrimethylammonium 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,Ammonium salts such as tetramethylammonium iodide, (ferrocenylmethyl)trimethylammonium bromide, (ferrocenylmethyl)dodecyl, hexadecyltrimethylammonium 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 Examples of suitable phosphonium salts include ammonium tetrafluoroborate, tetraethylphosphonium tetrafluoroborate, 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. Among these, ammonium salts are preferred in terms of good reaction yield, and Aliquat 336 is more preferred.

[0542] The 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; inorganic bases such as lithium hydroxide, sodium hydroxide, potassium hydroxide, cesium hydroxide, sodium carbonate, 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 may be mixed in any ratio. Among these, inorganic salts are preferred in terms of good reaction yield, and sodium carbonate or potassium carbonate is more preferred.

[0543] Production step (A) can be carried out at a temperature appropriately selected from 0°C to 240°C, and is preferably carried out at a temperature appropriately selected from 70°C to 220°C in terms of good yield, and more preferably at a temperature appropriately selected from 100°C to 200°C.

[0544] The production step (A) can also be carried out using a microwave reaction device.

[0545] The production step (A) is preferably carried out in an inert gas atmosphere such as argon gas or nitrogen gas, or in vacuum.

[0546] The reaction time depends on the compound used (general formula (mono-hal) or general formula (mono-X 1 Although it differs depending on the compound represented by -B), the solvent and the reaction temperature, usually 0.1 to 100 hours is preferred, and 1 to 78 hours is more preferred.

[0547] The conjugated polymer of this embodiment can be obtained by carrying out a conventional treatment after the completion of the production step (A). If necessary, the polymer may be purified by 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, and Soxhlet extraction.

[0548] 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 having a functional group such as a thienyl group or a phenyl group introduced at its terminal. The functional group may be introduced by a combination of known methods, for example, according to the method disclosed in Macromolecules, Vol. 48, pp. 6994-7006, 2015, etc.

[0549] The compound represented by the general formula (mono-hal) used in the production process (A) may be obtained by any method, but may be produced by referring to, for example, methods described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 19254-19259, 2012, and Journal of the American Chemical Society, Vol. 143, pp. 4281-4289, 2021). Alternatively, commercially available products may be used.

[0550] The general formula (mono-X) used in the manufacturing process (A) 1 The compound represented by formula (B) may be obtained by any method, and can 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, commercially available products may be used.

[0551] <Manufacturing process (B)> In the production process (B), a compound (monomer) represented by the general formula (mono-hal) is reacted with a compound (mono-X) represented by the general formula (mono-X) in the presence of a transition metal catalyst. 1This is a method for producing the conjugated polymer of this embodiment by coupling with a compound (monomer) represented by the formula (I)—Sn).

[0552] [ka]

[0553] (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 has the same meaning as above. M 3-Sn , and M 4-Sn each independently represents a tin-containing group.

[0554] M 3-Sn , and M 4-Sn Examples of the tin-containing group represented by formula (13-1) 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 the group represented by formula (13-1) is even more preferred.

[0555] [ka]

[0556] 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 chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, or oxides of metals," 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 viewpoint of high yield, palladium catalysts or nickel catalysts are preferred as the transition metal catalyst, with palladium catalysts being more preferred.

[0557] The palladium catalyst is not particularly limited, but examples thereof include the palladium catalysts exemplified in the explanation of the production step (A).

[0558] In terms of good yield, it is preferable to use palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), or bis(tri-tert-butylphosphine)palladium as the palladium catalyst.

[0559] The nickel catalyst is not particularly limited, but examples thereof include the nickel catalysts exemplified in the description of the production step (A).

[0560] These palladium catalysts or nickel catalysts may be used alone or in combination with a tertiary phosphorus compound or a carbene compound. Examples of the tertiary phosphorus compound or carbene compound that can be used include the tertiary phosphorus compounds or carbene compounds exemplified in the description of Production Step (A).

[0561] 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.

[0562] 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 more preferably in the range of 1:5 to 5:1 in terms of good yield.

[0563] As the transition metal catalyst 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 in terms of good yield.

[0564] The amount of the transition metal catalyst used is not particularly limited, but in terms of good yield, it is preferably 0.001 to 50 mol % and more preferably 0.001 to 20 mol % relative to the compound represented by the general formula (mono-hal).

[0565] A promoter may be used in the production step (B). The promoter is not particularly limited, 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 because it provides a good yield.

[0566] The amount of the co-catalyst used is not particularly limited, but in terms of good yield, it is preferably 0.001 to 50 mol % and more preferably 0.001 to 20 mol % relative to the compound represented by the general formula (mono-hal).

[0567] The production step (B) can be carried out in a solvent. The solvent that can be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include the solvents exemplified in the description of the production step (A). From the viewpoint of a good yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, fluorine-containing 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 fluorine solvents, mixed solvents of halogenated solvents and fluorine solvents, and mixed solvents of ether solvents and fluorine solvents are preferred; aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, mixed solvents of aromatic hydrocarbon solvents and fluorine solvents, mixed solvents of halogenated solvents and fluorine solvents, and mixed solvents of ether solvents and fluorine solvents are more preferred; and tetralin, toluene, monochlorobenzene, orthodichlorobenzene, and THF are even more preferred.

[0568] There is no particular limitation 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 the general formula (mono-hal).

[0569] The 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 the production step (A). Inorganic salts are preferred in terms of good reaction yield, and sodium carbonate or potassium carbonate is more preferred.

[0570] Production step (B) can be carried out at a temperature appropriately selected from 0°C to 240°C, and is preferably carried out at a temperature appropriately selected from 70°C to 220°C in terms of good yield, and more preferably at a temperature appropriately selected from 100°C to 200°C.

[0571] The production step (B) can also be carried out using a microwave reaction device.

[0572] The production step (B) is preferably carried out in an inert gas atmosphere such as argon gas or nitrogen gas, or in the open air.

[0573] The reaction time depends on the compound used (general formula (mono-hal) or general formula (mono-X 1 Although it differs depending on the compound represented by —Sn), the solvent and the reaction temperature, 0.1 to 100 hours is preferable, and 1 to 78 hours is more preferable.

[0574] The conjugated polymer of this embodiment can be obtained by carrying out a conventional treatment after the completion of the production step (B). If necessary, the polymer may be purified by 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, and Soxhlet extraction.

[0575] 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 having a functional group such as a thienyl group or a phenyl group introduced at its terminal. The functional group may be introduced by a combination of known methods, for example, according to the method disclosed in Macromolecules, Vol. 48, pp. 6994-7006, 2015, etc.

[0576] The compound represented by the general formula (mono-hal) used in the manufacturing process (B) may be obtained by any method, but may be manufactured by referring to, for example, methods described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 19254-19259, 2012, and Journal of the American Chemical Society, Vol. 143, pp. 4281-4289, 2021). Alternatively, commercially available products may be used.

[0577] The general formula (mono-X) used in the manufacturing process (B) 1The compound represented by formula (I) (—Sn) may be obtained by any method, and can 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, commercially available products may be used.

[0578] <Manufacturing process (C)> In the production process (C), a compound (monomer) represented by the general formula (mono-B) is reacted with a compound (mono-X) represented by the general formula (mono-X) in the presence of a transition metal catalyst. 1 This is a method for producing the conjugated polymer of this embodiment by coupling with a compound (monomer) represented by the formula (I)-hal.

[0579] [ka]

[0580] (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 has the same meaning as above. M 1-B and M 2-B Each independently represents a boron-containing group. 3-hal and M 4-hal each independently represents a halogen atom.

[0581] M 1-B and M 2-B As the boron-containing group represented by the formula (12-1), 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.

[0582] [ka]

[0583] M 3-hal , and M 4-hal As the halogen atom represented by the formula (I), a chlorine atom, a bromine atom, or an iodine atom is preferred, a bromine atom or an iodine atom is more preferred, and a bromine atom is even more preferred, in terms of improving the production efficiency of the conjugated polymer of this embodiment.

[0584] Examples of the compound represented by general formula (mono-B) include compounds represented by the following general formulae (mono-B-1) to (mono-B-60).

[0585] [ka]

[0586] [ka]

[0587] [ka]

[0588] [ka]

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[0605] In terms of increasing the film formability 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 formulae (mono-B-1) to (mono-B-48), more preferably any of the compounds represented by formulae (mono-B-1) to (mono-B-35), and more preferably any of formulae (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 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.

[0606] 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 chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, or oxides of metals," 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 viewpoint of high yield, palladium catalysts or nickel catalysts are preferred as the transition metal catalyst, with palladium catalysts being more preferred.

[0607] The palladium catalyst is not particularly limited, but examples thereof include the palladium catalysts exemplified in the explanation of the production step (A).

[0608] In terms of good yield, it is preferable to use palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), or bis(tri-tert-butylphosphine)palladium as the palladium catalyst.

[0609] The nickel catalyst is not particularly limited, but examples thereof include the nickel catalysts exemplified in the description of the production step (A).

[0610] These palladium catalysts or nickel catalysts may be used alone or in combination with a tertiary phosphorus compound or a carbene compound. Examples of the tertiary phosphorus compound or carbene compound that can be used include the tertiary phosphorus compounds or carbene compounds exemplified in the description of Production Step (A).

[0611] 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.

[0612] 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 more preferably in the range of 1:5 to 5:1 in terms of good yield.

[0613] As the transition metal catalyst 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 in terms of good yield.

[0614] The amount of the transition metal catalyst used is not particularly limited, but in terms of good yield, it is preferably 0.001 to 50 mol % and more preferably 0.001 to 20 mol % relative to the compound represented by general formula (mono-B).

[0615] A promoter may be used in the production step (C). The promoter is not particularly limited, 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 because it provides a good yield.

[0616] The amount of the co-catalyst used is not particularly limited, but in terms of good yield, it is preferably 0.001 to 50 mol % and more preferably 0.001 to 20 mol % relative to the compound represented by general formula (mono-B).

[0617] The production step (C) can be carried out in a solvent. The solvent that can be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include the solvents exemplified in the explanation of the production step (A). In terms of good yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, fluorine 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 fluorine solvents, mixed solvents of halogenated solvents and fluorine solvents, and mixed solvents of ether solvents and fluorine solvents are preferred. An ether solvent, a mixed solvent of an aromatic hydrocarbon solvent and water, a mixed solvent of a halogenated solvent and water, a mixed solvent of an ether solvent and water, a mixed solvent of an aromatic hydrocarbon solvent and a sulfoxide solvent, a mixed solvent of a halogenated solvent and a sulfoxide solvent, an ether solvent and a sulfoxide solvent, a mixed solvent of an aromatic hydrocarbon solvent and a fluorinated solvent, a mixed solvent of a halogenated solvent and a fluorinated solvent, or a mixed solvent of an ether solvent and a fluorinated solvent is more preferred, and tetralin, toluene, monochlorobenzene, orthodichlorobenzene, THF, a mixed solvent of toluene and water, a mixed solvent of tetralin and water, or a mixed solvent of tetralin and DMSO is even more preferred.

[0618] There is no particular limitation 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).

[0619] The production step (C) can also be carried out by adding a phase transfer catalyst. Examples of the phase transfer catalyst that can be used include the phase transfer catalysts exemplified in the explanation of the production step (A). In terms of good reaction yield, ammonium salts are preferred, and Aliquat 336 is more preferred.

[0620] 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 in terms of good reaction yield, and sodium carbonate or potassium carbonate is more preferred.

[0621] Production step (C) can be carried out at a temperature appropriately selected from 0°C to 240°C, and is preferably carried out at a temperature appropriately selected from 70°C to 220°C in terms of good yield, and more preferably at a temperature appropriately selected from 100°C to 200°C.

[0622] The production step (C) can also be carried out using a microwave reaction device.

[0623] The production step (C) is preferably carried out in an inert gas atmosphere such as argon gas or nitrogen gas, or in vacuum.

[0624] The reaction time is determined by the amount of the compound (general formula (mono-B) or general formula (mono-X)) used. 1 Although it differs depending on the compound represented by (-hal), the solvent and the reaction temperature, usually 0.1 to 100 hours is preferred, and 1 to 78 hours is more preferred.

[0625] The conjugated polymer of this embodiment can be obtained by carrying out a conventional treatment after the completion of the production step (C). If necessary, the polymer may be purified by 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, and Soxhlet extraction.

[0626] 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 having a functional group such as a thienyl group or a phenyl group introduced at its terminal. The functional group may be introduced by a combination of known methods, for example, according to the method disclosed in Macromolecules, Vol. 48, pp. 6994-7006, 2015, etc.

[0627] The compound represented by the general formula (mono-B) used in the production process (C) may be obtained by any method, but may be produced by referring to, for example, methods described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 19254-19259, 2012, and Journal of the American Chemical Society, Vol. 143, pp. 4281-4289, 2021). Alternatively, commercially available products may be used.

[0628] The general formula (mono-X) used in the manufacturing process (C) 1 The compound represented by formula (I) (I-hal) may be obtained by any method, and can 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, commercially available products may be used.

[0629] <Manufacturing process (D)> In the production process (D), a compound (monomer) represented by the general formula (mono-Sn) is reacted with a compound (mono-X) represented by the general formula (mono-X) in the presence of a transition metal catalyst. 1 This method involves a coupling reaction with a compound (monomer) represented by the formula (I)-hal, to produce the conjugated polymer of this embodiment.

[0630] [ka]

[0631] (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 has the same meaning as above. M 1-Sn and M2-Sn each independently represents a tin-containing group.

[0632] M 1-Sn and M 2-Sn Examples of the tin-containing group represented by formula (13-1) 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 the group represented by formula (13-1) is even more preferred.

[0633] [ka]

[0634] Examples of the compound represented by the general formula (mono-Sn) include compounds represented by the following general formulae (mono-Sn-1) to (mono-Sn-60).

[0635] [ka]

[0636] [ka]

[0637] [ka]

[0638] [ka]

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[0640]

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[0655] 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 chlorides, bromides, iodides, nitrates, sulfates, carbonates, oxalates, acetates, or oxides of metals," 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 viewpoint of high yield, palladium catalysts or nickel catalysts are preferred as the transition metal catalyst, with palladium catalysts being more preferred.

[0656] The palladium catalyst is not particularly limited, but examples thereof include the palladium catalysts exemplified in the explanation of the production step (A).

[0657] In terms of good yield, it is preferable to use palladium acetate, palladium acetylacetonate, bis(dibenzylideneacetone)palladium, tris(dibenzylideneacetone)dipalladium, tetrakis(triphenylphosphine)palladium (Pd(PPh3)4), or bis(tri-tert-butylphosphine)palladium as the palladium catalyst.

[0658] The nickel catalyst is not particularly limited, but examples thereof include the palladium catalysts exemplified in the description of the production step (A).

[0659] These palladium catalysts or nickel catalysts may be used alone or in combination with a tertiary phosphorus compound or a carbene compound. Examples of the tertiary phosphorus compound or carbene compound that can be used include the tertiary phosphorus compounds or carbene compounds exemplified in the description of Production Step (A).

[0660] 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.

[0661] 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 more preferably in the range of 1:5 to 5:1 in terms of good yield.

[0662] As the transition metal catalyst 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 in terms of good yield.

[0663] The amount of the transition metal catalyst used is not particularly limited, but in terms of good yield, it is preferably 0.001 to 50 mol % and more preferably 0.001 to 20 mol % relative to the compound represented by the general formula (mono-Sn).

[0664] A promoter may be used in the production step (D). The promoter is not particularly limited, 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 because it provides a good yield.

[0665] The amount of the co-catalyst used is not particularly limited, but in terms of good yield, it is preferably 0.001 to 50 mol % and more preferably 0.001 to 20 mol % relative to the compound represented by the general formula (mono-Sn).

[0666] Production step (D) can be carried out in a solvent. The solvent that can be used is not particularly limited as long as it does not inhibit the reaction, and examples thereof include the solvents exemplified in the description of production step (A). From the viewpoint of good yield, aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, amide solvents, sulfoxide solvents, fluorine-containing 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 fluorine-containing solvents, mixed solvents of halogenated solvents and fluorine-containing solvents, and mixed solvents of ether solvents and fluorine-containing solvents are preferred, and aliphatic hydrocarbon solvents, aromatic hydrocarbon solvents, halogenated solvents, ether solvents, and mixed solvents of ether solvents and fluorine-containing solvents are more preferred, and tetralin, toluene, monochlorobenzene, orthodichlorobenzene, and THF are even more preferred.

[0667] There is no particular limitation 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 the general formula (mono-Sn).

[0668] Production step (D) can be carried out at a temperature appropriately selected from 0°C to 240°C, and is preferably carried out at a temperature appropriately selected from 70°C to 220°C in terms of good yield, and more preferably at a temperature appropriately selected from 100°C to 200°C.

[0669] The production step (D) can also be carried out using a microwave reaction device.

[0670] The production step (D) is preferably carried out in an inert gas atmosphere such as argon gas or nitrogen gas, or in vacuum.

[0671] The reaction time is determined by the compound (general formula (mono-Sn) or general formula (mono-X)) used. 1 Although it differs depending on the compound represented by (-hal), the solvent and the reaction temperature, usually 0.1 to 100 hours is preferred, and 1 to 78 hours is more preferred.

[0672] The conjugated polymer of this embodiment can be obtained by carrying out a conventional treatment after the completion of the production step (D). If necessary, the polymer may be purified by 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, and Soxhlet extraction.

[0673] 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 having a functional group such as a thienyl group or a phenyl group introduced at its terminal. The functional group may be introduced by a combination of known methods, for example, according to the method disclosed in Macromolecules, Vol. 48, pp. 6994-7006, 2015, etc.

[0674] The compound represented by the general formula (mono-Sn) used in the production process (D) may be obtained by any method, but may be obtained by any method described in the literature (Journal of the American Chemical Society, Vol. 134, pp. 19254-19259, 2012, or Journal of the American Chemical Society, Vol. 143, pp. 4281-4289, 2021.) Alternatively, commercially available products may be used.

[0675] The general formula (mono-X) used in the manufacturing process (D) 1 The compound represented by formula (I) (I-hal) may be obtained by any method, and can 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, commercially available products may be used.

[0676] [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.

[0677] The film-forming composition of this embodiment is a film-forming composition containing the conjugated polymer of this embodiment and a solvent, which is obtained by dissolving or dispersing the conjugated polymer of this embodiment in a solvent.

[0678] The solvent is not particularly limited as long as it can dissolve or disperse the conjugated polymer of the present embodiment in the solvent. Examples of the solvent 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. Among these, aromatic hydrocarbons and halogenated solvents are preferred because they have high boiling points and are gently volatile, and toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3,4-dimethylanisole, chlorobenzene, and o-DCB are more preferred.

[0679] There is no particular limitation 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, and more preferably a concentration appropriately selected from 0.01 to 30 weight percent.

[0680] The conjugated polymer of this embodiment can be dissolved or dispersed in a solvent by methods well known to those skilled in the art, such as stirring, shaking, ball milling, etc. Heating may be performed during this process.

[0681] 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 limitations on the concentration of the binder, but a concentration of 0.1 to 10.0 weight percent is preferred for good coatability.

[0682] [Organic thin film] Next, an organic thin film containing the conjugated polymer of this embodiment (hereinafter referred to as "organic thin film of this embodiment"), more specifically, a method for forming an organic thin film using the film-forming composition, will be described.

[0683] 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 thereof 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; etc. Among these, spin coating, drop casting, and inkjet are preferred in terms of efficient film formation.

[0684] Although there are no particular limitations on the thickness of the organic thin film of this embodiment, it is preferably 1 nm to 1000 nm, more preferably 10 nm to 500 nm, in terms of increasing carrier mobility.

[0685] The organic thin film of this embodiment can be obtained by drying the solvent after film formation, and may be annealed at a temperature appropriately selected from the range of 40 to 400° C., if necessary.

[0686] [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.

[0687] A method for producing an organic thin film transistor element including the conjugated polymer of this embodiment (hereinafter referred to as "organic thin film transistor element of this embodiment"), particularly an organic thin film transistor element including a conjugated polymer in the active layer, will be described.

[0688] The organic thin film transistor element of this embodiment is obtained by forming the organic thin film of this embodiment as an insulating layer and an active layer on a substrate, and then providing a source electrode, a drain electrode, and a gate electrode thereon.

[0689] 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 an active layer (organic semiconductor layer), 2 is a substrate, 3 is a gate electrode, 4 is a gate insulating layer, 5 is a source electrode, and 6 is a drain electrode.

[0690] 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, hydrodoped 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 hydrodoped silicon are preferred, with glass being more preferred, due to their excellent transistor performance.

[0691] Examples of the gate electrode 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, and organic electrodes such as doped conductive polymers (PEDOT-PSS). Of these, inorganic electrodes are preferred because of their good conductivity, and gold is more preferred.

[0692] 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 polyolefin, 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. Among these, organic insulating layers are preferred in terms of their excellent insulating properties, and parylene C is more preferred. The surfaces of these insulating layers may 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. Among these, modification with octadecyltrichlorosilane, octyltrichlorosilane, β-phenethyltrichlorosilane, octadecylphosphonic acid, octylphosphonic acid, or hexamethyldisilazane is preferred in terms of improving the carrier mobility and current on-off ratio of the organic thin-film transistor element of this embodiment and reducing the threshold voltage.

[0693] As the source electrode and the drain electrode, electrodes similar to those exemplified for the gate electrode can be exemplified. Among these, inorganic electrodes are preferable in terms of good conductivity, and gold is more preferable. Further, in order to improve the carrier injection efficiency, surface treatment can be performed on these electrodes using a surface treatment material. Examples of such a surface treatment material include benzenethiol, pentafluorobenzenethiol, and the like.

[0694] Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

Examples

[0695] The monomers and their precursors used as raw materials in the examples 1 were subjected to structural analysis by 1H-NMR measurement. The molecular weight and molecular weight distribution of the conjugated polymer obtained in the examples were estimated by Gel Permeation Chromatography (GPC) measurement. Commercially available products were used for the reagents.

[0696] <NMR measurement conditions> Measuring device: Bruker ASCEND TM ADVANCE III HD (400 MHz) Measuring solvent: deuterated chloroform (CDCl3), deuterated dimethyl sulfoxide (DMSO-d6), deuterated benzene (C6D6) Internal standard substance: tetramethylsilane (TMS)

[0697] <GPC measurement conditions> Measuring device: Tosoh Corporation High Speed GPC Device HLC-8320GPC EcoSEC Column: TSKgel SuperMultiporeHZ-H, TSKgel SuperHZ2000 Measuring solvent: THF Measuring temperature: 25 °C Calibration curve: polystyrene standard

[0698] <High temperature GPC measurement conditions> Measuring device: Tosoh Corporation, High Temperature GPC Device HLC-8321GPC / HT Column: TSKgel GMH HR -H(20)HT Measurement solvent: 1,2,4-trichlorobenzene (TCB) Measurement temperature: 140 °C Calibration curve: Polystyrene standard

[0699] <TGA measurement conditions> Measuring device: SII Corporation, EXSTAR6000 TGA / DTA6200 Sample container: Aluminum pan Measurement atmosphere: Nitrogen Flow rate: 50 mL / min Heating rate: 10 °C / min T d3 、T d5 And T d10 Each represent the 3%, 5% and 10% weight loss temperatures, respectively.

[0700] <DSC measurement conditions> Measuring device: SII Corporation, EXSTAR6000 DSC6220 Sample container: Aluminum panMeasurement conditions: Nitrogen atmosphere, 10 °C / min, 0 - 300 °C, the results adopt the third Heating Scan.

[0701] <Ionization potential measurement conditions> Measuring device: Riken Keiki Co., Ltd., Atmospheric Photoelectron Spectrometer AC-5 Measurement conditions: Measurement under atmosphere, light quantity 3 nW

[0702] [Reference Example 1]

[0703] [Chemical formula]

[0704] 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 stirred for 1 hour. Then, triisopropylsilyl chloride (0.83 mL, 756 mg, 3.92 mmol) was added and stirred at room temperature for 2 hours. Water was added to the reaction solution, followed by extraction with hexane. The combined organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to yield a colorless solid, 2-triisopropylsilylthieno[3,2-b]thiophene (924 mg, 88%). 1 H-NMR (CDCl3,400MHz) 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).

[0705] [Reference example 2]

[0706] [ka]

[0707] 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. The solvent was then 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. 1H-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).

[0708] [Reference example 3]

[0709] [ka]

[0710] 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. 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 distilled off under reduced pressure to obtain 11-ethynyl-heneicosan-11-ol (14.0 g) as a pale yellow liquid.

[0711] 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(PPh3)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, followed by the addition of saturated aqueous ammonium chloride solution and extraction with ethyl acetate. 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 / chloroform = 4 / 1 → 3 / 1 → 2 / 1) to give a pale yellow liquid, 11-(5-triisopropylsilyl-thieno[3,2-b]thiophen-2-ylethynyl)-heneicosan-11-ol (5.05 g, 80%). 1 H-NMR(CDCl3,400MHz)δ7.31(d,J=0.8Hz,1H),7.28(d,J=0.4Hz,1H),1.77-1.70(m,4 H),1.56-1.51(m,4H),1.43-1.27(m,31H),1.12(d,J=7.2Hz,18H),0.90-0.86(m,6H).

[0712] [Reference example 4]

[0713] [ka]

[0714] 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), iodine (1.63 g, 6.44 mmol) was added at −15°C and stirred at −15°C for 5 hours. A saturated aqueous solution of sodium thiosulfate 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. The solvent was then 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 (CDCl3, 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).

[0715] [Reference example 5]

[0716] [ka]

[0717] 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 stirred for 1.5 hours. 11-Heneicosanone (237 mg, 0.763 mmol) was then added and stirred at room temperature for 2 hours. A saturated aqueous solution of ammonium chloride 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. The solvent was then 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(CDCl3,400MHz)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).

[0718] [Reference example 6]

[0719] [ka]

[0720] 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, (AMPHOS)PdCl (69 mg, 97 μmol) was added under an argon atmosphere and 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 layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The 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(CDCl3,400MHz)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).

[0721] [Reference example 7]

[0722] [ka]

[0723] 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), 1 M tetrabutylammonium fluoride in tetrahydrofuran (1.5 mL, 1.5 mmol) was added and 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. The solvent was then 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, 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(CDCl3,400MHz)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).

[0724] [Reference example 8]

[0725] [ka]

[0726] 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 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 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 / 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(C6D6,400MHz)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).

[0727] [Reference example 9]

[0728] [ka]

[0729] 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, 1 M tin tetrachloride in dichloromethane (100 μL, 100 μmol) was added under an argon atmosphere and stirred at −15°C for 5 hours. A saturated aqueous solution of sodium bicarbonate was added to the resulting mixture, which was then extracted with hexane. The combined organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered. The solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give (mono-hal-28) (78 mg, 70%) as a red solid. 1 H-NMR (C6D6, 400MHz) δ6.69 (s, 2H), 2.11-2.03 (m, 8H), 1.28-1.08 (m, 62H), 0.91-0.87 (m, 14H).

[0730] [Reference example 10]

[0731] [ka]

[0732] A hexane solution of n-butyllithium (0.27 mL, 0.420 mmol) was added to a mixture of (mono-hal-28) (200 mg, 0.191 mmol) obtained in Reference Example 9 and tetrahydrofuran (3.8 mL) at 0°C, and the mixture was 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), yielding (mono-Sn-28) as a red solid (131 mg, 56%). 1H-NMR(C6D6,400MHz)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).

[0733] [Example 1]

[0734] [ka]

[0735] 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, Pd2(dba)3·CHCl3 (2.0 mg, 1.9 μmol) and tri(o-tolyl)phosphine (2.3 mg, 7.6 μmol) were added and 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). 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 precipitation in methanol. The resulting solid was washed with methanol and dried under reduced pressure at 90°C to obtain a black solid (3-10) (65.3 mg, 67%). GPC(THF): Mn=10500g / mol, Mw=17800g / mol, PDI=1.69. GPC (TCB, 140℃): Mn=8900g / mol, Mw=30300g / mol, PDI=3.4. T d3 =396℃,T d5=403℃,T d10 =417℃. No phase transition was observed by DSC.

[0736] [Example 2]

[0737] [ka]

[0738] 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. Pd(dba)·CHCl (1.7 mg, 1.6 μmol) and tri(o-tolyl)phosphine (2.0 mg, 6.6 μmol) were added to this mixture and stirred at 180°C for 2 hours using a microwave reactor. 2-(tributylstannyl)thiophene (0.23 mL, 276 mg, 0.74 mmol) was then added to the reaction solution and 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 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). 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. The resulting solid was washed with methanol and then dried under reduced pressure at 90 °C to obtain a black solid (3-10) (60 mg, 71%). GPC(THF): Mn=21000g / mol, Mw=34000g / mol, PDI=1.62. GPC (TCB, 140℃): Mn=7000g / mol, Mw=21000g / mol, PDI=3.0. Td3 =364℃,T d5 =381℃,T d10 =397℃. No phase transition was observed by DSC.

[0739] [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.

[0740] 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.

[0741] Next, a Parylene C film was formed on a glass substrate by CVD as an underlayer. A shadow mask with a channel length of 100 μm and a channel width of 500 μm was 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 form an organic thin film of conjugated polymer (3-10). A Parylene C film was formed as a gate insulating film by CVD, 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).

[0742] The organic thin-film transistor device was connected to a semiconductor parameter analyzer (Keithley, Model 4200A-SCS) under atmospheric conditions, and the gate voltage (Vg) was scanned from +10 to -100 V in 1 V increments at a drain voltage (Vd = -100 V) to evaluate the transfer characteristics. The organic thin-film transistor device exhibited p-type characteristics, and its hole carrier mobility was 0.046 cm 2 After further annealing at 150°C for 15 minutes, the hole carrier mobility was 0.043 cm 2 This confirmed that the carrier mobility did not decrease even after heat treatment.

[0743] [Example 4] The same procedure as in Example 3 was repeated, except that the source electrode and the drain electrode were surface-treated with pentafluorobenzenethiol. The obtained organic thin-film transistor device exhibited p-type characteristics, and its hole carrier mobility was 0.078 cm 2 After further annealing at 150°C for 15 minutes, the hole carrier mobility was 0.074 cm 2 This confirmed that the carrier mobility did not decrease even after heat treatment.

[0744] [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 After further annealing at 150°C for 15 minutes, the hole carrier mobility was 0.075 cm 2 This confirmed that the carrier mobility did not decrease even after heat treatment.

[0745] [Example 6] A 0.5 wt% o-DCB solution of the conjugated polymer (3-10) synthesized in Example 1 was heated in a nitrogen atmosphere in a glove box to prepare a composition for forming an organic thin film. Next, a Parylene C film was formed as an underlayer on a glass substrate by CVD, and the solution prepared above was spin-coated in a nitrogen atmosphere in a glove box. 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.

[0746] [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.

[0747] [Reference example 11]

[0748] [ka]

[0749] 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 stirred at room temperature for 19 hours. Saturated aqueous ammonium chloride solution was added to the resulting mixture, which was then extracted with diethyl ether. The combined organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered. The solvent was removed under reduced pressure to yield 11-ethynyl-heneicosan-11-ol (1.51 g) as a pale yellow liquid.

[0750] 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(PPh3)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 and extracted with ethyl acetate. 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 → hexane / chloroform = 1 / 1) to give a yellow liquid, 7-(5-triisopropylsilyl-thieno[2,3-d]thiophen-2-ylethynyl)-tridecan-7-ol (2.80 g, 88%). 1H-NMR(CDCl3,400MHz)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).

[0751] [Reference example 12]

[0752] [ka]

[0753] 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), iodine (1.94 g, 7.66 mmol) was added at −15°C and stirred at −15°C for 5 hours. A saturated aqueous solution of sodium thiosulfate 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. The solvent was removed 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 (CDCl3, 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).

[0754] [Reference example 13]

[0755] [ka]

[0756] 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 stirred for 1.5 hours. 7-Tridecanone (966 mg, 4.87 mmol) was then added and stirred at room temperature for 2 hours. A saturated aqueous solution of ammonium chloride 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. The solvent was then 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(CDCl3,400MHz)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).

[0757] [Reference example 14]

[0758] [ka]

[0759] 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, (AMPHOS)PdCl (67.3 mg, 95.0 μmol) was added under an argon atmosphere and 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, filtered, and the solvent was removed under reduced pressure. The residue was purified by silica gel column chromatography (hexane / chloroform = 4 / 1 → 1 / 1) to give 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%) as a yellow solid. 1 H-NMR(CDCl3,400MHz)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).

[0760] [Reference example 15]

[0761] [ka]

[0762] To a mixture of 2-triisopropylsilyl-5-(1-hexyl-1-hydroxyheptyl)-6-thieno[3,2-b]thiophene-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), 1 M tetrabutylammonium fluoride in tetrahydrofuran (2.2 mL, 2.2 mmol) was added and 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. The solvent was then distilled off under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane / chloroform = 7 / 3) to give a yellow-brown liquid, 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(CDCl3,400MHz)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),1.9 2-1.71(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).

[0763] [Reference example 16]

[0764] [ka]

[0765] 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 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 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 / 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(C6D6,400MHz)δ7.04(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).

[0766] [Reference example 17]

[0767] [ka]

[0768] 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, 1 M tin tetrachloride in dichloromethane (130 μL, 130 μmol) was added under an argon atmosphere and stirred at −15°C for 1 hour. A saturated aqueous solution of sodium bicarbonate was added to the resulting mixture, which was then extracted with hexane. The combined organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate, and filtered. The solvent was removed under reduced pressure. The resulting residue was purified by silica gel column chromatography (hexane) to give (mono-hal-16) (85 mg, 87%) as a red solid. 1 H-NMR (C6D6, 400MHz) δ6.67 (s, 2H), 2.09-1.98 (m, 8H), 1.28-1.03 (m, 32H), 0.79-0.75 (m, 12H).

[0769] [Example 8]

[0770] [ka]

[0771] 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, bis(tri-t-butylphosphine)palladium(0) (2.4 mg, 4.8 μmol) was added and stirred at 80 °C for 62 hours. 2-thiopheneboronic acid (110 mg, 860 μmol) was then added to the reaction solution and stirred at 80 °C for 4 hours. Further, 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. 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.

[0772] [Example 9]

[0773] [ka]

[0774] 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, Pd2(dba)3·CHCl3 (2.5 mg, 2.4 μmol) and tri(o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added and 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). 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. The resulting solid was washed with methanol and dried under reduced pressure at 90°C to obtain black solid (3-166) (47 mg, 49%). GPC(THF): Mn=5200g / mol, Mw=11800g / mol, PDI=2.27.

[0775] [Example 10]

[0776] [ka]

[0777] 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 bubbled with argon for 30 minutes. To this mixture, Pd2(dba)3·CHCl3 (2.5 mg, 2.4 μmol) and tri(o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added and stirred at 120 °C for 66 h. The resulting mixture was cooled to room temperature and precipitated in a methanol / concentrated hydrochloric acid mixture (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, precipitated in methanol, and the precipitated solid was filtered. The resulting solid was washed with methanol and dried under reduced pressure at 90 °C to give (3-646) as a black solid (12 mg, 7%). GPC(THF): Mn=14800g / mol, Mw=30000g / mol, PDI=2.03.

[0778] [Example 11]

[0779] [ka]

[0780] 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 bubbled with argon for 30 minutes. To this mixture, Pd2(dba)3·CHCl3 (2.5 mg, 2.4 μmol) and tri(o-tolyl)phosphine (2.9 mg, 9.7 μmol) were added and stirred at 120 °C for 65 h. The resulting mixture was cooled to room temperature and precipitated in a methanol / concentrated hydrochloric acid mixture (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, precipitated in methanol, and the precipitated solid was filtered. The resulting solid was washed with methanol and dried under reduced pressure at 90 °C to give (3-666) as a black solid (78 mg, 40%). GPC(THF): Mn=5500g / mol, Mw=8400g / mol, PDI=1.53

[0781] [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, confirming its poor atmospheric stability. [Industrial Applicability]

[0782] 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 applied as a material for semiconductor devices such as organic thin-film transistor elements and organic thin-film solar cells. [Explanation of symbols]

[0783] 1. Organic semiconductor layer 2 boards 3. Gate electrode 4 Gate insulating layer 5. Source electrode 6 Drain electrode

Claims

1. A structural unit represented by the following general formula (1), 【Chemistry 1】 (In the formula, R １ and R ２ R each independently represents an alkyl group having 1 to 50 carbon atoms. １ and R ２ and may be taken together to form a ring together with the carbon atoms to which they are attached. ３ and R ４ R each independently represents an alkyl group having 1 to 50 carbon atoms. ３ and R ４ and may be taken together to form a ring together with the carbon atoms to which they are attached. ５ and R ６ Each of J independently represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. １ , J ２ , J ３ and J ４ each independently represents a chalcogen atom.) A conjugated polymer comprising a structural unit represented by the following general formula (2): 【Chemistry 2】 (In the formula, X １ 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.

2. 2. The conjugated polymer according to claim 1, which has structural units represented by the general formula (1) and structural units represented by the general formula (2) alternately.

3. R １ and R ２ are each independently an alkyl group having 1 to 34 carbon atoms, R １ and R ２ and may be taken together to form a ring with the carbon atoms to which they are attached, R ３ and R ４ are each independently an alkyl group having 1 to 34 carbon atoms, R ３ and R ４ and may be taken together to form a ring with the carbon atoms to which they are attached, R ５ and R ６ are each independently a hydrogen atom, an alkyl group having 1 to 34 carbon atoms, or a fluorine atom, J １ , J ２ , J ３ and J ４ 3. The conjugated polymer according to claim 1, wherein each of the groups independently represents an oxygen atom, a sulfur atom, or a selenium atom.

4. R ５ and R ６ is a hydrogen atom, J １ , J ２ , J ３ and J ４ The conjugated polymer according to any one of claims 1 to 3, wherein is a sulfur atom.

5. X １ is a divalent heteroaromatic ring linking group selected from the group consisting of the following general formulas (4) to (8): 【Transformation 3】 (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. 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. ７ may be the same or different. ８ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. ８ may be the same or different. １ and q １ each independently represents 0 or 1. 【Chemistry 4】 (In the formula, A ２ represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. ３ represents a chalcogen atom. ９ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. ９ may be the same or different. ２ and q ２ each independently represents 0 or 1. 【Transformation 5】 (In the formula, A ４ and A ５ R each independently represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. １０ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. １０ may be the same or different. １１ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. １１ may be the same or different. ３ and q ３ each independently represents 0 or 1. 【Transformation 6】 (In the formula, R １２ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. １２ may be the same or different. ４ and q ４ each independently represents 0 or 1. 【Transformation 7】 (In the formula, R １３ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. １３ may be the same or different. ５ and q ５ each independently represents 0 or 1.

6. A １ , A ２ , A ３ , A ４ and A ５ each independently represents an oxygen atom, a sulfur atom, a selenium atom, or a nitrogen atom optionally 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 are each independently an alkyl group having 6 to 50 carbon atoms or a hydrogen atom, and R １２ and R １３ and each independently represents an alkyl group having 6 to 50 carbon atoms.

7. A １ and A ２ is a sulfur atom, A ３ is an oxygen atom or a nitrogen atom which may be substituted with an alkyl group having 6 to 34 carbon atoms, A ４ is an oxygen atom, a sulfur atom, or a selenium atom, A ５ 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 are each independently an alkyl group having 6 to 34 carbon atoms or a hydrogen atom, R １２ and R １３ The conjugated polymer according to claim 5 or 6, wherein each of the groups independently represents an alkyl group having 6 to 34 carbon atoms.

8. A monomer represented by the following general formula (mono-hal): 【Transformation 8】 (In the formula, R １ and R ２ R each independently represents an alkyl group having 1 to 50 carbon atoms. １ and R ２ and may be taken together to form a ring together with the carbon atoms to which they are attached. ３ and R ４ R each independently represents an alkyl group having 1 to 50 carbon atoms. ３ and R ４ and may be taken together to form a ring together with the carbon atoms to which they are attached. ５ and R ６ Each of J independently represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. １ , J ２ , J ３ and J ４ Each independently represents a chalcogen atom. １－ｈａｌ and M ２－ｈａｌ each independently represents a halogen atom. In the presence of a transition metal catalyst, １ -B) 【Chemistry 9】 (In the formula, X １ 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. ３－Ｂ and M ４－Ｂ each independently represents a boron-containing group. A structural unit represented by the following general formula (1), 【Chemistry 10】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , J １ , J ２ , J ３ and J ４ represents the same meaning as above.) and a structural unit represented by the following general formula (2): 【Chemistry 11】 (In the formula, X １ represents the same meaning as above.)

9. A monomer represented by the following general formula (mono-hal): 【Chemistry 12】 (In the formula, R １ and R ２ R each independently represents an alkyl group having 1 to 50 carbon atoms. １ and R ２ and may be taken together to form a ring together with the carbon atoms to which they are attached. ３ and R ４ R each independently represents an alkyl group having 1 to 50 carbon atoms. ３ and R ４ and may be taken together to form a ring together with the carbon atoms to which they are attached. ５ and R ６ Each of J independently represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. １ , J ２ , J ３ and J ４ Each independently represents a chalcogen atom. １－ｈａｌ and M ２－ｈａｌ each independently represents a halogen atom. In the presence of a transition metal catalyst, １ -Sn) 【Chemistry 13】 (In the formula, X １ 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. ３－Ｓｎ and M ４－Ｓｎ each independently represents a tin-containing group. A structural unit represented by the following general formula (1), 【Chemistry 14】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , J １ , J ２ , J ３ and J ４ represents the same meaning as above.) and a structural unit represented by the following general formula (2): 【Chemistry 15】 (In the formula, X １ represents the same meaning as above.)

10. A monomer represented by the following general formula (mono-B): 【Chemistry 16】 (In the formula, R １ and R ２ R each independently represents an alkyl group having 1 to 50 carbon atoms. １ and R ２ and may be taken together to form a ring together with the carbon atoms to which they are attached. ３ and R ４ R each independently represents an alkyl group having 1 to 50 carbon atoms. ３ and R ４ and may be taken together to form a ring together with the carbon atoms to which they are attached. ５ and R ６ Each of J independently represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. １ , J ２ , J ３ and J ４ Each independently represents a chalcogen atom. １－Ｂ and M ２－Ｂ each independently represents a boron-containing group. In the presence of a transition metal catalyst, １ -hal) 【Chemistry 17】 (In the formula, X １ 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. ３－ｈａｌ and M ４－ｈａｌ each independently represents a halogen atom. A structural unit represented by the following general formula (1), [Chemistry 18] (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , J １ , J ２ , J ３ and J ４ represents the same meaning as above.) and a structural unit represented by the following general formula (2): 【Chemistry 19】 (In the formula, X １ represents the same meaning as above.)

11. A monomer represented by the following general formula (mono-Sn): 【Chemistry 20】 (In the formula, R １ and R ２ R each independently represents an alkyl group having 1 to 50 carbon atoms. １ and R ２ and may be taken together to form a ring together with the carbon atoms to which they are attached. ３ and R ４ R each independently represents an alkyl group having 1 to 50 carbon atoms. ３ and R ４ and may be taken together to form a ring together with the carbon atoms to which they are attached. ５ and R ６ Each of J independently represents a hydrogen atom, an alkyl group having 1 to 50 carbon atoms, or a fluorine atom. １ , J ２ , J ３ and J ４ Each independently represents a chalcogen atom. １－Ｓｎ and M ２－Ｓｎ each independently represents a tin-containing group. In the presence of a transition metal catalyst, １ -hal) 【Chemistry 21】 (In the formula, X １ 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. ３－ｈａｌ and M ４－ｈａｌ each independently represents a halogen atom. A structural unit represented by the following general formula (1), 【Chemistry 22】 (In the formula, R １ , R ２ , R ３ , R ４ , R ５ , R ６ , J １ , J ２ , J ３ and J ４ represents the same meaning as above.) and a structural unit represented by the following general formula (2): 【Chemistry 23】 (In the formula, X １ represents the same meaning as above.)

12. 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): 【Chemistry 24】 (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 represents the same meaning as above.)

13. X １ is a divalent heteroaromatic ring linking group selected from the group consisting of the following general formulas (4) to (8): 【Chemistry 25】 (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. 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. ７ may be the same or different. ８ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. ８ may be the same or different. １ and q １ each independently represents 0 or 1. 【Chemistry 26】 (In the formula, A ２ represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. ３ represents a chalcogen atom. ９ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. ９ may be the same or different. ２ and q ２ each independently represents an integer of 0 or 1. 【Chemistry 27】 (In the formula, A ４ and A ５ R each independently represents a chalcogen atom or a nitrogen atom which may be substituted with an alkyl group having 1 to 50 carbon atoms. １０ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. １０ may be the same or different. １１ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. １１ may be the same or different. ３ and q ３ each independently represents an integer of 0 or 1. 【Chemistry 28】 (In the formula, R １２ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. １２ may be the same or different. ４ and q ４ each independently represents an integer of 0 or 1. 【Chemistry 29】 (In the formula, R １３ represents an alkyl group having 1 to 50 carbon atoms or a hydrogen atom. １３ may be the same or different. ５ and q ５ each independently represents an integer of 0 or 1.

14. A film-forming composition comprising the conjugated polymer according to any one of claims 1 to 7.

15. An organic thin film comprising the conjugated polymer according to any one of claims 1 to 7.

16. An organic semiconductor device comprising the conjugated polymer according to any one of claims 1 to 7.

17. An organic transistor element comprising the conjugated polymer according to any one of claims 1 to 7.

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